EP3003982A1 - Integrierte anlage und verfahren zum flexiblen einsatz von strom - Google Patents
Integrierte anlage und verfahren zum flexiblen einsatz von stromInfo
- Publication number
- EP3003982A1 EP3003982A1 EP14724342.2A EP14724342A EP3003982A1 EP 3003982 A1 EP3003982 A1 EP 3003982A1 EP 14724342 A EP14724342 A EP 14724342A EP 3003982 A1 EP3003982 A1 EP 3003982A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- hydrogen
- natural gas
- plant
- electricity
- 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.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/025—Preparation in gaseous phase by using a plasma
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J3/00—Circuit arrangements for ac mains or ac distribution networks
- H02J3/008—Circuit arrangements for ac mains or ac distribution networks involving trading of energy or energy transmission rights
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
-
- C—CHEMISTRY; METALLURGY
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- the present invention relates to an integrated system and method for the flexible use of electricity.
- renewable energies such as wind power, solar energy and hydropower
- Electrical energy is typically supplied to a variety of consumers via long-range, supra-regional and transnationally coupled power grids, referred to as power grids. Since electrical energy in the power grid itself or without further devices can not be stored to a significant extent, the electrical power fed into the power grid must be matched to the consumer's power requirements, the so-called load.
- the load varies, as is known, time-dependent, in particular depending on the time of day, day of the week or season.
- the load profile is subdivided into the three areas of base load, medium load and peak load, and electrical power generators are suitably used in these three load ranges, depending on the type.
- a continuous synchronization of power generation and power take-off is necessary.
- Possible short-term deviations are compensated by so-called positive or negative balancing energy or balancing power.
- the difficulty arises that, for certain types, such as wind power and solar energy, the power generation power is not present and controllable at any time, but is e.g. Daytime and weather-related fluctuations are subject that are only partially predictable and usually do not match the current energy needs.
- Another approach is to save part of the output in the case of high generation from renewable energy sources and to recycle it in times of low generation or high consumption.
- pumped storage power plants are already being used today.
- the system should be flexibly operable, so that responding to a change in electricity supply and / or electricity demand particularly flexible, for example, to achieve economic benefits.
- the system should be able to be used for storage or supply of electrical energy even for longer periods of high or low electricity supply.
- the security of supply should be improved by the present invention.
- the system and the method should continue to have the highest possible efficiency.
- the method according to the invention should be able to be carried out using the conventional and widely available infrastructure.
- an integrated plant in which a plant for the electrothermic production of hydrogen cyanide, a separation device for the separation of hydrogen cyanide from the reaction mixture of the electrothermic production of hydrogen cyanide and a Device for introducing a gas into a natural gas network are connected so that from the separator, a gas stream containing hydrogen and / or hydrocarbons can be introduced into the natural gas network.
- the present invention accordingly provides an integrated plant which comprises a plant for the electrothermal production of hydrocyanic acid and a separation device for the separation of hydrocyanic acid from the reaction mixture of the electrothermic production of hydrocyanic acid to obtain at least one gas stream containing hydrogen and / or hydrocarbons, wherein the integrated plant a device for introducing a gas into a natural gas network, which is supplied from the separator via at least one line containing a gas stream containing hydrogen and / or hydrocarbons.
- the present invention also relates to a method for the flexible use of electricity in an integrated system according to the invention, in which a gas stream containing hydrogen and / or hydrocarbons, is fed into a natural gas network and depending on the electricity supply, the amount and / or composition of in the natural gas network fed gas stream is changed.
- the integrated system according to the invention and the method according to the invention have a particularly good property profile, whereby the disadvantages of conventional methods and systems can be significantly reduced.
- a plant for the electrothermal production of hydrocyanic acid can be operated dynamically well, so it can be adjusted variably to the electricity supply.
- the integrated system can also be used for longer periods of high or low electricity supply for storage or provision of electrical energy.
- surprisingly long terms of all components of the integrated system can be achieved, so that their operation can be made very economical.
- the system for the electrothermal production of hydrocyanic acid is designed to be controllable, wherein the regulation takes place as a function of the electricity supply.
- electricity from renewable energies is used for the electrothermal production of hydrocyanic acid.
- the process can be carried out with relatively few process steps, the same being simple and reproducible.
- the present integrated facility allows the provision of chemical derived products with a low release of carbon dioxide, since the hydrocyanic acid obtained at very high degrees of conversion and compared to alternative starting materials with less further energy input or higher heat release can be implemented to many chemically important secondary products.
- the integrated system according to the invention serves for the purposeful and flexible use of electrical energy, also referred to herein synonymously as electricity.
- the integrated system can store electrical energy with a high electricity supply and, in particular with a low electricity supply, feed electrical energy into a power grid.
- the term storage here refers to the ability of the system, with a high supply of electricity to convert this into a storable form, in this case as chemical energy, which chemical energy can be converted into electrical energy with a small supply of electricity.
