EP3523403A1 - Verfahren und system zur verbesserung der treibhausgas-emissionsminderungsleistung biogener kraft-, heiz- und brennstoffe und/oder zur anreicherung landwirtschaftlich genutzter flächen mit humus-c - Google Patents
Verfahren und system zur verbesserung der treibhausgas-emissionsminderungsleistung biogener kraft-, heiz- und brennstoffe und/oder zur anreicherung landwirtschaftlich genutzter flächen mit humus-cInfo
- Publication number
- EP3523403A1 EP3523403A1 EP17793576.4A EP17793576A EP3523403A1 EP 3523403 A1 EP3523403 A1 EP 3523403A1 EP 17793576 A EP17793576 A EP 17793576A EP 3523403 A1 EP3523403 A1 EP 3523403A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- biomass
- biochar
- conversion
- straw
- fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- C—CHEMISTRY; METALLURGY
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/14—Features of low-temperature carbonising processes
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- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Definitions
- the invention relates to the production of greenhouse gas, heating and fuel from biomass and the assurance or improvement of the quality of agricultural and forestry land by securing or improving their humus content.
- German Federal Environmental Agency According to the statistics of the German Federal Environmental Agency, the German share of European GHG emissions in 1990 was approx. 1,251 million tonnes C0 2 equivalents, so that for Germany in 2050 an emission target of a maximum of 63 - 250 million tonnes C0 2 -eq. results.
- the German Federal Government also confirmed this goal in its energy concept written in 2010. It was reaffirmed in 2014 in the action program "Climate Protection 2020" of the Federal Government and in 2016 in the "Climate Action Plan 2050" and fixed with measures highlighted.
- German policy program for 2020 states a residual GHG emission of a maximum of 751 million tons (minus 40% compared to 1990), for the year 2030 one of maximum 563 million tons (minus 55%) %) and for 2040 a reduction of up to 375 million tonnes (minus 70%) in GHG emissions.
- German GHG emissions had dropped from 1,251 million t C0 2 -eq in 1990 to 941 million t C0 2 -eq (-25%); in 2015 it was only 902 million t C0 2 -Eq (-28%). In 2016, however, it reached 906 million tonnes C0 2 -eq (-27.6%).
- greenhouse gas emissions in each of the remaining 4 years to 2020 will have to be reduced by 38.75 million t C0 2 -eq (-3.1 percentage points per year). 1990) and annually thereafter by 18.80 million t C0 2 -eq / year (-1.5% -points / a since 1990). It is already foreseeable that the measures adopted so far will not be sufficient to achieve the targeted GHG emission reduction benefits.
- the GHG emissions from transport are to be reduced mainly by reducing the use of energy by 12-16% compared to the energy input of 2005 by 2020, by 2030 compared to the previous year. 2005 by 21 - 31%, by 2040 by 31 - 45% and by 2050 by 40 - 60%.
- 2005 by 21 - 31%, by 2040 by 31 - 45% and by 2050 by 40 - 60%.
- the GHG reduction performance is to be achieved by 86% - 105% over the fuel consumption and to 14% to -5% above the specific energy-related GHG emission reduction (fuel consumption of 21% - 31% accounts for about 105% to 86% of GHG reduction from 20% to 36%).
- GHG reduction is still expected to reach 66% - 78% of fuel consumption and only 34% to 22% over the specific GHG emissions reduction (fuel consumption of 31% - 45% makes approx 78% to 66% of the GHG reduction from 40% to 68% off).
- 61% - 70% GHG reduction is to be achieved through fuel consumption and only 39% to 30% through the specific GHG emissions reduction (fuel consumption of 40% - 60% makes approx. 70% to 61% of the GHG reduction from 57% to 98% off).
- the study aims to achieve the GHG reduction performance mainly through the production of liquid and gaseous fuels from renewable electric power (Power to Liquid PtL and Power to Gas PtG), whereby the GHG emissions associated with the electricity production - almost as a sham-pack - not the traffic but be charged to the energy sector.
- renewable electric power Power to Liquid PtL and Power to Gas PtG
- the challenge is to eliminate the reliance of transport on oil, without sacrificing its efficiency and restricting mobility.
- existing resources need to be used sustainably to provide high quality mobility options.
- transport needs to consume more environmentally friendly, non-fossil energy, make better use of modern infrastructure and reduce its negative impact on the environment and important natural assets such as water, land and ecosystems.
- the European Council the European Commission, the European Parliament and the Member States have therefore set themselves the goal of reducing the current greenhouse gas emissions from the transport sector (see Directive 2015/1513 of the European Parliament and of the Council of 9 September 2015).
- suppliers of fossil fuels are expected to have at least lifecycle greenhouse gas emissions (LCA-GHG emissions) per unit of energy To reduce 6%. It will also encourage research and development into new advanced biofuels that will deliver high greenhouse gas emission reductions and will not compete directly with agricultural land for food and feed production.
- the EU (Council, Commission, Parliament, Member States) considers it desirable to achieve a significantly higher consumption of advanced fuels by 2020 compared to the currently consumed quantity, as they will play an important role in reducing transport-related C0, especially after 2020 2 emissions and in the development of C0 2 low-emission transport technologies.
- biogenic feedstocks are to be preferred which have no high economic value for uses other than the production of biofuels and which have high greenhouse gas emission reduction performance.
- waste and residual materials are of particular importance as potential feedstocks for fuel production.
- the Earth's atmosphere has a certain amount of greenhouse gases (GHG), including water vapor, carbon dioxide (C0 2 , also known as carbon dioxide), methane (CH 4 ) and nitrous oxide (nitrous oxide N 2 0, also known as nitric oxide) ).
- GFG greenhouse gases
- C0 2 also known as carbon dioxide
- CH 4 methane
- nitrous oxide nitrous oxide N 2 0, also known as nitric oxide
- nitrous oxide is approximately 298 times more polluting than carbon dioxide and methane about 25 times as polluting.
- Environmental damage is equated in this context with the temperature-increasing effect of greenhouse gases on the earth's atmosphere.
- GHG emission rate a reduction in the GHG emission rate
- GHG emission rate merely means that GHG emissions (the additional GHG) decrease, while a reduction in GHGs reduces the absolute levels of GHG levels in the Earth's atmosphere.
- ERL Emission Reduction Unit
- RMU Removal according to Annex to Commission Decision 13 / CMP.l Unit ", RMU).
- the experts take the lifecycle greenhouse gas emissions, which in the production, distribution and use of the (fossil) fuels (petrol) and diesel (diesel fuel) produced from fossil petroleum over the result in the entire manufacturing and usage path.
- the greenhouse gas emission (or greenhouse gas intensity, greenhouse gas pollution, greenhouse gas balance) of this fossil reference was 83.8 gC0 2 -eq / MJ according to EU Directive 2009/28 / EC, which is 301.7 gC0 2 -eq / kWh Hi .
- EU Council Directive 2015/652 of 20 April 2015 specifying the calculation methods for the quality of petrol and diesel fuels has detailed and redefined the procedure for calculating greenhouse gas intensity and corresponding standard values. To avoid repetition, please refer to this EU Directive for the calculation of GHG emission values (GHG intensity) and absolute GHG emission values, and in particular to July's "Well to Tank Report” (version 4) 2013 of the Joint Research Center-EUCAR-CONCAWE (JEC consortium).
- the default values for fossil fuels are 93.3 gC0 2 -eq / MJ (335.9 gC0 2 -eq / kWh Hi ) for petrol and 95.1 for diesel fuel, according to the sales-weighted average of the respective petrol sources gC0 2 -eq / MJ (342.4 gC0 2 -eq / kWh Hi ), for LPG 73.6 gC0 2 -eq / MJ (265.0 gC0 2 -eq / kWh Hi ), for compressed natural gas (CNG) 69 , 3 gC0 2 -eq / MJ (249.5 gC0 2 -eq / kWh Hi ), for liquefied natural gas (LNG) 74.5 gC0 2 -eq / MJ (268.2 gC0 2 -eq / kWh H i), for compressed Sabatier-derived synthetic methane (SynMethan) 3.3 g
- the weighted average of all fossil fuels is now 94.1 gC0 2 -eq / MJ (338.8 gC0 2 -eq / kWh Hi ), ie 10.3 gC0 2 -eq, according to EU Directive 2015/652 / MJ (37.1 gC0 2 -eq / kWh Hi ) more than before.
- a reduction of 1.00% in the (technical) reference value specified by the EU Commission corresponds to a reduction of the LCA-THG emission by 3.388 gC0 2 -eq / kWh H i.
- This reduction of the LCA greenhouse gas emission value and each multiple thereof as well as the initial value (fossil reference value) represent technical values, because the reduction of a (generally accepted) technical value is the (technical) result of a technical process. Accordingly, the terms "greenhouse gas emission savings", “greenhouse gas emission reduction” and “greenhouse gas emission reduction performance” also describe technical issues.
- GHG emissions are also not equivalent to C0 2 -binding measures.
- the former reduce the rate of fossil carbon emission
- the latter such as reforestation actually removes atmospheric carbon via photosynthesis, albeit not really permanently, but only over the lifetime of the respective tree or wood product (ie for about 20 to 500 years).
- the tree or the wood product rots, whereby the aerobic rotting represents a chemical oxidation process, which uses atmospheric oxygen, so that the atmospheric carbon finally ends up in the earth's atmosphere.
- EU Directive 2009/28 / EC reports on a large number of biogenic and synthetic fuels and their various production routes, how high they are with their GHG emissions.
- the emission values were determined according to the LCA method. None of the biofuels listed in the Directive, nor any of the listed synthetic fuels, has a GHG emissions of 0 gC0 2 -eq / MJ or 0 gC0 2 -eq / kWh H i.
- the greenhouse gas pollution is calculated as the sum of the (indirect) greenhouse gas emissions of all energies or of all energy sources involved in cultivation, harvesting, biomass storage, transport, conversion into marketable energy sources, energy storage, distribution and energy And (direct) GHG emissions emitted into the Earth's atmosphere in the form of N 2 O, CH 4 , C0 2 and other greenhouse gases.
- BEV battery-electric
- PHEV plug-in hybrid
- LLC Power to Gas
- PtL Power to Liquid
- the production of fuel from straw is such an energetic purpose. Assuming a conversion efficiency of 40%, a national straw transport of 8 - 15 million tonnes with a calorific value of approx. 33,000 - 61,000 GWh Hi (120 - 220 PJ) a fuel amount of about 13,100 - 24,500 GWh Hi (48 - 88 PJ) are produced. With a conversion efficiency increased to 70%, the amount of fuel that can be produced from German straw increases accordingly to 23,000 - 43,000 GWh Hi (83 - 155 PJ).
- a (minor) part of the straw-derived atmospheric carbon incorporated into the soil does not oxidize to C0 2 in the short-term, but remains with degressively decreasing levels for a while (maximum several decades) as part of the so-called active nutrient humus in the soil , In contrast, passive permanent humus remains in the soil for centuries and millennia.
- Humus is a complex mixture of living and dead organic matter contained above all in the field soil. This organic soil substance (OBS) is the basis of life for heterotrophic soil organisms.
- Scattering substances of plant origin such as chopped straw and litter of animal origin such as manure (manure, manure) are introduced to the soil by fungi, representatives of macrofauna (eg earthworms, woodlice, millipedes) or representatives of Mesofauna (eg Enchyträen , Collembola) in a permanent dismantling, rebuilding and construction process.
- macrofauna eg earthworms, woodlice, millipedes
- Mesofauna eg Enchyträen , Collembola
- humus consists of relatively short-chain substances of various kinds (polysaccharides, polypeptides, aliphatic groups (fats), polyaromatic lignin fragments), which form so-called aggregates with cations, sand and clay particles.
- humus content and soil fertility are set to each other more or less the same.
- the soil humus stocks are more easily divided into two fractions of different (biochemical stability and lifetime, namely the active and labile part of the nutrient humus and the passive and stable part of the permanent humus.)
- the greater part of the soil's humus resources has been in one since the last ice age It is chemically very stable and is therefore also known as "permanent humus.”
- Decomposition products from the organic substance supplied form solid bonds with the clay and fine silt particles of the soil, so that further degradation of this OBS occurs
- the long-term humus is therefore characterized by residence times of hundreds to thousands of years.
- This largely stable humus fraction comprises about 20% - 50% of the total humus content in light soils and more than 80% in heavy soils.
- the organic substances added in the form of harvest and root residues as well as manure belong to the so-called active nutrient humus, an unstable, partially highly labile humus fraction.
- This nutrient humus is subject to permanent biochemical conversion processes, which are more or less rapid.
- the biochemically very readily degradable components are used in the short term - usually within a few months - by the soil organisms (animals, microorganisms, fungi) as food and energy source and respired to carbon dioxide.
- These materials include, in particular, those with narrow C / N ratios, such as green manure.
- Heavy degradable organic substances such as crop and root residues with wide C / N ratios and high lignin contents such as straw, which has a C / N ratio of 70/1 to 100/1 (average 86/1), as well as Remains and metabolic products of soil organisms accumulate in the soil initially a bit until they are still degraded after a few decades. Ultimately, all organic substances that are not permanently chemically stabilized are completely degraded within 25 to 30 years.
- the degraded organic matter is finally released into the soil as (seepage) water and into the atmosphere as carbon dioxide.
- the nutrients incorporated with the plant and animal materials (especially the functional elements potassium and sodium) are mostly released in the first year after their introduction into the soil, because they are not incorporated in the plant cell structures.
- the organically bound basic nutrients nitrogen, phosphorus and sulfur and some trace elements are largely released in the medium term and are then available for plant growth. This release of chemical building materials is called mineralization.
- humus composition is determined by the type and quantity of crop and root residues, by the amount of dead soil and micro-organisms and the organic fertilizers, which are collectively referred to as organic primary substances (OPS). How long these OPS stay in the soil depends on the degradation intensity or the degradation resistance of the OBS.
- OPS organic primary substances
- OBS organic compound
- C / N ratio properties of the substrate to be decomposed
- degree and type of stabilization depends on the site-specific soil characteristics and the characteristics of the OBS.
- One form of stabilization of OBS is in interaction with minerals from the clay fraction (clay minerals, iron oxides). In the process, so-called clay-humus associates form. These compounds are so stable that they largely protect the plant's atmospheric carbon from oxidation by microorganisms and other chemical reactions.
- the humus also serves as a storage and transformer of nutrients, especially nitrogen, sulfur and phosphorus, a gradual release of these nutrients allows an improvement in nutrient utilization. Furthermore, humus serves as a buffer and filter, because it can immobilize toxic substances and sometimes detoxify. Humus consists essentially of organic carbon, organic oxygen, organic hydrogen, organic nitrogen, organic phosphorus and organic sulfur. These elements also occur in soil in inorganic compounds. An analytical separation between the organic and inorganic components is possible only for carbon. Therefore, the content of organic carbon is used as a measure of the humus content of a soil.
- Humus dry matter consists of 30% - 70% (weighted average 58%) of organic and thus of atmospheric carbon. Carbon is the most important constituent of soil organic matter (OBS) with this mass fraction.
- the humus content and the carbon content of the uppermost soil layer (crumb) in farmland are 1% - 4% humus (with an average C content of humus of 58% ie 0.58% - 2.32% humus concentration ) , in forest areas 2% - 8% humus (1,16% - 4,64% humus-C org ) and in grassland 4% - 15% (2,32% - 8,7% humus-C org ).
- the Soil Mapping Guide KA-2005 of the working group Soil of the German Federal Institute for Geosciences-Shafts and Raw Materials (BGR) the humus and C contents of the uppermost soil layer are divided into 7 stages.
- the degradation of OBS and thus of carbon is substrate-dependent degressive: with application of peat and wood after 1 year still 75% of the first C dose in the soil still present, after 2 years still 65% and after 3 years still 60%. Green manure is much shorter-lived: after 1 year only 15% are available, after 2 years only 10% and after 3 years only 5%. Only 35% of the native straw incorporated into the soil is present after 1 year, 25% after 2 years and 15% after 3 years. After 25-30 years of an OBS administration, apart from the final degradation products water (H 2 0) and carbon dioxide (C0 2 ), nothing is left in the soil and even these are usually seeped or evaporated after this time.
- H 2 0 water
- C0 2 carbon dioxide
- the rate of degradation of the OBS is i.a. determined by the C / N ratio, which is almost ideal for green organisms with the relation of 20 for soil organisms, which is already much higher for straw with 70-100 (on average 86) and extremely wide for peat / wood with up to 300 ,
- an aerobic physicochemical rotting process is used, which, as in composting, reduces part of the biomass in an exothermic oxidation. That is, a (highly-labile) part of the freshly supplied biomass is decomposed within a few weeks and months. Only the uncorrupted remainder of the supplied biomass enters the unstable pool of nutrient humus for a longer period (1-30 years).
- the so-called Humus equivalents H ⁇ Q which are measured in kg of humus equivalent / t of substrate, there are both for the wet mass H ⁇ Q as well as for the respective dry matter.
- the H ⁇ Q factors tend to be lower than with low supply quantities, because with high doses the degradation rate is higher.
- these H ⁇ Q values should be divided by the average factor of 1.724 or multiplied by the average percentage of 58%, bearing in mind that the range of carbon content is 30% - 70% depending on the location, which is H ⁇ Q Factors of 3.3-1.4.
- straw With its 41 - 83 kg H ⁇ Q / t straw FM, straw only provides approx. 12-58 kg of cotton / t straw-FM (on average 35 kg cotton / t straw-FM) into the soil and the rather solid phase of the fermentation residues listed above only 7-32 kg cotton / t FM (on average approx 20 kg C org / t FM). Due to the wide C / N ratio and the resulting degradation resistance, straw is still relatively well suited as a humus former, because it takes relatively long compared to other organic substrates until soil flora and soil fauna have completely decomposed.
- high humus levels in the soil are associated with high soil biological activity, which has positive phytosanitary effects and tends to reduce the need for pesticides.
- High humus contents generally result in increased aggregate stability, good soil aeration, improved water retention, increased root penetration, reduced soil erosion, less surface runoff, and reduced soil compaction.
- the cumulative humus content ceteris paribus does not increase any more.
- the respective soil has reached a so-called steady-state equilibrium, in which the input from the organic fertilizer corresponds exactly to the amount of organic substance which is mined annually via the mineralization.
- the organic fertilizer from the first year of application was completely degraded at this time. Accordingly, there is a new site-specific humus level. Accordingly, an increase in the supply level of organic materials leads to an increase in the humus supply and the humus content of the soil.
- straw humification is to be assumed to be 100 kg humus-C per metric ton of wet straw mass, with an average humus-carbon content of 58% approx. 58 kg org / t straw wet mass (range: 30 - 70 kg C org ).
- VDLUFA-humus accounting is straw with a humus reproduction power of 80 - rated 110 kg H ⁇ Q per tonne straw wet mass, which when applied to the full bandwidth of a carbon content of 24 - 77 kg C org / t straw FM corresponds to, and on average approx , 50 kg Corg / t straw-FM.
- Bavarian straw farms should achieve a humus reproduction capacity of 70 kg H ⁇ Q (41 kg C org ) per ton of straw wet mass.
- recuperate C0 2 in order to produce emission-reduced energy carriers from coal, natural gas or crude oil, firstly post-combustion capture technology, secondly superstoichiometric combustion (oxyfuel technology) and thirdly Pre Combustion Capture Technology.
- the post-combustion capture technology is mainly used in coal-fired power plants that burn fossil coal for power generation to separate and recuperate from their flue gas (fossil) C0 2 , so that the C0 2 emission rate of the coal-fired power plant and the GHG emission value of the generated electric current goes back.
- US 2007 / 0178035A1 White / Allam
- DE102008062497A1 Lide-KCA-Dresden
- DE102009043499A1 Uhde
- the extracted fossil C0 2 is to be sent to a geological disposal facility (so-called CCS process, whereby CCS stands for Carbon Capture and Storage).
- CCS Carbon Capture and Storage
- the additional and additional load of the earth's atmosphere with additional fossil C0 2 should be reduced and ideally avoided in the ideal case.
- WO 2004/094901 A1 (Abrams & Culvey) can be cited.
- WO2004 / 094901A1 teaches a two-stage combustion of solid carbon-containing fuels with pure oxygen and nitrogen-free associated gases such as argon and carbon dioxide, wherein initially a fuel gas is produced under nitrogen-free conditions. This fuel gas is burned (oxidized) with superstoichiometric addition of pure oxygen and argon to generate heat and convert it into steam in a boiler.
- the highly C0 2 -containing and largely free of nitrogen oxides flue gas from this superstoichiometric combustion is freed using flywheel and dust using cyclone technology.
- the resulting exhaust gas is freed from gaseous salts by means of an "acid gas scrubber" and sent to a C0 2 cryogenic separation plant
- the resulting pure C0 2 is returned to the first (or second) combustion stage to a lesser extent for control of the process , the produced C0 2 is used as an industrial product for the most part.
- Wh2004 / 094901A1 speaks of biomass as a fuel, but means all hydrocarbon-containing solid fuels including crude oil-based scrap tires and crude oil-based plastics.
- WO2004 / 094901A1 correctly states that every combustion of hydrocarbons produces the greenhouse gas carbon dioxide, but it gives as the intended use of the deposited C0 2 s only the use as an industrial product. That is to say, WO2004 / 094901A1 does not disclose a method or a system with which atmospheric carbon could be chemically-physically stabilized. WO 2004/094 901 Al also does not describe the chemical-physical stabilization of atmospheric carbon in order to avoid a reaction with atmospheric oxygen to (atmospheric) C0 2 neither as a method nor as a device. Also, WO2004 / 094901A1 does not disclose carbonation of atmospheric carbon still contained in conversion residues to biochar / biochar / biokoks.
- WO2004 / 094901A1 describes an incorporation of atmospheric carbon, which is stabilized chemically and physically, in agriculturally used soil in order to maintain or improve the humus content of this soil.
- WO2004 / 094901 AI also teaches no method that permanently removes atmospheric carbon from the earth's atmosphere, neither a process for sequestering atmospheric carbon as such nor the substitution of fossil C0 2 by atmospheric C0 2 , nor the production of GHG emissions synthetic methane from GHG emission-reduced hydrogen and atmospheric C0 2 , nor its use as a substitute for one or more fossil fuels.
- WO2004 / 094901 AI is also not suitable, because the WO2004 / 094901A1 distinguishes between neither fossil and atmospheric carbon nor between fossil and atmospheric C0 2 - which is an essential basis for the invention and for the evaluation of the invention - are still the devices of WO2004 / 094901A1 suitable to ensure that the total stock of the located in the earth's atmosphere Greenhouse gases are not further increased despite the production of power, heating or fuel.
- WO2004 / 094901A1 also does not teach to optimize the overall process of production, distribution and use of power, heating or fuel with respect to the emission of greenhouse gases.
- WO 2004/094 901 AI describes the combination of their system with a power, heating or fuel production and use system that the determined according to LCA GHG-positive GHG emission rates of a power, heating or fuel with also determined by the LCA method GHG emission levels of another, compatible power, heating or fuel to a balanced total amount of GHG of a corresponding power, heating or fuel mixture brings together.
- IGCC power plants Integrated Gasification Combined Cycle
- fossil fuels such as coal
- regenerative energy sources such as biomass or waste by gasification in partial oxidation substoichiometrically with water in convert a (fuel) gas that consists essentially of hydrogen and carbon monoxide.
- CO carbon monoxide
- H 2 hydrogen
- the (combustion) gas freed from C0 2 is emitted with high efficiency in gas turbines, but it can also produce pure hydrogen, methanol, ethanol or synthetic methane, octane, propane, butane or DME. Since the C0 2 is removed from this prior to use of the (fuel) gas, this technique is also referred to as "Pre Combustion Capture” technology, but as a by-product of the PCC process then only C0 2 and no coal or coke IGCC power plants have up to 15% lower GHG emission levels, which makes them seem relatively clean compared to conventional coal-fired power plants, yet their GHG emission reduction performance is only 15% and not 100%, let alone IGCC THG -negative emission values.
- CN102784544 (A) (XU et al.) Is an example of such a pre-combustion capture technique.
- This disclosure which falls within the Clean Coal Power Generation field, describes a system for PCC recuperation of C0 2 prior to use of the generated (combustible) gas.
- the invention relates to an IGCC-based precombustion C0 2 .
- a deposition system comprising a sulfur resistant conversion device, a MDEA (methyl di ethanol amine) desulfurizer and decarburizer and a sulfur and carbon separator
- the sulfur resistant converter is converted to a mixed gas for conversion of CO contained in the synthesis gas.
- the MDEA desulfurization and decarburization apparatus comprises an absorption tower and a desorption tower
- the absorption tower serves to receive the mixed gas in the sulfur-resistant conversion apparatus and to absorb C0 2 and H 2 S gases and d
- the desorption tower is used to hold C0 2 and H 2 S and to desorb C0 2 and H 2 S.
- the sulfur and carbon separator comprises a desulphurisation cleaner for receiving C0 2 and H 2 S gases in the desorption tower. And the H 2 S gas is absorbed by an H 2 S absorber, leaving the C0 2 gas.
- CN102784544 (A) does not differentiate between fossil and atmospheric carbon nor between fossil and atmospheric C0 2 - which is an essential basis for the invention and for the evaluation of the invention.
- the PCC technique of CN102784544 (A) does not produce any chemically-physically stabilized carbon, let alone a chemically-physically stabilized atmospheric carbon. Carbonation of atmospheric carbon still contained in conversion residues is also not taught by CN102784544 (A).
- CN 102 784 544 (A) does not include the incorporation of atmospheric carbon which has been chemically stabilized into agricultural soil for the purpose of maintaining or improving the humus content of that soil.
- the PCC technology does not even include the combination of a PCC system with a power, heating or fuel production and use system, which also meets the LCA-determined GHG emissions of a power, heating or fuel LCA methodology of another compatible fuel, heating or
- DE 197 47 324 C2 (Wolf) describes a device for producing fuel, synthesis and reducing gas from fossil and renewable fuels, biomass, waste and sewage sludge by means of pyrolysis (CHOREN method).
- the up to 500 ° C hot carbon and the resulting from the charring residual coke are converted in a reaction chamber at 500 ° C to 1200 ° C in fuel, synthesis or reducing gas, leaving only mineral slag that contains no carbon.
- DE19747324C2 knows neither the difference between fossil and atmospheric carbon nor the difference between fossil and atmospheric CO 2 - which is an essential basis both for the invention itself and for the evaluation of the invention. Accordingly, DE19747324C2 can also give no atmospheric carbon, let alone chemically-physically stabilized atmospheric carbon.
- DE19747324C2 can not remove C0 2 from the earth's atmosphere and thus can not decarburize the earth's atmosphere. Even if only biomass such as straw were used, the atmospheric carbon contained in the straw returns to the earth's atmosphere.
- Bioliq ® process of the Düsseldorf Institute of Technology (http://www.bioliq.de/55.php), which aims to produce synthetic fuels and basic chemical products from dry biomass.
- the Bioliq ® process comprises the five process steps of fast pyrolysis, energy compression, high-pressure fly-by-gas gassing, gas purification and fuel synthesis.
- Final products are designer fuels such as SynDiesel, SynBenzin, SynKerosin, SynDME and SynMethanol, synthesized by synthesis of Fischer-Tropsch, methanol or dimethyl ether from synthesis gas.
- many raw materials for the chemical industry can be produced from syngas.
- advantages of synthetic fuels produced from biomass compared to other biofuels and compared.
