WO2009116868A1 - Process for the use of alkali metal or alkali earth metal containing organic materials and composites in the microwave-assisted plasma decomposition of said compounds for the production of syngas - Google Patents

Process for the use of alkali metal or alkali earth metal containing organic materials and composites in the microwave-assisted plasma decomposition of said compounds for the production of syngas Download PDF

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Publication number
WO2009116868A1
WO2009116868A1 PCT/NO2009/000059 NO2009000059W WO2009116868A1 WO 2009116868 A1 WO2009116868 A1 WO 2009116868A1 NO 2009000059 W NO2009000059 W NO 2009000059W WO 2009116868 A1 WO2009116868 A1 WO 2009116868A1
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Prior art keywords
composite material
plasma
previous
carbon
carboxyl
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PCT/NO2009/000059
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French (fr)
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Atie Mundheim Ylikangas
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Co2Co
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Priority claimed from NO20080915A external-priority patent/NO20080915L/en
Application filed by Co2Co filed Critical Co2Co
Publication of WO2009116868A1 publication Critical patent/WO2009116868A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122Incoherent waves
    • B01J19/126Microwaves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0875Gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0892Materials to be treated involving catalytically active material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to a method for resolving organic material and/or manufacturing synthetic gas, as it appears in claim 1.
  • the invention also relates to a composite material and a method for manufacturing for use in the abovementioned method.
  • the invention deals in particular with the manufacturing of carbon based composite material which can initiate the generation of plasma conditions under the influence of microwaves, whereby synthesis gas is produced as indicated in the introduction to the following patent claim 3.
  • the invention aims for a utilization of the synthesis gas generated from the carbon containing composite material by microwave generated plasma according to the invention.
  • the invention deals with the technology that has to do with an energy efficient way of generating plasma with high internal plasma temperature in the size order of 3-9000 degrees Celsius, whereby this may be used for decomposing or splitting organic materials and gases.
  • organic materials which may be treated using the method according to the present invention is meant a material which at the starting point can be incinerated at contact with air.
  • organic waste materials wood, charcoal, fossil coal, peat, peat moss and cellulose.
  • the invention further deals with the technology that has to do with decomposing organic materials/gases and converting the decomposed products into energy with minimum emission of nitrous fumes NOx, carbon dioxide CO 2 or carbon monoxide CO into the air.
  • the invention also deals with the technology that has to do with converting CO 2 captured from flue gas from traditional energy production, or being able to recycle CO 2 from own production, converting this to CO and using it in new energy production in repeated cycles.
  • the invention also deals with the technology that has to do with converting organic material and/or waste into CO 2 neutral or CO 2 negative energy. This means that CO 2 emissions are highly unwanted.
  • the invention also deals with the technology that has to do with converting organic sludge from water cleaning processes to CO 2 neutral or CO 2 negative energy.
  • the invention also deals with the technology that uses synthesis gas in fuel cells, gas turbines, and for production of methanol and ethanol.
  • the invention also deals with the technology that has to do with the destruction of toxic links in organic raw materials at high temperature combustion.
  • Plasma Arc method and the “Plasma Torch” method. Both have a basis of plasma being induced by subjecting an anode and a cathode with a certain internal distance to very high voltage.
  • the "Plasma Arc” method carries out the combustion using a "welding” principle, where a plasma arc forms very high temperatures over time in the combustion chamber and thermally oxidizes the combustion material, while simultaneously a carbon cathode is used in a manner corresponding to a welding pin during welding.
  • This reaction may be carried out by having the anode/cathode placed in pollution containing remains from the reaction in the form of oxide slag.
  • the "Plasma Torch” method induces plasma to the gas between the anode and the cathode, either directly between the anode/cathode or by leading the cathode in a slag mixture with pollution.
  • Both methods result in full combustion of the organic material, with CO 2 and H 2 O as the main residual product. Both methods are known to use the residual product for production of synthesis gas, as well as CO gases and H 2 in further well-known process steps.
  • microwave technology can be used to induce plasma from carbon sources for the appliance of coating on a substratum base in known PVD/CVD processes. These processes take place in an inert atmosphere in a chamber where microwaves are processed (fed) into the chamber from the outside through a crystal glass. Different fumes and conditions such as pressure and temperature control the coating process in the inert atmosphere where no combustion takes place.
  • the known features of this method are unfit for use in generating plasma for energy production, which is the aim of the present invention, as it is developed for other purposes. The whole process differs significantly from the present invention.
  • Microwaves are electromagnetic waves whose wavelengths are longer than the wavelengths of infrared light, but shorter than those of radio waves.
  • the wavelength of microwaves is in the area of 30 centimeters (frequency: 1 GHz) to 1 millimeter (frequency: 300 GHz).
  • the microwave area includes "ultra-high frequency” (UHF, 0.3-3 GHz), “superhigh frequency” (SHF, 3-30 GHZ), and “extremely high frequency” (EHF, 30-300 GHz).
  • microwaves are used within a frequency area of 2450 MHz: the added heating effect, which has been used in the following tests, is typically 600 watts and up.
  • the last-mentioned parameters are applicable for the present invention, but in industrial plants one could also move outside the distinct microwave area and still accomplish the same effect.
  • US-3.850.588 mentions production of synthesis gas that is enriched with carbon monoxide. It is produced by feeding a mixture of carbon dioxide and an organic material into a reaction zone which is kept at a temperature of 1000 to 3000 degrees Fahrenheit (approximately 600 to 1700 degrees Celsius).
  • Suitable organic materials are connections of carbon, hydrogen and oxygen where the oxygen content is at least 10 weight %.
  • Alkaline metal carbonates catalyze the reaction. However, this process produces no plasma, which is necessary for the use of the present invention. The process is driven by temperature. The added alkaline metal carbonates improve the process at infusion of oxygen, as well as by having the alkaline metal in the mentioned processes lowering the threshold value for binding strength between the singular and especially the double compounds of the elements of H, C and O that are included in the process described in US-3.850.588.
  • alkaline metal ions are brought directly to plasma, with an inner plasma temperature of approx. 3500 degrees Celsius as a direct cause of the added microwave energy directly energizing the electron(s) of the alkaline metal so that separation of (COOH)n immediately enters at a very low surrounding temperature as a result of influence from alkaline metals in plasma condition.
  • the abovementioned two reactions are further catalyzed at an inner increase in temperature at C caused by the high ability of C to adsorb the applied microwave rays, because all kinetic reactions happen more easily at higher temperatures.
  • the alkaline metals of group I comprise the metals lithium, sodium, potassium, rubidium, cesium and francium.
  • the earth alkaline metals in group Il comprise beryllium, magnesium, calcium, strontium, barium and radium.
  • the composite material with a binding agent included so that the material may be in solid form, such as flakes, granulate, or powder.
  • a binding agent included so that the material may be in solid form, such as flakes, granulate, or powder.