- the storage can be done in the form of coupling product hydrogen, which inevitably arises in the electrothermal production of hydrocyanic acid from methane or higher hydrocarbons.
- the storage can also take place in the form of products which can be formed in the electrothermal production of hydrogen cyanide in a running parallel to the formation of hydrogen cyanide endothermic reaction, for example by reacting two molecules of methane to ethane and hydrogen.
- methane methane
- ethane C 2 H 6
- hydrogen ethane
- the integrated system according to the invention comprises a plant for the electrothermal production of hydrocyanic acid.
- electrothermal refers to a process in which hydrogen cyanide is produced in an endothermic reaction of hydrocarbons or coal and the heat required to carry out the reaction is generated by electric current.
- gaseous or vaporized hydrocarbons are used, more preferably aliphatic hydrocarbons.
- Particularly suitable are methane, ethane, propane and butanes, especially methane.
- hydrogen is obtained as co-product.
- the electrothermal production of hydrocyanic acid can be carried out by reacting hydrocarbons with ammonia or nitrogen in an arc reactor.
- the electrothermal production of hydrocyanic acid can take place in a one-step process, in which an ammonia and at least one hydrocarbon-containing gas mixture is passed through the arc.
- a nitrogen and a hydrocarbon-containing gas mixture which may additionally contain hydrogen, are passed through the arc.
- Suitable plants and processes for a one-stage electrothermal production of hydrogen cyanide are known from GB 780,080, US 2,899,275 and US 2,997,434.
- the electrothermal production of hydrocyanic acid can be carried out in a two-stage process in which nitrogen is passed through the arc and at least one hydrocarbon is fed behind the arc into the plasma generated in the arc.
- a suitable plant and a process for a two-stage electrothermal production of hydrocyanic acid are known from US 4,144,444.
- the arc reactor is preferably operated with an energy density of 0.5 to 10 kWh / Nm 3 , especially 1 to 5 kWh / Nm 3 and in particular 2 to 3.5 kWh / Nm 3 , wherein the energy density on the gas volume passed through the arc refers.
- the temperature in the reaction zone of the arc reactor varies due to the gas flow, wherein in the center of the arc up to 20,000 ° C can be achieved and at the edge, the temperature can be about 600 ° C.
- the average temperature of the gas is preferably in the range of 1300 to 3000 ° C, more preferably in the range of 1500 to 2600 ° C.
- the desired production capacity is usually achieved by a parallel arrangement of several arc reactors, which can be controlled together or separately.
- the residence time of the starting material in the reaction zone of the arc reactor is preferably in the range of 0.01 ms to 20 ms, more preferably in the range of 0.1 ms to 10 ms and especially preferably in the range of 1 to 5 ms.
- the gas mixture exiting the reaction zone is quenched, i. subjected to a very rapid cooling to temperatures of less than 250 ° C in order to avoid decomposition of the thermodynamically unstable intermediate hydrogen cyanide.
- a direct quenching process such as, for example, the introduction of hydrocarbons and / or water or an indirect quenching process, such as rapid cooling in a vapor recovery heat exchanger may be used.
- Direct quenching and indirect quenching can also be combined.
- the gaseous mixture leaving the reaction zone is only quenched with water.
- This embodiment is characterized by relatively low investment costs. The disadvantage, however, is that in this way a considerable part of the energy contained in the product gas is not used or exergetically inferior.
- the gaseous mixture leaving the reaction zone is mixed with a hydrocarbon-containing gas or liquid, wherein at least a portion of the hydrocarbons are endothermically cleaved.
- a more or less broad product spectrum is generated, eg.
- hydrocyanic acid and hydrogen also shares in ethane, propane, ethene and other lower hydrocarbons. In this way, the resulting heat can be supplied to a much higher extent of a further use such as the endothermic cleavage of hydrocarbons.
- solid components, in particular carbon particles, separated and the gas mixture depending on the starting materials in addition to hydrogen cyanide and hydrogen other substances, such as Ethyne, ethene, ethane, carbon monoxide and volatile sulfur compounds, such as H 2 S and CS 2 may contain, further processing for the production of hydrogen cyanide supplied.
- hydrogen cyanide and hydrogen other substances such as Ethyne, ethene, ethane, carbon monoxide and volatile sulfur compounds, such as H 2 S and CS 2 may contain, further processing for the production of hydrogen cyanide supplied.
- the electrothermal production of hydrocyanic acid is carried out by reacting hydrocarbons with ammonia in the presence of a platinum-containing catalyst by the so-called BMA process with electrical heating of the reactor.
- the electrical heating can be effected by resistance heating, as described for example in WO 2004/091773, by electric induction heating, as described, for example, in WO 95/21 126, or by microwave heating, as described, for example, in US Pat. No. 5,529,669 and US Pat. No. 5,470,541.