- the developers of the Bioliq ® process specify the following: Synthesis products that are produced from coal in the CtL process or from natural gas using the GtL process: Conservation of fossil fuels; partial independence of energy imports; broad spectrum of raw materials; no use or area competition for food production; Contribution to strengthening regional agriculture; existing infrastructure usable without change; no change to the vehicle technology necessary; Provision of a wide range of fuel types (SynDiesel, SynKerosin, SynBenzin) possible; Customization ("designer fuels”) possible on different engine types, no change in driving habits (range) required, reduction of anthropogenic C0 2 emissions.
- the chopped biomass is converted into hot carbonization gas (pyrolysis vapors) and fine coke at 500 ° C in a twin-screw reactor within seconds.
- pyrolysis vapors hot carbonization gas
- fine coke 500 ° C in a twin-screw reactor within seconds.
- a heat transfer circuit in which a 5-10-fold excess of sand is mixed with the biomass in the reactor.
- the pyrolysis vapors are quench cooled to ambient temperature and thereby liquefied to a heavy oil-like aqueous condensate (slurry).
- a smoldering agent and a flammable pyrolysis gas which consists essentially of carbon dioxide and monoxide and hydrocarbons and is burnt together with part of the pyrolysis residue contained in the sand - a fine coke.
- the resulting flue gas heats the circulating sand in the circulation.
- the product of rapid pyrolysis is the energy-condensed, flowable heavy oil-like condensate.
- dust-like pyrolysis coke and the pyrolysis condensate are mixed together to form a suspension called BioliqSyncrude.
- the BioliqSyncrude is atomized in an air flow gasifier with the addition of hot oxygen and converted at over 1200 ° C to a tarry, low-methane raw synthesis gas.
- the carburettor type used for this purpose is particularly suitable for ash-rich biomass such as straw.
- the reaction is carried out under pressures which are determined by the subsequent synthesis.
- Fischer-Tropsch syntheses require process pressures of up to 30 bar, methanol or dimethyl ether syntheses (DME) up to 80 bar.
- the installed in the demonstration project Bioliq ® -Pilotvergaser is for 5 megawatts (1 t / h) and two pressure stages 40 and 80 bar and designed based on the multi-purpose Lurgi gasification (MPG) concept.
- MPG multi-purpose Lurgi gasification
- By-products are heat and electricity, which cover a large part of the process energy and thus contribute to the required high C0 2 emission reduction performance.
- gas purification www.bioliq.de/69.php
- KIT high-pressure high-temperature processes developed by KIT are used. These can be expected in a later commercialization energy savings through optimal temperature control or heat transfer.
- particle separation ash, coke, soot
- ceramic filter cartridges is first carried out at 800 ° C.
- the fuel synthesis (www.bioliq.de/73.php) is carried out in two stages via dimethyl ether (DME) as an intermediate, for the synthesis of a hydrogen to carbon monoxide ratio of about 1: 1, as it usually occurs from biomass gasification, is advantageous.
- DME dimethyl ether
- the DME synthesis proceeds at about 250 ° C and a pressure of about 55 bar.
- the DME will be converted directly to a high-octane engine gasoline. This is a zeolite-catalyzed dehydration, oligomerization and isomerization at temperatures of about 350 ° C and a pressure of about 25 bar. Based on known processes (MtG Methanol to Gasoline), this results in high selectivity fuel with gasoline quality. Unreacted synthesis gas is returned to the reactor via a gas recycle.
- the Bioliq ® process of the KIT is intended primarily to use decentralized biogenic residues from agriculture and forestry, such as straw and thinnings. According to (www.bioliq.de/212.php), all types of dry biomass with less than 15% water, even those with high ash contents such as straw, and rapidly growing biomass such as wood from short rotation plantations are suitable as feedstocks.
- the Bioliq ® process does not produce any carbon-containing conversion residue, so that the Bioliq ® process does not allow chemical-physical stabilization of atmospheric carbon.
- the method can provide neither biochar / biochar nor biocoks nor atmospheric C0 2 . Consequently, the 3 options of sequestration of atmospheric C0 2 s, substitution of fossil C0 2 s with atmospheric C0 2, and production of synthetic fuels such as SynMethane from atmospheric C0 2 are also eliminated. Without biochar / biochar / biokoks, no stabilized atmospheric carbon can be sequestered. Thus fuels produced in accordance with the Bioliq ® process can at best achieve GHG neutrality, but not GHG negativity. Certainly not the Bioliq ® - Process to ensure or improve the humus content of (used in agriculture or forestry) soils contribute.
- DE 10 2005 045 166 B4 / EP 1943 463 B1 discloses a method and devices for generating thermal energy, in which biomass, in particular cereal or stalk-like energy carriers, are continuously fed to a pyrolysis reactor and in which the pyrolysis gas obtained in the pyrolysis reactor is fed to a FLOX burner for flameless oxidation and in which the exhaust gas of the FLOX burner preheats its combustion air, wherein the pyrolysis reactor is externally charged with the exhaust gas of the FLOX burner.
- the biomass is converted at about 500 ° C to pyrolysis gas that enters the FLOX burner.
- DE102005045166B4 / EP1943463B1 does not know the difference between fossil and atmospheric CO 2 and also does not describe any atmospheric carbon. Moreover, DE102005045166B4 / EP1943463B1 also does not use any conversion residues from an upstream first conversion process.
- DE102005045166B4 / EP1943463B1 describes the combination of such a method or system with a power, heating or fuel production and use system, the determined according to LCA GHG-positive GHG emission rates of a power, heating or fuel combined with likewise determined by the LCA method GHG emission levels of another compatible power, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture.
- the dry matter loss occurring in the process is very high at 85%, ie only 15% of biocokes and ash remain.
- EP 1 767 658 A1 (Griffin et al.), which discloses a process for the production of bioethanol from lignocellulose-containing feedstocks such as straw (lOGEN process). About the whereabouts of the conversion remains makes this disclosure no information.
- EP1767658 AI does not know the difference between fossil and atmospheric C0 2 and also describes no atmospheric carbon. Further, no chemical-physical stabilization of atmospheric carbon still contained in digestate to avoid reaction with atmospheric oxygen to (atmospheric) C0 2 is described neither as a method nor as a device.
- EP1767658 AI discloses an incorporation of atmospheric carbon, which comes from the residues of an upstream first biomass conversion and which is chemically-physically stabilized, in agriculturally used soil in order to maintain or improve the humus content of this soil.
- EP1767658 AI describes the combination of such a method or system with a power, heating or fuel production and use system that the determined according to LCA GHG emission levels of a power, heating or fuel with also determined by the LCA method, GHG negative emission levels of another, compatible fuel, heating or fuel merges to a balanced zero amount of GHG of a corresponding power, heating or fuel mixture.
- Another method for the production of bioethanol for the production of bioethanol from lignocellulosic biomass by alcoholic fermentation describes the US 2002/019 27 74 AI (Ahring et al.).
- the process comprises 8 steps, namely 1.) transfer of the biomass into an aqueous suspension; 2.) heating the aqueous suspension and / or transferring the aqueous suspension from step 1 into an oxygen-enriched atmosphere to achieve at least partial separation of the biomass into cellulose, hemicellulose and lignin; 3.) at least partial hydrolysis of the cellulose and hemicellulose cleaved in step 2 for the purpose of a microorganism-fermentable sugar-containing suspension suitable as a starting material for ethanol production; 4.) alcoholic fermentation of the microorganism-fermentable sugar-containing suspension from step 3 to ethanol; 5.) Separation of the ethanol from the fermented mass, resulting in a vinasse containing substances that would inhibit alcoholic fermentation when returned to the process; 6.) Treatment of the vinasse with the aim of
- the lignoethanol produced according to the process can at best achieve THG neutrality, but not GHG negativity.
- the process can certainly not contribute to the protection or improvement of the humus content of soils used for agriculture or forestry, because there is no material from which humus C, nutrient humus or permanent humus could be produced.
- the method can provide neither biochar / biochar nor biococ. Without biochar / biochar / biokoks, stabilized atmospheric carbon can not be sequestered. Thus, the lignoethanol produced according to the process can at best achieve GHG neutrality, but not GHG negativity. Certainly, the process can not contribute to the protection or improvement of the humus content of soils used for agriculture or forestry because there is no material from which humus C, nutrient humus or permanent humus could be produced.
- the disclosure DE4332789A1 (Eliasson & Killer) is also previously known.
- a mixture of hydrogen and carbon dioxide is reacted in a reactor in methane and / or methanol.
- fossil carbon dioxide from the exhaust gas of fossil-heated power generation plants is used.
- the methane or methanol produced can be used as an energy source for vehicles, power plants and heating systems.
- the method is only suitable for reducing the GHG emission rate, because of the production of fossil C0 2 s, the greenhouse gas inventory in the Earth's atmosphere is still increasing.
- DE4332789A1 also describes no chemical-physical stabilization of atmospheric carbon in order to avoid a reaction with atmospheric oxygen to (atmospheric) C0 2 neither as a method nor as a device. Not at all DE4332789A1 describes the incorporation of atmospheric carbon, which has been chemically-physically stabilized, in agriculturally used soil in order to maintain or improve the humus content of this soil.
- DE4332789A1 describes the combination of its system with a power, heating or fuel production and utilization system, which also determines the GHG-positive GHG emission quantities of a power, heating or fuel determined in accordance with the LCA LCA method determines GHG negative emission levels of another compatible fuel, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture brings together.
- DE102004030717A1 discloses a similar method and apparatus for converting geothermal and regenerative energy into electrical energy and feeding it into a grid, wherein an excess of electrically generated energy is converted into a hydrocarbon and an alcohol by means of carbon dioxide. stored as chemical energy in a container. The energy stored in the container is converted back to electrical energy for on-demand control in a power generation process, while the surplus of chemically stored energy feeds a natural gas pipeline with synthetically produced methane and generates hydrogen for a filling device with the surplus of reconverted electrical energy , DE102004030717A1 does not differentiate between atmospheric and fossil C0 2 . Thus, this invention can not reduce the GHG inventory of the earth's atmosphere and thus also cause no GHG negativity.
- DE102004030717A1 also describes no chemical-physical stabilization of atmospheric carbon in order to avoid a reaction with atmospheric oxygen to (atmospheric) C0 2 neither as a method nor as a device. Not at all, DE102004030717A1 describes the incorporation of atmospheric carbon, which has been chemically and physically stabilized, into agriculturally used soil in order to maintain or improve the humus content of this soil.
- DE102004030717A1 describes the combination of their system with a power, heating or fuel production and use system, which also according to LCA determined GHG emission levels of a (fossil) power, heating or fuel with The LCA method determines GHG negative emission levels of another compatible fuel, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture brings together.
- the published patent application DE102009018126A1 relates primarily to the property of the renewability of the generated energy and energy carriers and not to their GHG emission reduction performance. These two properties can fall apart.
- the method and the system of DE102009018126A1 at most the GHG-neutral energy carrier "hydrogen gas" can be generated and only if absolutely pure GHG-neutral stream and absolutely pure atmospheric C0 2 are used.
- this invention can not reduce the GHG inventory of the Earth's atmosphere and thus cause no GHG negativity, which is the prerequisite for the compensation of positive GHG Emissions associated with the production, distribution and use of fossil fuels are also not described in DE102009018126A1 for avoiding a reaction with atmospheric oxygen to (atmospheric) C0 2 either as a process or as a device DE102009018126A1 d
- DE102009018126A1 describe the combination of its system with a power, heating or fuel production and use system which determines the GHG-positive GHG emission quantities of a fuel, heating or fuel determined according to LCA, also according to the LCA standard.
- the method determines the GHG-negative emission levels of another, compatible fuel, heating or fuel to a balanced zero quantity of a corresponding power, heating or fuel mixture brings together.
- US 2010/0272619 A1 (Frydman & Liu), which describes a complex overall system consisting essentially of a gasification system, a so-called water-gas-shift (WGS) reactor, a gas purification unit, a C0 2 dewatering system. and compression unit and a methanation unit. Output of the total system is methane gas, the Substituted natural gas and therefore by US2010 / 0272619A1 as Substitute Natural Gas (SNG) is called.
- the starting materials are all carbon-containing substances, eg coal, oil coke, agricultural waste, wood-like materials, tar, asphalt and coke gas.
- US2010 / 0272619A1 does not differentiate between atmospheric and fossil carbon.
- the carbon-containing fuels are converted in the gasification system under high pressure (20 bar to 85 bar), high temperatures (700 ° C to 1,600 ° C) and with the addition of pure oxygen by steam reforming in a so-called raw syngas, which consists essentially of Carbon monoxide and hydrogen.
- a so-called raw syngas which consists essentially of Carbon monoxide and hydrogen.
- carbonization of the carbon-containing fuels takes place, which converts it into carbon-containing coke ash (char) and a residual gas consisting of carbon monoxide, hydrogen and nitrogen.
- the coke ash produced by charring can react with carbon dioxide and water vapor to form carbon monoxide and hydrogen.
- Product is a raw syngas that is about rd.
- the raw syngas is fed into the WGS reactor, where carbon monoxide reacts with water to form carbon dioxide and hydrogen.
- the hydrogen-enriched crude syngas is supplied to the gas purification unit. This removes unwanted gas components such as HCL, HF, COS, HCN and H 2 S from the raw syngas.
- Product is a purified syngas with a share of about 55% hydrogen, about 40% carbon dioxide and about 3% carbon monoxide.
- the gas purification unit may comprise a C0 2 - separation system, which also removes the too low levels ( ⁇ 2%) contained in the raw syngas carbon dioxide from the raw syngas.
- the carbon dioxide separated from the raw syngas is delivered to the C0 2 dewatering and compressor unit, which dewaters and densifies it.
- the dewatered and compressed C0 2 is stored or used. It can be piped to a sequestration plant, such as a so-called EOR plant, which uses the C0 2 to better recycle oil wells (enhanced oil recovery) or to a facility that stores it in geological strata with salty groundwater ,
- the purified syngas is passed to a methanation unit which reforms the hydrogen and carbon monoxide in an exothermic reaction to methane (CH 4 ) and water (H 2 O).
- CH 4 methane
- H 2 O water
- the heat contained in the methane and in the water is released via heat exchangers to water, which converts into high-temperature steam.
- SynMethane SynMethane
- the synthetic methane (SynMethane) produced in the methanation unit is fed to the C0 2 dewatering and compression unit, which dehydrates, densifies and injects the SynMethane into a (special) SNG pipeline for further use. This can transport it to a gas deposit or to a methane-processing industrial plant.
- US2010 / 0272619A1 uses coal and crude oil-based substances such as oil coke, tar, asphalt and coke gas as feedstock, fossil carbon gets into the earth's atmosphere, so that a reduction in the CO 2 content of the earth's atmosphere is simply not possible.
- the US 2010/027 26 19 AI gives for the C0 2 generated by the system, although the purpose of the sequestration, but does not distinguish between fossil and atmospheric carbon nor between atmospheric and fossil C0 2 - what essential basis for the invention and for the evaluation of Invention is.
- the system of US2010 / 0272619A1 can therefore at best reduce the emission of additional fossil carbon or C0 2 s into the atmosphere (ie the positive GHG emission rate), but not the C0 2 content of the earth's atmosphere.
- US2010 / 0272619A1 describes a material substitution of fossil C0 2 s by atmospheric C0 2 or the incorporation of atmospheric carbon, which is chemically-physically stabilized, in agriculturally used soil in order to maintain or improve the humus content of this soil.
- US2010 / 0272619A1 describes the combination of their system with a power, heating or fuel production and use system, the determined according to LCA GHG emission levels of a power, heating or fuel with also after LCA method determines GHG negative emission levels of another compatible fuel, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture brings together.
- EP 07 846 568.9 discloses a biogas plant and a method for producing biogas from straw, in which the fermentation residues from the anaerobic bacterial fermentation are pressed into fuel pellets or fuel briquettes after dehydration, is also previously known.
- This book also does not know the difference between fossil and atmospheric carbon and fossil and atmospheric C0 2 . It also mentions no chemical-physical stabilization of atmospheric carbon, which could possibly still be contained in the digestate, in order to avoid a reaction with atmospheric oxygen to (atmospheric) C0 2 neither as a method nor as a device.
- EP07846568.9 discloses the incorporation of atmospheric carbon, which is chemically-physically stabilized, in agriculturally used soil for the purpose of maintaining or improving the humus content of this soil.
- EP07846568.9 describes the combination of such a process or system with a power, heating or fuel production and use system, the determined according to LCA GHG-positive GHG emission levels of a power, heating or fuel with likewise GHG-negative emission quantities determined according to the LCA method another, compatible power, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture brings together.
- US 2008/153145 Al (Harper) is known, which teaches a method and a system for the disposal of farmyard manure, in particular the conversion of dairy cow excrement to ethanol, methane, carbon dioxide and fertilizers.
- the system of US2008 / 153145A1 consists of a waste excrement bunker, a "methane outlet" fermentation reactor, a methane drying and compression unit, a methane pressure tank, a distillation column, ethanol and C0 2 storage tanks, and a rotary kiln Dairy cow manure consisting of manure, urine and water is collected in the receiving bunker and, when the manure is transferred to the anaerobic fermentation reactor, a weakly acidic solution is added as a pre-treatment measure to complete the first step of anaerobic digestion.
- the livestock feed including cereal grains, cereal-based silage, hay and legumes
- a basic substance is added to neutralize the acidified hydrolysis mass.
- the hydrolyzed manure is added after neutralization with the addition of a weak aqueous sugar solution (0.01%) and microorganisms of the species "Saccharomyces cerevisiae" in the fermentation reactor.
- the anaerobic digestion carried out by these microorganisms is said to produce ethanol and carbon dioxide, which are said to remain dissolved in the water.
- the microorganisms contained in the slurry also produce ethanol, carbon dioxide and methane.
- US2008 / 153145A1 Although the use of dairy cattle manure only returns atmospheric carbon to the earth's atmosphere, US2008 / 153145A1 also mentions the GHG effect of the gases methane and carbon dioxide, but does not take measures to remove these greenhouse gases or the underlying carbon from the earth's atmosphere. Rather, the inventor of US2008 / 153145A1 is subject to the erroneous fallacy that the sale of the C0 2 s or its "compression" to dry ice or the use of methane to generate electricity remove the (atmospheric) carbon from the earth's atmosphere - but this is not the case (see introductory remarks) The method and the system of US2008 / 153145A1 are therefore not suitable for reducing the CO 2 content of the earth's atmosphere.
- WO 2010/043799 A2 (Morin), which describes a method and a system for extracting carbon dioxide from the earth's atmosphere.
- the system consists essentially of a biomass high temperature dryer, a Verschwelungsreaktor, a thermochemical converter consisting of a combustion chamber and an associated oxidation chamber, a gas reformer and a plant for the production of synthetic carbon compounds.
- the photosynthesis-conditioned a natural buffer atmospheric C0 2 s represents.
- the comminuted biomass which has a water content of 40% to 55%, is dried in the biomass high-temperature dryer with 400 ° C to 600 ° C hot, low-oxygen exhaust air from the oxidation chamber to a residual moisture content of 10% to 15%.
- the unspecified exhaust air of the oxidation chamber which accounts for more than 70% of the exhaust gases of the entire system, is discharged after the drying process together with the extracted from the biomass water from the biomass dryer into the atmosphere.
- the dried biomass is in the pyrolysis reactor using additional oxygen in a coming out of the oxidation chamber, 400 ° C to 800 ° C hot solid bed of metal oxide at 700 ° C to 1000 ° C to a carbonization.
- the material composition of the carbonization gas coming from the carbonization reactor is "adjusted" at 1,200 ° C to 1,400 ° C by an oxygen-assisted combustion of the substances contained in the carbonization gas tar and methane, consisting essentially of carbon monoxide and water vapor .
- the resulting combustion in the reactor during the combustion of Verschwelungsrestes C0 2 is cooled, dedusted, dewatered and then divided into 3 partial streams: a C0 2 substream 1 is compressed for removal and after appropriate transport stored in groundwater-containing earth layers; a C0 2 sub-stream 2 is passed into the scrubbing reactor for controlling or regulating the reactions taking place there, and a C0 2 sub-stream 3 is returned to the combustion reactor for controlling the reactions taking place there.
- oxygen is supplied to the oxidation chamber.
- the 400 ° C to 600 ° C hot exhaust gas of the oxidation chamber is allegedly made of low-air (meaning probably low-oxygen) exhaust air, which is fed into the biomass dryer.
- the C0 2 level of the atmosphere is only reduced if the C0 2 is really permanently removed from the Earth's atmosphere. This is not the case with WO2010 / 043799A2.
- this C0 2 storage is not permanent.
- the groundwater can return to the surface of the earth after a relatively short time and release the C0 2 dissolved in the water there again - thus rendering the entire C0 2 sequestration obsolete.
- the conversion of the atmospheric carbon or C0 2 s, for example, into electrical energy or into a fuel does not remove the carbon from the atmosphere, because when using the energy carrier or fuel generated according to WO2010 / 043799A2 combustion of the carbon with Atmospheric oxygen instead, which produces C0 2 - bringing the C0 2 back into the atmosphere.
- the omission of the C0 2 emissions at the (carbon) use stage shows that WO 2010/043799 A2 does not carry out the greenhouse gas analysis or the determination of the GHG quantities with the LCA method.
- WO2010 / 043799A2 also does not describe the chemical-physical stabilization of atmospheric carbon to avoid a reaction with atmospheric oxygen to (atmospheric) C0 2 neither as a method nor as a device. Not at all WO2010 / 043799A2 describes a material substitution of fossil C0 2 s by atmospheric C0 2 or the incorporation of atmospheric carbon, which is chemically-physically stabilized, in agriculturally used soil in order to maintain or improve the humus content of this soil.
- WO2010 / 043799A2 describes the combination of its system with a power, heating or fuel production and utilization system, which also includes the GHG-positive GHG emission quantities of a power, heating or fuel determined according to LCA GHG-negative emission quantities of another compatible fuel, heating or fuel, determined according to the LCA method, can be combined to form a balanced zero quantity of a corresponding fuel, heating or fuel mixture.
- the deposited and recuperated atmospheric C0 2 is a) either fed to a geological repository or b) used as a substitute for fossil C0 2 or c) fed to a reforming plant in which it is reformed to CH 4 and / or CH 3 OH.
- the energy sources used are used as GHG emissions-reduced fuels.
- the fermentation residues from the one- or multi-stage anaerobic bacterial fermentation substitute either mineral fertilizer or they are prepared after separation into a rather solid and a more liquid phase to fertilizers or fertilizer components.
- the GHG emission reduction performance of the generated energy sources can be so high that they become GHG negative.
- the generated, possibly GHG-negative BioMethan can be mixed with natural gas (CNG) to a mixed gas whose GHG emission value is adjusted via the admixed CNG content. That is, the mixed gas can assume both positive GHG emission values and negative GHG emission values. It is also possible, via the mixing of GHG-negative bio-methane and GHG-positive CNG, to produce a precisely GHG-neutral mixed gas whose GHG emission value at 0.0 gC0 2 -eq / MJ or 0.0 gC0 2 -eq / kWh Hi .
- DE 10 2010 017 818.7 / EP 253 68 39A1 which already knows and discusses the difference between fossil and atmospheric CO 2 , still does not describe any atmospheric carbon.
- EP2536839A1 describes the combination of such a process or system with a power, heating or fuel production and use system that the determined according to LCA GHG emission levels of a power, heating or Combines fuel with likewise determined by the LCA method GHG emission levels of another, compatible power, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture.
- the resulting absolute GHG emissions reductions in the Earth's atmosphere and the GHG surplus produced by (fossil) fuel consumption are combined to form a total GHG, with the resulting IPCC (LCA) determined in the technical unit gC0 2 -equivalent / MJ or gC0 2 -equivalent / kWh H i measured LCA-THG emission value of the at least one fuel produced by at least 5%, preferably by at least 50%, particularly preferably at least 85% and in particular relieved by 100%.
- LCA-THG emission value of the at least one fuel produced by at least 5% preferably by at least 50%, particularly preferably at least 85% and in particular relieved by 100%.
- DE102011051250 / EP2724081 which already knows and discusses the difference between fossil and atmospheric CO 2 , still does not describe any atmospheric carbon.
- DE 10 2011 051250 / EP 272 40 81 describes the combination of such a method or system with a power, heating or fuel production and use system that determines the GHG-positive GHG emission quantities of a force determined according to LCA -, heating or Brennschers merges with likewise determined by the LCA method GHG emission levels of another, compatible power, heating or fuel to a balanced zero amount of a corresponding power, heating or fuel mixture.
- the invention provides a method according to claim 1 and a system according to claim 27.
- Advantageous developments are disclosed in the dependent claims and in this description. The wording of all claims is incorporated by reference into the content of the specification.
- the present invention relates to a method and a system for improving the GHG emission reduction performance of power, heating and fuel and for enrichment of agricultural land with humus C, these tasks can be preferably fulfilled simultaneously but need not be met simultaneously.
- the GHG emission reduction performance of the power, heating or fuel is so high that not only compared to the fossil reference, a significant GHG emission reduction can be achieved, but that the GHG balance or the GHG emission amount of the generated force, Heating or fuel can even be negative, ie, that after the production, provision and use of power, heating or fuel, a smaller amount of greenhouse gas in Erdatmo- sphere are than before.
- the effect of decarburization of the earth's atmosphere, which can lead to a GHG negativity (or to a negative GHG emission amount) is achieved according to the invention first by carbon-containing residues of a first biomass conversion by means of a chemical-physical treatment such.
- carbonization selection from pyrolysis, carbonization, torrefaction, hydrothermal carbonization HTC, vapothermal carbonation, gasification and any combination of these treatment methods
- biochar or biochar or biocoks is thus chemically-physically is stabilized that he under normal circumstances - to which does not belong the combustion - or hardly reacts with other substances, especially not with (air) oxygen.
- thermochemical mixed conversion of biomass-containing aqueous suspension under oxygen deficiency and under pressure of> 1.2 bar at a reaction temperature of more than 150 ° C and less than 350 ° C are understood to be products of HTC process water and HTC coal. Accordingly, “torrefaction” is understood to mean the thermochemical conversion of biomass under oxygen deficiency at a reaction temperature of more than 150 ° C. and less than 350 ° C., the product of torrefaction being torrefied biomass.
- “Pyrolysis” accordingly means the thermochemical conversion understood biomass under oxygen deficiency at a reaction temperature of more than 300 ° C to 1000 ° C, wherein products of pyrolysis are combustible gas, biochar / biochar and oils.
- “pyrolysis” is mentioned, and the low-temperature pyrolysis and the high-temperature pyrolysis should also be included, unless something different arises from the respective context.
- “Gasification” accordingly refers to the thermochemical conversion of biomass Under moderate to no oxygen deficiency at a reaction temperature of more than 500 ° C to 1200 ° C understood, wherein products of gasification are combustible gas and biochar / biochar.
- “Combustion” is correspondingly understood to mean the thermochemical conversion of biomass under excess oxygen at a reaction temperature of more than 650 ° C. to 1600 ° C., products of the combustion being hot exhaust gas (flue gas) and ash.
- the natural reactivity of the atmospheric carbon with (air) oxygen is suppressed or severely limited by the chemical-physical stabilization, so that C0 2 can no longer arise except through combustion. If the biochar / biochar or bio-coke is protected (stored) from aggressive conditions, carbon is removed from the earth's atmosphere - a decarbonization of the earth's atmosphere occurs (desired).
- the generated biochar / biochar or biocoks in soils (agricultural or forest-used soils, deserts, permafrost, scree fields, etc.), water masses (oceans, lakes, aquifers) or introduced into abandoned quarries, caverns or mines, easy only weatherproof stored in buildings or incorporated into the (field) soil.