  • COOH hydrocolloid
  • alkaline metals that remain in ash residue after separation of organic material may be regenerated and reused.
  • the method according to claim 1 is characterized in that the organic material is placed in a chamber and exposed to microwave radiation to produce plasma separation of the material. Preferred embodiments are evident from claims 2-5.
  • the method according to claim 6 is characterized by having one or more alkaline metals from main group I or Il in the periodic table added to carbon-containing material, where the preferred metal is cesium, sodium preferably as a hydroxide compound or carbonates or bicarbonates, but where also silicone (Si) may be included as the only metal not in main group I and II. Preferred executions are evident from claims 8-12.
  • the composite material is distinguished by a mixture of one or more alkaline metals from main group I or Il in the periodic table and a carbon-containing material.
  • the alkaline metal is cesium, sodium, potassium, preferably as hydroxide or carbonates or bicarbonates, as also silicone (Si) may also be included, as the only metal not in main group I or II. Preferred executions in claims 14-20.
  • a carbon/carboxyl/-alkaline metal-containing composite material which is suitable for exposure to microwaves in order to form plasma at very low energy supply, where the main components are carbon, wherein one or more alkaline metals hydroxide or carbonates or bicarbonates are added, as well as a carboxyl-containing compound and wherein also water/liquid or a binding agent may be included so that the material may be in the form of powder, granulate, flakes, solids or as a slurry, for the purpose of the material producing plasma under the influence of microwaves in an atmosphere or in a stream of CO 2 , or by adding O 2 whereby carbon is also added from the composite material and C thereby forms the desired CO from split O 2 in CO 2 or splits the added O 2 .
  • a use for the composite material is also achieved where it is subjected to microwave energy which transforms this into plasma for production of synthesis gas for use in further energy/methanol/ethanol production, or for operation of machinery.
  • the present invention there has also been produced a method and use for the composite material for the reuse and recycling of CO 2 .
  • the invention is characterized by using one or more naturally fine particular or ground carbon-containing materials, preferably with a particle size of less than 1000 micron, but far larger particle sizes and clumps may be used.
  • Pure mineral coal or charcoal is preferred, but most other materials rich in carbon may also be used, such as peat, peat moss, sawdust, soy bean flour, corn or other vegetable carbon-containing species, dried grass, carbon-containing sludge and similar.
  • the invention is further characterized by mixing the carbon material with a carboxyl- containing compound.
  • a carboxyl- containing compound typically, this would be carboxyl acid, organic material with a high content level of carboxyl, such as hydrocolloid, pectin from fruit waste, or a material with a sufficient amount of both carbon and carboxyl, such as peat moss, which can be used as it is, without further additions.
  • the invention is further characterized by having one or more alkaline metals mixed in, preferably as hydroxide dissolved in liquid.
  • alkaline metals mixed in, preferably as hydroxide dissolved in liquid.
  • the most reactive metals with the lowest electron compound are usually preferred, such as cesium, sodium and potassium, but in principle all alkaline metals may be used in order for the process to work.
  • carboxyl and alkaline metal may be mixed in advance.
  • sodium, cesium and potassium formate which is formic acid neutralized to an alkaline solution with an alkaline metal.
  • Na-alginate has carboxyl and 7% alkaline metal (Formula: Na(C 6 H 9 O 7 ). If the carbon content of the sludge is high enough, the dehydrated/dried sludge may be brought to plasma without further addition of reactive components.
  • the invention is characterized by using the composite material as described above as powder, granulate, in flake form, sludge or solid form.
  • the invention is characterized by having the composite material as described above in dry form or having a liquid/water content of up to 95 %, where the preferred content level of dry material is 40-60 %.
  • the invention is further characterized by the method for producing the composite material as granulate, flakes or solid shape being generated by an addition of hydrocolloid which is driven to bind with carbon, and then reacted by cross-binding with hydrocolloid, where this is reacted in a liquid water into gel, which is dehydrated/dried/hardened.
  • the invention is further characterized by the content of CO 2 donors in the composite material being regulated by need in the applied process.
  • the content of possible CO 2 donors is regulated by adding NaCO 3 , Na 2 C O 3 , NaHCO 3 or CaCO 3 to the composite material.
  • the invention is further characterized by placing the composite material in a chamber where it is exposed to microwaves, whereby these put the alkaline metal electrons into motion, with very low energy input.
  • carbon absorbs microwaves very well, and is heated. Heat further escalates the electrons of alkaline metal.
  • alkaline metal is easily transformed into plasma.
  • glow temperature for alkaline metal is much lower than for carbon, the carbon also plays a part in the alkaline metal reaching this temperature quickly.
  • plasma begins at a very low temperature in alkaline metal, this triggers the compounds of carboxyl to break, and CO and O and H are liberated and can further contribute to plasma.
  • These components start the plasma separation of carbon, and the plasma process will typically be steady already at 100 degrees Celsius.
  • Alkaline metals function as a trigger for the plasma process, after which carboxyl separates and initiates carbon separation. Plasma arises, and the energy input may be reduced as long as the process is kept continuous.
  • the invention is further characterized by the produced plasma converting CO 2 into CO, and H 2 appearing from added CH n or H 3 O or hydrocarbon in the composite material.
  • the invention is further characterized by the fact that a separation of organic material using the present invention can thermally break down organic material as plasma in the process stays at a temperature in the size order of 3500-5000 degrees Celsius, by placing the process in a chamber with material to be incinerated, and recycling CO 2 , with extracting of CO for the syngas process.
  • the invention is further characterized by having only composite material, subjected to microwave technology, infused with CO 2 and water, be sufficient for production of synthesis gas.
  • the invention is also characterized by injecting O 2 in order to create a gasification process.
  • the invention is also characterized by a measured amount of pure carbon, inert atmosphere, addition of COOH and alkaline metal in the form of silicone silicate being able to apply think film coat of SI on substrate placed in the plasma used in known PVD PPVD processes (Plasma Vapor Deposition/Puls Plasma Vapor Deposition): Advantages of the present new method
  • the present invention distinguishes itself from existing plasma technologies by using very little energy. Very little needs to be introduced for the alkaline metals to become plasma, especially with help from surrounding heat from carbon.
  • the accelerating help caused by carboxyl causes the whole composite material to become plasma using much less energy than other technologies are able to.
  • the alkaline metal remains in the carbon composite and is now at a temperature so high that the carbon reaches explosive plasma separation. Thus very little energy is needed to keep the process going. It actually does not take much more energy than what it takes to keep the alkaline metal electrons in an energized state, and they will keep the process going. Thus the energy balance can be counted from a starting temperature of just below 100 degrees Celsius, versus the regular plasma starting temperature for carbon of 3000 degrees Celsius.
  • the present invention distinguishes itself from existing plasma technologies for the production of synthesis gas and separation of organic material, by the fact that CO 2 can be separated into CO, and CO may be used in synthesis gas or water change process with surplus energy.