- the integrated system according to the invention also comprises a separation device for the separation of hydrogen cyanide from the reaction mixture of electrothermic production of hydrogen cyanide to obtain at least one gas stream containing hydrogen and / or hydrocarbons, and a device for introducing a gas into a natural gas network, from the separator via a Line at least one gas stream containing hydrogen and / or hydrocarbons is supplied.
- hydrogen cyanide is separated from hydrogen and hydrocarbons.
- Hydrocyanic acid can be separated from the gas mixture by selective absorption in water.
- hydrogen cyanide formed ethyne can then be separated from the gas mixture by selective absorption in a solvent.
- Suitable solvents are, for example, water, methanol, N-methylpyrrolidone or mixtures thereof.
- Suitable methods for the separation of hydrogen cyanide and ethyne from the gas mixture are known from the prior art, for example from Ullmann's Encyclopedia of Industrial Chemistry, 2012 Wiley-VCH Verlag GmbH & Co.
- the separated from hydrogen cyanide, containing hydrogen and / or hydrocarbons mixture can be fed directly to the device for introducing a gas into a natural gas network.
- hydrogen may be separated from the mixture separated from hydrogen cyanide and optionally hydrogen or a resulting hydrocarbonaceous gas may be supplied to the apparatus for introducing a gas into a natural gas network.
- hydrogen and a hydrocarbon-containing gas may be supplied via separate lines from the separation device for removing hydrogen cyanide from the reaction mixture of the electrothermal production of hydrogen cyanide of the apparatus for introducing a gas into a natural gas network.
- the separation of hydrogen and hydrocarbons can also be incomplete, without any incomplete separation adversely affecting the operation of the system, so that can be reduced compared to the complete separation of equipment and energy consumption for the separation.
- the apparatus for introducing a gas into a natural gas network is not particularly limited. Suitable are all devices with which hydrogen, alkanes and alkenes can be introduced individually or mixed gaseously into a natural gas network.
- the device for introducing a gas into a natural gas network comprises at least one reservoir for hydrogen.
- the type of memory is not critical, so that for this purpose a pressure tank, a liquid gas storage, a memory with gas adsorption on a solid or a chemical storage in which hydrogen is stored by a reversible chemical reaction, can be used.
- the capacity of the reservoir is preferably sized so that the amount of hydrogen produced by the plant for the electrothermal production of hydrocyanic acid under full load can be absorbed within 2 hours, more preferably the amount produced within 12 hours, and most preferably within 48 hours Hours produced amount.
- the use of a relatively large hydrogen storage allows a time-extended supply of hydrogen in the natural gas network, with which a maximum content of hydrogen in the natural gas network specified by the network operator can be maintained.
- Many terminals connected to the natural gas network can only be operated safely within a comparatively narrow band in the so-called Wobbe Index, and a widening of the band would require expensive additional installations at the terminals.
- the Wobbe index describes the burning properties of natural gas.
- a feed of hydrogen into the natural gas usually leads to a lowering of the Wobbe index.
- the Technical Rules, Worksheet G 260 of the DVGW specify lower limits for the Wobbe index. Depending on the composition of the natural gas, these limits can already be reached when a few percent by volume of hydrogen is fed into the natural gas grid.
- the apparatus for introducing a gas into a natural gas network preferably comprises at least one storage for a hydrocarbon-containing gas.
- a storage tank a pressure tank, a liquid gas storage, a storage in which the hydrocarbons are absorbed in a solvent, or a storage having gas adsorption to a solid can be used.
- the capacity of the reservoir is preferably such that the amount of gaseous hydrocarbons produced by the plant for the electrothermal production of hydrocyanic acid under full load can be absorbed within 2 hours, more preferably the amount produced within 12 hours, and most preferably within 48 hours produced amount.
- the device for introducing a gas into a natural gas network preferably comprises a device for mixing gases.
- the device for mixing gases is preferably designed to adjust the Wobbe index, the calorific value or the density of the gas introduced into the natural gas network, or a combination of these gas properties.
- the device for mixing gases comprises a measuring device for determining Wobbe Index, calorific value or density of the mixed gas, with which the mixture of the gases can be regulated.
- the device for mixing gases is connected to a storage for hydrogen, in a further preferred embodiment additionally also with a storage for a hydrocarbon-containing gas.
- the device for introducing a gas into a natural gas network comprises a methanization reactor for converting hydrogen with carbon dioxide or carbon monoxide to methane.
- the device for introducing a gas into a natural gas network comprises a Fischer-Tropsch reactor for converting hydrogen and carbon monoxide into hydrocarbons.
- the device for introducing a gas into a natural gas network comprises a hydrogenation reactor for converting hydrogen and unsaturated hydrocarbons to saturated hydrocarbons. Suitable methanation reactors, Fischer-Tropsch reactors and hydrogenation reactors are known to those skilled in the art.