- soils agricultural or forest-used soils, deserts, permafrost, scree fields, etc.
- water masses oceans, lakes, aquifers
- caverns or mines easy only weatherproof stored in buildings or incorporated into the (field) soil.
- the effect of decarbonization which can lead to GHG negativity (or to a negative GHG emission level), is achieved secondly by stabilizing, only partially stabilized or unstabilized atmospheric carbon in the form of biochar / biochar / Biokoks, native straw or straw-containing digestate is introduced into deeper soil layers in which there is no soil respiration or an aerobic Rotte. That is, neither soil organisms nor atmospheric oxygen attack the introduced carbon.
- stabilization of the atmospheric carbon by pyrolysis or torrefaction / HTC / vapothermal carbonation, etc. is not necessarily required.
- a preferred embodiment of the process according to the invention can therefore be that a selection of native straw, straw-containing fermentation residues, wood, partially stabilized biochar and biochar and unstabilized biochar and biochar and any combination of these substances is introduced into deeper soil layers, where there is no soil respiration or aerobic rotting.
- the permanent storage of this atmospheric carbon corresponds to a sequestration, ie the atmospheric carbon becomes permanent the earth's atmosphere removed.
- This decarbonization of the earth's atmosphere is attributed to the product of the process - ie the energy source produced (fuel, fuel, fuel).
- the GHG negativity (negative GHG emission quantity) of the generated energy source arises from the fact that the negative effect of decarbonization described above (converted into C0 2 equivalents) is (significantly) greater than the sum of all (converted into C0 2 equivalents) positive GHG effects of production, provision and use of power, heating or fuel.
- MaW after the production, supply and use of the energy carrier (power, heating or fuel) is a smaller amount of greenhouse gas in the earth's atmosphere than before.
- the soil quality In particular, the humus content and the humus C content of these soils, in particular the humus C population in the stable, permanent humus pool, are increased.
- the permanent sequestration of chemically stabilized atmospheric carbon prevents it from reacting with (atmospheric) oxygen to CO 2 or - as in paddy fields - by anaerobically converting soil organisms into methane (CH 4 ).
- the sequestration of chemically stabilized atmospheric carbon prevents the emission of a CH 4 mass by a factor of 1,336 (1 / 74,866%). is greater than the mass of the sequestered carbon, that is, 1.336 tons of CH 4 per 1 ton of carbon C. Since it is known that the greenhouse gas methane GHG effect is 25 times higher than that of the greenhouse gas carbon dioxide, the non-emission of 1.336 metric tons of methane corresponds to the non-emission of 33.4 metric tons of C0 2 .
- not only stabilized biochar / biochar / biocoks can be applied to the soil, but also a first mixture of stabilized and less stabilized (partially stabilized) biochar / biochar and a second mixture of stabilized and even non-stabilized biochar / biochar / biokoks.
- a third four-part mixture consisting of a) stabilized biochar / biochar / biokoks and b) partially stabilized biochar / biochar / biokoks, c) unstabilized biochar / biochar / and / or d) can not be applied treated digestate.
- the proportions of the four components of this mixture can each be 0% to 100% under the obvious additional condition that the sum of the four components does not exceed 100%.
- the stabilization of or biochar / biochar / biokokses (to be more precise: contained in the biochar / biochar or in biococ atmospheric carbon) is inventively achieved in that the carbon-containing residues from a first biomass conversion (anaerobic bacterial Fermentation to biogas, fermentation to ethanol, transesterification to BioDiesel or BioKerosin, gasification and synthesis to synthetic diesel or synthetic gasoline or synthetic kerosene or synthetic methanol, methanol synthesis, DME synthesis, etc.) under oxygen deficiency at a temperature of 100 ° C - 1,600 ° C, preferably at a temperature of 200 ° C - 1,200 ° C, in particular at 300 ° C - 1,000 ° C and in the best case at 400 ° C - 900 ° C are subjected to a carbonization.
- a first biomass conversion anaerobic bacterial Fermentation to biogas, fermentation to ethanol, transesterification to BioDiesel or BioK
- the loss of atmospheric carbon occurring during the at least partial chemical-physical stabilization of the conversion radicals is preferably at most 95%, particularly preferably at most 60%, in particular at most 40% and at most at most 30%.
- the dry matter loss occurring during the carbonation of the conversion residues from the single-stage or multistage biomass conversion is preferably not more than 95%, particularly preferably not more than 60%, in particular not more than 40% and at most not more than 30%.
- the carbon content of the produced biochar / biochar or biocok produced is at least 20%, preferably at least 40%, particularly preferably at least 60%, in particular at least 70% and in the best case at least 80%.
- the heating and carbonization of the residues from the first biomass conversion take place according to any selection from the following reaction parameters: heating relatively slow, reaction time relatively long, reaction temperature relatively high, reaction pressure relatively high.
- the heating of the mass to be carbonized at reaction temperature therefore lasts longer than 1 second, particularly preferably longer than 10 minutes and in particular longer than 100 minutes.
- the reaction mass is exposed to the reaction temperature for more than 1 second, more preferably for more than 50 minutes and more preferably for more than 500 minutes.
- the reaction temperature is preferably more than 150 ° C, more preferably more than 300 ° C, and especially more than 600 ° C.
- the pressure in the reaction vessel preferably corresponds to the pressure of the environment, particularly preferably> 1 bar and in particular> 5 bar and in the best case> 10 bar.
- the carbonization takes place in the form of a pyrolysis. Pyrolysis works better or more effectively the drier the reaction mass is.
- the residues to be pyrolyzed from the first biomass conversion therefore preferably have a dry matter content (TS content) of at least 35%, particularly preferably at least 50% DM and in particular at least 60% DM.
- pyrolysis coals Due to their very porous outer and inner surface, which is much larger in pyrolysis coals than in HTC coals, pyrolysis coals have a high water absorption capacity, which, when incorporated into the soil, results in the formation of pyrolysis coal Can save water better. Except in clay-rich loamy soil, the water storage capacity of sandy soils after the administration of bioliquids / bioliquids / biokoks increases significantly, with an increase in plant-available water even in heavy clay soils, if they are treated with pyrolyzed straw. In contrast, no such effect can be achieved with wood chips.
- the substrate straw has advantages here that is based on a different pore structure. Particularly positive are the effects of coal application of pyrolysis coals on the water storage capacity in sandy soils.
- straw-containing residues of a first biomass conversion are therefore preferably subjected to pyrolysis, particularly preferably high-temperature pyrolysis, and the resulting straw coal is applied in particular to sandy soils.
- the advantageous embodiment of the partial stabilization of bioliquids / bioliquids or, more precisely, of the atmospheric carbon contained in the bioliquids / biochar / biokoks is achieved by the carbon-containing radicals from the first conversion (any form the biomass conversion, preferably the anaerobic bacterial fermentation to biogas or fermentation to ethanol) under oxygen deficiency at 150 ° C - 450 ° C, preferably at 200 ° C - 400 ° C, in particular at 250 ° C - 300 ° C torrefaction
- Low-temperature pyrolysis is understood below to mean those pyrolyses in which the reaction temperature is less than 450 ° C., high-temperature pyrolyses in which the reaction temperature is more than 600 ° C.).
- biochar / biochar / biokoks are produced, they are not as reactive and resistant to degradation as pyrolysis coal, which can be positive for the content of active nutrient humus contained in the soil.
- the partial stabilization of the bioliquids / bioliquids or, more precisely, of the atmospheric carbon contained in the bioliquids / biochar / biokoks is achieved by the carbon-containing radicals from the first conversion in the presence of water or steam, under oxygen deficiency and under pressure of a hydrothermal carbonation (HTC) are subjected.
- the temperature is 130 ° C - 400 ° C, preferably 150 ° C - 300 ° C and in particular 180 ° C - 250 ° C.
- the pressure is 1.2-200 bar, preferably 10-100 bar and in particular 20-50 bar.
- Products of HTC are so-called HTC coal and process water.
- the HTC coal like the torrefied biomass, is not as reactive and resistant to degradation as pyrolysis coal, which can be positive for the content of the active nutrient humus contained in the soil.
- the process of the invention and the system according to the invention preferably produce pyrolysis coal.
- HTC and torrefaction coals are degraded much faster in the soil within a few decades.
- Pyrolysis coals have a relatively high proportion of complex polyaromatic carbon structures and are therefore much more stable than HTC coals, whose content of polyaromatic carbon compounds is lower and whose content of easily mineralisable (degradable) C compounds is correspondingly higher.
- the stability of HTC and torrefaction coals is more akin to compost and peat. Therefore, a long-term sequestration (atmospheric) carbon is not or only partially possible with such coals.
- the molar H / C ratio of the biochar / biochar produced according to the method of the invention and the biocok produced is ⁇ 0.8, particularly preferably ⁇ 0.6, and their molar O / C ratio is ⁇ 0, 8, more preferably ⁇ 0.4.
- the molar H / C ratio indicates the degree of charring, which correlates with the chemical stability of the biochar, biochar and biochar. This ratio is one of the most important properties of a biochar or biochar. In order to ensure a sufficient resistance to permanent sequestration, the H / C ratio should be below 0.8.
- the stream of conversion residues emerging from the process step of mono- or multistage biomass conversion can therefore have up to 4 substreams before the thermochemical treatment, namely the first substream "pyrolysis coal", the second substream “torrefaction”. Coal ", the third sub-stream” HTC coal “and the fourth sub-stream” unconverted conversion residues ".
- the partial flows can each have a share of 0% to 100% of the total flow and of the product produced, ie each partial flow can represent both the total flow and zero.
- Biochar / Biochar / Biococ produced from straw reaches 25% carbon depending on the type of straw used, the method of charring used, the type of equipment used and the process parameters (temperature rise curve, maximum temperature, duration of treatment, pressure). 79%. Therefore, such charring processes, plants and / or process parameters are preferred which produce a biochar / biochar / biokoks with a relatively high carbon content, preferably biochar / biochar / biokoks with a carbon content of> 25%, more preferably Biochar / biochar / Biokoks with a carbon content of> 50% and in particular biochar / biochar / Biokoks with a carbon content of> 70%.
- biochar / biochar / biokoks produced with high temperatures from straw have high pH values of up to 11.3, making them predestined for incorporation into acidic soils.
- Alkaline biochar / biochar / biokoks like most pyrolysis coals, raise the pHs of acidic and weakly basic soils with their high pH values, leading to an improvement in the mineralization of organic sulfur compounds, to an improvement in other humus - Mineralization and to improve the microbial degradation of OBS.
- the application of basic pyrolysis coal in acidic soils results in an increase in the earthworm population.
- the biochar / biochar / biococs are therefore at least partially produced by means of high reaction temperatures from straw-containing conversion residues.
- the biochar / biochar / biokoks produced from straw-containing conversion residues have a pH of> 7.0, particularly preferably> 8.5 and in particular> 10.0.
- the biochar / biochar / biocoks produced from straw-containing conversion residues are applied to acidic soils.
- Organic / biochar / biokoks have a large capacity for sorption, binding and storage of nutrient ions as well as inorganic and organic compounds. This results from their very large inner and outer surface, which is significantly larger in pyrolysis coals than in torrefaction and HTC coals.
- the recuperated residues from the first biomass conversion are therefore primarily subjected to pyrolysis, preferably> 1% of the recuperated residues, particularly preferably> 50% of the recuperated residues and in particular> 75% of the recuperated residues from the first biomass conversion.
- the availability of biochar phosphorus in the first year after application is about 15% and that of nitrogen is only about 1%, while up to 50% of potassium in the first year is available to the plant.
- the stabilized and partially stabilized biochar / biochar or biococcus are therefore enriched with nutrients prior to application in soils, in particular when the soils are agricultural soils.
- This enrichment with nutrients which is preferably an enrichment with nitrogen compounds, particularly preferably an enrichment with organic nitrogen compounds, is also referred to as charging.
- the charge also leads due to the nutrient enrichment to a rapid activation of the surface of the carbon skeleton by microbial colonization.
- the scaffold is thus covered with metabolizable organic materials that become part of the active nutrient humus, while the scaffolding itself remains part of the passive permanent humus. Short-term negative effects on the nitrogen balance can thus be minimized. They are also overcompensated by later positive effects.
- the charging of the stabilized, partially stabilized or non-stabilized biochar / biochar can be carried out by the pyrolysis or torrefaction coming from the hot and absolutely dry biochar / biochar / biokoks with a nutrient-containing aqueous Suspension is extinguished, preferably with a selection from the aqueous suspensions manure, percolate, manure, urine, leachate from silage, distillate from ethanol production, liquid residues from anaerobic digestion, process water, treated or purified process water, liquid digestate, permeate , rather liquid phase of a dehydration, rather solid phase of dehydration, any phase of a separation, other nutrients containing suspensions and similar suspensions.
- the extinguished biochar / biochar / biokoks remains dry.
- “Dry” in this context means that the slaked biochar / biochar / biokoks do not give off any free water after quenching, most preferably the suspension containing the hot biochar / biochar / s is quenched to the more liquid phase of dehydrogenation of the residues from the single or multi-stage biomass conversion, which takes place before pyrolysis or torrefaction.
- biochar / biochar / biochar consisting of carbon and very stable carbon compounds will react on its outer and, in part, on inner surfaces, acting as both a catalyst and a reagent.
- amino, phenolic, hydroxyl, carbonyl or carboxyl groups are formed.
- the negative charge of the surfaces increases, resulting in increased cation exchange capacity. Therefore, biochar / biochar / biokoks can absorb, bind and maintain nutrients available for microorganisms, fungi and plants over a longer period of time. Due to their polarity, hydrophilic groups also lead to improved storage of water.
- the charged biochar / biochar / biokoks can therefore preferably also be used as a soil conditioner.
- pyrolysis coal treated soils will also release less nitrous oxide (N 2 O) into the atmosphere than untreated soils.
- biomass with relatively low nitrogen contents such as straw and wood are used.
- the large outer and inner surfaces of the biofuel / biochar, especially the pyrolysis coals, and the coal age-increasing negative surface charge have the effect, as already explained, of increasing the capacity of the treated soils to exchange cations .
- the increase in K storage is particularly relevant for plant nutrition.
- the incorporation of bioliquids / bioliquids into the soil also has a positive effect on the plant availability of Mn and Cu.
- the bioavailability of micronutrients is also improved by the application of bioliquids / bioliquids / biokoks.
- the biochar / biochar / biococcus produced according to the method of the invention can therefore also be used as macro- and micro-fertilizers and in particular as potassium fertilizers.
- the introduction of pyrolysis coals into cereal crops has the further positive effect of causing intensified and advantageous colonization of wheat roots with symbiotic soil fungi (arbuscular mycorrhiza fungi - AMF). Therefore, in a preferred embodiment of the invention, the bioliquids / biochips / biococcus produced according to the invention are applied as pyrolysis coals prior to the cultivation of cereal crops.
- the process according to the invention preferably uses conversion straws containing wheat straw, since a significant decrease in the plant parasitic nematodes can be observed when wheat straw-based pyrolysis coal is applied.
- biochar / biochar / biococ provided by the method and system of the invention is preferably used to enhance at least one of these yield-limiting soil properties.
- bioliquids / bioliquids on the soil fauna and flora are a function of the properties of the coal used (starting material, production process, post-treatment, charging) and the chemical and physical characteristics of the site.
- the functional structure is very complex, changes in the chemical and physical soil properties by application of bioliquids / bioliquids / biokoks influence the population densities of the soil organisms and thus the soil biological activity and these in turn the soil properties.
- microorganisms are believed to utilize pyrolysis coal only to a very limited extent as a nutrient or energy source, if at all, because of their chemical stability, and therefore microbial activity does not increase immediately after the introduction of such coal into the soil.
- the process according to the invention primarily produces pyrolysis coals and, after being charged with nutrients as soil improvers or as fertilizer, is introduced into agricultural soils.
- bioliquids / bioliquids / biokoks can result in an increase in plant growth and crop yield.
- the yield-increasing effect of the application of biochar / biochar / biokoks is dependent on the amount of coal incorporated into the soil: the more "right" biochar / biochar / biocoks are used, the sooner a yield-increasing effect occurs, whereas (Very high) upper limits for the application, beyond which opposite effects occur
- Light, sandy and humus-poor locations require the use of 20 - 100 tons of biochar / biochar / dry biomass per hectare, experimental growing trials in the greenhouse have shown that on sandy and loamy soils, coal yields ⁇ 3 t / ha will not lead to increases in rye yields, bearing in mind that coal applications usually only need to be done once every 100 years, while fermentation residues and compost are applied annually or every 3 years In order for significant soil- and yield-improving effects to occur, so are certain minimum amounts required for biochar
- bioliquids / bioliquids / biococcus produced according to the method of the invention are therefore preferably used in amounts such that the yield of agriculturally used areas increases.
- at least 5 tons of biochar / biochar / dry biocum solids are applied per hectare, more preferably at least 20 tons, in particular at least 50 tons and in the best case at least 100 tons.
- These quantities can refer to both fully and partially stabilized atmospheric carbon as well as to the applied biochar / biochar quantities.
- the incorporation of 25 t of biochar / biochar / biokoks per hectare thus corresponds to a relative proportion of 0.50% of the soil mass and the administration of 50 l to a relative proportion of 1.00%.
- the biochar / biochokes / biococci produced according to the methods of the invention are preferably produced by the sub-process of high-temperature pyrolysis. It is thus clear that pyrolysis coals, in particular high-temperature pyrolysis coals, not only better stabilize atmospheric carbon, but that these coals are also better suited for application in arable soils than other bioliquids / bioliquids / biococcus. Special services are provided by straw-produced pyrolysis coal in many respects (see above).
- Pyrolysis coal produced from relatively high temperature straw is not suitable for incorporation in light, sandy arable soils but also in heavy soils and thus for long-term C sequestration.
- straw or straw-containing conversion residues are therefore used in particular.
- Negative effects of the introduction of bioliquids / bioliquids / biococcus into the soil such as the supply of pollutants (eg heavy metals) and increased release of substances that endanger the protected goods air and water or health risks to plants, animals and humans but can be minimized by the selection of low-emission starting materials, by appropriate process control and by appropriate post-treatment.
- pollutants eg heavy metals
- the effect of decarbonisation of the produced fuel can be achieved thirdly by using in the production of the force Atmospheric C0 2 , which is composed of atmospheric carbon and atmospheric (air) oxygen, is recuperated and replaces fossil C0 2 (eg in the beverage industry), which usually consists of fossil carbon.
- Atmospheric C0 2 which is composed of atmospheric carbon and atmospheric (air) oxygen
- fossil C0 2 eg in the beverage industry
- CNG extra fossil natural gas
- the substitution of this fossil carbon dioxide by atmospheric C0 2 avoids the emission of fossil C0 2 s, which relieves the earth's atmosphere (additional sub-process Zla).
- the resulting in the production of power, heating or fuel atmospheric C0 2 be recuperated and made available for industrial use.
- the effect of the decarbonization or GHG emission reduction of the produced fuel can be achieved in the fifth, by the in the production of atmospheric fuel, heating or fuel produced and recuperated atmospheric C0 2 is used to produce C0 2 -basêt energy sources such as generated by wind power by water electrolysis hydrogen gas, which according to Sabatier with C0 2 in synthetic methane (SynMethan) kon - is converted (additional sub-procedure Zlc).
- the recuperated carbon dioxide can therefore be made available for corresponding production processes, preferably in the liquid state of aggregation.
- the effect of decarbonisation of the generated fuel (fuel, fuel), which preferably results in a GHG negativity (or in a negative GHG emission amount), can be achieved sixth by reducing the atmospheric C0 2 , the arises in the physico-chemical stabilization of the atmospheric carbon still contained in the conversion residues, is recuperated and fossil C0 2 replaced (additional sub-process Z2a). According to the invention, therefore, the atmospheric C0 2 produced in the chemical-physical stabilization of the atmospheric carbon still contained in the conversion residues can be recuperated and made available for industrial use.
- the decarbonization or GHG emission reduction of the fuel produced (fuel, fuel), which preferably results in a GHG negativity (or in a negative GHG emission amount), can be achieved seventh by the atmospheric C0 2 , at the chemical-physical stabilization of the atmospheric carbon contained in the conversion remains, is recuperated and a sequestration is supplied (additional sub-process Z2b).
- the resulting in the physico-chemical stabilization of the atmospheric carbon contained in the conversion residues atmospheric C0 2 recuperated, liquefied and transported in this aggregate state to the geological oil or gas deposits or other sequestration sites (aquifers, ocean, lakes, etc.) ,
- the effect of decarbonization of the generated fuel can be achieved by using the atmospheric C0 2 , the in the chemical-physical stabilization of the atmospheric carbon contained in the conversion remains, is recuperated and used to produce C0 2 -based energy sources such as generated by wind electricity by water electrolysis hydrogen gas, the Sabatier with C0 2 in synthetic methane (SynMethan) is converted (additional sub-method Z2c). Therefore, according to the invention, the atmospheric C0 2 produced in the chemical-physical stabilization of the atmospheric carbon still contained in the conversion residues can be recuperated and made available to corresponding production processes, preferably in a liquid state.
- Very particularly advantageous GHG effects occur when the stabilization of the atmospheric carbon, which is still contained in the residues from a first biomass conversion, with one of the sub-processes Zla to Zlc and one of the sub-processes Z2a until Z2c is combined.
- the GHG negativity (or the negative GHG emission quantity) of the power, heating or fuel thus generated makes it possible for this to be admixed, at least proportionally, with a compatible THG-positive power, heating or fuel without the resulting GHG -
- the emission value of the mixed fuel turns into positive. This results in a significant increase in the available at least THG-neutral amount of fuel (fuel, fuel).
- the generated energy source power, heating or fuel
- An option for a first conversion of biomass into a (marketable) energy source is the anaerobic bacterial fermentation of straw to biogas and its preparation to BioMethan.
- a straw input of 1 ton of wet mass with a usual water content of 14% (dry matter content 86%) produces up to 2,860 kWh of H i straw gas.
- the GHG emission value of the process according to the invention has a GHG value of up to -648 kg C0 2 eq, despite the GHG emissions occurring during the various production steps.
- the method and system according to the invention are able to ensure the maintenance of the humus content of the soil with the application of stabilized biochar charged with vegetable nutrients, it is not necessary for further fractions to remain in the fields in addition to the non-salable portion of the straw growth.
- the method according to the invention and the system according to the invention thus increase the amount of straw that can be used for energy in Germany alone from the approx. 8.0 - 13.0 million tonnes of straw FM / a by a factor of 2.0 - 4.5 to approx. 35.85 million t straw-FM / a.
- THG-positive energy carriers such as CNG or LNG
- the blending proportion is as shown above up to 90.8%. This means that up to 68,600 GWh H i produced from manure and haulm without straw can be mixed with up to 62,300 GWh H i CNG or LNG. without the GHG emission value of the resulting mixed gas amount of up to 130,900 GWh H i (471 PJ) changing to positive.
- This additional mixed gas quantity represents another 20% of the calorific value of all fuels used in German road traffic in 2016.
- the inventive method and the system according to the invention can thus with the German straw and the national emergence of farmyard manure and herb waste and without further biomass imports up to 100% provide the total amount of energy consumed by German road transport, including the proportion of German fuel consumption attributable to diesel propulsion (passenger cars, light commercial vehicles and trucks and buses, tractors and special vehicles).
- the invention is based on the finding that, in the case of a recuperation and sequestration of fossil carbon carried out as part of a fuel production, even in the best case there is only a non-increase in the amount of greenhouse gas present in the earth's atmosphere, ie the GHG emission reduction power is at most 100%.
- the production, distribution and use of a fossil fuel or fuel but usually more fossil If energy sources are used whose fossil carbon can not be recuperated, fossil energy products can only theoretically achieve high decarbonisation effects or GHG emission reduction performance.
- the invention is based on the further realization that a partial recuperation and sequestration of atmospheric carbon carried out within the framework of a fuel production can not only lead to a 100% GHG emission reduction performance, but also to GHG emission reduction achievements which go far beyond that. If, in the context of a fuel manufacturing process, only those substances are used whose carbon content consists of atmospheric carbon (which is the case for biomass, see below) and only a part of this atmospheric carbon is used for the production of the fuel and the remaining carbon part or A large part of this remaining carbon part is recuperated and permanently sequestered in a carbon sink, creating a certain decarbonation effect, which is usually attributed to the product of the process.
- the energy sources required for the biomass conversion are only burdened with low GHG emissions and thus play only a relatively small role in the GHG balance or for the GHG emission value of the energy source generated, essentially the relation between the carbon fraction, which enters into the energy source and the carbon fraction that is permanently sequestered in a carbon sink, about how high the GHG emission reduction performance of the generated sustainable energy source is.
- the relative share of biomass-derived carbon in the sustainable energy source is low and the relative proportion of sequestered (biomass-derived) carbon is high, the resulting decarburization effect on the energy source is very high.
- the generated energy carrier which may be a fuel
- there is a GHG emission reduction performance which relative to the generated energy unit (MJ or kWh H i) can amount to several hundred percent or even more compared to the fossil reference.
- the amount of sequestered carbon is multiplied by a factor of 3.664 to achieve the THG effect.
- the substances which consist of atmospheric carbon, include all plants and plant-derived feedstocks like all animals and animal products, because the plants have absorbed their carbon from the earth's atmosphere by means of photosynthesis, and animals are known to live on plants or other animals, to eat the plants. That is, the carbon in animals and animal products also consists of atmospheric carbon. Accordingly, the carbon content of biowaste comes from the earth's atmosphere.
- the basic method according to the invention for which protection is claimed, consists only of the three method steps 1.) one-stage or multi-stage conversion of biomass containing atmospheric carbon into a marketable energy source, 2.) generation of conditions which at least partially chemical allow physical stabilization of the atmospheric carbon contained in the residues of single or multi-stage biomass conversion, 3.) performing at least partial chemical-physical stabilization of the in the Res- th the biomass conversion still contained atmospheric carbon (see claim 1).
- this stabilization of the atmospheric carbon is sufficient to produce the desired decarbonization effect, because unless deliberate combustion occurs, the carbon will no longer react with atmospheric oxygen, no matter where it is stored (which may be the case in mine tunnels and caverns, for example).
- the additional process steps of selecting and / or harvesting or collecting at least one biogenic, atmospheric carbon-containing feedstock are preceded, preferably, by the (originally first) process step of single or multistage conversion of the biomass into a marketable energy carrier in that the selection is made from the feedstock groups cultivated biomass, straw (cereal straw, maize straw, rice straw, etc., pure or as part of a silage), straw-containing solid manure (cattle slurry, pig manure, poultry manure, dry chicken manure, horse manure, etc.) , Straw-containing remains from mushroom cultivation, manure, manure, fresh grassy plants (ryegrass, switchgrass, miscanthus, post-pipe), catch crops before and after main crops, silage from grassy plants, maize whole plant cut, maize silage, whole crop cut, silage from cereal whole plant cut, cereal grains, corn grains, wood, biomass processing waste, biomass by-product, non-food cellul
- the GHG emission or the GHG emission value of some of these starting materials is sometimes particularly low. Since the GHG emission quantity and the GHG balance of a biomass-based fuel production route are essentially determined by the starting material or by its GHG emission value, a corresponding selection from the starting materials listed above is advantageous.
- At least a portion of the atmospheric carbon contained in the biomass is converted into a gaseous and / or liquid energy carrier (biogas, bio-methane, bioethanol, biodiesel, FT-fuel, syndiesel, bio-kerosene, synkerosin, bio-methanol, DME, butane, propane, and the like), so that a remaining portion of the atmospheric carbon passes into the process steps of stabilizing the carbon (generation of conditions, performing stabilization), preferably a proportion of at least 0.1%, especially preferably a proportion of at least 40% and in particular a proportion of at least 65%.