  • the present invention uses alkaline metals as an aid in order to have low microwave energy run the process, by having the electrons of the alkaline metals set in the necessary motions to easily be brought to an energized state.
  • Alkaline metals are easily recyclable, as there is complete combustion of organic material.
  • a binding agent in the form of hydrocolloid reacted with alkaline metal the composite material can be adjusted to the process.
  • the composite material used may be dry or moist.
  • the plasma process supplies necessary carbon to CO 2 in the conversion of this when it passes through the plasma field.
  • the invention makes room for CO production of CO 2 and continuous recycling of CO 2 as raw material for synthesis gas rather than releasing it into the air.
  • the invention can produce synthesis gas without releasing NOx.
  • the invention can, by capturing CO 2 , recycle CO 2 for hydrogen production.
  • the invention may be adjusted for recycling CO 2 in a closed process by adding CO 2 donors as carbonates and bicarbonates in the composite material.
  • the utilization of the invention includes separation of organic material as well as waste, in a utilization where CO 2 from other industry processes can be fed as process gas and again be used for synthesis gas, or that O 2 can also be used as well in a gasification process.
  • the present invention is distinguished by processing CO 2 through a plasma field for conversion into CO, where the plasma field is generated by microwaves applied to composite material of carbon-containing organic material, carboxyl and alkaline metal.
  • Figure 1 shows a principle sketch for the use of the composite material in a microwave plasma process.
  • FIG. 2 shows in more detail a reactor for use in the present invention, namely:
  • FIG. 2 shows a sketch of how a reactor which can be used in the process of the present invention may be constructed.
  • the reactor is shown by 10 as a closed container.
  • a generator unit that can impress microwaves on the carbon/metal ion-containing material is shown at 30, surrounding the reactor container.
  • the inlets 12, 14 show how carbon/metallic ion-containing material and carbon dioxide are supplied to the container.
  • a draining wire for outtake of gases and charcoal dust (nano coal).
  • an outlet 24 for extraction of sludge, meaning ashes in the form of metal oxides of alkaline and earth alkaline metals (and, optionally) silica SiO 2 .
  • a cooling spiral 16 is placed inside the reactor chamber in order to contribute to the cooling of the gases to temperatures lower than the re-reaction temperatures.
  • alkaline/earth alkaline metal-containing material or silicone-containing material
  • plasma is formed with very high point temperatures in the area shown at around 20, meaning centrally inside the reactor. This is the area where the mentioned splitting of materials to atomic elements happens. And with a quick cooling off adjacent to the plasma area, one avoids re-combinations in the suitable time span so that for instance atomic carbon (nano coal) may be extracted from the reactor area, for instance through the outlet 18.
  • T2 temperature of surroundings (20° C (293.K)
  • Net energy surplus will then be 253,174 kJ.
  • the composite material is brought to plasma at a starting temperature below 100 degrees, whereupon the catalytic effect from alkaline metal drives carboxyl to plasma with a large catalytic effect, upon which the two components drive carbon to bind with separated O from CO 2 in plasma or with O extracted from carboxyl or carbon-containing material or added O.
  • Input to get plasma is the energy that it takes to bring alkaline metal electrons to an energized state, meaning the plasma temperature in the energy consideration must be calculated from 100 degrees Celsius as this is the starting temperature for driving the 3 step catalysis process alkaline metal, carboxyl, carbon in plasma by adding microwave energy.
  • this will give a total theoretical energy input of 175.784 kJ/mol versus 312.826 kJ/mol without the catalysis effect according to the invention. This means a reduction of energy input of 56.19 % as a result of the catalysis effect achieved by the composite material according to the invention.
  • the microwave oven was set to 900W and switched on, and, surprisingly, plasma was immediately formed in the oven, and all organic material decomposed at combustion/plasma. Only inorganic material remained as ashes.
  • Test 3 Na-alginate from test 1 and 2 was attempted replaced with NaOH, then Na carbonate and then bicarbonate. It was not possible to bring the composite materials to plasma in the microwave oven.
  • Coal and caesium formate (formic acid neutralized with CeCo 3 with a total water content of 40%) was attempted mixed, and plasma formation took place with very little mixing of formate was immediately noted.
  • Soy bean flour and Na-formate was mixed into a paste, which was then exposed to microwaves. This immediately turned to plasma and was completely incinerated.
  • a microwave oven with 2,45 GHz wave length and controlled feed and CO2 atmosphere for combustion was used in further tests with coal and alkaline metal and carboxyl and varying amounts of water content. Temperature feeler in the chamber was available for continuous observation, and the GC (gas chromatograph) was hooked on the flue gas outlet for detection of gas peaks and gas measuring. The tests were carried out with control of weight of composite material before and after the process. The tests were done from surrounding temperature of 450 degrees Celsius, whereby the process was stopped.
  • Gas peak took place in all cases with Na present as alkaline metal at a temperature below 100 degrees. By using caesium as alkaline metal, gas peak was read at below 60 degrees. At 450 degrees, approx. 30 % of organic material was decomposed. Flue gases were H2 and Co, and approximately no CO2, and thereby reforming in plasma was confirmed with the help of multistep catalysis effect from the components of the composite material.

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Abstract

A method for decomposing organic material and/or producing synthesis gas is disclosed, and it is characterized by the organic material being placed in a chamber and subjected to microwave radiation in order to produce plasma decomposition of the material, and especially used is organic composite material of carbon, carboxyl and alkaline metal, in dry form or with a liquid, of which at least one of the aforementioned components contains hydrogen. The invention also relates to a composite material as well as the production thereof, as well as a number of uses for the method and the material. The invention is particularly used in a process for recycling CO2, as well as combustion of organic material.

Description

Process for the use of alkali metal or alkali earth metal containing organic materials and composites in the microwave-assisted plasma decomposition of said compounds for the production of syngas
The present invention relates to a method for resolving organic material and/or manufacturing synthetic gas, as it appears in claim 1.
The invention also relates to a composite material and a method for manufacturing for use in the abovementioned method.
It also relates to uses of the method as indicated in the introduction.
The invention deals in particular with the manufacturing of carbon based composite material which can initiate the generation of plasma conditions under the influence of microwaves, whereby synthesis gas is produced as indicated in the introduction to the following patent claim 3.
The invention aims for a utilization of the synthesis gas generated from the carbon containing composite material by microwave generated plasma according to the invention.
The invention deals with the technology that has to do with an energy efficient way of generating plasma with high internal plasma temperature in the size order of 3-9000 degrees Celsius, whereby this may be used for decomposing or splitting organic materials and gases.
By organic materials which may be treated using the method according to the present invention is meant a material which at the starting point can be incinerated at contact with air. Examples include organic waste materials, wood, charcoal, fossil coal, peat, peat moss and cellulose.
The invention further deals with the technology that has to do with decomposing organic materials/gases and converting the decomposed products into energy with minimum emission of nitrous fumes NOx, carbon dioxide CO2 or carbon monoxide CO into the air.