- All three embodiments allow hydrogen to be converted to products whose density, volume-specific calorific value and Wobbe index are higher than that of hydrogen. If hydrocarbons with at least 2 carbon atoms are generated, the density, the volume-specific calorific value and the Wobbe index are even higher than those of natural gas. Together with such hydrocarbons, hydrogen can be fed into the natural gas grid in larger proportions, without falling below the limits imposed by the regulations for the density, the calorific value and the Wobbe index.
- the integrated system according to the invention preferably additionally comprises a plant for generating electricity, which is supplied from the separator via a line at least one gas stream containing hydrogen and / or hydrocarbons. Suitable plants for power generation are all systems with which electrical power can be generated from the product gas. Preferably, a plant is used for power generation, which has a high efficiency.
- the plant for power generation comprises a fuel cell.
- the plant for power generation is preferably supplied to a gas stream which consists essentially of hydrogen.
- the plant for power generation comprises a power plant with a turbine.
- the plant comprises a gas turbine containing hydrogen and / or hydrocarbon Gas is operable.
- a gas turbine is used which can be operated with mixtures of hydrogen and hydrocarbon-containing gases of varying composition.
- the power plant with a turbine is a gas and steam turbine power plant (Gu D power plant), also called gas and steam combined cycle power plant.
- a gas turbine generally serves, among other things, as a heat source for a downstream waste heat boiler, which in turn acts as a steam generator for the steam turbine.
- the plant for power generation in addition to the supplied from the separator gas stream even more substances are supplied, for example, additional hydrogen for the operation of a fuel cell or additional fuel for the operation of a turbine or the heating of a steam generator.
- the capacity of the plant for power generation can be selected depending on the production capacity of the plant for the electrothermal production of hydrocyanic acid.
- the power of the plant for power generation is selected so that the power requirements of the plant for the electrothermal production of hydrocyanic acid at full load can be fully covered by the plant for power generation.
- the power can be achieved by a single device or a combination of multiple devices, the merger (pool) can be achieved via a common control.
- electrical energy for the plant for the electrothermal production of hydrogen cyanide can be obtained from the mains.
- the plant for power generation can be dimensioned so that in addition to the plant for electrothermic production of hydrogen cyanide also supplies other power consumers or beyond the needs of the plant for the electrothermal production of hydrocyanic exceeding electrical energy is fed into a grid.
- the plant for the electrothermal production of hydrogen cyanide comprises a steam generator with which steam is generated from the waste heat of the electrothermal process
- the plant for generating electricity comprises a Apparatus in which electricity is generated from steam
- the integrated equipment comprises a steam line with which steam generated in the steam generator is supplied to the device in which electricity is generated from steam.
- an indirect quench of the reaction gas obtained in a hydrogen cyanide reactor is used as a steam generator.
- the device in which electricity is generated from steam is preferably a steam turbine or a steam engine and more preferably a steam turbine.
- the steam turbine is part of a gas and steam turbine power plant.
- the integrated system according to the invention additionally comprises a storage for hydrocyanic acid.
- This store makes it possible to continue downstream conversion of hydrocyanic acid to other products, even if little or no hydrocyanic acid is produced in the plant for the electrothermal production of hydrocyanic acid at low power supply.
- the storage of hydrocyanic acid takes place in liquid form.
- the integrated system according to the invention is connected to a weather forecast unit.
- a weather forecasting unit makes it possible to adjust the operation of the system so that on the one hand the possibility of using cheap excess electricity and the possibility to provide electricity from the plant for power generation with low electricity supply and correspondingly high electricity price can be used and on the other always provide sufficient hydrocyanic acid for the continuous operation of a downstream, hydrocyanic acid-consuming plant.
- a storage for hydrocyanic acid can be brought to a high or low level.
- a plant for the further processing of hydrocyanic acid can be prepared and adjusted for changed operating modes. In a longer-term supply of electricity, these parts of the system can be reduced to a reduced level Production performance can be adjusted so that a business interruption due to lack of hydrogen cyanide can be avoided.
- the integrated system may be connected to a unit for generating a consumption forecast, wherein this unit preferably has a data memory that includes data on the historical consumption.
- the historical consumption data may include, for example, the course of the day, the course of the week, the course of the year, and other trends related to electricity demand and / or electricity generation.
- the consumption forecast data can also take into account specific changes, for example, in the access or omission of a large consumer.
- the data store may also contain data about the historical history of electricity prices.
- the inventive method for the flexible use of electricity is carried out in an integrated system according to the invention and from the device for introducing a gas into a natural gas network, a gas stream containing hydrogen and / or hydrocarbons, fed into a natural gas network.
- the integrated system is operated in such a way that, depending on the electricity supply, the quantity and / or the composition of the gas flow fed into the natural gas grid are changed. In this way, the amount of electrical energy that is stored by generating or modifying the gas fed into the natural gas network in the form of chemical energy in the natural gas network can be adjusted.