- a gaseous and / or liquid energy carrier biogas, bio-methane, bioethanol, biodiesel, FT-fuel, syndiesel, bio-kerosene, synkerosin, bio-methanol, DME, butane, propane, and the like
- the proportion of the chemically-physically stabilized carbon reaches the original (at the beginning of the process) in the Biomass contained atmospheric carbon a choice of the following proportions: 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% , 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, each of which may also vary within a range of at least +/- 2.5 percentage points, except for 0.1% at which the fluctuation range can be -0.1 percentage points to + 2.4 percentage points and at the unit value 100%, where the fluctuation range is -2.5 percentage point to 0.0 % Points.
- the at least partially chemical-physical stabilization of the atmospheric carbon still contained in the residues of the biomass conversion is carried out by a chemical-physical treatment of the conversion residues, preferably by a carbonation of the conversion residues to biochar / biochar / biokoks, particularly preferably by a choice of the following carbonization processes: pyrolysis, carbonization, torrefaction, hydrothermal carbonization (HTC), vapothermal carbonation, gasification, and any combination of these treatments.
- a chemical-physical treatment of the conversion residues preferably by a carbonation of the conversion residues to biochar / biochar / biokoks, particularly preferably by a choice of the following carbonization processes: pyrolysis, carbonization, torrefaction, hydrothermal carbonization (HTC), vapothermal carbonation, gasification, and any combination of these treatments.
- the biochar / biochar / biokok produced according to this basic process and, with it, the at least partially chemically-physically stabilized atmospheric carbon are at least partially distributed in the soil, in stagnant water, in aquifers or in an additional process step sequestered in the ocean, preferably in agricultural or forestry soils, more preferably in non or no longer agricultural or forestry soils, and especially in desert or permafrost soils and, at best, in other carbon sinks.
- the sequestration of the (bi) / biochar / Biokokses or the at least partially chemically-physically stabilized atmospheric carbon may thus also include their or their disposal in geological formations, aquifers or other waters.
- the sequestered carbon fraction at the atmospheric carbon initially contained in the biomass reaches a selection of the following proportions: 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, each of which is stated here additionally, within a range of at least +/- 2.5 percentage points, except at the 0.1% level where the range of fluctuation can range from -0.1% point to + 2.4% point and at 100%, where the fluctuation range can be -2.5 percentage points to 0.0 percentage points.
- the energy source used as fuel, fuel or fuel preferably consists of biogas, biodiesel, bioethanol, bio-kerosene, hydrogen, bio-methane, FT-fuel, DME, butane, propane or bio-methanol.
- the technical GHG balance and / or the GHG emission quantity of the generated energy source is strongly negative, ie after completion of the production, distribution and Utilization of the generated energy carrier, which is preferably a fuel, more preferably a gaseous fuel, and especially bio-methane, has a lower amount of greenhouse gas in the earth's atmosphere than before.
- the negative GHG emission quantity) of the generated energy carrier allows the admixture of such a quantity of a suitable (compatible) positive GHG-loaded energy source, that an absolutely GHG-free energy source is created (suitable or compatible here means "same fuel type and same state of aggregation"). That is, bioethanol and / or lignoethanol produced in this way can be mixed with fossil gasoline, biodiesel produced with fossil diesel, bio-kerosene produced in this way with fossil kerosene, bio-methane produced in this way with fossil natural gas (CNG or LNG) and / or SynMethan, such produced FT Diesel with fossil diesel, Synekerosin thus produced with fossil kerosene, hydrogen thus produced with hydrogen vapor-reformed from natural gas, etc.
- CNG or LNG fossil natural gas
- SynMethan such produced FT Diesel with fossil diesel, Synekerosin thus produced with fossil kerosene, hydrogen thus produced with hydrogen vapor-reformed from natural gas, etc.
- the amount of energy produced according to the method according to the invention preferably such a quantity of a suitable compatible (suitable) GHG positive energy carrier are admixed that the GHG em Issue value of the energy carrier mixture just barely changes to positive or remains negative.
- the THG-free energy carrier mixture makes all vehicles that use the THG-neutral energy carrier mixture, regardless of their size and consumption, abruptly turn into genuine zero emission vehicles. If the admixing of THG-positive energy carriers fails or fails completely, the process according to the invention produces a strongly THG-negative energy carrier whose use is very positive for the environment, because after completion of the production, distribution and use of the energy source produced, preferably a fuel is, particularly preferably a gas fuel and in particular bio methane, there is a lower amount of greenhouse gas in the earth's atmosphere than before.
- the invention preferably consists of an extended process and advanced facilities for straw digestion and suitable facilities for converting straw into GHG-negative biogas, treating GHG-negative biogas into GHG-negative (bi) methane, treating it with ( GHG-positive) to mix natural gas into a GHG-neutral mixed gas, feed the mixed gas into the natural gas grid and transfer the energy equivalent of the injected mixed gas quantity at arbitrary exit points to gas stations that deliver it to CNG and LNG vehicles, regardless of their Size and fuel efficiency due to the GHG neutral fuel are immediately traveling as zero emission vehicles without any GHG emissions.
- the mixing of the GHG-negative (bi) methane with fossil natural gas can also take place in the natural gas grid or, if both components are liquefied, in an LNG tank.
- GHG emissions in the formation of the mixed gas can be considered, preferably GHG emissions emanating from the use of electricity, particularly preferably GHG emissions emanating from the use of power and fuel, and especially those GHG emissions, which only occur downstream after mixing, eg the GHG emissions generated by compression of the extracted gas from the natural gas network to the discharge pressure (usually 250-300 bar) and / or as methane slip in the refueling of vehicles and / or in the liquefaction of the mixed gas to the LNG substitute Liquefied BioMethane "(LBM), ie a slightly THG-negative mixed gas is produced, the absolute amount of which is equivalent to the absolute amount of GHG emissions associated with the downstream effects.
- LBM Liquefied BioMethane
- the new technology disclosed here can prevent the increasingly required abolition of the internal combustion engine, the production of which should be discontinued as early as 2030 due to the long service life of a car so that in 2050 zero emission mobility is achieved.
- the absolutely THG-free zero emission fuels of the method according to the invention and of the system according to the invention a comprehensive zero-emission mobility is already possible today despite the use of combustion technology, which, from the point of view of customers and users, is quite clear both for electric mobility and for H 2 Mobility is superior.
- RDE Real Driving Emissions
- CNG and LNG gas vehicles powered by the mixed gas of the present invention
- electric and hydrogen powered vehicles electrical cars use the national or European power mix, both of them far and wide
- emissions of coal-based electricity generation and / or the risks of nuclear power are burdened after 2040.
- the method according to the invention provides "affordable" zero-emission mobility despite the use of the internal combustion engine, thus ensuring jobs in the automotive industry and in its supply industry, because established industrial plants (devices for producing crankshafts, connecting rods, cylinder heads, camshafts, etc.) Engine works and gear factories) can be further manufactured and used.
- raw materials that are initially not subject to GHG emissions include straw, which according to EU Directive 2009/28 (RED I) is not subject to GHG emissions until the time of collection / harvest.
- the GHG emissions arising from the cultivation of crops and their harvest are allocated solely to the grains.
- all other biogenic substances, such as wood can also be used, but the GHG emission balance or the GHG emission value is then not quite as good as when using straw. It is thus advantageous if straw or straw-containing conversion residues are used in the process according to the invention.
- straw falls like a campaign only for a short period of time, namely during the grain crop harvest in summer and early autumn.
- the supply chain begins with the laying of the mown and threshed straw in the swath behind the self-propelled combine harvester, which turns off its chaff.
- the loose straw stored in the swath has a density of approx. 25 kg / m 3 and is therefore not transportable.
- a compaction is required.
- a baler pulled by an agricultural tractor picks up the straw swath and compacts the native straw into straw bales.
- the straws can keep their length from 20 cm to 120 cm when compacted into straw bales or chopped into straw chaff, the length of which can then be 5 cm - 20 cm.
- the straw bales can be round bales or square bales.
- square bales are preferred, especially those square bales that are produced with high-pressure presses. While round bale a density of 110 - having 130 kg / m 3, it is conventional square bales 130-165 kg / m 3 and in high-pressure bales 170-210 kg / m 3. As the density increases, the transportability of the straw increases. In the case of very long transport distances, pellet presses (so-called pellet harvester) drawn and driven by agricultural tractors can also pellet the straw swath directly into straw pellets, which increases the density up to 600 kg / m 3 and increases the transportability even more.
- bales are produced.
- the pressed bales are preferably deposited in groups on the stubble field. This facilitates the subsequent harvesting steps of the collection and loading of the first means of transport.
- a modern square baler has a throughput of 35 tons of fresh straw per hour.
- the tractor should have a capacity of at least 150 kW.
- Such tractors consume approx. 18 liters of diesel equivalent per hour of operation thus a (heating) amount of energy of about 178 kWh H i / h.
- Each ton of straw accounts for an energy input of approx. 5 kWh H i and a THG emission of 1.741 gC0 2 .
- the method according to the invention involves the use of tractors which have CNG or LNG engines and use THG-free straw gas or a THG-neutral fuel mixture as the fuel.
- the first tractors with CNG drive are already available. They are just as normal as conventional tugs available.
- the energy used to crush the straw remains approximately the same when using CNG or LNG tractors fueling a GHG-neutral gas fuel. They also amount to approx. 5 kWh hi / t straw FM, only the GHG emission goes back to 0.0 gC0 2 / kWh Hi and thus also to 0.0 gC0 2 -eq / t straw FM.
- Farms usually use existing technology to collect bales of straw and load the first means of transport.
- Front loader or so-called Manitous take the bales individually or in pairs and loaded agricultural means of transport for the first transport to the straw belt. This practice is relatively time consuming and energy intensive.
- Wheel loaders with 6-fold multiple gripper eg from the Dutch company Meijer can quickly load up to 6 square bales at once on trucks with semi-trailers. Collecting and loading 6 large square bales on a semi-trailer takes just 180 seconds, 30 seconds per bale.
- tractors with front loaders load tractor-mounted low-floor loader wagons or low-floor semi-trailers with double-axle carriages. These bring the bales over relatively short distances (up to 10 km) to a straw warehouse, where the up to 3.5 m 3 large and up to 0.7 t heavy straw bales are unloaded with telescopic loaders from the loader wagons and piled up into so-called straw belts .
- semitrailers with low-floor trailers pick up the straw bales directly from the field.
- Wheel loaders collect them with multiple grippers and load them onto the truck as a 6-pack. The load takes about 30 seconds per bale (see above).
- the truck has a loading capacity of 3-4 layers of 11-12 bales, so that the loading of the total of 36-48 bales only takes about 18-24 minutes.
- the loading with 3 layers and 12 bales results in a payload of 17.1 tonnes, which almost fully utilizes the truck's weight capacity.
- the straw is according to the invention brought directly from the field to a central storage area in the vicinity of the biogas plant.
- the truck trains take the bales of straw via highways to the biogas plants, where they are unloaded either with telehandlers or with cranes that are equipped with multiple grippers. If the biogas plant is located on a shipping lane or in the vicinity of a port, the straw can also be delivered in the form of pellets and deleted.
- the truck With an average procurement distance (distance from the field or from the decentralized straw store to the biogas plant) of 50 km and a load of 20 tons of straw, the truck will provide a transport capacity of 1,000 tkm per load. At a consumption of 33 liters of diesel equivalent per 100 km, an amount of energy of approx. 163 kWh H i used for long-distance transport, with a consumption of 28 liters when driving back to the decentralized warehouse again 137 kWh H i. Overall, the energy required for long-distance transport is thus approx. 300 kWh H i per load.
- the straw bales are handled as in large straw cogeneration plants by means of gantry cranes with multiple grippers and conveyor belts. It is also possible to supply bulk goods with straw pellets, which are then stored in suitable silos.
- the storage in the central warehouse will take place predominantly in bale form. Since multiple-gripper cranes are used, and these are operated electrically and thus highly efficiently, the energy and GHG emissions for unloading the trucks and the construction of the central straw belts are negligible.
- the removal of the straw bales from the central warehouse, the transport to the biogas plant and the handling of straw bales in the biogas plant are carried out with stationary conveyor technology, which is also operated electrically and thus highly efficient.
- any known biomass conversion can be used for the first single- or multi-stage biomass conversion whose goal or task is to convert the biomass into a (marketable) energy source.
- preference is given to a process variant and a corresponding system for carrying out this process, in which the biomass to be converted consists at least proportionally of straw.
- the first biomass conversion is preferably a conversion of straw-containing biomass into energy carriers, particularly preferably a selection from the following conversion methods: conversion of straw-containing biomass into biodiesel, conversion of straw-containing biomass into bioethanol, conversion of straw -containing biomass in ligno-ethanol, conversion of straw-containing biomass into Fischer-Tropsch fuels, conversion of straw-containing biomass into methanol, conversion of straw-containing biomass into DME, conversion of straw-containing biomass into hydrogen, conversion of straw containing biomass in biogas, combination of these conversion methods.
- the process according to the invention and the straw system according to the invention produce the GHG-negative gas BioMethane, which can be distributed in gaseous form as a natural gas substitute or in a liquefied state as an LNG substitute.
- the liquefaction of (bio-) methane to liquefied (bio) methane (LBM) is just as well-known as the art as the processing of biogas to bio methane.
- the first biomass conversion consists of a conversion of straw-containing biomass into biogas, particularly preferably a conversion of straw-containing biomass into biogas, which is carried out by the process of solidification and in particular from a fermentation of solids using a garage fermenter, plug flow fermenter or upstream fermenter.
- the at least one garage fermenter is operated with a fermentation cycle which lasts shorter than 24 days, in particular shorter than 15 days and at best shorter than 9 days.
- the first conversion takes place as anaerobic bacterial fermentation by the wet process.
- a suspension is prepared from the biomass and a liquid in a marketable energy source, preferably from the biomass and an aqueous suspension, particularly preferably from the Biomass and process water.
- the suspension has a dry matter content (TS content) of 1% to 60%, preferably a TS content of 5% to 30%, particularly preferably a DS content of 8% to 18% and in particular a DM content of 9% - 14%.
- Straw is not a feedstock like any other biomass, it has specific properties that make it unusually difficult to process or use.
- Native straw - ie non-preprocessed straw in natural state - is due to its specific characteristics [in particular: particle length of the straws 20 - 120 cm; waxy surface; Fibril structure; Microfibrils structure; high fiber content; high lignin content; high strength; very wide C / N ratio of 70-100; high potassium content; high chlorine content; very low density of about 25 kg / m 3 ; very high TS content and correspondingly very low residual water content; difficult shredding; increased tendency to dust and concomitantly increased risk of explosion; high surface tension; low solubility in water ser; combustion significantly different from wood combustion such as low softening temperature, tendency to tar formation and sintering of the combustion chamber by a factor of 10 higher ash content, much higher chlorine and nitrogen content in the flue gas, significantly higher dust emissions, etc.] no feedstock like any other solid, especially not for use
- native (long) straw consists of heavily fibrous straws, which are usually 20 to 70 cm long and sometimes up to 120 cm long.
- native straw can not be used in standard mills.
- fibrous materials such as straw, therefore, a special mill technology is required. It is therefore wrong to assume that any solid biomass processing facility would also be capable of processing native (long) straw.
- at least chopping devices are generally required.
- the lignin content which accounts for about 21% of the straw solids, obstructs the path to cellulose and hemicellulose which are partly converted into biogas during straw fermentation ,
- native, unresolved straw can be converted into biogas only to a small extent by biogas plants within the usual residence times (hydraulic retention time HRT) of 20-60 days.
- the relatively low nitrogen content in the straw means that straw has a very wide C / N ratio. Typically, this is 70-100. Anaerobic microorganisms, however, require a C / N ratio of 6-20 for growth and propagation. Therefore, recultivation and recycle of nitrogenous suspensions into the process are either required or required for the fermentation of straw Admixture of single or multiple nitrogen-containing fermentation substrates such as Poultry excrement, which has a particularly narrow C / N ratio.
- the use of straw as an anaerobic fermentation substrate therefore requires special pre- and / or post-treatment measures, including the digestion of the native straw and / or the admixture of nitrogen / nitrogen compounds or of such fermentation substrates, which have a very low C / N ratio.
- the relevant state of the art also includes the digestion or pre-treatment measures of chopping, grinding, soaking, mashing and pretreatment with hot water, steam, saturated steam, thermal pressure hydrolysis, wet oxidation, steam reforming, steam explosion etc. and the support of the first phase of anaerobic digestion (hydrolysis) by application of exo-enzymes.
- the achievable conversion efficiency and the dynamics of biogas production depend crucially on the type of pretreatment. If the pretreatment consists of several days of aerobic composting, the biogas yield is significantly reduced, since in particular the easily accessible and readily digestible carbon compounds for microorganisms are oxidized to C0 2 . This in turn diffuses from the reaction mass into the atmosphere and is then no longer present, so that a part of the carbon is lost.
- the biomass to be converted into a GHG-reduced marketable energy carrier (power, heating or fuel) of a conversion which may preferably be an anaerobic fermentation or an alcohol fermentation, only after a suitable, from the Subject to the prior art previously known measure, preferably from the following measures: mixing with water, aqueous suspensions or process water, soaking with water, aqueous suspensions or process water, crushing (bale dissolution, shredding / shredding, grinding, etc.) of the biomass residues the first fermentation, extrusion of this biomass, pressureless treatment of this biomass with hot water or steam, pressurized treatment of this biomass with hot water or steam, treatment of this biomass with saturated steam, thermal pressure hydrolysis of this biomass, wet oxidation of this biomass, D Steam explosion of this biomass, steam reforming of this biomass mass, other known pretreatment of this biomass, any combination of these measures.
- a GHG-reduced marketable energy carrier power, heating or fuel
- a conversion which may preferably be an anaerobic fermentation or an alcohol
- the biomass to be converted into a GHG emission-reduced biomass is a multiple (two to tenfold), preferably a double conversion, which is particularly preferably a double anaerobic fermentation, a double alcohol fermentation or a combination anaerobic fermentation and alcohol fermentation is subjected, preferably the second conversion takes place after an intervening measure, which consists of a suitable, previously known from the relevant prior art measure and which is particularly preferably selected from the following measures: mixing with water or aqueous Suspensions, crushing (dissolution, shredding / shredding, grinding) of the conversion residues from the first conversion, extrusion of these conversion residues, pressureless treatment of these conversion residues with hot water or steam, pressurized treatment of this conversion recipe treatment with hot water or steam, treatment of these conversion radicals with saturated steam, thermal pressure hydrolysis of these conversion radicals, wet oxidation of these conversion radicals, steam explosion of these conversion radicals, steam reforming of these conversion radicals, other known aftertreatment of
- the biomass is subjected before the conversion of a thermal treatment, preferably a multi-stage first temperature and second temperature, particularly preferably a multi-stage first, second and third temperature and in particular a multi-stage first, second, third and fourth temperature.
- the tempering of the biomass can in each case take place at temperature levels which, under the additional condition that the subsequent temperature level is higher than the previous one, consists of a selection from the following temperatures: 0.1 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, 100 ° C, 105 ° C, 110 ° C, 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195
- At least a portion of the biomass is replaced or supplemented by suitable feedstocks known from the relevant prior art, preferably by starting materials from the selection of percolate, Manure, manure, grass, hay, grass silage, maize silage, whole crop silage, straw and other silage silage, hay, cereal grains, potatoes, industrial beets, sugar beets, sugar cane, molasses, field beans, wild flowers, landscape preservation products, Roadside green, residues from the processing of agricultural products, distillate from ethanol production, oilseed rape, rapeseed cake, cultivated biomass, wood, wood waste, organic waste, biowaste, organic residues, biomass processing residues, biomass by-products, non-cellulosic Food material, lignocellulosic feedstock , Forestry residues, cereals and other high-starch crops, sugar plants, oil crops, algae, biomass fraction of mixed waste, household waste, straw
- the fermentation of the straw does not take place in a classic "wet plant” which operates on the stirred tank principle with a slurry-like aqueous suspension, but in a solids fermentation plant which functions according to the garage principle
- the anaerobic digestion of the straw should not be limited to solid fermentation plants by this embodiment, it can in principle also the wet process which is carried out in classic wet facilities.
- bales of straw are not subjected to a saturated steam treatment as a whole before fermentation (see patent application EP15001025.4 of the inventor), they are dissolved before fermentation.
- the loose straw is then crushed with a shredder and a grinder.
- the degree of comminution can be varied so that the straw particles are on average between 0.01 mm and 30.0 mm long.
- the comminution can therefore only include the chopping of the straw (to about 5 cm - 20 cm) but also an additional grinding, e.g. using hammer or granulators.
- the degree of comminution depends on which conversion efficiency is to be achieved: the higher the degree of comminution, the higher the conversion efficiency, all the more ceteris paribus.
- a high degree of comminution requires a high energy input (for the mills).
- the bacterial fermentation of the straw to ensure a C / N ratio of 20-40 together with nitrogen-containing fermentation substrate (poultry manure, manure) and / or together with nitrogen-containing process water, which is particularly preferably previously extracted from the digestate.
- nitrogen-containing fermentation substrate proultry manure, manure
- nitrogen-containing process water which is particularly preferably previously extracted from the digestate.
- anaerobic bacterial fermentation only a very few N fractions of the fermentation substrate produced in the fermenter are converted into biogas; the much larger part remains in the fermentation mass, which results in N enrichment in the fermentation mass or in the fermentation residues.
- the fermentation substrates are enriched with N-containing process water before or during fermentation, the amount of N-containing fermentation substrates used can be reduced. This reduction is beneficial to the properties of the bioliquids / bioliquids produced by digestate.
- the solids fermentation is preferably carried out in a solid manure-like debris, which after closing the "garage door” under exclusion of air in the "garage” from above with percolate (percolated) is.
- the heap-type fermentation mass sucks to the limit, from which free (process) water or a free suspension (percolate) is formed, with this percolate, which consists of the infiltration fluids of the fermentation mass of the previously ended fermentation cycle and / or from process water, which is generated in subsequent process steps.
- the bacteria-containing percolate seeps through the Gärmasse heap, is recuperated and is available for another shower.
- the anaerobic bacterial fermentation that takes place in a wet plant can be one-stage only be carried out in the garage fermenter or in two stages.
- at least a portion of the percolating organic acid-loaded percolate is passed into a high-performance methanizer in which immobilized microorganisms perform the known methanogenesis.
- the percolate which is facilitated with some of the organic acids, is led out of the methanizer and percolated onto the mass of fermented mass and the circulation begins again.
- the so-called garage process the fermentation takes place in cycles, which usually take 21 - 28 days.
- the introduction of the fresh digestate into a plurality of garage fermenters is usually done with a wheel loader, as well as the previous mixing of the fresh fermentation mass with inoculation (a part of the old digestate from the previous fermentation cycle) and the removal of the fermented digestate from the garage fermenters.
- the garage fermenters are operated with a time lag, so that biogas production is more or less continuous.
- the garage method has the advantage on the one hand that no liquid fermentation mass is used, in the straw pieces i.d.R. Float, form floating layers and clog overflows. The straws are rather trapped in the solid manure-like pile.
- the straw-containing fermentation residues are not present in small-scale, liquid form, but as a heap with TS contents of approx. 30% - 40%. While liquid fermentation residues can be subjected to only one HTC without an exceptionally high technical effort (see above), the solid-mist-like consistency of the fermentation residues makes the desired pyrolysis possible, preferably after a possible dehydration of the fermentation residues to approx. 50% DM.
- the comminution has proven itself as a pre- and post-treatment, in particular the grinding, which is preferably carried out after a chopping, particularly preferably after a bale resolution, followed by a chopping and a grinding.
- pre- and post-treatment measures mixing or treatment with warm water (15 ° C - 99 ° C), mixing or treatment with hot water (> 99 ° C), the gradual heating of the digestate, the Treatment with (saturated) steam, with thermal pressure hydrolysis, with wet oxidation, with the steam explosion, with steam reforming, the biological treatment with mushrooms, mixing or mixing with (possibly treated or cleaned) pro- tessenwasser, the repeated fermentation after a post-treatment and the combination of these measures proven.
- the process step "Pretreatment &Fermentation” requires an energy input of 21.4 kWh e
- the dry substance of the straw is converted into biogas, in which methane has a share of 53.50% by volume, carbon dioxide has a share of 44.60% by volume, hydrogen Proportion of 0.15% by volume, oxygen a proportion of 0.75% by volume, nitrogen a proportion of 0.75% by volume, sulfur-hydrogen a proportion of 0.05% by volume and ammonia one Share of 0.20% by volume.
- the calorific value of the biogas is determined essentially by the methane content.
- methane With a methane yield of 2,860 kWh H i / t straw FM (conversion efficiency 70%) and a specific calorific value of 9.978 kWh H i / Nm 3 CH 4 , this results in a methane volume of 286.6 Nm 3 and a total biogas volume of 535.7 Nm 3 . At this biogas volume, methane has a share of 286.6 Nm 3 , carbon dioxide 238.9 Nm 3 , hydrogen 0.804 Nm 3 , oxygen 4.018 Nm 3 , nitrogen 4.018 Nm 3 , hydrogen sulfide 0.268 Nm 3 and ammonia 1.071 Nm 3 .
- An essential element of the invention is to treat residues from a first biomass conversion into (marketable) energy carriers, preferably straw-containing conversion residues, in such a way that the atmospheric carbon still contained in these fermentation residues is at least partially stabilized by chemical physics.
- the first biomass conversion can be any biomass conversion that produces carbon-containing conversion residues (eg, the conversion of biomass into biodiesel, the conversion of biomass into bioethanol, the conversion of biomass into ligno-ethanol, the conversion of biomass into fisheries). Tropsch fuels, the conversion of biomass into hydrogen, the conversion of biomass into biogas and similar previously known methods).
- the chemical-physical stabilization of the atmospheric carbon remaining in the remnants of the first biomass conversion is preferably carried out in such a way that the atmospheric carbon does not and / or does not react with other substances (atmospheric oxygen) for decades, particularly preferably for centuries and especially for millennia soil respiration decays (ie is not decomposed by soil organisms).
- the physicochemical stabilization is achieved by a thermo-chemical treatment, which is particularly preferably a carbonization and in particular consists of a selection of the following known carbonization processes: pyrolysis, torrefaction, carbonization, gasification, hydrothermal carbonization (HTC), vapothermal carbonation, any Combination of these measures.
- a thermo-chemical treatment which is particularly preferably a carbonization and in particular consists of a selection of the following known carbonization processes: pyrolysis, torrefaction, carbonization, gasification, hydrothermal carbonization (HTC), vapothermal carbonation, any Combination of these measures.
- HTC hydrothermal carbonization
- vapothermal carbonation any Combination of these measures.
- corresponding devices known from the relevant prior art are preferably used for this purpose.
- the carbonization of the residues from the first biomass conversion preferably produces a biochar or biochar, in which at least partially stabilized or partially stabilized atmospheric carbon is contained.
- the proportion of stabilized or partially stabilized atmospheric carbon in the dry matter of the biofuel / biochar produced is preferably more than 1%, particularly preferably more than 15%, in particular more than 45% and especially more than 70%.
- the treatment of the treated residues from the first biomass conversion to the reaction temperature is as far as possible in a preferred embodiment of the invention slowly.
- the heating to the reaction temperature therefore lasts longer than 1 second, in particular longer than 10 minutes and at best longer than 100 minutes.