The invention also deals with the technology that has to do with converting CO2 captured from flue gas from traditional energy production, or being able to recycle CO2 from own production, converting this to CO and using it in new energy production in repeated cycles. The invention also deals with the technology that has to do with producing hydrogen and carbon monoxide. These fumes are flammable when in contact with air, and are used in different processes. (Syngas=synthesis gas).
The invention also deals with the technology that has to do with converting organic material and/or waste into CO2 neutral or CO2 negative energy. This means that CO2 emissions are highly unwanted.
The invention also deals with the technology that has to do with converting organic sludge from water cleaning processes to CO2 neutral or CO2 negative energy.
The invention also deals with the technology that uses synthesis gas in fuel cells, gas turbines, and for production of methanol and ethanol.
The invention also deals with the technology that has to do with the destruction of toxic links in organic raw materials at high temperature combustion.
Known methods that are used today.
In connection with combustion of organic material in order to produce energy there are presently two main principles when it comes to combustion of plasma. These are the
"Plasma Arc" method and the "Plasma Torch" method. Both have a basis of plasma being induced by subjecting an anode and a cathode with a certain internal distance to very high voltage.
The "Plasma Arc" method carries out the combustion using a "welding" principle, where a plasma arc forms very high temperatures over time in the combustion chamber and thermally oxidizes the combustion material, while simultaneously a carbon cathode is used in a manner corresponding to a welding pin during welding. This reaction may be carried out by having the anode/cathode placed in pollution containing remains from the reaction in the form of oxide slag.
The "Plasma Torch" method induces plasma to the gas between the anode and the cathode, either directly between the anode/cathode or by leading the cathode in a slag mixture with pollution.
Both methods result in full combustion of the organic material, with CO2 and H2O as the main residual product. Both methods are known to use the residual product for production of synthesis gas, as well as CO gases and H2 in further well-known process steps.
The limitations and disadvantages of using these methods for combustion are that an extremely high consumption of electricity is required, and that CO2 is formed. The methods are not profitable for energy production unless combustion of waste is the main purpose. The production of syngas into energy is a cost reducing factor in which case the cost of handling waste is reduced.
It is also known that microwave technology can be used to induce plasma from carbon sources for the appliance of coating on a substratum base in known PVD/CVD processes. These processes take place in an inert atmosphere in a chamber where microwaves are processed (fed) into the chamber from the outside through a crystal glass. Different fumes and conditions such as pressure and temperature control the coating process in the inert atmosphere where no combustion takes place. The known features of this method are unfit for use in generating plasma for energy production, which is the aim of the present invention, as it is developed for other purposes. The whole process differs significantly from the present invention.
Microwaves are electromagnetic waves whose wavelengths are longer than the wavelengths of infrared light, but shorter than those of radio waves. The wavelength of microwaves is in the area of 30 centimeters (frequency: 1 GHz) to 1 millimeter (frequency: 300 GHz). The microwave area includes "ultra-high frequency" (UHF, 0.3-3 GHz), "superhigh frequency" (SHF, 3-30 GHZ), and "extremely high frequency" (EHF, 30-300 GHz).
According to the present invention, microwaves are used within a frequency area of 2450 MHz: the added heating effect, which has been used in the following tests, is typically 600 watts and up. The last-mentioned parameters are applicable for the present invention, but in industrial plants one could also move outside the distinct microwave area and still accomplish the same effect.
From US patent document 4.190.636 it is known that using the "Plasma Arc" method to produce plasma, with subsequent current of CO2 gas through induced plasma, where CO2 gas was mixed with charcoal powder which followed the CO2 stream through the plasma zone, achieved conversion of as much as 99% CO2 conversion to CO at the reaction CO2 + C -> 2CO reacted with plasma arc.
It can be calculated theoretically and is also referred to in the mentioned patent that the optimal addition of carbon/charcoal source is 0.54 g/l CO2. Tests using "Plasma Arc" shows that energy consumption for processing charcoal dust/CO2 through plasma for conversion into CO was 27 kWh for a 90-95 % conversion of 9 m3 CO2 to CO.
It is common knowledge that CO2 becomes CO at 1000 degrees Celsius.
For the production of synthesis gases (syngas) for energy production from a combustion process it is known that this occurs at the reaction pattern: C + O2 "» CO2
CO2 + C -» 2CO
C + H2O -» CO + H2
It is further known that for fuel cells the following reaction takes place where hydro carbon, generally CnHm is converted with H2O (water) with the following reaction pattern:
CnHm + nH20 * nC0+ (m/2 + n) H2
CO + H2O -» CO2 + H2
Further, it is known that CO, with added water vapor, can produce additional H2 from the water split reaction:
CO + H2O -> CO2 + H2
Furthermore, we refer to the publications US 2007/0084308, US-3.850.588, US-5.266.175 and WO2005/007565.
For example, US-3.850.588 mentions production of synthesis gas that is enriched with carbon monoxide. It is produced by feeding a mixture of carbon dioxide and an organic material into a reaction zone which is kept at a temperature of 1000 to 3000 degrees Fahrenheit (approximately 600 to 1700 degrees Celsius).
Suitable organic materials are connections of carbon, hydrogen and oxygen where the oxygen content is at least 10 weight %. Alkaline metal carbonates catalyze the reaction. However, this process produces no plasma, which is necessary for the use of the present invention. The process is driven by temperature. The added alkaline metal carbonates improve the process at infusion of oxygen, as well as by having the alkaline metal in the mentioned processes lowering the threshold value for binding strength between the singular and especially the double compounds of the elements of H, C and O that are included in the process described in US-3.850.588.
In the present invention, alkaline metal ions are brought directly to plasma, with an inner plasma temperature of approx. 3500 degrees Celsius as a direct cause of the added microwave energy directly energizing the electron(s) of the alkaline metal so that separation of (COOH)n immediately enters at a very low surrounding temperature as a result of influence from alkaline metals in plasma condition. The abovementioned two reactions are further catalyzed at an inner increase in temperature at C caused by the high ability of C to adsorb the applied microwave rays, because all kinetic reactions happen more easily at higher temperatures. It is a purpose of the invention to produce a new composite material that includes a carbon source, where the material, under the influence of microwave radiation, can produce plasma and complete plasma separation of all organic material by adding far less energy than what the known industrial methods for carbon plasma use, and where the added energy is much lower than the energy released by the process.
Furthermore it is an aim of the invention to produce a new composite material containing carbon where carboxyl is also included.
It is furthermore an aim of the invention to produce a composite material of carbon where also an alkaline metal or earth alkaline metal from main group I or Il of the periodic table is included.
The alkaline metals of group I comprise the metals lithium, sodium, potassium, rubidium, cesium and francium.
The earth alkaline metals in group Il comprise beryllium, magnesium, calcium, strontium, barium and radium.