- a surplus of electricity results if more electricity is generated from renewable energies at a time than total electricity is consumed at that time. Electricity surplus also occurs when large amounts of electrical energy are supplied from fluctuating renewable energies and throttling or shutting down power plants is associated with high costs. A power shortfall arises when comparatively small amounts of renewable energy are available and inefficient or high-cost power plants have to be operated.
- the cases of surplus power and power shortage described here can be identified in various ways. For example, the prices on the power exchanges are an indicator of the current situation, with a surplus of electricity leading to lower and a power shortfall to higher electricity prices. An electricity surplus or electricity shortage can also exist without any direct effect on the electricity price.
- the plant for electrothermic production of hydrocyanic acid depending on the electricity supply operated from the separator at least one gas stream containing hydrogen and / or hydrocarbons, the device for initiating a Gases fed into a natural gas network and fed from the device for introducing a gas into a natural gas network, a gas stream containing hydrogen and / or hydrocarbons in a natural gas network.
- the plant for electrothermic production of hydrogen cyanide preferably comprises a plurality of reactors arranged in parallel, and depending on the electricity supply, all, only a part or none of the reactors are operated.
- the reactors are operated for this purpose under constant, optimized reaction conditions and the adaptation of the plant operation to the electricity supply takes place only by shutting down or starting up reactors.
- individual or all reactors are operated at variable throughputs and correspondingly variable power consumption.
- a second embodiment of the method according to the invention for the flexible use of electricity is in an integrated system according to the invention comprising a plant for power generation, which is supplied from the separator via a line at least one gas stream containing hydrogen and / or hydrocarbons, depending on the electricity supply Amount ratio between gas from the separator of the device for introducing a gas into a Natural gas network is supplied and gas, which is supplied from the separator of the plant for power generation, changed and fed from the apparatus for introducing a gas into a natural gas network, a gas stream containing hydrogen and / or hydrocarbons in a natural gas network.
- the quantitative ratio is changed so that at a higher power supply, a larger proportion of the gas is fed into the natural gas grid.
- the gas from the separator completely or for the most part in particular more than 80%, supplied to the plant for power generation and taken at a high electricity supply, the plant for power generation out of service and the gas from the separator completely or in an average power supply for the most part, in particular more than 80%, fed into the natural gas grid.
- the second embodiment of the method according to the invention enables uniform operation of the plant for the electrothermal production of hydrocyanic acid both at medium and at high power supply, resulting in a high system utilization for this system.
- additional electrical energy can be used in the event of high electricity supply and effectively stored in the form of chemical energy in the natural gas grid.
- the gas mixture leaving the arc reactor is mixed with a hydrocarbon-containing gas or a hydrocarbon-containing liquid for cooling, wherein the type and / or amount of the gas and / or the liquid is changed depending on the electricity supply, from the resulting reaction mixture in the separation device at least one gas stream containing hydrogen and / or hydrocarbons, separated and the device for introducing a gas into a Natural gas network supplied and fed from the apparatus for introducing a gas into a natural gas network, a gas stream containing hydrogen and / or hydrocarbons in a natural gas network.
- the gaseous mixture leaving the arc reactor is treated with a larger amount of hydrocarbonaceous gas or liquid, or the nature of the gas and / or liquid is changed so that a greater part of the heat energy of the gaseous mixture leaving the arc reactor is used for endothermic splitting of components of the gas and / or the liquid.
- the hydrocarbons obtained by the endothermic cracking can be completely supplied to the apparatus for introducing a gas into a natural gas network.
- the apparatus for introducing a gas into a natural gas network can be supplied and the remainder supplied as feedstock for the production of hydrogen cyanide of the plant for the electrothermic production of hydrogen cyanide.
- the plant for electrothermic production of hydrocyanic acid is operated depending on the electricity supply and at high power supply, the ratio between gas, which is supplied from the separator of the device for introducing a gas into a natural gas network and gas, which from the Separating device of the plant is supplied to generate electricity, changed.
- the method according to the invention particularly preferably comprises the steps
- the thresholds are set depending on the actual level of the hydrocyanic acid storage or depending on the forecasts of the evolution of consumption and production of hydrocyanic acid in the next few hours. For example, if the level of the hydrocyanic acid storage tank falls to a low level, the threshold below which the output of the hydro-genic acid-producing plant of hydrocyanic acid is reduced is set to a lower value.
- the supply of electricity can be determined either directly through coordination with electricity producers and / or electricity consumers or indirectly through trading platforms and / or through OTC procedures and an associated electricity price.
- the electricity supply is determined by coordination with power generators from wind energy and / or solar energy.
- the electricity supply is determined via the electricity price on a trading platform.