- the residues from the first biomass conversion are split into two, three or four substreams, the first substream being pyrolysed, the second substream being a selection of low temperature pyrolysis, short term pyrolysis, carbonization, gasification, torrefaction , HTC and vapothermal torrefaction, resulting in at least partial stabilization of the carbon, the third substream being treated by a choice of low temperature pyrolysis, short term pyrolysis, torrefaction, HTC, carbonization, gasification and vapothermal torrefaction, and no stabilization of the carbon and the fourth partial stream is not subjected to any thermo-chemical treatment.
- the pyrolysis is a high-temperature pyrolysis, which are exposed at the residues from the first biomass conversion under oxygen deficiency at a temperature of 150 ° C - 1,600 ° C, preferably a temperature of 500 ° C - 1,000 ° C and in particular a temperature of 600 ° C - 900 ° C.
- the reaction mass is exposed to the reaction temperature for more than 1 second, more preferably for more than 50 minutes and more preferably for more than 500 minutes.
- the pressure in the reaction vessel which is used for the thermo-chemical treatment of the residues from the first biomass conversion, preferably corresponds to the pressure of the environment, particularly preferably> 1 bar and in particular> 5 bar.
- the carbonization-exposed conversion radicals are present in the form of pellets or briquettes, wherein they preferably substantially maintain this shape during carbonation and / or the output of the carbonization devices has substantially the form of pellets or briquettes.
- a special two-, three- or four-part digestate / biochar mix consisting of digestate and low- and high-temperature coals is produced and introduced into the field soil as a substitute for straw left over from the field.
- the carbon fraction subjected to pyrolysis of pyrolysis is chemically stabilized in such a way that, after incorporation into the field soil, it can neither be degraded by the process of soil respiration nor by the process of aerobic rotting and consequently becomes part of the permanent humus.
- the untreated digestate and the torrefaction coal become part of the nutrient humus.
- the digestate / biochar mix can be enriched (charged) with organic nutrients beforehand.
- the molar H / C ratio is a) of the (partially) stabilized atmospheric carbon, b) of the produced highly C-containing bioliquids / biochecks E to G, c) of the biochar / biochar mixture H and / or d) the biochar / biochar conversion radical mixture I at ⁇ 0.8, particularly preferably at ⁇ 0.6, and / or its molar O / C ratio at ⁇ 0.8, particularly preferably at ⁇ 0, 4th
- Such bioliquids / biolocs or biochar / biochar mixtures or biochar / biochar / biocoks conversion residue mixtures are at least partially chemically stabilized in such a way that the stabilized part of the / Biochar / biokoks contained atmospheric carbon within a certain long-term period (10 years, 30 years, 100 years, 500 years, 1,000 years, 10,000 years, 100,000 years) neither through the process of soil respiration nor through the process of aerobic compost nor by reaction can be degraded with atmospheric oxygen. It is therefore sufficient to protect against weathering stored bio / bioliquids / biococcuit to extract carbon from the earth's atmosphere and bring about a decarbonization of the earth's atmosphere.
- Such storage may e.g.
- biocoenes / bioliquids produced by the method according to the invention or the biococcans at least partially in agriculturally used soil, in particular in Ackerkrume incorporate either alone or together with non-carbonated residues from single or multistage biomass conversion.
- the amount of short-term, medium-term and long-term stabilized atmospheric carbon is greater by a factor of 1.5 - 5.7 than if the farmer had left the straw entirely on the field and by a factor of 2.0 - 8 , 2 larger than if, according to good technical practice, he had lost 30% of the straw growth from the field.
- the straw is run off the field with a maximum (future) proportion of up to 87% and although gas is produced from this straw, the method considerably improves the soil quality and the farmer as if the straw was broken.
- the method achieves high and very high humus effects from the combination of short- and medium-term humification with nutrient humus and long-term sequestration of stabilized biochar, resulting in a whole series of positive secondary effects , These have been listed above.
- the user of the method and the system according to the invention can take in a very advantageous manner access to the entire share of Strohauswuchses, which previously had to remain in addition to the non-recoverable Strohanteil (stubble, Kaff, chaff) in addition to the field to the To ensure the level of humus content of the soil.
- the process / system according to the invention can produce significantly more advanced biofuel from the German straw than with all other methods of straw conversion, namely without admixing natural gas up to 100,000 GWh Hi (360 PJ) and with natural gas admixture to 125,000 GWh Hi (450 PJ).
- the amount of fuel of 100,000 GWh Hi without an admixture of natural gas would be strong GHG negative and with the addition of GHG neutral.
- the water content (the dry matter) of the digestate must be from approx. 65% (35% DM) to at least 50% (50% DM) ) reduced (increased).
- this dehydration can be carried out in two steps, first via solid / liquid separation by means of a decanter / screw press to a DM content of up to 40% and then to a DM content of 50-70% by means of drying , which is preferably a low-temperature drying.
- drying which is preferably a low-temperature drying.
- the energy required for the drying is obtained from the drying plant, preferably in the context of process heat recirculation from high-temperature pyrolysis.
- the coming from the low-temperature drying approx. 100 ° C hot, straw-containing fermentation residue stream can be divided into a first partial stream, which is not treated, a second Partström subjected to a weak Torrefiz réelle, a third partial stream, which is subjected to a strong Torrefiz réelle and a fourth partial stream, which is pyrolyzed.
- the partial flows can each have a share of 0% - 100% of the total flow under the additional condition that the sum of the partial flows does not exceed 100%.
- a division of the total flow into 3 partial flows will be described as an exemplary embodiment, but in other embodiments a division into 1 partial flow, 2 partial flows and 4 partial flows is also possible.
- the hot torrefiziert and pyrolysed biochar / biochar / biococ are quenched with a selection of the following nutrient-containing aqueous suspensions: manure, percolate, manure, from the Ethanol production, liquid residues from anaerobic digestion, urine, seepage water from silage, process water, treated or purified process water, liquid digestate, permeate, rather liquid phase of dehydration, rather solid phase of dehydration, any phase of a separation, other nutrients containing Suspensions and similar suspensions (eg Sus pensions from water and mineral fertilizer), mixed with the non-treated digestate and if necessary to reduce the biochar delivery composition and / or for easier handling again subjected to a low-temperature drying.
- the produced bioliquids / biochips / biococci can be extinguished either individually or as coal mixtures or carbon-conversion-mixture.
- the carbonization of the straw-containing fermentation residue is preferably carried out in closed devices in which the gases released during the Verschwelungsvorgang (pyrolysis gases) are particularly preferably used for heating the Verschwelungs styles (pyrolysis).
- the carbonization can be done in parallel and in a serial circuit.
- the carbonators are used for both torrefaction and pyrolysis.
- the difference is only in the chosen reaction temperature and the selected reaction time, both of which are higher in the pyrolysis than in the torrefaction.
- other processes can also be used for the carbonization, such as e.g. hydrothermal carbonization (HTC) or vapothermal carbonation.
- HTC hydrothermal carbonization
- vapothermal carbonation vapothermal carbonation
- a pyrolysis system requires no heat supply, on the contrary, it generates considerably more heat than is needed for smoldering.
- the power consumption of the system is currently approx. 55.6 kWh e! per t fuel TS. It is foreseeable that the specific use of electricity will continue to decline as the size of these plants increases (economies of scale).
- the output from the low-temperature drying is 282 kg of wet solids, of which 169 kg DM and 113 kg water. 134.2 kg of the 169 kg TS are carbon (see above). 6.67% of the dried fermentation residue (18.8 kg of FM, of which 7.5 kg of water, 11.3 kg of DM, of which 8.9 kg of C) are initially put aside to later mix with the produced biochar with the aim To deliver the soil flora and fauna easily digestible biomass (OBS).
- OBS soil flora and fauna easily digestible biomass
- the side-by-side digestate, the biochar resulting from the torrefaction and the output of the high-temperature pyrolysis are mixed together to form a high-quality humus-C-containing biochar / biochar mixture.
- the biochar masses E to G produced according to the process according to the invention are mixed with a biochar mixture H before or after their mixing enriched exactly with the organic nutrients contained in the cereal plant.
- the biogas plant extracts these nutrients from the percolate, which is produced in the first step of the fermentation in the first step of the anaerobic bacterial fermentation - the hydrolysis - in the garage fermenter from straw.
- the straw ingredients which are organic nutrients except for the ash content, are at least partially washed out of the straw and accumulate in the percolate.
- the enrichment of organic / biochar mixture with organic nutrients is preferably by quenching with a selection of the following nutrient-containing aqueous suspensions: manure, percolate, manure, liquid residues from anaerobic digestion, vinasse from an ethanol production, urine, leachate from silage, (possibly treated or purified) process water, liquid digestate, permeate, rather liquid phase of dehydration, rather solid phase of dehydration, any phase of a separation, other nutrients containing suspensions and similar suspensions.
- the amount of heat contained in the hot biochar / biochar is lower than the amount of heat required to evaporate the water supplied (only the water vaporizes upon quenching, the organic nutrients dissolved in the water remain in the biochar / biochar mixture), so the biochar / biochar mixture becomes wet again, otherwise it remains dry.
- the moist biochar / biochar mixture is, if necessary, in a second low-temperature drying plant to a TS content of at least 86% dried.
- Stabilized biochar / biochar (s) E, semi-stabilized biochar / biochar F, non-stabilized biochar / biochar / biokoks G, from bioliquids / bioliquids / biokoks E bis G composite biochar / biochar / biochar mixture H and the biochar / biochar / biocoke conversion mixture I composed of the biochar / biochar / biofuel mixture H and conversion residue D may or may not be individually charged with organic nutrients. That is, it is possible and may be advantageous to charge only individual components of these mixtures or mixtures with organic nutrients and not others. It is also possible to charge all biochar / biochips E to G with organic nutrients and none. Furthermore, it is possible and may be advantageous to charge all the components of the biochar / biochar / biofuel mixture H and the biochar / biochar / biocconversion remainder mixture I with organic nutrients and none.
- the side-by-side fermentation residue has a temperature of about 25 °
- the temperature of the biochar coming from the torrefaction is about 250 ° C. and that of the output of the high-temperature pyrolysis about 700 ° C.
- the aqueous suspension used during the quenching (preferably a selection of the following nutrient-containing suspensions: manure, percolate, manure, distillate from an ethanol production, liquid residues from an anaerobic digestion, urine, leachate from silage, (possibly treated or purified )
- Process water, liquid digestate, permeate, rather liquid phase of dehydration, rather solid phase of dehydration, any phase of a separation, other nutrients containing suspensions and similar suspensions) which is particularly preferably made of percolate from the fermentation of straw-containing fermentation mass, previously at least partially concentrated by means of filtration, ultrafiltration and reverse osmosis and to an average TS content of about 5.0%.
- 1 kg of aqueous suspension consists of 50 g of TS and 950 g of water.
- 34.0 kg of percolate are required, which consists of 1.7 kg DM and 32.3 kg Water exist.
- the carbon content remains at 85.6 kg C.
- Energy input The energy input required during mixing and after-treatment is so low that it can be neglected.
- GHG emissions The mixing of fermentation residues with fresh biochar and their after treatment virtually eliminates GHG emissions.
- bioliquids / biochips / biococcus or bioliquids / biochar / biokoks mixtures can be stored either in bulk form or in the form of granules, flour, crumbs, pellets or briquettes. Furthermore, it is possible to initially store these bioliquids / bioliquids / biococcans loosely and to granulate, shred, grind, grind, pelletize or briquette them shortly before transporting them to the purchasers.
- the BigBags are taken from the silos or intermediate storage and delivered by truck, preferably trucks that have a CNG or LNG drive and use GHG-free GHG produced according to the method of the invention.
- trucks that have a CNG or LNG drive and use GHG-free GHG produced according to the method of the invention.
- the fermentation residue / biochar mixture charged with organic nutrients and filled into BigBags is removed from the interim storage facility by means of a telescopic loader or crane and loaded on trucks, preferably on truck semi-trailers.
- the truck can also be equipped with a crane, so that the loading and unloading can also take place in those places where no suitable charging technology is available.
- the truck With an average delivery distance (distance from the biochar interim storage facility to the regional interim storage facility and / or farm) of 50 km and a loading of 20 tonnes of biochar (bulk density 0.36 t / m 3 ), the truck will provide a transport service of 1,000 tkm. At a consumption of 33 liters of diesel equivalent per 100 km, an amount of energy of approx. 163 kWh H i used for long-distance transport, with a consumption of 28 liters when driving back to the decentralized warehouse again 137 kWh H i. Overall, the energy required for long-distance transport is thus approx. 300 kWh H i per load and 15 kWh H i per ton of biochar. Since the delivery trucks will be equipped with CNG or LNG engines that will refuel and use GHG-free mixed gas produced by the process of the present invention, transporting the biochar to customers will not cause GHG emissions.
- the process according to the invention can be used at a biogas conversion efficiency of 70%.
- This energy input is not linked to the emission of greenhouse gases for the reasons listed above.
- the content of the delivered BigBags is filled on the farm or at the edge of the field, if necessary together with mineral fertilizer in a fertilizer spreader and alone or as usual with this together on the field and then incorporated into the soil, preferably in the field crop , Apart from the negligible work that results from filling the fertilizer spreader, there is no additional effort, because the farmer plows the process of plowing or breaking the field crop anyway. As this does not result in any additional energy expenditure, it also does not result in GHG emissions.
- the application of the charged bio / biochar mixture can of course also be done without mixing with mineral fertilizer.
- the digestate / biochar mixture which may also consist only of biochar or a biochar mixture, may also be mixed with solid manure, e.g. when loading solid manure spreaders.
- the digestate / biochar mixture is then spread along with the solid manure on the agricultural land and incorporated into the soil.
- the digestate / biochar mixture which can also consist only of biochar or a biochar mixture, can also be mixed with liquid manure or liquid digestate - if necessary after prior comminution to a correspondingly fine degree - e.g. before or after the loading of manure transporters and / or manure spreaders.
- the digestate / biochar mixture is then applied together with the slurry or the liquid digestate on the agricultural land and incorporated into the soil.
- biogas produced from straw by the process according to the invention typically amounts to approximately 51, 0% of methane, about 0,10% of hydrogen, about 0,20% of ammonia, about 0,05% of hydrogen sulphide, about 0,50% of oxygen, about 0, 50% nitrogen and about 47.65% atmospheric C0 2 ).
- This atmospheric C0 2 can - as practiced since 2011 by the German company CropEnergies AG in the production of bioethanol - be liquefied and distributed to industrial customers and replace those previously used fossil C0 2 (eg in the food industry) or - as of Norwegian oil company StatOil practiced - to be sequestered in the long term (eg as propellant gas in almost exhausted oil deposits).
- the increase in the amount of C0 2 present in the earth's atmosphere is prevented; in the second case, atmospheric C0 2 is removed from the earth's atmosphere. Both result in extended decarbonisation effects recognized by the European Renewable Energy Directive (RED) 28/2009.
- Recuperated atmospheric C0 2 can also be used as a basis for the production of synthetic energy sources such as synthetic methane, which is generated according to Sabatier from hydrogen and C0 2 . If the hydrogen gas is generated by electrolysis from grid-decoupled EE electricity such as wind power, the synthetic energy source is approximately THG-neutral. Except for the case of the sequestering of the recuperated C0 2 s is a preparation or purification of C0 2 s application requirement.
- waste or residue accumulating atmospheric carbon dioxide (C0 2 ) is therefore preferably subjected to a selection of the following process steps: recuperation, purification, liquefaction, treatment, sequestration (in geological formations such as oil or gas deposits) , Substitution of fossil C0 2 s, production of C0 2 -based energy sources (SynMethan, SynMethanol), any combination of these process steps as far as possible and reasonable.
- the recuperated atmospheric C0 2 is sequestered in oil or natural gas deposits from which it is still being extracted.
- the recuperated atmospheric C0 2 replaces fossil C0 2 .
- inventive method and the system of the invention so that only from the German straw with a corresponding proportion of fossil natural gas make a large part of the German road vehicle fleet to real zero emissions vehicles and at the same time improve the humus content of German arable land significantly and sustainably. Because of the size of this potential vehicle population, the technology disclosed here is clearly more than just a transition technology to electric and hydrogen mobility.
- Cryogenic separation processes are advantageous for the process according to the invention because it makes it possible to use the CO 2 obtained in the biogas treatment and the bio-methane produced must anyway be liquefied in the production of the LNG substitute LBM (Liquefied BioMethane).
- the C0 2 should therefore be liquefied after cleaning and delivered in a liquid state by truck to the industrial customers. Since the C0 2 with approx.
- 70% has a high mass fraction of the biogas produced and it should be present in the liquid state in the end, it is advantageous for the separation of the carbon dioxide (sublimation point at -78.5 ° C) and possibly also the other gases (ammonia, hydrogen sulfide , Oxygen, hydrogen) of methane to use a cryogenic process or cryogenic plants. These are offered by various manufacturers.
- Ammonia has the highest boiling point of all gases in the biogas at -33.3 ° C at atmospheric pressure. Ammonia is thus the first liquid in a cryogenic separation process.
- the hydrogen sulfide can be washed out of the biogas before the cryogenic separation using conventional technology.
- Hydrogen sulfide (hydrogen sulfide) has the second highest boiling point at -60 ° C at atmospheric pressure. Hydrogen sulfide becomes liquid in a cryogenic separation process.
- the hydrogen sulfide can be washed out of the biogas before the cryogenic separation using conventional technology.
- Carbon dioxide has the third highest boiling point or sublimation point at -78.5 ° C at normal pressure.
- C0 2 becomes liquid in a cryogenic separation process as a third.
- Methane has the fourth highest boiling point at -161.5 ° C at atmospheric pressure. Thus, methane becomes the fourth liquid in a cryogenic separation process.
- the biogas pre-purified in this way is pressurized (1.1-50 bar, preferably 3-30 bar, in particular 5-15 bar and at best 6). 8 bar) and gradually cooled.
- the C0 2 becomes liquid and can be diverted and possibly at - 162 ° C, the methane, if liquefied LBM is needed.
- the liquefaction of C0 2 s generously requires a power input of 365 kWh e
- methane has a share of 40.99 Nm 3 , carbon dioxide 38.30 Nm 3 , hydrogen 0.08 Nm 3 , oxygen 0.40 Nm 3 , nitrogen 0.40 Nm 3 , hydrogen sulfide 0.04 Nm 3 and ammonia 0.16 Nm 3 . Assuming a conversion efficiency of 70%, the preceding and following quantities are higher or lower by a factor of 7.
- the amount of raw biogas used per ton of straw originally used is approx. 535.7 Nm 3 .
- the feed-in of bio methane into the national natural gas network is established technology, in Germany there are approx. 200 biogas plants that feed biogas processed into BioMethane into the natural gas grid.
- the energy input for the compression in transmission networks is about 1% of the calorific value of the amount of biomethane to be compressed.
- the inventive method produces per ton of straw input rd. 2,860 kWh H i of bio methane. Its compression for transmission through the national grid therefore requires an electric current of 28.6 kWh e
- the amount of fossil natural gas generated is to be admixed to the produced GHG-negative bio-methane or the produced straw gas in order to produce a gas mixture whose GHG balance is neutral or whose GHG emission value is zero or its GHG emission reduction performance is exactly 100% compared to the fossil reference (fuel base value) - ie 94.1 kilograms of carbon dioxide equivalent per gigajoule or 338.76 gC0 2 -eq / kWh H i.
- the admixing amount is dependent on the GHG negativity (or of the negative GHG emission amount) of the BioMethans produced.
- the pressing of the straw requires an energy input of 5 kWh H i / t straw FM.
- the tractors which pull the straw press have a CNG or LNG drive which uses the THG-free mixed gas as fuel.
- the pressing of the straw into square bales is therefore not associated with GHG emissions.
- bales of straw and the loading of the trucks with wheel loaders require the use of a quantity of fuel amounting to 3.4 kWh H i per ton of wet straw mass.
- the wheel loaders that collect and load the bales of straw have a CNG or LNG drive which uses the THG-free mixed gas as fuel. Collecting and loading the square bales are therefore not associated with GHG emissions.
- the long-distance transport of the straw by means of loaded trucks requires a fuel input of 15 kWh H / t straw-FM.
- 15 kWh Hi x 342.36 gC0 2 -eq / kWh Hi 5.134 gC0 2 -eq would be emitted into the atmosphere per tonne of straw FM.
- the method according to the invention provides that the trucks will be equipped with CNG or LNG engines refueling and using GHG-free mixed gas produced by the method according to the invention, also the long-distance transport of the straw will not cause GHG emissions.
- the treatment of the straw with steam requires transferred to the entire amount of straw, although a heat input of approx. 8 kWh H i / t straw-FM, which, however, is covered by process heat from the torrefaction or pyrolysis of the digestate and is therefore not contaminated with GHG emissions.
- the conversion of straw into biogas is associated with a flat-rate electricity use of 21.4 kWh e i.
- the German electricity mix will generate a corresponding GHG burden of 21.4 kWh e
- + 11,556 gC0 2- eq / t straw-FM.
- the wheel loader causes an energy expenditure of 9.6 kWh H i per ton of straw FM. Since the wheel loader has a CNG or LNG drive and it is operated by means of the method according to the invention produced, absolutely GHG-free mixed gas produced by the operation of the wheel loader no GHG emissions.
- the first dehydration of the straw-containing fermentation residues by means of phase separation requires, according to the above, a power requirement of 1.81 kWh e / t straw FM.
- a power requirement 1.81 kWh e / t straw FM.
- this gives a GHG emission of 8.07 x 540 +978 gCQ 2- eq / ton straw FM.
- the drying of the dehydrated fermentation residue to a TS content of 60% requires a heat input of 81.8 kWh H
- the torrefaction and pyrolysis of the straw-containing digestate which is produced with an input of 1 ton of straw FM, has a power requirement of 8.7 kWh e
- results in a GHG emission of 8.7 x 540 +4.698 gC0 2 -eq / t straw-FM.
- the delivery of the biochar / biochar mixture H or of the biochar / biochar fermentation residue mixture I requires, based on the input of 1 ton of straw FM, a fuel quantity of 1.90 kWh H i. This use of energy is not linked to the emission of greenhouse gases for the reasons stated above.
- the biogas upgrading to BioMethan requires a power input of approx. 80.4 kWh e! per ton of straw input.
- results in a GHG emission of 80.4 x 540 +43.416 gC0 2 -eq / t straw-FM.
- CNG compressed natural gas
- the GHG emission reduction performance is correspondingly 1,728,692 gC0 2 -eq / t straw FM or 100% or 338.76 gC0 2 / kWh Hi or 94.1 kg C0 2 -eq / GJ.
- the amount of natural gas added to the generated GHG-negative bio-methane increases advantageously when not only straw is used as feedstock, but also largely GHG-free feedstocks such as slurry, solid manure, beet and potato herb and legume waste.
- the process of the present invention could provide an additional 5,600 - 39,200 GWh of Hi (20-140 PJ) gaseous fuel in addition to the straw-produced bio-methane.
- a further 1.0 - 3.1 million t of chemically stabilized biochar and biochar would be added to the arable land as permanent humus, with a further decarbonisation effect of -3.8 million t C0 2 -eq to -11.3 million t C0 2 -eq.
- This negative GHG effect allows the admixture of from 0.2 to 8.0 kWh H i fossil natural gas per 1 kWh BioMethan. Based on the German manure / manure / herb consumption (60%), the BioMethan generated could be approx. 10,000 - 45,000 GWh Hi (36 - 160 PJ) of fossil natural gas without exceeding the GHG value of 0,0 gC0 2 -eq / kWh H i.
- the method of the invention can provide up to 50,000 GWh Hi (180 PJ) of zero emission fuel as an additional GHG-neutral mixed gas through the use of manure, solid manure and cabbage, resulting in a future Real Driving annual fuel consumption of approx. 3,000 kWh H i per gasoline car and year covers the (gas) fuel demand of a further 17 million gasoline passenger car equivalents.
- the transport and outfeed of the energy equivalent of the mixed gas generated from straw gas and natural gas from the natural gas network requires no effort, because the distribution is usually made only virtually.
- the generated straw-gas molecules and the added natural gas are physically used in a completely different location than at the virtual exit point, namely mostly near the entry point.
- the energy equivalent of the mixed gas formed from straw gas and natural gas is preferably delivered as a fuel, particularly preferably as CNG or LNG substitute to the end user (motor vehicles with CNG or LNG drive).
- CNG or LNG substitute to the end user (motor vehicles with CNG or LNG drive).
- the process according to the invention generates 2,860 kWh of H i BioMethane / t straw FM. Due to the GHG negativity (or the negative GHG emission amount) of the produced gaseous fuel BioMethan a CNG amount of 2,243 kWh H i can be mixed, so that results in a mixed gas amount of 5,103 kWh H i.
- the straw produced bio methane is in any case GHG negative no matter how high the biogas conversion efficiency is.
- certain fuels eg the gas fuel "mixed gas”
- other fuels eg by conventional diesel fuel
- the GHG negativity or the negative GHG emission amount of the produced BioMethans, but without becoming GHG positive.
- the system according to the invention with its system limits “straw collection” and “delivery of the energy equivalent of gas fuel to the end user", is supplied with straw, fuel and electric power as external energy sources or energy.
- the straw used has a (lower) calorific value of 4,750 kWh H
- the fuel is needed a) for the operation of the tractor (tractor) that pulls and drives the straw baler b) for the wheel loader, which picks up the square bales with a multi-gripper and loads a truck c) for the truck carrying the straw transport to the D) for the wheel loader, who clears and refills the garage fermenter in the biogas plant and e) for the truck, which carries out the transport of the digestate-biochar mixture back to the straw supplier and returns empty again.
- the electric current is used a) during the conversion of the straw into biogas (various plants of the biogas plant), b) during the dehydration of the digestate (screw press or similar), c) during the torrefaction and pyrolysis of the digestate (drive of the plant) , (d) the natural gas network in the treatment of biogas to BioMethan, e) that occurred when the Biomet Hans compression), f) in the liquefaction of the recuperated C0 2 s and g) in the delivery to the end user (compression to 250 bar).
- the so-called C0 2 emission factor for domestic electricity consumption for 2013 amounts to 615 gC0 2 -eq / kWh e
- this factor is by 2020 to 540 GC0 2 eq / kWh e
- the methane slippage which possibly occurs during the opening of the garage fermenter, the gas mass change, the biogas upgrading and the delivery of the gas fuel to the end user are offset by the inventor with the unequally higher GHG emission reduction capacities which the process of the invention upstream by the energetic utilization of nitrogen-containing and very GHG-intensive farm manure (manure, solid manure, poultry manure), whose co-fermentation in the garage fermenters is advantageous simply because it contributes to achieving the C / N ratio of 20-40 (when using the recycle line). containing percolates or process water) or this C / N ratio can be produced solely by an appropriate amount of farm manure.
- the (lower) calorific value of the straw input regardless of the subsequent conversion efficiency, is 4,085 kWh H i / t straw FM.
- the (lower) calorific value of the fuel used amounts to a total of 34.9 kWh H i.
- the tractor, the truck and the wheel loader as described above on CNG or LNG drives and use the generated GHG-free mixed gas.
- the GHG emission associated with fuel use is therefore 0 gC0 2 -eq / ton straw FM.
- B7 diesel which is 7% FAME, 83% mineral diesel and 20% GHG-free mixed gas.
- FAME has been burdened with only 88.6 gC0 2 / kWh Hi since 2015 (see above), mineral diesel according to EU Directive 2015/652 with 95.1 gC0 2 -eq / MJ, which is 342.4 gC0 2 - eq / kWh H i corresponds.
- B7 diesel thus has a GHG emission value of 324.6 gC0 2 -eq / kWh H i.