It is furthermore an aim of the invention to produce a new composite material where the plasma reaction, as a consequence of the influence of microwaves, takes place in a stream of only CO2 atmosphere, whereby reacted carbon is included as an addition in the reaction:
CO2 + C -» 2CO
in the optimal mixture so that CO for further synthesis gas process is achieved from added CO2 stream after all CO2 is processed through the induced high temperature plasma with following conversion of CO2 into CO.
It is furthermore an aim of the invention to produce the mentioned composite material in the form of powder for dosing in the processed stream of CO2 through a microwave chamber where plasma is induced as a result of the dosed composite material.
It is also an aim of the invention to produce the composite material with a binding agent included so that the material may be in solid form, such as flakes, granulate, or powder. Preferably by then using hydrocolloid (COOH)n converted with mono- or multivalent ions as a binding agent.
It is also an aim of the invention to include water and/or liquid in the composite material so that H2 in the plasma chamber is produced by the reaction H2O + C -> H2 + CO. It is an aim of the invention to be able to add the composite material as slurry of carbon- containing materials, carboxyl and water and dissolved alkaline metal preferably as hydroxide, and also slurry where alkaline metal formate is added to carbon-containing materials.
In addition to the use of CO2 it is also an aim of the invention to simultaneously be able to add rich hydrogen gas to plasma produced by the composite material so that the reaction
CHn + CO2 -» 72 h2 + 2CO
appears as a partial reaction which enriches the synthesis gas.
It is also an aim of the invention to be able to include a CO2 generating substrate in the composite material to compensate for an O deficiency in a closed process system. Then with O added, bound to an alkaline metal such as carbonate or bicarbonate.
It is also an aim of the invention to be able to make synthesis gas to be used for conversion into energy in gas turbines, fuel cells, or for production of methanol/ethanol, or for hydrogen production, or for energy for propulsion of machinery.
It is also an aim of the invention to be able to use CO2 intercepted from other energy production by processing such CO2 to plasma according to the invention, and converting this to CO in a hydrogen-containing synthesis gas, for use in methanol/ethanol production or for new energy production with known technology.
It is an aim of the invention to use CO2 repeated times where this is recycled through plasma produced according to the invention, converted to CO, used in synthesis gas from where energy is extracted, where the remaining end product discharge is CO2, which is recycled. Then in a process where the residue as a consequence of adding carbon to the composite material is extracted as methanol/ethanol.
It is also an aim of the invention that the alkaline metals that remain in ash residue after separation of organic material may be regenerated and reused.
It is furthermore an aim of the invention to produce a use for gasification of organic material, waste and sludge where O2 is also added.
It is also an aim of the invention to use this to produce synthesis gas from material present in nature which includes one or more of the components carbon, carboxyl or alkaline metal, where the missing components are added. It is also an aim of the invention to use composite material to thin film silicon plasma coating/puls plasma coating of solar cell panels by using an alkaline silicate as alkaline metal addition.
The method according to claim 1 is characterized in that the organic material is placed in a chamber and exposed to microwave radiation to produce plasma separation of the material. Preferred embodiments are evident from claims 2-5.
The method according to claim 6 is characterized by having one or more alkaline metals from main group I or Il in the periodic table added to carbon-containing material, where the preferred metal is cesium, sodium preferably as a hydroxide compound or carbonates or bicarbonates, but where also silicone (Si) may be included as the only metal not in main group I and II. Preferred executions are evident from claims 8-12.
The composite material is distinguished by a mixture of one or more alkaline metals from main group I or Il in the periodic table and a carbon-containing material.
According to a preferred execution of the composite material, the alkaline metal is cesium, sodium, potassium, preferably as hydroxide or carbonates or bicarbonates, as also silicone (Si) may also be included, as the only metal not in main group I or II. Preferred executions in claims 14-20.
The applications appear in claims 21-30.
According to the present invention there is hereby produced a carbon/carboxyl/-alkaline metal-containing composite material which is suitable for exposure to microwaves in order to form plasma at very low energy supply, where the main components are carbon, wherein one or more alkaline metals hydroxide or carbonates or bicarbonates are added, as well as a carboxyl-containing compound and wherein also water/liquid or a binding agent may be included so that the material may be in the form of powder, granulate, flakes, solids or as a slurry, for the purpose of the material producing plasma under the influence of microwaves in an atmosphere or in a stream of CO2, or by adding O2 whereby carbon is also added from the composite material and C thereby forms the desired CO from split O2 in CO2 or splits the added O2.
According to the present invention a use for the composite material is also achieved where it is subjected to microwave energy which transforms this into plasma for production of synthesis gas for use in further energy/methanol/ethanol production, or for operation of machinery.
According to the present invention there has also been produced a method and use for the composite material for the reuse and recycling of CO2. According to the present invention there has also been produced a method and use for the composite material for the conversion of sludge and waste, as well as conversion of carbon and carboxyl-containing materials present in nature into synthesis gas and thereby also energy/methanol/ethanol.
The invention is characterized by using one or more naturally fine particular or ground carbon-containing materials, preferably with a particle size of less than 1000 micron, but far larger particle sizes and clumps may be used. Pure mineral coal or charcoal is preferred, but most other materials rich in carbon may also be used, such as peat, peat moss, sawdust, soy bean flour, corn or other vegetable carbon-containing species, dried grass, carbon-containing sludge and similar.
The invention is further characterized by mixing the carbon material with a carboxyl- containing compound. Typically, this would be carboxyl acid, organic material with a high content level of carboxyl, such as hydrocolloid, pectin from fruit waste, or a material with a sufficient amount of both carbon and carboxyl, such as peat moss, which can be used as it is, without further additions.
The invention is further characterized by having one or more alkaline metals mixed in, preferably as hydroxide dissolved in liquid. The most reactive metals with the lowest electron compound are usually preferred, such as cesium, sodium and potassium, but in principle all alkaline metals may be used in order for the process to work.
Also here carboxyl and alkaline metal may be mixed in advance. In this case, it is preferable to use sodium, cesium and potassium formate, which is formic acid neutralized to an alkaline solution with an alkaline metal.
Also preferred is sodium and potassium based hydrocolloids such as for example alginates, especially when these are used to separate sludge with reaction with mono- /multivalent ions. Na-alginate has carboxyl and 7% alkaline metal (Formula: Na(C6H9O7). If the carbon content of the sludge is high enough, the dehydrated/dried sludge may be brought to plasma without further addition of reactive components.
The invention is characterized by using the composite material as described above as powder, granulate, in flake form, sludge or solid form.
The invention is characterized by having the composite material as described above in dry form or having a liquid/water content of up to 95 %, where the preferred content level of dry material is 40-60 %.
The invention is further characterized by the method for producing the composite material as granulate, flakes or solid shape being generated by an addition of hydrocolloid which is driven to bind with carbon, and then reacted by cross-binding with hydrocolloid, where this is reacted in a liquid water into gel, which is dehydrated/dried/hardened.