- the electric power of the plant for power generation is preferably changed when exceeding the first threshold according to the surplus of electricity and falls below the second threshold, the power of the plant for electrothermic production of hydrogen cyanide accordingly changed the power penalty.
- the electric power of the plant for power generation is preferably changed to a predetermined lower value when exceeding the first threshold and below the second threshold, the power of the plant for electrothermic production of hydrogen cyanide to a predetermined changed lower value.
- the plant for the electrothermal production of hydrocyanic acid comprises a steam generator with which from the waste heat of the electrothermal process steam is generated and the plant for power generation comprises a steam turbine, which is driven by this steam.
- the device for introducing a gas into a natural gas network comprises a reservoir for hydrogen and from this reservoir hydrogen is introduced into a natural gas line, wherein the amount of hydrogen introduced in dependence on the gas flow in the natural gas line is adjusted so that the Wobbe index, the calorific value or the density of the gas in the gas pipeline or a combination of these gas properties is kept within predetermined limits.
- the introduction of the hydrogen can be regulated by measuring these gas properties in the natural gas line after the introduction of the gas to be introduced into the natural gas network.
- the device for introducing a gas into a natural gas network can also include a storage for a gas mixture of hydrogen and hydrocarbon-containing gases and from this memory, the gas mixture are introduced into a natural gas line, wherein the amount of introduced gas mixture depending on the gas flow in the natural gas line adjusted is that the Wobbe index, the calorific value or the density of the gas in the natural gas line or a combination of these gas properties is kept within predetermined limits.
- the device for introducing a gas into a natural gas network comprises separate reservoirs for hydrogen and hydrocarbon-containing gases and a device for mixing gases connected to these reservoirs.
- the apparatus for mixing gases hydrogen and hydrocarbon-containing gases are mixed, the proportion being adjusted so as to keep the Wobbe index, calorific value or density of the resulting gas mixture or a combination of these gas properties within predetermined limits.
- Hydrocarbons containing two or more carbon atoms in particular ethane, ethene, propane, propene, butane and / or butene, which have been separated off from the reaction mixture of the electrothermal production of hydrocyanic acid in the separation apparatus for removing hydrogen cyanide, are preferably used as the hydrocarbon-containing gases.
- the gas mixture resulting after adjusting the gas properties is then fed into the natural gas grid.
- the Wobbe index of the resulting gas mixture is adjusted so that the ratio of the Wobbe index of the gas fed into the natural gas network to the Wobbe index of the gas in the natural gas network is in the range of 0.9: 1 to 1: 0.9, especially Range from 0.95: 1 to 1: 0.95.
- the device for introducing a gas into a natural gas network comprises a methanation reactor for converting hydrogen with carbon dioxide or carbon monoxide to methane, wherein from the separator a hydrogen-containing gas stream is fed to the methanization reactor and methane produced in the methanation reactor into the methane Natural gas network is fed.
- the conversion of hydrogen to methane avoids the restrictions on the supply of hydrogen to a natural gas network and the gas also in a Feed in natural gas network at a location with low gas flow in the gas pipeline.
- the device for introducing a gas into a natural gas network comprises a Fischer-Tropsch reactor for converting hydrogen and carbon monoxide into hydrocarbons, wherein a hydrogen-containing gas stream is fed from the separator to the Fischer-Tropsch reactor and gaseous hydrocarbons generated in the Fischer-Tropsch reactor are fed into the natural gas grid.
- the apparatus for introducing a gas into a natural gas network comprises a hydrogenation reactor, wherein from the separator, a gas stream containing unsaturated hydrocarbons is fed to the hydrogenation reactor and saturated hydrocarbons generated in the hydrogenation reactor are fed into the natural gas network.
- This embodiment can be used particularly advantageously when the electrothermal production of hydrocyanic acid is carried out in an arc reactor, the gas mixture leaving the arc reactor for cooling is admixed with a hydrocarbon-containing gas or a hydrocarbon-containing liquid, unsaturated hydrocarbons being formed by cracking, from the resulting gas mixture a gas stream containing hydrogen and unsaturated hydrocarbons is separated and this gas stream is fed to the hydrogenation reactor.
- a gas stream containing hydrogen and unsaturated hydrocarbons is separated and this gas stream is fed to the hydrogenation reactor.
- the plant for the electrothermal production of hydrocyanic acid draws electricity from a gas-fired power plant, which is operated with gas from the natural gas grid depending on the electricity supply.
- the method according to the invention preferably comprises the steps a) setting a first threshold and a second threshold for a supply of electricity,
- the thresholds are set depending on the actual level of the hydrocyanic acid storage or depending on the forecasts of the evolution of consumption and production of hydrocyanic acid in the next few hours. For example, if the level of the hydrocyanic acid storage tank falls to a low level, the threshold below which the output of the hydro-genic acid-producing plant of hydrocyanic acid is reduced is set to a lower value.