- the electricity used including the electricity used for the compression of the mixed methane and natural gas gas, amounts to 481.4 kWh e
- . This electricity consumption will cause a GHG emission of 481.4 x 540 259.956 gC0 2 -eq / t straw FM in 2020.
- Option A produces GHG emissions of 259.956 gC0 2 -eq per ton of straw input (wet mass). Based on the output of 2,860 kWh H i, this is 90.9 gC0 2 / kWh H i.
- option B GHG emissions increase by 3,092 g to 263,048 gC0 2- eq / t straw-FM and in option C by 9,064 g to 269,020 gC0 2- eq / t straw-FM. Based on the output of 2,860 kWh Hi , this is 92.0 or 94.1 gC0 2 / kWh Hi .
- This GHG emissions overcompensates the inventive method with the sequestration of atmospheric C0 2 s and / or with the replacement in industry (eg in the food industry) used fossil C0 2 s recuperated in the biogas plant atmospheric C0 2 .
- the incorporation and sequestration of the permanently stabilized carbon content of the digestate Biochar Mixture has a negative THG effect of -256,580 gC0 2- eq / t straw-FM.
- the GHG effect of the substitution of fossil C0 2s by atmospheric C0 2 is -472,400 gC0 2 -eq / t straw-FM. Together, these two measures produce a decarburization effect of -728,980 gC0 2- eq / t straw-FM.
- a specific GHG emission factor of -164 gC0 2 -eq / kWh H i results.
- a specific GHG emission factor of -163 gC0 2- eq / kWh results H i.
- GHG negativities allow the admixture of fossil and GHG positive natural gas. If the absolute value of the GHG emission associated with this natural gas admixture is the same as the absolute value of the GHG negativity determined above for the BioMethan, a mixed gas will result whose specific GHG emission factor is 0.0 gC0 2 -eq / kWh H i. Thus, despite the use of a fossil fuel, the invention produces a zero emission fuel.
- the life-cycle greenhouse gas intensity of the mixed gas production pathway according to the invention for a mixture of THG-negative bio-methane and THG-positive natural gas thus always has the value 0.0 gC0 2 -eq / kWh Hi or 0.0 gC0 2 -eq / MJ.
- BioMethan Depending on the biogas conversion efficiency of the BioMethan produced from straw, it has a different GHG negativity (or different negative GHG emission values) before being mixed with natural gas: Produced with a BG conversion efficiency of 10% BioMethan has a life-cycle greenhouse gas intensity of -1.635 gC0 2 -eq / kWh H i, bio-methane produced with a BG conversion efficiency of 40%, a life cycle greenhouse gas intensity of -329 gC0 2 -eq / kWh H i and with a BG conversion efficiency of 70% produced bio methane a life cycle greenhouse gas intensity of approx. -164 gC0 2 -eq / kWh H i.
- the GHG effect resulting from a different evaluation of individual influencing factors which can not eliminate GHG negativity but only reduces it, can thus heal the system of the invention by simply reducing the produced GHG-negative BioMethan to a smaller amount of GHG. positive natural gas (CNG). Although this reduces the available amount of (true) zero-emission fuel (mixed gas), the zero-emission fuel GHG emissions remain at 0 gC0 2 -eq / kWh H i and 0 gCO 2 -eq / MJ, respectively.
- CNG GHG. positive natural gas
- the process according to the invention and the system according to the invention can be further improved by the recuperation, purification and liquefaction of atmospheric C0 2 which results from the carbonation of the residues from the one- or multistage biomass conversion, preferably during the pyrolysis and / or torrefaction of these conversion residues become.
- the available amount of atmospheric C0 2 increases substantially so, and thus the fossil for a substitution C0 2 s available amount of atmospheric C0 2, the amount of atmospheric C0 2 available for capture and the -based for the production of C0 2 Fuels (fuels, fuels) available amount of atmospheric C0 2 . Accordingly, the GHG negativity continues to improve and with it - after admixing an additional amount of natural gas - the amount of available GHG-neutral mixed gas.
- the energy recovery, purification and liquefaction of C0 2 which is formed during the carbonisation of residues from the single or multi-stage biomass conversion, preferably from the pyrolysis and / or torrefaction, of course, also alone without recuperation, purification and liquefaction of C0 2 , which occurs during the treatment of biogas to bio methane.
- the invention is based on an anaerobic bacterial fermentation of straw into biogas and its treatment into bio-methane. It will be understood, however, that the method and system of the present invention may also be based on the fermentative production of ethanol from biomass, in particular on the production of ligno-ethanol from straw or wood, as well as on the production of other biomass energy sources, e.g. on the production of FT fuels (SynDiesel, SynBenzin, DME, BioMethanol etc.) from straw or wood, from BioDiesel from rapeseed or palm oil, from hydrogen from biomass, etc. In this regard, all biomass conversion methods should be included, which the competent expert are known in the relevant state of the art and / or in practice.
- the one- or multistage biomass conversion consists of an anaerobic bacterial fermentation of fermentation substrate in biogas, an alcoholic fermentation of biomass in bioethanol, an (enzymatic) conversion of biomass into ligno-ethanol, a conversion of biomass into biodiesel or FAME or HVO (eg transesterification), a conversion of biomass into Fischer-Tropsch fuels, a conversion of biomass into hydrogen (eg steam reforming), a conversion of biomass into bio-methanol (methanol synthesis) or a conversion of biomass into DME (DME- Synthesis).
- An advantageous embodiment of the invention comprises a method in which process water is obtained from the course of a process step, preferably from the course of anaerobic fermentation or alcohol fermentation, particularly preferably by means of a selection of the following processes: separation, decantation, pressing, filtration, ultrafiltration , Reverse osmosis, heating, evaporation, evaporation, sedimentation, crystallization, catalysis, phase separation, addition or use of polymers, any combination of these methods.
- a further advantageous embodiment of the invention comprises the purification or treatment of process water recovered from the process before its reuse with a selection of the following processes: separation, decantation, pressing, filtration, ultrafiltration, reverse osmosis, heating, evaporation, evaporation, sedimentation, crystallization , Catalysis, phase separation, addition or use of polymers, any combination of these methods.
- the reuse of purified process water is known to reduce the cost of water consumption of any water-using biomass conversion.
- a further advantageous embodiment of the invention is that in the case of anaerobic (bacterial) fermentation, the average hydraulic residence time of the feed in the fermentor lasts less than 250 days, preferably less than 120 days, more preferably less than 70 days, especially less than 40 days and at best less than 20 days.
- low HRTs reduce the specific investment and capital costs of each biomass conversion, based on one unit of energy (kWh H i, MJ).
- process heat is returned from a process step into the process, preferably from a thermal treatment of the biomass or the conversion radical in a heating or heating step, particularly preferably from a thermal treatment of the biomass before its conversion into a GHG emission-reduced energy source, and in particular process heat from the chemical-physical stabilization of the atmospheric carbon.
- the return of the process heat by means of a countercurrently functioning heat exchange, particularly preferably by means of water, in particular by means of pressurized water and / or steam, and at best by means of process water.
- the atmospheric carbon mass of the soil / biochar sequestered biochar can decrease by less than 40% by the process of soil respiration or other chemical-physical processes after 5 years, preferably by less than 10%. , more preferably less than 5%, and more preferably less than 1%; or the mass of atmospheric carbon of biochar / biochar sequestered in soil after 50 years is reduced by less than 50% by the process of soil respiration or by other chemical-physical processes, preferably by less than 25%, more preferably less than 10%, and more preferably less than 5%; or the mass of atmospheric carbon of the biochar / biochar sequestered in the soil is, after 100 years, reduced by less than 60% by the process of soil respiration or other chemical-physical processes, preferably by less than 30%, more preferably less than 15% and in particular less than 6%; or the mass of atmospheric carbon of the biochar / biochar / biochar sequestered in the soil goes down by less than 70% after 500 years by the process of soil respiration or by other chemical-physical processes, preferably
- the highly C0 2 -containing flue gas is freed of fly ash and dust from the pyrolysis or torrefaction of the residues from the mono- or multistage biomass conversion using cyclone technology.
- the resulting exhaust gas is freed from gaseous salts by means of an "acid gas scrubber" and passed to a C0 2 -Abborgestrom, which is particularly preferably a cryogenic separation plant.
- this is designed so that the resulting GHG emission reduction performance of the generated power, heating or fuel compared to the greenhouse gas emission of each reference fossil fuel, heating or fuel based on the same amount of energy reaches a relative value between 1% and 10,000%, preferably a value between 5% and 5,000%, particularly preferably a value between 50% and 500% and in particular a value between 80% and 200%.
- the biomass consists of at least a portion of lignocellulose-containing biomass, preferably at least a proportion of straw, particularly preferably at least a proportion of wood.
- energy is used in the production, distribution and use of the energy sources produced (fuels, heating fuels or fuels), in C stabilization and in the incorporation of the produced biofuels.
- the energy sources produced fuels, heating fuels or fuels
- C stabilization in the incorporation of the produced biofuels.
- Bioliquids, mixtures and mixtures such that those energy sources are used whose GHG emission values or GHG emission values are reduced compared to their fossil reference, particularly preferably to 0.0 gC0 2 -eq / kWh or 0.0 gC0 2 - eq / MJ and in particular GHG negative, ie have a negative GHG emission value.
- the biogas plant described by US2006 / 0275895A1 (Jensen & Jensen) and the method disclosed therein for producing biogas from straw and / or straw-containing feedstocks are linked to at least one of the embodiments of the present invention, preferably with the chemical-physical stabilization of atmospheric carbon according to the invention, particularly preferably with the according to the invention production of multipart bio / biochar / Biokoks mixtures or biochar / biochar / Biokoks-Conversionsrest mixtures and in particular with the inventive incorporation of such biochar / biochar / biokoks mixtures or biochar / biochar / biocconversion mixtures in agricultural used floors.
- the biogas plant described by the inventor in EP 2167631B1 (Feldmann) and the process for producing biogas from lignocellulosic renewable raw materials disclosed therein are combined with at least one of the embodiments of the present invention, preferably with the chemical-physical stabilization of atmospheric carbon according to the invention, particularly preferably with the production according to the invention of mono- or multi-part biochar / biochar mixtures or biochar / biochar / biococconversion remainder mixtures and in particular with the incorporation according to the invention of such biochar / biochar mixtures or biofuels. Biochar / biocok-conversion remainder mixtures in agricultural soils.
- EP 2183374B1 Fraunhofer
- the method disclosed by EP 2183374B1 for conversion of biomass from renewable raw materials to biogas in anaerobic fermenters with at least one of the embodiments of the invention, preferably with the inventive chemical-physical stabilization atmospheric carbon, particularly preferably with the production according to the invention of mono- or multi-part biochar / biochar mixtures or biochar / biochar / biocconversion mixture mixtures and in particular with the incorporation according to the invention of such biochar / biochar mixtures or biochar / biochar / biokoks Conversion remainder mixtures in agricultural soils.
- the method published under the application file EP 13 807 989.2 (Verbio) and the biogas plant disclosed therein for producing biogas from lignocellulose-containing biomass, preferably straw are linked to at least one of the embodiments of the invention , preferably with the chemical-physical stabilization of atmospheric carbon according to the invention, particularly preferably with the preparation according to the invention of mono- or multisubstance biochar / biochar mixtures or biochar / biochar / biococconversion residue mixtures and in particular with the incorporation of such bioparticles according to the invention. / Biochar / Biocoke mixtures or biochar / biochar / biocoks-conversion remainder mixtures in agricultural soils.
- the method according to the invention and the system according to the invention are capable, in various embodiments, of producing greenhouse-gas-reduced energy carriers, preferably wise greenhouse gas emission-reduced biogas and / or greenhouse gas emission-reduced bio-methane, particularly preferably greenhouse-gas-negative energy sources and in particular greenhouse gas-negative biogas and / or greenhouse gas-reduced bio-methane.
- Fig. 1 shows a schematic representation of a complex embodiment of the method and system according to the invention, in which a biomass of many available biomass selected, harvested and pretreated before the (first) conversion, wherein the energy generated by the (first) conversion with other energy sources is mixed, the conversion residue is divided into four substreams A to D and the conversion residues A to C are dehydrogenated, wherein the dehydration may be associated with a nutrient extraction and discards nutrient-containing process water; after comminution and, if appropriate, pelleting of the optionally so treated conversion residues, conditions for a chemical-physical stabilization of atmospheric carbon are generated in a reaction vessel; as soon as they are present, the atmospheric carbon contained in the conversion residues A to C is chemically-physically stabilized, namely A fully stabilized, B partially stabilized and C unstabilized; The result of this (partial) stabilization are biochar masses E to G, which are extinguished with the nutrient-containing process water and charged with these nutrients; the biochar masses are mixed together to
- FIG. 2 shows in a further schematic representation an embodiment variant of the method and system according to the invention without the conversion residue D indicated in FIG. 1 and with a first recuperation of atmospheric carbon dioxide (CO 2 I) on the occasion of the (first) conversion of the selected biomass into a generated one energy; Furthermore, a second recuperation of atmospheric carbon dioxide (C0 2 II) on the occasion of the chemical-physical stabilization of atmospheric carbon is shown; the C0 2 I and the C0 2 II are combined, liquefied and geologically sequestered, used as a substitute for fossil C0 2 or used for the production of C0 2 -based energy sources. 8.
- CO 2 I atmospheric carbon dioxide
- C0 2 II atmospheric carbon dioxide
- the elements provided with reference signs can indicate both an operation and a device as well as the product of an operation, possibly also simultaneously.
- FIG. 1 shows a schematic representation of a complex embodiment variant of the method and system according to the invention, which in essence can only consist of the conversion of biomass 4 into a generated energy carrier 5 by means of suitable devices and the generation of suitable conditions for the chemical-physical Stabilization 20 of the atmospheric carbon still contained in the conversion residues and carrying out the carbon stabilization 21.
- suitable devices which are known to the person skilled in the art from the relevant prior art and which at least in part have already been or will be described.
- Even without sequestration 33 of the biofuel or biochar produced it is already ensured with the stabilization 21 of the atmospheric carbon that it can no longer react with atmospheric oxygen to CO 2 or with hydrogen to form CH 4 . This decarbonates the earth's atmosphere.
- the used at least one biomass is selected in a process step 1 from a variety of available biomasses (see claim 21). Some biomass are burdened until the production step of the biomass attack only with small amounts of GHG emissions, some are even GHG-neutral (eg in the cereal grain crop resulting straw) and some are highly polluting such as outdoors stored manure or poultry manure, the CH 4 and Emit N 2 0. Their early use in a biomass conversion process prevents these GHG emissions, so that early recovery helps prevent GHG emissions. This GHG avoidance is allocated or technically linked to the product of the conversion process, so that the utilization of certain manure even becomes a GHG. negative initial effect. The selection of one or more suitable biomasses for the conversion process 4 can therefore be advantageous.
- Selection 1 is still advantageous for a second reason.
- Some feedstocks can not or only partially be suitable for C stabilization.
- Liquid feeds such as e.g. Fermented manure can only be carbonized using the HTC method. This method provides only partially stabilized bioliquids / bioliquids that do not remain stable for centuries or millennia.
- the at least one biomass which is preferably lignocellulosic biomass, more preferably straw, is harvested or collected in a step 2.
- harvesting and collection involve transport from the place of seizure of the at least one input material to the location of use of the at least one input material.
- the GHG-emission-reduced preferably GHG-neutral and particularly preferably use GHG emission-negative power, heating and fuel.
- These include, for example, combine harvester, corn harvester, tractor, wheel loader, manitou, truck, tractor-trailer, and all similar CNG or LNG propelled harvesting and hauling machines known in the art.
- the GHG footprints or the GHG emission values of the generated energy sources 5, 7 and 9 are reduced, preferably to 0.0 gC0 2 -eq / kWh H i, particularly preferably to less than 0 , 0 gC0 2 -eq / kWh H i.
- Process 2 may be limited to a collection if the at least one biomass is a by-product, residue or waste.
- Harvesting is required when it comes to agricultural or forest-based biomass or an agricultural by-product (residue) such as straw.
- Straw for example, usually has to be pressed into straw bales after being deposited by the combine harvester in the swath, since loose straw is not transportable. The pressing is done with tractor-drawn and -driven straw bale presses, which usually have a pressing capacity of approx. Reach 35 tons per hour.
- the straw stored in the swath can also be pressed by the tractor-drawn pellet presses (pellet harvesters) already in the field into very transportable pellets.
- the press capacity of the pellet presses is currently only approx. 5 tons per hour, which blocks valuable tractor and personnel performance, which is scarce in the harvest campaign.
- Straw pellets with a bulk density of 600 - 700 kg / m 3 are much more transportable than straw bales, especially when using the long-distance means of transport rail or ship.
- HGV means that, at the moment, there is no longer an increase in transport efficiency, in which the load makes full use of the transport capacity of the lorry. This is the case when the straw is pressed into high-pressure bales with a density of about 200 kg / m 3 and the loading volume is exhausted.
- the straw harvest includes the collection of straw bales and the loading of a first means of transport.
- a pre-collection can be made by each 3 - 4 straw bales are dammed before they are placed in a group on the stubble field.
- the routes or the loading games of the loader are reduced, which load the (first) means of transport, with which the straw bales are driven from the field.
- the (first) means of transport usually consists of agricultural trailers in operation, larger farms consist of low loader semi-trailers mounted on tractor-driven double-axle carriages or tractor-drawn low-floor trailers.
- the loading of the means of transport is usually done with front loaders (tractors or so-called Manitous), which record the bales individually or in pairs and load on the means of transport.
- the loaded straw is driven from the first means of transport to the edge of the field or onto the farm. There it is unloaded again with front loaders or Manitous and piled up in the open to straw straps or stored in weather-protected warehouses. The route exceeds 10 km only very rarely.
- the straw bales can be square or round bales. Bale collection vehicles are known from Spain, with which square bales are collected and unloaded at the edge of the field.
- the (second) means of transport consists of truck-towed trailers or semi-trailers pulled by tractor-trailers. That is, the semitrailer go directly into the field or - if a harmful compaction of the soil is to be avoided - at least to the edge of the field.
- the loading is usually done with wheel loaders, which have a special gripper, with which up to 6 square bales can be gripped at once and loaded on the (second) means of transport.
- so-called high-pressure or ultra-high-pressure presses are used, the density of the square bales reaches up to 0.210 t / m 3 , which almost fully utilizes the weight-bearing capacity of the trucks (around 20 t) with full utilization of the loading volume.
- the straw transport can then take place over several hundred kilometers, which is currently being practiced, from the Magdeburg area to the Netherlands and Belgium, where there is a high demand for straw for champion breeding.
- the straw is stored at a regional straw warehouse from arson, before it goes into the long-distance transport. It is advantageous in the method and system shown in FIG. 1 to use those harvesting and transporting techniques that are used for larger quantities of straw, because they are more energy-efficient than the commonly used small-scale technology. So the harvest can be made with a lower use of valuable energy sources 5, 7 or 9.
- the (first) one- or multi-stage biomass conversion 4 can be any type of biomass conversion known from the relevant prior art which has the purpose of producing a marketable energy carrier.
- these include in particular the Bioliq ® process of KIT, the sunliquid ® process of Clariant AG (formerly Süd-Chemie GmbH), which lodges process for the production of ethanol from lignocellulosic biomass, the CHOREN process, the process of Verbio AG for the production of biogas from straw, the Lehmann process for the production of biogas from straw, the Fraunhofer process for the production of biogas from biomass, the process All processes of Hoffmann for the production of biogas from biomass, all processes of Lutz (Bekon) for the production of biogas from biomass, all processes of Schiedermeier (BioFerm) for the production of biogas from biomass , all processes of Eggersmann for the production of biogas from biomass, all processes for the production of ethanol from biomass, all processes for the production of FT fuel from biomass, all processes for the production of methanol from biomass,
- the various forms of mono- or multistage biomass conversion 4 are each made with devices, plants, devices or systems which are previously known in the art and which are suitable, preferably for the purpose of achieving economies of scale with plants of industrial size.
- the devices for the one-stage or multistage conversion of biomass can particularly preferably consist of a selection of the following devices: devices for the anaerobic bacterial fermentation of biomass into biogas and / or bio-methane, devices for the alcoholic fermentation of biomass to bio-ethanol or ligno-ethanol, devices for Biomass smoldering to smoldering gas, biomass gasification to pyrolysis gas and / or pyrolysis slurry devices, biodiesel transesterification plant oils (FAME), vegetable oil hydrogenation (HVO) (mineral oil refinery), refining equipment Vegetable oils in HVO (NesteOil method), devices for gasification / pyrolysis of biomass to process gas, devices for converting biomass-derived process gas into synthesis gas, apparatus for synthesis of biomass-derived synthesis
- the one-stage or multistage biomass conversion 4 is carried out with biogas plants, in particular with agricultural biogas plants and, at best, with biogas plants of medium or industrial size (see claim 34).
- the method of wet fermentation in wet fermenter can be used, but also the process of solidification in solid fermenters, preferably in garage or plug flow fermenters.
- these are operated with a fermentation cycle of ⁇ 180 days, preferably with a fermentation cycle of ⁇ 60 days, more preferably with a fermentation cycle of ⁇ 35 days, in particular with a fermentation cycle of ⁇ 21 days and at best with a fermentation cycle of ⁇ 14 days (see claim 34).
- the biomass which is preferably lignocellulosic biomass, more preferably straw, may be pretreated (but it does not have to).
- the conversion 4 is preferably an anaerobic bacterial fermentation, which is carried out in a biogas plant, particularly preferably a solid fermentation and in particular a fermentation in a garage fermenter (cf claim 23).
- the conversion 4 is carried out in devices known from the relevant prior art which are suitable for such a conversion.
- the fermentation in a solid fermentation plant has the advantage that the digestate 10 produced after fermentation is present in a heap (and not in liquid form) and thus pyrolysis can be carried out after dehydration and / or drying in devices suitable for this purpose with liquid conversion residues would be possible only under very high technical and energy costs.
- pyrolysis can be carried out after dehydration and / or drying in devices suitable for this purpose with liquid conversion residues would be possible only under very high technical and energy costs.
- a more or less high conversion efficiency results. Long HRTs lead to desirable high conversion efficiencies and short HRTs to low conversion efficiencies.
- the average hydraulic residence time of the fresh mass in the fermenter in the case of anaerobic (bacterial) fermentation less than 250 days, preferably less than 120 days, more preferably less than 70 days, in particular less than 40 days and at best less than 20 days.
- the pre-treatment 3 upstream of the conversion 4 can consist of a multiplicity of previously known measures which are likewise known prior art as well as the installations, devices and systems used therefor. It is e.g. it is possible to subject the straw to comminution, preferably chopping or shredding, more preferably the comminution combination consisting of chipping or shredding and milling, and in particular the comminution combination consisting of bale breaking, chopping / shredding and grinding.
- an average final particle length of ⁇ 20 cm preferably to an average final particle length of ⁇ 5 cm, particularly preferably to an average final particle length of ⁇ 10 mm, in particular to an end particle length of ⁇ 3 mm and in the best case to an end particle length of ⁇ 1 mm (cf claim 24).
- pretreatment of the extrusion of the straw with which the straws are crushed and shredded and similar methods known from the relevant prior art.
- the biomass 1, which is preferably lignocellulosic biomass, particularly preferably straw and / or wood, in addition to or instead of the treatment described above is subjected to a treatment which consists of a suitable, previously known from the relevant prior art treatment, preferably from a selection of the following treatment methods: comminution, soaking / mixing / mashing in cold water or aqueous suspensions inclusive Lyes and acids, soaking / mixing / maceration in 20 ° C - 100 ° C warm water or aqueous suspensions including alkalis and acids, biological treatment with mushrooms, pressurization to> lbar up to 500 bar, treatment with> 100 ° C hot water, treatment with saturated steam, treatment by means of thermal pressure hydrolysis, treatment by means of wet O xidation, treatment by extrusion, ultrasonic treatment, steam reforming treatment, steam explosion treatment, drying, treatment with process water of any kind
- the system shown in FIG. 1 may comprise devices which are suitable for subjecting biomass 1/2 before or during conversion 4 or residues 10 after biomass conversion 4 to a selection from the following treatment methods: admixing / mixing in cold water or aqueous suspensions, admixing / mixing in 20 ° C - 100 ° C warm water or aqueous suspensions, biological treatment with mushrooms, pressurization to> lbar - 500 bar, treatment with> 100 ° C hot water, treatment with saturated steam, treatment by thermal pressure hydrolysis, steam explosion, treatment by wet oxidation, heating, treatment by extrusion, ultrasonic treatment, steam reforming, evaporation, sedimentation, crystallization, catalysis, drying, use of polymers, phase separation, particle extraction, combination from a selection of these treatment methods (see claim 39).
- Prior art additives are provided, preferably with a selection of the following additives: lime, enzymes, enzyme-containing solutions, fungi, acids, alkalis, yeasts, water, recycled process water, purified process water, filtered process water, ultrafiltered process water, reverse osmosis treated process water, treated process water, acid-water mixtures, lye-water mixtures, percolate, silage seepage fluids, manure, microorganisms, any grain grain distillate from ethanol production, any residue from the production of ligno-ethanol, any by-product / Residue from the production of Pyro lyse or synthesis gas, any byproduct / residue from FT synthesis, any by-product / residue from the DME synthesis, any byproduct / residue from the
- conversion residue 10 At least a portion of the residues from the mono- or multistage biomass conversion 4 (conversion residue 10) is recuperated and made available to the further process steps (see claim 22).
- the conversion residues 10 may in particular be residues from a one-stage or multi-stage anaerobic bacterial fermentation 4 (digestate).
- the energy carrier 5 produced in the step of the single or multistage conversion 4 may be a selection from biogas, bio-methane, pyrolysis gas, synthesis gas, biodiesel, bio-rosin, Fischer-Tropsch fuel, bio-methanol, DME or bioethanol (cf. Claim 14).
- this energy source 5 is processed so that it can be used as fuel, fuel or fuel, preferably as fuel in traffic, particularly preferably as a fuel in traffic (see claim 14).
- the conversion 4 is preferably carried out by means of suitable devices, systems or systems known from the relevant prior art.
- the generated energy source 5 may be a gaseous or liquid Accept state of aggregation, ie, for the liquid state of aggregation, the energy carrier 5 is liquefied with suitable, known from the relevant prior art devices.
- the generated energy source 5 which is preferably a fuel, particularly preferably a gaseous fuel and in particular bio-methane
- the generated energy source 5 which is preferably a fuel, particularly preferably a gaseous fuel and in particular bio-methane
- the generated energy carrier 5 which is preferably a fuel, particularly preferably a gas fuel and especially bio methane, a smaller amount of greenhouse gas in the earth's atmosphere than before, the generated energy source 5 is thus GHG negative (see claim 16).
- the generated energy source 5 is mixed with a compatible sustainable energy source 6 to form an energy carrier mix 7, wherein the compatible and sustainably generated energy carrier 6 can originate from a different conversion process, which can have a higher THG emission value than energy carrier 5.
- the energy carrier mix 7 resulting from the mixing is particularly preferably used as fuel in traffic.
- the proportion of the energy carrier 5 in the energy carrier mix 7 can be between 0% and 100%; accordingly, the share of the sustainable energy carrier 6 in the energy carrier mix 7 can be between 100% and 0%.
- the mixing preferably takes place with suitable devices, systems or systems known from the relevant prior art.