The invention is further characterized by the content of CO2 donors in the composite material being regulated by need in the applied process. The content of possible CO2 donors is regulated by adding NaCO3, Na2C O3, NaHCO3 or CaCO3 to the composite material.
The invention is further characterized by placing the composite material in a chamber where it is exposed to microwaves, whereby these put the alkaline metal electrons into motion, with very low energy input. Simultaneously, carbon absorbs microwaves very well, and is heated. Heat further escalates the electrons of alkaline metal. Thus alkaline metal is easily transformed into plasma. While glow temperature for alkaline metal is much lower than for carbon, the carbon also plays a part in the alkaline metal reaching this temperature quickly. As plasma begins at a very low temperature in alkaline metal, this triggers the compounds of carboxyl to break, and CO and O and H are liberated and can further contribute to plasma. These components start the plasma separation of carbon, and the plasma process will typically be steady already at 100 degrees Celsius. Alkaline metals function as a trigger for the plasma process, after which carboxyl separates and initiates carbon separation. Plasma arises, and the energy input may be reduced as long as the process is kept continuous.
The invention is further characterized by the produced plasma converting CO2 into CO, and H2 appearing from added CHn or H3O or hydrocarbon in the composite material.
The invention is further characterized by the fact that a separation of organic material using the present invention can thermally break down organic material as plasma in the process stays at a temperature in the size order of 3500-5000 degrees Celsius, by placing the process in a chamber with material to be incinerated, and recycling CO2, with extracting of CO for the syngas process.
The invention is further characterized by having only composite material, subjected to microwave technology, infused with CO2 and water, be sufficient for production of synthesis gas.
The invention is also characterized by injecting O2 in order to create a gasification process.
The invention is also characterized by a measured amount of pure carbon, inert atmosphere, addition of COOH and alkaline metal in the form of silicone silicate being able to apply think film coat of SI on substrate placed in the plasma used in known PVD PPVD processes (Plasma Vapor Deposition/Puls Plasma Vapor Deposition): Advantages of the present new method
The present invention distinguishes itself from existing plasma technologies by using very little energy. Very little needs to be introduced for the alkaline metals to become plasma, especially with help from surrounding heat from carbon.
The accelerating help caused by carboxyl causes the whole composite material to become plasma using much less energy than other technologies are able to. The alkaline metal remains in the carbon composite and is now at a temperature so high that the carbon reaches explosive plasma separation. Thus very little energy is needed to keep the process going. It actually does not take much more energy than what it takes to keep the alkaline metal electrons in an energized state, and they will keep the process going. Thus the energy balance can be counted from a starting temperature of just below 100 degrees Celsius, versus the regular plasma starting temperature for carbon of 3000 degrees Celsius.
The present invention distinguishes itself from existing plasma technologies for the production of synthesis gas and separation of organic material, by the fact that CO2 can be separated into CO, and CO may be used in synthesis gas or water change process with surplus energy.
The reaction CO2 + C -> 2CO requires the energy ΔH1 = 172 kJ/mol at plasma temp 3000 0C. It also requires ΔH2 = +141 kJ/mol at plasma temp 3000 0C in order to separate organic material into C and CO2. The total addition of energy necessary would then be ΔH1 + ΔH2 = 312 kJ/mol.
This would normally destroy the energy balance of the process, but as the invention in principle only drives energy input to microwave induced alkaline metal plasma and maintains this at below 100 0C this will typically require added energy of only 3-4 kJ/mol. The alkaline plasma temperature will then be in the area of 4-5000 0C, and the COOH groups in carboxyl, as well as C, are thus brought to plasma with positive addition on the energy balance so that negative contributions from reforming added CO2 to CO is voided or gives a huge profit in context.
The present invention uses alkaline metals as an aid in order to have low microwave energy run the process, by having the electrons of the alkaline metals set in the necessary motions to easily be brought to an energized state.
Alkaline metals are easily recyclable, as there is complete combustion of organic material. By using a binding agent in the form of hydrocolloid reacted with alkaline metal, the composite material can be adjusted to the process.
The composite material used may be dry or moist.
The plasma process supplies necessary carbon to CO2 in the conversion of this when it passes through the plasma field.
The invention makes room for CO production of CO2 and continuous recycling of CO2 as raw material for synthesis gas rather than releasing it into the air.
The invention can produce synthesis gas without releasing NOx.
The invention can, by capturing CO2, recycle CO2 for hydrogen production.
The invention may be adjusted for recycling CO2 in a closed process by adding CO2 donors as carbonates and bicarbonates in the composite material.
The utilization of the invention includes separation of organic material as well as waste, in a utilization where CO2 from other industry processes can be fed as process gas and again be used for synthesis gas, or that O2 can also be used as well in a gasification process.
The present invention is distinguished by processing CO2 through a plasma field for conversion into CO, where the plasma field is generated by microwaves applied to composite material of carbon-containing organic material, carboxyl and alkaline metal.
The device according to the invention shall be explained further in the following description with reference to the accompanying figures, tests and examples, wherein:
Figure 1 shows a principle sketch for the use of the composite material in a microwave plasma process.
1) Shows CO2 inlet. (If composite media is dosed as powder it will be dosed through this inlet with CO2).
2) Shows the feed of composite material. In theory, 54 kg material pr. 1000 m3CO2 is used to balance the C required for approximately 10O % conversion of all CO2 to CO.
3) Shows supply of microwave energy.
4) Shows reaction chamber. 5) Shows outlet for synthesis gas prior to addition of H2O steam for, for example, hydrogen production at the water shift process. H2O may also be included in the plasma chamber.
6) Shows energy outtake which is many times larger than energy input.
Figure 2 shows in more detail a reactor for use in the present invention, namely:
Figure 2 shows a sketch of how a reactor which can be used in the process of the present invention may be constructed. The reactor is shown by 10 as a closed container. A generator unit that can impress microwaves on the carbon/metal ion-containing material is shown at 30, surrounding the reactor container.
The inlets 12, 14 show how carbon/metallic ion-containing material and carbon dioxide are supplied to the container. At the top of the reactor 10 is a draining wire for outtake of gases and charcoal dust (nano coal). At the bottom of the reactor there is an outlet 24 for extraction of sludge, meaning ashes in the form of metal oxides of alkaline and earth alkaline metals (and, optionally) silica SiO2.
A cooling spiral 16 is placed inside the reactor chamber in order to contribute to the cooling of the gases to temperatures lower than the re-reaction temperatures.
When the reactants carbon-containing material, alkaline/earth alkaline metal-containing material (or silicone-containing material) is supplied to the chamber and exposed to microwaves from the generator 30, plasma is formed with very high point temperatures in the area shown at around 20, meaning centrally inside the reactor. This is the area where the mentioned splitting of materials to atomic elements happens. And with a quick cooling off adjacent to the plasma area, one avoids re-combinations in the suitable time span so that for instance atomic carbon (nano coal) may be extracted from the reactor area, for instance through the outlet 18.