- the supply of electricity can be determined either directly through coordination with electricity producers and / or electricity consumers or indirectly through trading platforms and / or through OTC procedures and an associated electricity price.
- the electricity supply is determined by coordination with power generators from wind energy and / or solar energy.
- the electricity supply is determined via the electricity price on a trading platform.
- the absolute magnitude of the first threshold above which power reduction of the power plant is performed is not essential to this embodiment of the present method and may be determined by economic criteria.
- the second predetermined value below which there is a reduction in the power of the plant for the electrothermal production of hydrocyanic acid.
- the first threshold and the second threshold are chosen equal.
- the electrical energy used to produce hydrogen cyanide is at least partly derived from renewable energies, particularly preferably from wind power and / or solar energy.
- renewable energies particularly preferably from wind power and / or solar energy.
- the electricity supply is calculated from the data of a weather forecast.
- the above-mentioned threshold values for an electricity supply are then preferably selected such that, on the one hand, a planned amount of hydrocyanic acid can be produced in the forecasting period.
- the present integrated plant and method are suitable for the production of hydrocyanic acid in a very economical and resource-saving manner.
- Hydrocyanic acid can be converted into many valuable intermediates, whereby a surprising reduction of carbon dioxide emissions can be achieved.
- This surprising reduction is based on several synergistic factors.
- hydrogen can be obtained at a very high power efficiency, which without release of carbon dioxide to generate electrical energy can be used.
- heat is often released during the production of the valuable secondary products. This waste heat can often be used to cover the heat demand in other parts of the process (eg distillative separation processes). Accordingly, the carbon dioxide emissions are reduced, if otherwise an oxidation of hydrocarbons to produce the process heat would be necessary.
- hydrocyanic acid produced is used to produce sodium cyanide, acetone cyanohydrin or methionine.
- FIG. 1 shows schematically the structure of an integrated system according to the invention, a plant 1 for the electrothermic production of hydrogen cyanide, a separation device 2 for the separation of hydrogen cyanide from the reaction mixture 3 of the electrothermic production of hydrogen cyanide, and a device 4 for introducing a gas into a natural gas network.
- 5 includes.
- hydrocyanic acid is generated from a hydrocarbon-containing starting material, which is supplied via a line or a conveying member 14.
- Suitable hydrocarbon-containing starting materials are natural gas and lower hydrocarbons, in particular C 2 -C 4 -hydrocarbons. Nitrogen and ammonia are suitable as nitrogen-containing starting material.
- electrical power from a power grid 16 is obtained via a power line.
- the reaction mixture 3 obtained in the electrothermal production of hydrocyanic acid is fed to a separator 2 in which hydrogen cyanide is separated from the reaction mixture and obtained via a line 17 as a product.
- hydrogen and optionally hydrocarbons, and other components, such as carbon black and sulfur-containing compounds are separated.
- Hydrogen and hydrocarbons can be obtained in the separator in the form of a gas stream containing hydrogen and hydrocarbons.
- the apparatus 4 for introducing a gas into a natural gas network additionally comprises a hydrogen storage 8, a hydrocarbon-containing gas storage 9 and a gas mixing apparatus 10, with the hydrogen, hydrocarbon gas and optionally Other gases can be mixed so that a gas stream can be introduced with a targeted composition via the connecting line 18 into the natural gas network 5.
- the integrated system also comprises a plant 1 1 for power generation, which is supplied from the separator 2 via a line 12, a gas stream containing hydrogen and / or hydrocarbons.
- electricity is generated from the gases. This can be done via a combustion process, preferably in a gas and steam power plant, in which electricity is generated by gas and steam turbines. Alternatively, fuel cells can also be used to generate electricity from hydrogen and / or hydrocarbon-containing gas.
- the power generated in the plant 1 1 for power generation can be supplied via the power lines 19 and 15 of Appendix 1 for the electrothermal production of hydrogen cyanide and used for the electrothermal production of hydrocyanic acid.
- the power generated in the plant 1 1 for power generation can also be fed into the power grid 16, in particular if the plant 1 for electrothermic production of hydrogen cyanide is out of order or consumes less power than is generated in the plant 1 1 for power generation.
- hydrogen and / or hydrocarbons can also from the memories 8 and / or 9 of the device 4 for Introduction of a gas in a natural gas network of the plant 1 1 are supplied to generate electricity.
- the plant 1 1 for power generation can also be supplied with additional fuel via a device not shown in Figure 1.