- the mixing of the generated energy carrier 5 with the compatible, sustainably produced energy source 6 to form an energy carrier mix 7 is preferably carried out in such a way that after the production, distribution and use of the generated energy carrier mixes 7 according to life cycle analysis or stoichiometric analysis, a smaller amount of greenhouse gas in the earth's atmosphere located as after the production, distribution and use of an equal amount of energy of the fossil equivalent of the produced energy mix 7,
- mineral diesel fuel is the fossil equivalent for all diesel substitutes
- mineral petrol (gasoline) the fossil equivalent for all substitutes of petrol
- Mineral kerosene is the fossil equivalent for all kerosene substitutes
- natural gas (CNG) is the fossil equivalent for all natural gas substitutes
- LNG is the fossil equivalent for all LNG substitutes
- LPG is the fossil equivalent for all LPG substitutes
- the weighted average is mineral Ott o fuel and mineral diesel is the fossil equivalent for all other fuels, heating and fuels (cf. Claim 17).
- the mixing of the generated energy carrier 5 with the compatible, sustainably generated energy carrier 6 takes place in such a way that, after the production, distribution and use of the generated energy carrier mixes 7 according to life cycle analysis or Stoichiometric analysis is a lower amount of greenhouse gas in the earth's atmosphere than before. That is, the GHG emission value of the energy carrier mix 7 is GHG negative (see claim 18).
- the energy carrier 5 is preferably biogas upgraded to bio-methane, particularly preferably straw gas which, by means of anaerobic bacterial fermentation, is at least partly composed of straw-containing and possibly other feedstocks (farm fertilizer, beet and potato herb and waste of pulses, wood ) was generated. More preferably, the compatible sustainable energy source 6 is SynMethane generated from wind and atmospheric C0 2 or another biogas.
- the mixing of the energy carrier 5 and the energy carrier 6 takes place such that after the production, distribution and use of the energy carrier mix 7 according to life cycle analysis or stoichiometric analysis, a smaller amount of greenhouse gas (measured in tonnes C0 2 equivalent) is present in the earth's atmosphere as after the production, distribution and use of an equal amount of energy of the fossil fuel equivalent of the energy mixture 7, at best, so that after the production, distribution and use of the energy carrier mix 7 is a smaller amount of greenhouse gas in the earth's atmosphere than before, the generated energy carrier mix 7 is THG negative.
- the mixing of the energy carrier 5 with SynMethan 6 can take place such that the resulting mixed gas 7 is GHG-neutral (see claim 19).
- the amount of SynMethane 6 added depends on its GHG value, because the higher it precipitates, the lower the amount of synmethane 6 which can be mixed.
- the mixing is preferably carried out using suitable devices, installations or systems known from the relevant prior art .
- the energy carrier mix 7 can assume a gaseous or liquid state of aggregation, ie, for the liquid state of aggregation, the generated energy carrier 5 and the sustainably produced compatible energy carrier 6 are liquefied before or after mixing with suitable devices known from the relevant state of the art.
- an energy carrier mix 9 can be produced from the energy carrier mix 7 and at least one compatible fossil energy carrier 8 by mixing as the end product.
- the energy mixture 9 resulting from the mixing is particularly preferably used as fuel in traffic.
- the proportion of the energy carrier 7 in the end product 9 can be between 0.1% and 100.0%; accordingly, the fraction of the fossil energy carrier 8 in the end product 9 can be between 99.9% and 0.0%.
- the energy carrier mix 7 is bio-methane-treated biogas mixed with other biogas or SynMethan 6, at best straw produced from straw-containing feedstocks mixed with other biogas or SynMethan.
- the mixing preferably takes place with suitable devices, systems or systems known from the relevant prior art.
- the compatible fossil energy source 8 is natural gas or LNG (liquefied natural gas).
- the mixing of the energy carrier mix 7 and the fossil energy carrier 8 is carried out so that after the production, distribution and use of the energy carrier mix 9 according to life cycle analysis or stoichiometric analysis a smaller (in tons C0 2 equivalent measured) greenhouse gas in the The atmosphere of the earth is considered to be smaller, corresponding to the production, distribution and use of an equal amount of energy of the fossil fuel equivalent of the energy carrier mixture 9, particularly that after the production, distribution and use of the energy carrier mixture 9, a smaller amount of greenhouse gas is present in the fuel mixture Earth's atmosphere is as before, the generated energy carrier mix 9 is THG negative.
- the mixing of the energy carrier mix 7 with natural gas (CNG) 6 can take place such that the resulting mixed gas is GHG-neutral.
- the amount of the added natural gas 6 depends on the GHG emission value of the energy carrier mix 7, because the higher this precipitates, the lower is the immiscible natural gas quantity 8.
- the energy carrier mix 9 may assume a gaseous or liquid state of aggregation, that is, for the liquid state, the produced energy carrier mix 7 and the compatible fossil energy carrier 6 are liquefied before or after mixing with suitable devices known in the art.
- the amount of the resulting conversion residue 10 is dependent on the conversion efficiency which is achieved in the conversion of the biomass 4 (reference numerals 1 and 2) into the energy carrier 5. If the resulting conversion residues are completely recuperated and the conversion efficiency is, for example, 10%, approximately 90% of the atmospheric carbon contained in the biogenic feedstock is contained in the conversion residue 10. If, for example, the conversion efficiency at complete conversion of the conversion radical is 70%, approximately 90% of the atmospheric carbon contained in the biogenic starting material is contained in the conversion radical 10.
- recuperated portion of the stream of conversion residues emerging from the process step of single or multistage biomass conversion is divided in the method and system variant shown in FIG. 1 in an additional method step 11 into up to four substreams A to D (reference numerals 12 to 15) in the first sub-stream "production of stabilized pyrolysis coal", in the second sub-stream “production of partially stabilized Torrefiz ists- or HTC coal", in the third sub-stream "production of unstabilized biochar / biochar” and in the fourth sub-stream "non-carbonized conversion residues" (see claim 9).
- biochar / biochar mixture or mixture of biocorps which is better suited for soils used for forestry and agricultural purposes than biochar / biochar consisting only of fully stabilized, semi-stabilized or biochar non-stabilized atmospheric carbon - these options should not be excluded.
- biochar / biochar mixture or mixture of biocorps which is better suited for soils used for forestry and agricultural purposes than biochar / biochar consisting only of fully stabilized, semi-stabilized or biochar non-stabilized atmospheric carbon - these options should not be excluded.
- the partial flows A to D can each have a proportion of 0% to 100% of the total current, ie, each partial flow 12 to 15 can represent both the total current and zero and each component in between (see claim 9 ).
- the partial flow A with the reference numeral 12 "generation of stabilized pyrolysis coal" has a share of> 1% of the total flow, more preferably a share of> 25%, in particular a share of> 50% and in the best case a share of> 75% (see claim 9)
- the higher the proportion of fully stabilized carbon in the biochar / biochar mixture the greater the permanent decarbonisation effect and the resulting effect on the GHG emission levels of fuels 5, 7 and 9.
- the division of the partial flows A to D can be made with a switch, which deflects the outgoing from the conversion 4 KR-stream 10 in various suitable funding such as lines, conveyors, slides, elevators, etc. (not shown) or container.
- suitable funding such as lines, conveyors, slides, elevators, etc. (not shown) or container.
- the partial flow A (BZ 12) is used for full stabilization of atmospheric carbon, this full stabilization is carried out in the process steps 20 and 21, preferably by means of a pyrolysis, particularly preferably by means of a high-temperature pyrolysis and in particular by means of a high-temperature pyrolysis , which is made after a slow heating up.
- Biochar / biochar with fully stabilized atmospheric carbon advantageously increases the continuous humus content of the soil.
- the partial flow B (BZ 13) is used for partial stabilization of atmospheric carbon in the process steps 20 and 21, preferably by means of HTC, particularly preferably by means of low-temperature pyrolysis (torrefaction) and in particular by means of low-temperature pyrolysis (torrefaction), which after a slowly made heating is done.
- Biochar / biochar with partially stabilized atmospheric carbon advantageously increases the nutrient humus content of the soil.
- Sub-stream C (BZ 14) is used to produce biochar / biochar that contains unstabilized atmospheric carbon.
- Any carbonation process, including pyrolysis, must be used only briefly enough and / or aggressively enough (very fast heating, very high reaction temperatures).
- Biochar / biochar with non-stabilized atmospheric carbon advantageously increases the OPS or OBS content of the soil.
- the partial flow D (BZ 15) serves to advantageously increase the OPS or OBS content of the soil. It is comparable with conversion residues 10, which are applied directly to fertilizer on agricultural land after a single or multistage conversion 4 without any subsequent treatment.
- conversion residues are e.g. Fermentation residues from anaerobic bacterial fermentation or vinasse from the alcoholic fermentation of biomass to bioethanol.
- the up to four products (biochar masses E to G and conversion residue D) which are or are not produced in the process steps following the conversion residue division 11 can in principle be processed or treated in parallel or in series with the respective systems and devices.
- the unprocessed partial flows are conveyed by means of suitable conveyor technology (not shown), which is known from the relevant prior art, to suitable temporary storage facilities (not shown) and stored there until further processing is commenced. So it is e.g. possible to carry out a high-temperature pyrolysis with one and the same apparatus for carrying out the C stabilization first and then with significantly lower reaction temperature and / or with a significantly shorter reaction time torrefaction.
- Devices which are suitable for high reaction temperatures are usually also suitable for lower reaction temperatures. The same applies to the parameters heating rate, reaction time and reaction pressure.
- the partial streams A to C undergo three optional process steps, namely the dehydration / nutrient extraction 16, the comminution 18 and the pelleting / briquetting 19.
- the goal is also achieved if the conversion residues 10 and the partial streams 12 to 14, the process steps 16 to 19 do not go through and they are immediately performed in the process steps 20 and 21.
- the allocation is made preferably with a suitable, known from the relevant prior art switch or the like. performed.
- the conversion residual partial streams A to D (BZ 12 to 15) generated by division 11 can be stored in a silo, container, bunker or the like Prior art prior art devices are stored until they are needed. This requirement may be due to the downstream dehydration / nutrient extraction 16, the downstream comminution 18, the downstream pelleting / briquetting 19, the downstream C stabilization 20/21 or the downstream mixing 27.
- the conversion residues 12 to 14 by means of suitable, known from the relevant prior art plants, facilities or systems drained.
- devices are included which are suitable for at least a portion of the organic nutrients still contained in the remainders of the mono- or multistage biomass conversion or at least a portion of the water still contained in the residues of the mono- or multistage biomass conversion more preferably, these devices may consist of a selection of the following devices: devices for soaking, for mixing, for mashing and similar devices, centrifuges, centrifuges, cyclones, decanters, presses, separators, sieves, device for Filtration, ultrafiltration device, reverse osmosis devices, similar devices, combination of these devices (see claim 31).
- the dewatering 16 is advantageous because the downstream stabilization of the atmospheric carbon works better and more effectively the higher the dry matter content of the biomass to be treated in process steps 20 and 21.
- the drainage is therefore carried out in such a way that the dry matter content (TS content) of the resulting rather solid phase is> 35%, preferably> 50% TS, particularly preferably> 60% TS (cf. Claim 4).
- devices known from the relevant prior art are used, preferably those which are suitable for extracting or separating at least a portion of the water contained in the conversion radicals 12 to 14, these devices particularly preferably being selected from the following devices consist of: centrifuges, centrifuges, cyclones, decanters, presses, separators, sieves, filtration devices, ultrafiltration devices, reverse osmosis devices, similar devices, combination of these devices.
- These devices for dewatering are preferably suitable for dewatering the conversion residues 12 to 14 from the single- or multi-stage biomass conversion 4, preferably to a DM content of> 35%, particularly preferably to a dry matter content of> 50% DM and in particular to> 60% TS (see claim 31).
- the product of the dewatering 16 is a rather liquid phase, which is referred to here by the term process water 17.
- process water 17 a rather liquid phase
- Rather solid in this context means that the solid phase also contains water, as does the "rather liquid” phase dry substance contains. That is, the TS content of the rather solid phase is not 100% but, unless otherwise stated, is only higher than the TS content of the more liquid phase.
- the process water 17 can be used to possibly extinguish the biochar / biochar coming from the C stabilization or the biococcus coming from the C stabilization, which are usually very hot. This happens in process step 25. However, it can also be used to in the process to replace (fresh) water demand for example in process step 3 (eg pretreatment by soaking in water or aqueous suspensions) and / or in process step 4 (eg anaerobic bacterial fermentation in a wet fermenter) and / or in process step 19 (evaporation of to be pelleted or briquetted conversion 12-14).
- process step 3 eg pretreatment by soaking in water or aqueous suspensions
- process step 4 eg anaerobic bacterial fermentation in a wet fermenter
- process step 19 evaporation of to be pelleted or briquetted conversion 12-14.
- the system shown in FIG. 1 can comprise devices known from the relevant prior art which are suitable for recuperating process water arising in the process and for supplying it to other system components (lines, containers, bunkers, storage, pumps, etc.), preferably after treatment or Purification of the recuperated process water in corresponding prior art devices, more preferably after purification of the recuperated process water by means of a selection from the following devices: centrifuges, centrifuges, cyclones, decanters, presses, separators, sieves, apparatus for filtration, apparatus for ultrafiltration, reverse osmosis devices, similar devices, combination of these devices (see claims 1-31 and 32).
- the process water 17 contains valuable organic nutrients in a technically relevant extent.
- the (organic) nutrients contained in the biogenic feed are largely still in existence, ie, they are in the recuperated conversion residue 10 or contain the KR substreams 12 to 15. For the most part they are in solution. That is, the process water 17 exiting from the conversion residues 12 to 14 may be an aqueous suspension enriched with (organic) nutrients. In their composition, these nutrients correspond exactly to the nutrient composition that was removed from the field crop during the cultivation of the biomass or during the growth of the biomass. As indicated above, it is beneficial for the field crop if the applied biochar / biochar is loaded with nutrients.
- the organic nutrients still contained in the residues of the single-stage or multi-stage biomass conversion 4 are therefore at least partially precluded by means of suitable devices, systems or systems known from the relevant prior art prior to the chemical-physical treatment of the conversion residues 12 to Conversion residues removed, preferably together with process water 17, particularly preferably by a selection of the methods spin, decantation, pressing, separation, filtration, reverse osmosis, addition of polymers, combination of these process steps and in particular with appropriate appropriate facilities and facilities (see claim 4) ,
- the recovered process water 17, which is preferably an aqueous suspension containing organic nutrients, is recycled into the process, particularly preferably way by means of suitable facilities such as lines, tanks, tanks, bunkers and pumps (see claim 4) and in particular after a purification of inhibitors or residues.
- the conversion residues 12 to 14, which were possibly dehydrogenated in process step 16 and / or from which organic nutrients were optionally extracted in the same process step 16, can be comminuted in an optional process step 18 with suitable comminution devices known from the relevant prior art ( see claim 38) to an average particle length of 0.01 mm to 300 mm, preferably to an average particle length of 0.1 mm to 100 mm, particularly preferably to average particle lengths of 1.0 mm to 30 mm and in particular to average particle lengths from 1.5 mm to 20 mm.
- the comminution may be advantageous because the produced biochar / vegetable carbon 22-24 can be better distributed on the soil and / or better incorporated into the soil.
- a high degree of fineness is particularly advantageous if the biochar / vegetable carbons 22-24 produced are to be mixed with liquid manure with or without nutrient charge, in order to reduce or prevent annoying odor development of the manure and / or to result in manure spreading to reduce environmentally harmful N 2 0 emissions.
- comminution 18 can also be made later in the process, for example immediately after C stabilization 20/21, immediately after quenching / loading with nutrients 25, immediately after mixing to a biochar Mixture H 26 or immediately after mixing to a biochar conversion mixture 27.
- the optional comminution 18 with suitable comminution devices known from the relevant prior art can be advantageous for a second reason, namely as a preparatory measure for an optionally downstream pelletizing or briquetting 19.
- pyrolysis methods and - devices can be used, which can pyrolyze only lumpy or lumpy feedstocks.
- pelleting / briquetting of the conversion residues 12 to 14 is required. This in turn may require a comminution of the conversion residues 12 to 14. If crushing has not already taken place in the course of pretreatment 3 to the degree of fineness required for pelleting / briquetting, then crushing must take place at the latest before process step 19 (pelleting / briquetting).
- the optional comminution 18 with suitable comminution devices known from the relevant prior art can be advantageous for a third reason, namely as a preparatory measure for the downstream C stabilization 20/21.
- the chemical-physical stabilization 20/21 is to consist of a carbonization of the conversion residues 12 to 14 and these from a pyrolysis, then pyrolysis methods and facilities can be used, which can only pyrolyze feedstocks with a certain degree of fineness.
- the PYREG 500 pyrolysis device from Pyreg GmbH currently only processes feedstocks that do not exceed a certain particle length.
- the optional pelletizing / briquetting 19 may be required if the chemical-physical stabilization 20/21 is to consist of a carbonation of the conversion residues 12 to 14 and these from a pyrolysis.
- pyrolysis methods and devices can be used, which are only lumpy or lumped feedstocks can pyrolyze.
- pelleting / briquetting 19 of the conversion residues 12 to 14 may be necessary.
- the system of Figure 1 may comprise prior art devices known in the art capable of pelleting or briquetting the conversion residues prior to performing the C stabilization 21 and / or performing the associated sub-functions, namely, the pellets to be pelletized. if necessary, steam or briquetting the briquetting mass, to cool, store and transport the pellets / briquettes produced (cf claim 33).
- the generation of conditions which permit at least partial chemical-physical stabilization of the atmospheric carbon contained in the residues of the (first) one-stage or multistage biomass conversion (fermentation, fermentation, pyrolysis or synthesis residues) ( 20), may refer to any of the prior art prior art methods and devices for chemical-physical stabilization of carbon.
- this process step 20 the choice of Karbonleiters-process, the choice of the state of matter to be carbonized, the choice of the reaction vessel (reactor), the heating to a certain Reaction temperature, the heating to reaction temperature in a certain time, the reaction of the reaction for a certain time (duration), the pressurization of the reaction mass, a certain type of pretreatment of the reaction mass, the nature of the cooling of the reaction product, any other treatment of the reaction product and the selection of the corresponding devices.
- the execution of these parameters depends on the conversion partial flow 12 to 14 as described below in the comment on method step 21 or on the type of biochar mass E to G (BZ 22 to 24).
- the conditions of method step 20 and / or the implementation of method step 21 are selected or set so that the atmospheric carbon still contained in conversion radicals 12 and 14 is at least partially stabilized such that it less than 30%, preferably less than 20%, more preferably less than 10% and, preferably, less than 5% by the processes of soil respiration, weathering, aerobic composting and / or reaction with, within a given period of time Atmospheric oxygen is degraded (mineralized), whereby the specific period may be a selection from the following periods: 10 years, 30 years, 100 years, 500 years, 1,000 years, 10,000 years, 100,000 years,> 100,000 years (see claim 2) ,
- the prior art system of Figure 1 comprises prior art devices suitable for effecting the carbonation of the conversion residues 12 and 13 such that the carbon content of the resulting biochar masses 22 and 23 is less than a certain amount over a given period of time 50%, preferably less than 20%, more preferably less than 10%, and most preferably less than 5% is degraded (mineralized) by the processes of soil respiration, weathering, aerobic composting and / or reaction with atmospheric oxygen , where the specific period may be a selection from the following periods: 10 years, 30 years, 100 years, 500 years, 1,000 years, 10,000 years, 100,000 years,> 100,000 years (see claim 30).
- This degradation resistance is achieved in the case of carbonation of the conversion residues 12 and 13 when the molar H / C ratio of the biofuel biochar 22 produced and biochip 22 and 23 ⁇ 0.8, preferably ⁇ 0.6, or when their (its) molar O / C ratio is ⁇ 0.8, preferably ⁇ 0.4.
- this degradation resistance is achieved when, in the case of carbonization, the molar H / C ratio of the biofuel / biochar 22/23 produced is ⁇ 0.8, preferably ⁇ 0.6, and if the latter is (that) molar O / C ratio ⁇ 0.8, preferably ⁇ 0.4.
- the conditions of method step 20 are therefore selected or adjusted in such a way that the molar H / C ratio of the produced biochar / biochar 22 and 23 ⁇ 0, 8, preferably ⁇ 0.6, and / or whose (its) molar O / C ratio is ⁇ 0.8, preferably ⁇ 0.4 (cf claim 6).
- the conditions for the chemical-physical treatment of the conversion residues (BZ 20) are therefore preferably set such that the thermal or thermo-chemical carbonation of the (if necessary according to FIGS. 16, 18 or 19) ) Conversion residues 12 and 13 to biochar / biochar / biokoks by a choice of the following thermo-chemical carbonation processes: pyrolysis, carbonization, torrefaction, hydrothermal carbonation (HTC), vapothermal carbonation, gasification and any combination of these treatment methods. This carbonization is particularly preferably carried out by pyrolysis or torrefaction.
- the prior art system shown in FIG. 1 comprises prior art devices for the carbonation of conversion residues, preferably those suitable for pyrolysis and / or torrefaction (see claim 36).
- reaction temperatures of 100 ° C - 1600 ° C preferably at reaction temperatures of 200 ° C - 1.200 ° C, particularly preferably at reaction temperatures of 300 ° C - 1000 ° C, in particular at reaction temperatures of 350 ° C - 1000 ° C and in the best case at reaction temperatures of 400 ° C.
- the system of FIG. 1 comprises suitable devices known from the relevant prior art for the carbonation of conversion radicals, preferably those which are suitable for ensuring reaction temperatures of 100 ° C.-1600 ° C., preferably reaction temperatures of 200 ° C.-1,200 ° C, especially preferential reaction temperatures of 300 ° C - 1,000 ° C, in particular reaction temperatures of 350 ° C.
- the conversion radicals A (BZ 12) are subjected to pyrolysis, particularly preferably high-temperature pyrolysis, the proportion of conversion radicals A in the total recuperated conversion radical stream 10 preferably having a fraction of> 1%, particularly preferably> 50%. and in particular> 75%.
- the conversion radicals B (BZ 13) are preferably subjected to low-temperature pyrolysis, HTC or torrefaction, the proportion of the conversion radicals B in the total recuperated conversion residual stream 10 preferably being ⁇ 99%, particularly preferably ⁇ 50 %, in particular of ⁇ 25% and at best of ⁇ 10%.
- the heating of the conversion radicals 12 to 14 to be treated lasts longer than 1 second at the reaction temperature, preferably longer than 10 minutes, particularly preferably longer than 50 minutes and in particular longer than 100 minutes (cf. Claim 20).
- the less aggressive C stabilization conditions 20 result in better or more complete outgassing of the conversion residues 12-14, leaving a firmer and less reactive carbon backbone, which in turn results in higher degradation resistance.
- some pyrolysis plants require a dewatering to at least 50% dry matter (TS) .
- the conditions for the C stabilization 20 are preferably set such that the dewatering of the latter used conversion residues 12 to 14 to> 35% TS, particularly preferably to> 50% TS and in particular to> 60% TS (see claim 5).
- the conditions of method step 20 are selected or adjusted so that the loss of atmospheric carbon, which inevitably occurs in the at least partial chemical-physical stabilization of the conversion residues, is at most 99%, preferably not more than 60%, particularly preferably not more than 40% and in particular not more than 30%.
- This can i.a. in that the heating of the conversion radicals 12 to 14 to be treated lasts for more than 1 second at the reaction temperature, preferably for more than 10 minutes, particularly preferably for more than 50 minutes and in particular for more than 100 minutes (see above).
- the reaction time being relatively long, preferably longer than 1 second, more preferably longer than 60 minutes, especially longer than 240 minutes, and at best longer than 600 minutes.
- the devices for generating conditions which permit at least partial chemical-physical stabilization of the atmospheric carbon still present in the residues of the biomass conversion may comprise all devices known from the relevant prior art which are suitable for a chemical-physical treatment of these radicals make.
- they include devices for thermally or thermo-chemically carbonating the conversion residues 12-14 to biochar / biochar / biokoks 22-24, more preferably comprising a selection of the following thermo-chemical carbonation of biomass / biochar / biochar / Biocoks: pyrolysis devices, carbonization devices, torrefaction devices, hydrothermal carbonation (HTC) devices, vapothermal carbonation devices, gasification devices, any combination of these devices, the carbonization devices of the conversion radicals preferably being suitable, to carry out the carbonization under oxygen deficiency and / or at reaction temperatures of 100 ° C - 1600 ° C, particularly preferably at reaction temperatures of 200 ° C - 1,200 ° C, especially at reaction temperatures of 300 ° C - 1,000 ° C, in
- the devices for generating conditions which permit at least partial chemical-physical stabilization of the atmospheric carbon still contained in the residues of the biomass conversion are operated in such a way that the carbon fraction of the generated Organic / vegetable coals or biocokes produced within a certain period of time to less than 50%, more preferably less than 20%, in particular less than 10% and at best less than 5% by the processes of soil respiration, the Weather that aerobic decomposition and / or reaction with atmospheric oxygen will build (mineralize), whereby the particular period may be a selection from the following periods: 10 years, 30 years, 100 years, 500 years, 1,000 years, 10,000 years, 100,000 years,> 100,000 years.
- the C stabilization is carried out.
- the manner of carrying out the stabilization of the atmospheric carbon contained in conversion radicals 12 to 14 may be part of the conditions set in method step ie the method steps 20 and 21 are closely linked. So z.
- the speed of heating the conversion residuals 12 to 14 may be both a parameter for generating C stabilization conditions 20 and a parameter for performing C stabilization 21.
- Reaction temperature falls in the process step 21, it also takes longer than 1 second here, preferably longer than 10 minutes, more preferably longer than 50 minutes and in particular longer than 100 minutes.
- the parameter reaction time also plays into the method step 20 as well as into the method step 21. Therefore, the C stabilization 21 is preferably carried out in a period lasting more than 1 second, more preferably more than 60 minutes, in particular more than 240 minutes, and at best more than 600 minutes.
- the C stabilization is carried out under pressure, preferably at a reaction pressure of> 1 bar, particularly preferably at> 5 bar and in particular at> 10 bar.
- the inventive method is more efficient in terms of GHG emission reduction of the generated energy carrier 5, the lower the losses of (atmospheric) carbon in the implementation of the C-stabilization 21 precipitate.
- the chemical-physical stabilization of the atmospheric carbon contained in the conversion residues 12 to 14 or the carbonation of the conversion residues 12 to 14 deshal b is carried out such that the occurring loss of atmospheric carbon relative to the state before the C stabilization / KR carbonization is not more than 99%, particularly preferably not more than 60%, in particular not more than 40% and at most not more than 30% (cf claim 3). As stated above, this can be achieved by slow heating to the reaction temperature and / or by a high reaction temperature and / or by a long reaction time.
- biochar / biochar or the produced biococcus in the soil not only the (stabilized) carbon content contained in the biochar / biochar unfolds its effect, but the entire biochar / biochar, including the non-carbon content contained therein other substances.
- the purchasers of the biofuels / bioliquids produced mainly consider the amount per manufacturer per hectare. graced total.
- the dry matter loss occurring when carrying out the carbonation (BZ 21) of the conversion residues 12 to 14 is at most 99%, particularly preferably at most 60%, in particular maximum 40% and at most 30% at best (see claim 6).
- C stabilization 21 is therefore carried out in such a way that the carbon content of the produced biochar / biochar or biocok produced is at least 20%, preferably at least 40%, especially preferably at least 60%, in particular at least 70% and in the best case at least 80% (cf claim 6).
- the C stabilization 21 is performed differently depending on the KR substream.
- the KR substream A (BZ 12) is processed in such a way that the atmospheric carbon still contained in the conversion residue is stabilized as completely as possible and as permanently as possible under the secondary conditions of the lowest possible carbon loss.