The tests described in the following are carried out in a reactor similar to the one shown in figure 2.
Example 1 :
The energy balance for separation of carbon, CO2 and H2O to the synthesis gas H2+CO in process 1 with following water change reforming of CO+H2O to H2+CO2 in process 2 as well as reforming to methanol in process 3 will be
Process 1 :
C + CO2 -> 2 CO Delta H = + 172 kJ/mol Normal energy input for achieving plasma temperature (set to 3000° ( 3273. K)
where
E= C.m (T2— T1)
where
C= Specific heat capacity
M= mass
T2= plasma temperature
T2= temperature of surroundings (20° C (293.K)
C for CO2: 0.0372 kJ/mol -» E1 =0.0372(3000-20)=110.796 kJ/mol
C for C (carbon): 0.0101 kJ/mol -> E2=0.0101(3000-20)=30.03 kJ/mol
This gives a total theoretic energy input of Ein= 312,826 kJ/mol
Process 2: Steam reforming process
CO + H2O -» CO2 + H2 Delta H = 41 kJ/mol
2 CO + 2 H2O -» 2 CO2 + 2 H2 Delta H = -82 kJ
Energy potential from combustion of H2.
2 H2O + 2 O2 -> 2 H2O Delta H= -484 kJ
This gives a total theoretical energy production of 566 kJ/mol.
Net energy surplus will then be 253,174 kJ.
Where 1 KW = 3599 kJ -» 253.174 = 0.0703 KW
Utilization of CO + H2 for methanol synthesis in process 3 will be
CO + 2 H2 -» CH3OH Delta H = 100 kJ/mol
This reaction is endothermic (requiring heat), so that 153,174 kJ/mol is gained for each mol methanol produced. Example 2:
Energy gain by the execution of the same process steps as described in example 1 with the composite material is explained by the following:
According to the invention, the composite material is brought to plasma at a starting temperature below 100 degrees, whereupon the catalytic effect from alkaline metal drives carboxyl to plasma with a large catalytic effect, upon which the two components drive carbon to bind with separated O from CO2 in plasma or with O extracted from carboxyl or carbon-containing material or added O. Input to get plasma is the energy that it takes to bring alkaline metal electrons to an energized state, meaning the plasma temperature in the energy consideration must be calculated from 100 degrees Celsius as this is the starting temperature for driving the 3 step catalysis process alkaline metal, carboxyl, carbon in plasma by adding microwave energy.
The energy consideration will then be as follows:
Process 1 :
C + CO2 -> 2 CO Delta H = + 172 kJ/mol remains unchanged
Change in starting temperature gives
C for CO2: 0.0372 kJ/mol -» 0.0372(100-20)=2,976 kJ/mol
C for C (carbon): 0.0101 kJ/mol -> 0.0101(100-20)=0.808 kJ/mol
According to the invention, this will give a total theoretical energy input of 175.784 kJ/mol versus 312.826 kJ/mol without the catalysis effect according to the invention. This means a reduction of energy input of 56.19 % as a result of the catalysis effect achieved by the composite material according to the invention.
Process 2: Steam reforming process remains unaltered as in example 1.
CO + H2O -» CO2 + H2 Delta H = 41 kJ/mol
2 CO + 2 H2O -» 2 CO2 + 2 H2 Delta H = -82 kJ/mol
Energy potential from combustion of H2 remains unchanged.
2 H2 + 2 O2 ^ 2 H2O Delta H = -484 kJ/mol
This gives a total theoretical energy production of 566 kJ/mol. Net energy surplus will then be 390.216 kJ/mol.
Where 1 KW= 3599 kJ -» 390,216 = 0.1084 KW
Utilization of CO + H2 to methanol synthesis in process 3 will still be
CO + 2 H2 ^ CH3OH Delta H = 100 kJ/mol
This reaction is endothermic, resulting in 290,216 kJ/mol gained for each mol methanol produced.
This represents an improvement of the energy balance of 52.78 % according to the invention compared with other known technology.
Test 1
A slurry of sludge with 40 % water separated from a water cleansing process consisting of coal, humus, where Na-alginate (Na-C6H9O7) and added CaOH had been used for separating the pollution (coal/humus) from the water phase, was placed in the microwave oven for quick drying in air atmosphere. The microwave oven was set to 900W and switched on, and, surprisingly, plasma was immediately formed in the oven, and all organic material decomposed at combustion/plasma. Only inorganic material remained as ashes.
Test 2
Charcoal powder, 40 % water, sodium alginate, and Ca++ was then attempted to be brought to plasma with the same conditions, and with the same result. Then, the components were one by one successively removed prior to microwave processing. It was found that only the following created plasma:
Coal, water, sodium alginate.
Coal, sodium alginate.
No other combinations with one or more components removed gave any formation of plasma.
Test 3 Na-alginate from test 1 and 2 was attempted replaced with NaOH, then Na carbonate and then bicarbonate. It was not possible to bring the composite materials to plasma in the microwave oven.
Test 4
Coal and sodium formate (formic acid neutralized with NaOH with a total water content of 40 %) was attempted mixed, and a plasma formation with very little mixing of formate was immediately noted.
Test 5
Coal and caesium formate (formic acid neutralized with CeCo3 with a total water content of 40%) was attempted mixed, and plasma formation took place with very little mixing of formate was immediately noted.
Test 6
Formate from test 4 and 5 was replaced with citric acid which had been neutralized with NaOH, and mixing with coal again gave immediate plasma formation in the microwave oven.
Test 7
Coal from previous tests was replaced with dried peat moss, which gave equivalent to complete combustion and plasma using alkaline formates, alkaline metal/citric acid solution.
Test 8
As peat moss contains large amounts of humic matter and thereby carboxyl, there was an attempt to add NaOH dissolved to saturation in water, and plasma was achieved, but it was noted that it took a while for the process to start. However, when small amounts of coal dust was mixed in to get a temperature contributor to the composite material, plasma was immediately created, as in the previously mentioned successful tests. It was determined that carbon, carboxyl and alkaline metal were ideal, and that alkaline metal and carboxyl need a certain amount of heat for the process to happen under low microwave influence. Test 9
Soy bean flour and Na-formate was mixed into a paste, which was then exposed to microwaves. This immediately turned to plasma and was completely incinerated.
Test 10
Peat moss and lye (NaOH) saturated water was completely incinerated at microwave feed, after which water was added to the ash remains, and peat moss was brought to absorption of the solution. Again, complete combustion and plasma formation was achieved by adding microwaves. This test shows that alkaline metals can be recycled.