- the integrated system additionally comprises a steam generator (not shown) in the plant 1 for the electrothermal production of hydrogen cyanide, a steam turbine (not shown) in the plant 1 1 for power generation, and a steam line 13, with the in steam supplied to the steam generator is supplied to the steam turbine.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Power Engineering (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013209882.0A DE102013209882A1 (de) | 2013-05-28 | 2013-05-28 | Integrierte Anlage und Verfahren zum flexiblen Einsatz von Strom |
PCT/EP2014/058777 WO2014191147A1 (de) | 2013-05-28 | 2014-04-30 | Integrierte anlage und verfahren zum flexiblen einsatz von strom |
Publications (1)
Publication Number | Publication Date |
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EP3003982A1 true EP3003982A1 (de) | 2016-04-13 |
Family
ID=50732114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP14724342.2A Withdrawn EP3003982A1 (de) | 2013-05-28 | 2014-04-30 | Integrierte anlage und verfahren zum flexiblen einsatz von strom |
Country Status (6)
Country | Link |
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US (1) | US20160122194A1 (ja) |
EP (1) | EP3003982A1 (ja) |
JP (1) | JP2016521668A (ja) |
AR (1) | AR096420A1 (ja) |
DE (1) | DE102013209882A1 (ja) |
WO (1) | WO2014191147A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US10337110B2 (en) | 2013-12-04 | 2019-07-02 | Covestro Deutschland Ag | Device and method for the flexible use of electricity |
US9915399B1 (en) * | 2017-04-18 | 2018-03-13 | Air Products And Chemicals, Inc. | Control system in a gas pipeline network to satisfy demand constraints |
US20220127209A1 (en) * | 2019-01-15 | 2022-04-28 | Sabic Global Technologies B.V. | Use of renewable energy in olefin synthesis |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2899275A (en) | 1959-08-11 | Manufacture of hydrocyanic acid | ||
GB780080A (en) | 1953-10-19 | 1957-07-31 | Knapsack Ag | Manufacture of hydrogen cyanide |
US2997434A (en) | 1958-11-19 | 1961-08-22 | Knapsack Ag | Process for preparing hydrogen cyanide |
US3674668A (en) * | 1969-02-24 | 1972-07-04 | Phillips Petroleum Co | Electric arc process for making hydrogen cyanide, acetylene and acrylonitrile |
US4144444A (en) | 1975-03-20 | 1979-03-13 | Dementiev Valentin V | Method of heating gas and electric arc plasmochemical reactor realizing same |
US5470541A (en) | 1993-12-28 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Apparatus and process for the preparation of hydrogen cyanide |
EP0742781B1 (en) | 1994-02-01 | 2004-09-29 | INVISTA Technologies S.à.r.l. | Preparation of hydrogen cyanide |
CA2271448A1 (en) * | 1999-05-12 | 2000-11-12 | Stuart Energy Systems Inc. | Energy distribution network |
EP1459399A2 (en) * | 2001-12-21 | 2004-09-22 | Nuvera Fuel Cells | Fuel processor modules integration into common housing |
DE10317197A1 (de) | 2003-04-15 | 2004-11-04 | Degussa Ag | Elektrisch beheizter Reaktor und Verfahren zur Durchführung von Gasreaktionen bei hoher Temperatur unter Verwendung dieses Reaktors |
US20070020173A1 (en) * | 2005-07-25 | 2007-01-25 | Repasky John M | Hydrogen distribution networks and related methods |
EP1829820A1 (en) * | 2006-02-16 | 2007-09-05 | Sociedad española de carburos metalicos, S.A. | Method for obtaining hydrogen |
US8814983B2 (en) * | 2009-02-17 | 2014-08-26 | Mcalister Technologies, Llc | Delivery systems with in-line selective extraction devices and associated methods of operation |
DE102009018126B4 (de) * | 2009-04-09 | 2022-02-17 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg | Energieversorgungssystem und Betriebsverfahren |
DE102010017027B3 (de) * | 2009-10-23 | 2011-06-22 | Erdgas Südwest GmbH, 76275 | Verfahren zum Betrieb von Anlagen zur Erzeugung von anthropogenen und/oder biogenen, methanhaltigen Gasen am Erdgasnetz |
AU2013363314A1 (en) * | 2012-12-18 | 2015-07-30 | Invista Technologies S.A.R.L. | Apparatus and method for hydrogen recovery in an Andrussow process |
-
2013
- 2013-05-28 DE DE102013209882.0A patent/DE102013209882A1/de not_active Withdrawn
-
2014
- 2014-04-30 US US14/893,528 patent/US20160122194A1/en not_active Abandoned
- 2014-04-30 EP EP14724342.2A patent/EP3003982A1/de not_active Withdrawn
- 2014-04-30 JP JP2016515688A patent/JP2016521668A/ja active Pending
- 2014-04-30 WO PCT/EP2014/058777 patent/WO2014191147A1/de active Application Filing
- 2014-05-26 AR ARP140102068A patent/AR096420A1/es unknown
Also Published As
Publication number | Publication date |
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WO2014191147A1 (de) | 2014-12-04 |
US20160122194A1 (en) | 2016-05-05 |
JP2016521668A (ja) | 2016-07-25 |
AR096420A1 (es) | 2015-12-30 |
DE102013209882A1 (de) | 2014-12-04 |
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