- the dry mass loss of the conversion radical 12 should be as low as possible and the carbon content of the biochar mass 22 produced should be as high as possible.
- the KR substream A (BZ 12) is preferably exposed to a temperature of 150.degree. C. to 1,600.degree. C. under oxygen deficiency, more preferably to a temperature of 500.degree. C. to 1000.degree. C. and in particular to a temperature of 600.degree. C. to 900.degree C.
- the reaction mass is exposed to the reaction temperature for more than 1 second, more preferably for more than 50 minutes and more preferably for more than 500 minutes.
- the molar H / C ratio of the highly carbonated biochar / vegetable carbon E (BZ 22) produced is preferably ⁇ 0.8, particularly preferably ⁇ 0.6, and / or its molar O / C ratio ⁇ 0.8, more preferably ⁇ 0.4.
- Biochar / biochar E (BZ 22) with fully stabilized atmospheric carbon advantageously increases the continuous humus content of the soil when applied appropriately, since the atmospheric carbon contained in biochar / biochar E can no longer be converted to C0 with atmospheric oxygen for centuries and millennia 2 or react with hydrogen to form CH 4 .
- the partial stream A (BZ 12) is lignocellulose-containing, particularly preferably wood-containing and in particular straw-containing. If it is straw-containing, the variant of the method according to the invention disclosed in FIG. 1 allows access to that 2/3 of the annual straw growth which until now had to remain in the field to secure the humus content of the soil.
- the KR partial stream B (BZ 13) treated in the course of the C stabilization 21 is processed so that the atmospheric carbon still contained in the conversion radical is partially stabilized under the secondary conditions of the lowest possible carbon loss.
- the dry matter loss of the conversion radical 13 should be as low as possible and the carbon content of the biochar mass 23 produced should be as high as possible.
- This can be achieved by carbonizing the KR substream B (BZ 13), this carbonization 21 preferably by means of a low-temperature pyrolysis or torrefaction is carried out, particularly preferably by means of a hydrothermal carbonation HTC and in particular by means of a low-temperature pyrolysis or torrefaction, which is carried out after a rapid heating.
- Partial stabilization can also be achieved by precipitating the reaction parameters of a pyrogenysis aggressively, ie, the heating rate to reaction temperature is rapid, the reaction temperature is relatively low, and / or the reaction time is relatively short.
- the KR partial stream B (BZ 13) is exposed under oxygen deficiency to a reaction temperature which is lower than the reaction temperature used for the partial flow A (BZ 12).
- the reaction mass is exposed to the reaction temperature for a shorter period of time than the reaction time used for substream A (BZ 12).
- the molar H / C ratio of the produced, strongly C-containing biolines / vegetable carbon F (BZ 23) is higher than in the bioliquids / biochar E (BZ 22).
- the molar O / C ratio of the produced, strongly C-containing organic / Pflazenzohlen F (BZ 23) is higher than in the bio / vegetable carbon E (BZ 22).
- Biochar / biochar F (BZ 23) with partially stabilized atmospheric carbon advantageously increases the nutrient humus content of the soil when applied accordingly, since the atmospheric carbon contained in the biotech / biochar F can no longer be at least pro rata for decades react with atmospheric oxygen to C0 2 or with hydrogen to CH 4 .
- the KR substream C (BZ 14) treated in the context of the C stabilization 21 is processed so that the atmospheric carbon still contained in the conversion residue is not or hardly stabilized under the secondary conditions of the lowest possible carbon loss.
- the dry matter loss of the conversion radical 14 should be as low as possible and the carbon content of the biochar mass 24 produced should be as high as possible.
- Non-stabilization can also be achieved by making the reaction parameters of pyrolysis very aggressive, i. the heating to reaction temperature is very fast, the reaction temperature is very low and / or the reaction time is very short.
- the KR substream C (BZ 14) is exposed under oxygen deficiency to a reaction temperature which is less than the reaction temperature used for substream B (BZ 13).
- the reaction mass is exposed to the reaction temperature for a shorter period of time than the reaction time used for substream B (BZ 13).
- the molar H / C ratio of the highly C-containing biochar / vegetable carbonates G (BZ 24) produced is preferably higher than that of the biofuel B (BZ 23).
- the molar O / C ratio of the produced, strongly C-containing organic / Pflazenzohlen G (BZ 24) is higher than in the bio / vegetable carbon F (BZ 23).
- Bio- / biochar G (BZ 24) with non-stabilized atmospheric carbon increases with appropriate application in an advantageous manner the OPS or OBS content of the soil, because the contained in the bio / biochar G atmospheric carbon is the soil flora and fauna at least pro rata for years as a food or energy supplier.
- Biochar masses (BKM) 22 to 24 are thus the biochar masses (BKM) 22 to 24.
- BKMs 22 to 24 are generated at least proportionally from straw-containing conversion residues (cf claim 11).
- the application of fresh, untreated biochar / biochar or fresh, untreated biococcus may lead to the effect of temporary nitrogen immobilization and / or immobilization of other micronutrients and macronutrients, especially if the biochar or biochar or Biokoks was produced with low temperatures and / or by the HTC process. As mentioned above, this effect has its reasons, inter alia, in the binding of the NH 4 -one and the resulting reduction in nitrification and in increased soil respiration.
- the biochar masses E to G produced in process step 25 (deletion / charging with nutrients) enriched with exactly the organic nutrients that are contained in the cereal plant before they are mixed into a biochar mixture H (the enrichment with organic nutrients can also take place immediately after their mixing into a biochar mixture H).
- process step 25 comprises charging with nitrogen compounds, particularly preferably enrichment with organic nitrogen compounds.
- nitrogen compounds particularly preferably enrichment with organic nitrogen compounds.
- the charging of the biochar masses E to G (BZ 22 to 24) with nutrients can be carried out BKM-specific, by deleting the hot torrefied or pyrolyzed biochar / biochar / biococcus separately with process water 17, which in process step 16 from the Conversion residues 12 to 14 was extracted, preferably together with nutrients, particularly preferably with exactly the nutrients that have been lost to the soil on which the biofuel / vegetable coals are applied, previously by the cultivation of the biomass from which the bio / biochar come.
- the process water 17 and / or the nutrients extracted from the conversion residues 12 to 14 in process step 25 can be supplemented or replaced in this process step 25 by extinguishing or mixing the biomass coals 22 to 24 with a selection of the following nutrient-containing aqueous suspensions : Manure, percolate, manure, liquid residues from anaerobic fermentation, vinification from an ethanol production, urine, leachate from silage, (possibly treated or purified) process water, liquid digestate, permeate, rather liquid phase of dehydration, rather solid Phase of dehydration, any phase of a separation, suspensions prepared with mineral fertilizer, other nutrients containing suspensions and similar suspensions (see claim 8).
- the amount of heat contained in the hot biofuel (s) 22 to 24 is less than the amount of heat required to evaporate the water supplied during the quenching (only the water evaporates upon quenching, the organic dissolved in the water) Nutrients are left behind in the biochar / biochar mixture), the bioliquids / biochips / biokokes 22 to 24 or the biochar / biochar mixture H 26 get wet again, otherwise they stay dry.
- the extinguished biochar / biochar / biokoks remains dry. If necessary and if necessary, the extinguished biochar / vegetable carbon 22 to 24 may be subjected to drying (not shown in FIG.
- low-temperature drying preferably low-temperature drying.
- the low-temperature drying known to those skilled in the art is advantageous because, in contrast to high-temperature drying, no harmful dioxins and furans are formed in the latter.
- Corresponding devices are previously known from the relevant prior art. Such a need exists in particular if fungal formation and spontaneous combustion are to be prevented and / or if the transport weight of the nutrient-loaded biochar / biochar mixture is to be reduced.
- the low-temperature drying is preferably carried out to a TS content of at least 86%, since fungus formation can be prevented only from this TS content.
- the biochar / biochar / biococcus produced can be extinguished both individually and as a coal mixture H (BZ 26) or as a coal-conversion mixture I (BZ 27) or charged with nutrients, in particular with N-containing nutrients ,
- the corresponding, previously known from the relevant prior art devices need only be arranged or switched accordingly (see claim 36).
- the biochar masses E to G (BZ 22 to 24) produced by means of quenching / charging 25 can be present in a silo, container, bunker or the like known from the relevant prior art Devices are stored, preferably sorted until it is needed.
- This demand may be from the downstream mixing 26, from the downstream mixing 27, from the downstream pelleting / briquetting 28, from the downstream bottling to BigBags 30, or from the downstream loose distribution, e.g. by tanker via regional interim storage 31.
- method step 26 mixing to form a biochar mixture H
- the up to three biochar masses E to G are mixed in any combination and with any proportions to form a biochar mixture H (BZ 26).
- the biochar mixture 26 can also consist only of one of the three biochar masses E to G (BZ 22 to 24) (see claim 10).
- the biochar masses E to G (BZ 22 to 24) can, but do not have to be extinguished beforehand with process water.
- biochar masses E to G (BZ 22 to 24) may or may not have been loaded with nutrients before being mixed together.
- special designer biochar mixtures can be produced with different properties.
- the proportions of the up to three biochar masses E to G (BZ 22 to 24) on the biochar mixture H (BZ 26) can each be between 0% and 100% under the obvious additional condition that the sum of the proportions does not exceed 100% (see claim 10).
- the biochar mass E (BZ 22) preferably has a proportion of> 1% of the total coal mixture H (BZ 26), particularly preferably a proportion of> 50% and in particular a proportion of> 75%.
- the biochar mass F (BZ 23) has a share of ⁇ 99% in the total coal mixture H (BZ 26), particularly preferably a proportion of ⁇ 50%, in particular a proportion of ⁇ 25% and at best a proportion of ⁇ 10%.
- the coal mixture H (BZ 26) is at least partially generated from straw-containing conversion residues (see claim 11).
- a partial stream of the biochar mixture H (BZ 26) produced in the mixing step 26 can be stored in a silo 29, container, bunker or similar devices known from the relevant prior art until it is needed. This need may be based on bottling in BigBags 30 (or other containers), from loose distribution e.g. by tanker via regional intermediate storage 31, from the (not shown in Figure 1) pelletizing / briquetting 28 or (not shown in Figure 1) of the mixture 27.
- the proportion of the partial flow of Biochar-Mixtur-H total flow can be between 0% and 100%.
- the mixing 26, the mixing 27 and the intermediate storage in the silo 29 are suitable for this purpose known from the relevant prior art devices used (see claim 36).
- the mixing 26 of the up to three biochar masses E to G takes place only on the occasion of the application 32 (not shown in FIG. 1).
- the delivery or distribution devices consist of up to three compartments in which the single-variety biochar masses E to G (BZ 22 to 24).
- Suitable sensors known from the relevant prior art which are mounted in front of the distribution devices in the direction of travel (eg on the tractor), measure the content of the soil, preferably the field soil, of OPS, OBS, nutrient humus, persistence hum, organic carbon on the occasion of application 32 , Nitrogen and / or other substances and the biochar mass-specific gifts are then made according to the resulting need or so that the set target value is reached.
- the same is possible with the inclusion of the conversion condition D (BZ 15).
- biochar conversion radical mixture I In process step 27 (mixing to form a biochar conversion radical mixture I), the biochar mixture H (BZ 26) and the conversion radical D (BZ 15) are mixed with any proportions to form a biochar conversion radical mixture I (BZ 27).
- the biochar conversion radical mixture I 27 can also consist only of one of the three biochar masses E to G (BZ 22 to 24) or only of the biochar mixture H (BZ 26) (cf claim 10).
- the biochar conversion mixture I 27 may, but need not previously, be quenched with process water 17. Likewise, the biochar conversion mixture I 27 or its components may have been charged with nutrients prior to their preparation, but need not. According to the invention, 27 special designer biochar mixtures can be produced with different properties by this mixing.
- the biochar conversion mixture I (BZ 27) is generated, at least partly, from straw-containing conversion radicals (cf claim 11).
- the mixing 27 takes place only on the occasion of the application 32 (not shown in FIG. 1).
- the application or distribution devices fertilizer spreader, solid manure spreader, liquid manure spreaders and similar known from the relevant prior art distribution devices
- the varietal biochar masses E to G (BZ 22 to 24) and the conversion residue D (BZ 15) or the biochar mixture H (BZ 26) and the conversion residue D (BZ 15) are located.
- Suitable sensors known from the relevant prior art which are mounted in front of the distribution devices in the direction of travel (eg on the tractors), measure the content of the soil, preferably the field soil, of OPS, OBS, nutrient humus, persistence humus, organic on the occasion of application 32 Carbon, nitrogen and / or other substances and the biochar mass-specific delivery then takes place according to the resulting need or so that the set target values are achieved.
- the transportability of the generated biochar mixture H (BZ 26) and / or the biochar conversion mixture I (BZ 27) is increased and / or its downstream application 32 facilitated by the process step 28 (pelletizing).
- Pelleting is carried out as previously known in the art and the relevant art, i.e., it may comprise a selection of the following sub-processes: drying, comminution, steaming, pressing, cooling, conveying, storage, storage.
- Pelleting 28 is done with suitable devices and systems previously known in the art.
- the biochar / biochar pellets or biocoke pellets produced by means of pelleting 28 can be stored in a silo 29 container, bunker or similar devices known from the relevant prior art until they are needed. This need may be determined by the downstream bottling in BigBags 30 (or other containers) or by the downstream loose distribution e.g. go by tanker via regional interim storage 31.
- the intermediate storage of the biochar / biochar pellets or biocoks pellets in the silo 29 and all associated upstream and downstream sub-processes are suitable for use with, from the relevant Prior art prior art devices and systems made.
- biochar conversion mixture I which is also composed only of the biochar mixture H (BZ 26) or only one of the biochar masses E to G (BZ 22 to 24) may consist (see above), not pelletized and loosely packed in BigBags in the subsequent process step 30 or distributed loosely in the downstream process step 31.
- the possibly filled pellets of biochar conversion mixture I (BZ 27) filled in BigBags and also only from the biochar mixture H (BZ 26) or only from one of the biochar masses E to G (BZ 22 up to 24), may be distri- minded in regional interim storage facilities, preferably by rail, ship and / or lorry.
- the biochar conversion mixture I (BZ 27) filled in BigBags can also be sent directly to the end consumer (Farmers) are delivered.
- the possibly pelletized biochar mixture H (BZ 26) and / or the possibly pelletized biochar conversion mixture I (BZ 27) can also be loosely attached to the interspaces and / or distributed to end users.
- suitable, known from the relevant prior art devices are used, preferably tankers, which are geared to the transport of pellets or dust-like products such as cement or flour.
- the loose or prepackaged biochar conversion mixture I (BZ 27), which also consists only of the biochar mixture H (BZ 26) or only one of the biochar masses E to G (BZ 22 to 24) may be delivered directly to the agricultural or forestry holding from the biomass conversion plant or from one of the regional interim storage facilities and filled, with or without intermediate storage, into equipment suitable for use in the biochar conversion mixture I (BZ 27)
- equipment suitable for use in the biochar conversion mixture I (BZ 27) To distribute biochar mixture H (BZ 26) and / or at least one of the biochar masses E to G (BZ 22 to 24) on the surfaces in which these biochar / vegetable coals or - mixtures are to be incorporated.
- biochar / vegetable coals or - mixtures are to be incorporated.
- bioliquids can also be mixed with solid fertilizers, solid manure or other substances, so that the fertilizer spreaders or solid manure spreaders can load and disperse appropriate mixtures. If these other substances are liquid, the application of the bioliquids / vegetable coals or mixtures may also be carried out with manure spreaders or functionally equivalent devices. In the latter case, it may be advantageous to previously reduce the biochar / vegetable coal or the mixtures to such a degree of fineness that the liquid manure spreaders or the functionally identical devices do not become clogged.
- biochar / vegetable coal or mixtures on the agricultural and forestry areas is carried out after the loading of the distribution devices as known from the relevant prior art or from practice.
- step 33 the applied on the agricultural or forest land biochar / biochar or the corresponding mixtures are incorporated into the soil, preferably in the field crop.
- This incorporation is as previously known from the relevant prior art and practice, preferably by plowing, grazing or harrowing, with prior art devices known from the prior art, preferably by tractor-driven plows, cultivators, harrows or similar devices.
- the biolines / vegetable coals or the corresponding mixtures (BZs 22 to 24, 26 and 27) incorporated in the soil, preferably in the field soil are at least partially composed of lignocellulose-containing feedstocks , preferably produced from straw. Most preferably, these feedstocks were exposed to high reaction temperatures.
- the biofuel (s) produced from straw-containing conversion residues have a pH of> 7.0, more preferably one of> 8.5 and especially one of> 10.0.
- the biochar / biochar generated from straw-containing conversion residues is applied to acidic soils (cf claim 11).
- uncharged ⁇ ) stabilized biochar / biochar / biokoks are incorporated into overfertilized and / or sandy soils in order to reduce overfertilization and / or nitrogen leaching.
- from 0.1 to 5,000 t of biochar / biochar / dry biocum solids are applied per hectare, more preferably 1 to 1,000 l of biochar / biochar / dry biocum, in particular 10 to 500 t of biochar / biochar / biokoks. Dry matter and, at best, up to 20 - 100 tonnes of biochar / biochar / biocoke dry matter.
- At least 5 tons of biochar / biochar / hectare are incorporated per hectare and 100 years into the soil, more preferably at least 50 tons of biochar / biochar / hectare per 100 years, and most preferably at least 100 tons of biochar / biochar / hectare per hectare 100 years (see claim 12).
- the produced biochar / vegetable coal mixtures with a high proportion of pyrolysis coals are applied before the cultivation of cereal crops, preferably with a proportion of> 50% and in particular with a proportion of> 75%.
- the biochar conversion mixture I (BZ 27) incorporated in the soil, preferably in the field soil, is generated at least partly from straw-containing conversion radicals (cf., claim 11).
- the produced biochar / biochar conversion radical mixture I (BZ 27) is incorporated into the soil, preferably into the field soil, that the proportion of biomass growth, preferably the fraction the straw growth, which had to remain on the fields before application of the method for maintaining the humus content of the soil, can be reduced and thus increased access to the biomass growth, preferably on the straw growth, is possible.
- the increased access relative to the total biomass growth or to the total straw growth is> 0.1% -points, particularly preferably> 30% -points, in particular> 50% -points and in the best case> 75% -points ( see claim 12).
- At least a portion of the atmospheric carbon-containing biochar mixture H (BZ 26) is used. not incorporated in utilized agricultural or forestry soil, but sequestered / stored in geological formations, in stagnant waters, in aquifers or in the ocean, in non or no longer agricultural or forestry soils or in bogs, desert soils, permafrost soils (cf. Claim 7).
- the incorporated biochar / vegetable coal or the corresponding mixtures unfold their effect.
- This consists in securing, preferably in improving the quality of the soil. This is achieved by securing, preferably increasing, the OPS or OBS content, the nutrient humus content, the persistence humus content and / or the content of organic carbon. How this can be done is described above. To avoid repetition, reference is made to the above statements.
- biochar / biochar mixtures provided by the method and system of FIG. 1 are preferably used to enhance at least one of the yield limiting soil properties.
- the desired main effect of method steps 33/34 is that atmospheric carbon is permanently removed from the earth's atmosphere as part of a fuel or fuel production process. This decarbonization prevents thousands of years of atmospheric carbon (again) from reacting with atmospheric oxygen to form C0 2 or with hydrogen to form CH 4 . Accordingly, the GHG emission value of the product of the method according to the invention, the energy carrier mix 9 (which can also consist only of the generated energy source 5 or the energy carrier mix 7), compared to.
- the GHG emission value of its fossil counterparts preferably to such an extent that no GHG emissions are associated with the production, distribution and use of the energy carrier mix 9, particularly preferably so far that after the production, distribution and use of the energy carrier Mixes 9 less greenhouse gases or GHG levels in the Earth's atmosphere than before.
- FIG. 1 can be modified in many ways. For example, individual process steps can be omitted without the end products (ET mix 9 and / or the effect in soil & in the earth's atmosphere 34) changing.
- end products ET mix 9 and / or the effect in soil & in the earth's atmosphere 34
- FIG. 1 some embodiments are described which describe circumstances in which individual method steps and accordingly the use of corresponding devices can be omitted. These embodiments are not all-encompassing, for those skilled in the art, which are aware of the invention, other circumstances are obvious in the presence of individual process steps 1 to 3, 6 to 9, 11 to 19 and 22 to 34 may be obsolete or not absolutely necessary.
- a briquetting 19 can for example be made without prior comminution 18. This is also the case with pelleting 19 if the conversion residues A to C to be pelletized (BZ 12 to 14) are small enough. Also, the dehydrogenation 16 is not absolutely necessary, namely, for example, if in the process steps 20/21, for example, an HTC is to be performed or if the conversion residues A to C (BZ 12 to 14) have a TS content that is suitable for efficient pyrolysis or torrefaction is sufficient. Nutrient extraction 16 can also be dispensed with, as can pelleting 19, for example, when carbonization processes which operate without pelletized starting materials are used in process steps 20/21.
- a pretreatment 3 of the starting materials 1/2 is not absolutely necessary, for example, if in the conversion 4 no high conversion efficiencies should be achieved and / or the focus is more on ensuring that the largest possible proportion of the at least one feedstock contained atmospheric carbon remains in the conversion radical 10, so that the highest possible decarbonation effect 34 is achieved.
- the harvest & collection 2 can be omitted, for example, if the at least one input material anyway accumulates and therefore neither harvested nor must be collected. If the substance used 1/2 is specified, for example, the process step 1 is superfluous.
- the charge of nutrients 25 may be omitted.
- the quenching 25 can be omitted if there is a corresponding alternative to cooling hot biochar / biochar, eg cooling with air.
- the mixtures 26 and 27 can be omitted if only one biochar mass E, F or G (BZ 22 to 24) to be generated.
- the filling in BigBags 30 can be omitted if, for example, is filled into bags or if the produced biochar / biochar mixture is to be distributed in a loose state.
- the distribution into regional interim storage facilities 31 becomes obsolete, for example, if the end customer is supplied directly or if he picks up the biochar / biochar mixture in the biomass conversion plant itself.
- the loading of spreading devices & the spreading 32 as well as the incorporation into the field soil become superfluous if the produced biochar mixture H (BZ 26) is sequestered elsewhere than in land used for agriculture or forestry.
- These subsidies and / or intermediate storage may include the sub-operations of a first production, storage, storage, outsourcing and second production.
- biochar masses produced, biochar / biochar mixtures, biochar conversion mixture mixtures or the soil may be provided with additives before or after the incorporation of the biochars (mixtures) produced, as is known from the relevant art State of the art or from the horticultural practice and / or the cultivation of plants are already known.
- biochar masses produced, biochar / biochar mixtures, biochar conversion mixture mixtures are supplied to other uses known from the relevant prior art than incorporation into the soil 33.
- Figure 2 shows a schematic representation of another embodiment of the method and system according to the invention and indeed for the sake of clearer presentation without the conversion residue D indicated in FIG. 1 and its use. It is understood that the embodiment shown in Figure 2 as shown in Fig. 1 can also be performed with the conversion residue D and its use.
- the C0 2 -l (BZ 35) can by-product or as the remainder of the conversion 4 occur.
- the recuperation of C0 2 -l (BZ 35) is carried out on the occasion of this (first) conversion 4 of the selected biomass 1/2 into a generated energy source 5.
- Such recuperation is possible, for example, in the production of bioethanol and in the treatment of biogas to bio methane.
- suitable known from the relevant prior art devices are used, preferably provided with valves piping, particularly preferably pressurized gas lines.
- the second recuperation of atmospheric carbon dioxide (C0 2 II) takes place in process step 21 on the occasion of the performance of the chemical-physical stabilization of atmospheric carbon.
- the C0 2 -ll (BZ 36) can occur as a by-product or as a residue of C stabilization 21.
- Such C0 2 reekuper réelle 36 is for example possible in the carbonation of biomass, especially in the pyrolysis of biomass.
- the combustion of pyrolysis gas produces a flue gas which is strongly C0 2 -containing.
- recuperated C0 2 I (BZ 35) and the recuperated C0 2 II (BZ 36) are combined, purified (BZ 37), liquefied (BZ 38) geologically sequestered (BZ 39), used as a substitute for fossil C0 2 ( BZ 40) or for the production of C0 2 -based energy sources (BZ 41), preferably for the production of SynMethan (see claim 13).
- devices known from the relevant prior art are used, which are suitable for recuperating, liquefying, purifying, preparing, storing, transporting (preferably in a liquid state of aggregation) atmospheric carbon dioxide (CO 2 ) produced in the process according to the invention ) to submit to the industry, to introduce them into geological formations, to convert them into CO 2 -based power, heating or fuel, to perform a combination of these functions (see claim 37).
- CO 2 atmospheric carbon dioxide
- Fossil energy source power, heating or fuel
- Energy mix 9 whose mixing is preferably carried out so that after the production, distribution and use of the energy carrier mix according to life cycle analysis or stoichiometric analysis, an equal or lower (measured in tonnes C0 2 - equivalent) greenhouse gas amount in the earth's atmosphere than after the production, distribution and use of an equal amount of fossil energy
- bio / biochar / biokoks possibly packed in BigBags, preferably to regional distribution points Loading of agricultural / forestry fertilizer, manure and / or solid manure spreaders, possibly after further intermediate storage in agricultural or forestry operations and application of bioliquids / bioliquids E / G or biochar / biochar / biokoks Mixtures H and / or with biochar / biochar / biocconversion mixtures I preferably together with fertilizer, solid manure and / or liquid manure
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Abstract
Description
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DE102016011952 | 2016-10-07 | ||
DE102017005627.7A DE102017005627A1 (de) | 2016-10-07 | 2017-06-14 | Verfahren und System zur Verbesserung der Treibhausgas-Emissionsminderungsleistung biogener Kraft-, Heiz- und Brennstoffe und/oder zur Anreicherung landwirtschaftlich genutzter Flächen mit Humus-C |
PCT/EP2017/075516 WO2018065591A1 (de) | 2016-10-07 | 2017-10-06 | Verfahren und system zur verbesserung der treibhausgas-emissionsminderungsleistung biogener kraft-, heiz- und brennstoffe und/oder zur anreicherung landwirtschaftlich genutzter flächen mit humus-c |
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EP (1) | EP3523403A1 (de) |
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AU (1) | AU2017339091A1 (de) |
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CA (1) | CA3039567A1 (de) |
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-
2017
- 2017-06-14 DE DE102017005627.7A patent/DE102017005627A1/de not_active Withdrawn
- 2017-10-06 AU AU2017339091A patent/AU2017339091A1/en not_active Abandoned
- 2017-10-06 WO PCT/EP2017/075516 patent/WO2018065591A1/de unknown
- 2017-10-06 EP EP17793576.4A patent/EP3523403A1/de active Pending
- 2017-10-06 BR BR112019006885A patent/BR112019006885A2/pt not_active IP Right Cessation
- 2017-10-06 CN CN201780073466.6A patent/CN110520510A/zh active Pending
- 2017-10-06 CA CA3039567A patent/CA3039567A1/en active Pending
- 2017-10-06 US US16/339,596 patent/US20210285017A1/en not_active Abandoned
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AU2017339091A1 (en) | 2019-05-02 |
CA3039567A1 (en) | 2018-04-12 |
WO2018065591A1 (de) | 2018-04-12 |
DE102017005627A1 (de) | 2018-04-12 |
BR112019006885A2 (pt) | 2019-06-25 |
US20210285017A1 (en) | 2021-09-16 |
CN110520510A (zh) | 2019-11-29 |
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