Test 11
A microwave oven with 2,45 GHz wave length and controlled feed and CO2 atmosphere for combustion was used in further tests with coal and alkaline metal and carboxyl and varying amounts of water content. Temperature feeler in the chamber was available for continuous observation, and the GC (gas chromatograph) was hooked on the flue gas outlet for detection of gas peaks and gas measuring. The tests were carried out with control of weight of composite material before and after the process. The tests were done from surrounding temperature of 450 degrees Celsius, whereby the process was stopped.
Gas peak took place in all cases with Na present as alkaline metal at a temperature below 100 degrees. By using caesium as alkaline metal, gas peak was read at below 60 degrees. At 450 degrees, approx. 30 % of organic material was decomposed. Flue gases were H2 and Co, and approximately no CO2, and thereby reforming in plasma was confirmed with the help of multistep catalysis effect from the components of the composite material.

Claims

P A T E N T C L A I M S
I . Method for decomposing organic material and/or producing synthesis gas, characterized in that the organic material is placed in a chamber and exposed to microwave radiation in order to produce plasma separation of the material.
2. Method according to claim 1 , characterized by using organic composite material which contains compounds of carbon, carboxyl and alkaline metal, in dry form or with a liquid, where at least one of the abovementioned components contains hydrogen.
3. Method according to one of the previous claims, characterized by the production taking place in an atmosphere where CO2 is added and/or exists and/or is produced in the plasma chamber.
4. Method according to one of the previous claims, characterized in that O in the form of oxygen or as carbonate or bicarbonate is added to the plasma chamber.
5. Method in accordance with one of the previous claims, characterized by the optional injection of a hydrogen- and carbon-containing gas into the chamber.
6. Method for producing a composite material, characterized by the addition of carbon- containing material to compounds of one or more alkaline metals from main group I or Il of the periodic table, where the preferred materials are caesium, sodium, potassium preferably as hydroxide or carbonates or bicarbonates, but where also Si is acceptable as the only metal not in main group I or II.
7. Method according to claim 6, characterized by adding a carboxyl compound to the material, preferably carboxyl acid, acetate or organic material with high carboxyl content.
8. Method according to one of the previous claims 6-7, characterized by adding to the material carboxyl and alkaline metal compounds in the form of alkaline metal formate.
9. Method according to one of the previous claims 6-8, characterized by adding to the material carboxyl and alkaline metal in the form of water dissolved or or non-dissolved alkaline based hydrocolloid, preferably Na and/or K and/or Cs alginate and/or pectin and/or carrageenan.
10. Method according to one of the previous claims 6-9, characterized by the main component of the material consisting of carbon, preferably charcoal, fossil coal, peat, peat moss, cellulose or wood chips.
I 1. Method according to one of the previous claims 6-10, characterized by the composite material containing/being infused with 0-95 % water, where the preferred moisture of the material is 40 %, and preferably between 15 % and 60 %, wherein the concentration of alkaline metals is sufficiently high to start and maintain plasma formation at low microwave feed.
12. Method according to one of the previous claims 6-11 , characterized by the composite material being produced only by mixing the components, or by suspending the composite material or part components [/component parts] thereof in a water mixture, whereon hydrocolloid is added, wherein alkaline metal is added to gel the carbon material, whereon the flocculate is dehydrated, and/or formed and or dried to powder, granulate, flakes or solid form.
13. Composite material, characterized by a mixture of one or more alkaline metals from main group I or Il of the periodic table and a carbon-containing material.
14. Composite material according to claim 13, characterized by the alkaline metal being caesium, sodium, potassium, preferably as hydroxide or carbonates or bicarbonates, as Si as the only metal not in main group I or Il may also be used.
15. Composite material according to claims 13-14, characterized by adding carboxyl to the material, preferably carboxyl acid, acetate or organic material with high carboxyl content.
16. Composite material according to claims 13-15, characterized by the material comprising added carboxyl and alkaline metal in the form of alkaline metal formate.
17. Composite material according to claims 13-16, characterized by adding to the material carboxyl and alkaline metal in the form of water dissolved or -non-dissolved alkaline based hydrocolloid, preferably Na and/or K and/or Cs alginate and/or pectin and/or carrageenan.
18. Composite material according to claims 13-17, characterized by the main component of the material being carbon, preferably charcoal, fossil coal, peat, peat moss, cellulose, or wood chips.
19. Composite material according to claims 13-18, characterized by the composite material containing/being infused with 0-95 % water, where the preferred water content in the material is 40 %, and most preferably between 15 % and 60 %, wherein the concentration of alkaline metals is sufficiently high to start and maintain plasma formation at low microwave feed.
20. Composite material according to claims 13-19, characterized by the composite material being a mixture of the materials, or the composite material or part components [/component parts] thereof are suspended in a water mixture, whereon hydrocolloid is added, wherein alkaline metal is added in order to gel carbon material, whereon the flocculate is dehydrated, and/or formed and/or dried into powder, granulate, flakes, or solid form.
21. Use of the composite material according to the previous claims, for processing plasma using microwave energy to produce synthesis gas for the utilization of H2 and CO.
22. Use of the composite materials according to the previous claims, for processing plasma using microwave energy to decompose and/or combust organic material.
23. Use of the composite material according to the previous claims, for processing plasma with the help of microwave energy for the recycling of CO2 in pure energy manufacturing which includes use of synthesis gas.
24. Use of the composite material according to the previous claims, for processing plasma with the help of microwave energy for further use of synthesis gas in an energy production process which includes production and/or utilization of H2 and/or CO.
25. Use of the composite material according to the previous claims, for processing plasma to form synthesis gas for propulsion of turbines, motors and machinery.
26. Use of the composite material according to the previous claims for processing plasma to reform natural gas to synthesis gas.
27. Use of the composite material according to the previous claims, for processing plasma for the decomposing of organic sludge and waste into synthesis gas to be used for energy.
28. Use of the composite material according to the previous claims, for processing plasma for production of H2 and CO for methanol and ethanol production.
29. Use of the composite material according to the previous claims, for processing plasma for production of synthesis gas for reforming to electricity.
30. Use of the composite material according to the previous claims, for processing plasma where one or more components are included in use in fuel cells.
31. Use of the composite material according to the previous claims, for processing plasma for use as thin film coating on a substrate.
PCT/NO2009/000059 2008-02-21 2009-02-23 Process for the use of alkali metal or alkali earth metal containing organic materials and composites in the microwave-assisted plasma decomposition of said compounds for the production of syngas WO2009116868A1 (en)

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NO20081603A NO20081603L (en) 2008-02-21 2008-04-01 Process and product for the destruction of CO2 and the production of nanocarbon, and applications thereof

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PCT/NO2009/000060 WO2009104972A1 (en) 2008-02-21 2009-02-23 Process for the use of alkali metal or alkali earth metal containing organic composites in the microwave-assisted plasma decomposition of carbon dioxide in the production of carbon

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WO2021190734A1 (en) 2020-03-24 2021-09-30 Efenco Oü Nanosized ceramic plasma catalyst for stabiliting and assisting plasma combustion

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