WO2009104972A1

WO2009104972A1 - 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

Info

Publication number: WO2009104972A1
Application number: PCT/NO2009/000060
Authority: WO
Inventors: Mundheim Ylikangas Atie
Original assignee: Co2Co
Priority date: 2008-02-21
Filing date: 2009-02-23
Publication date: 2009-08-27
Also published as: WO2009116868A1; NO20081603L

Abstract

A method is discussed for handling and removing CO₂ and/or producing carbon in powder form, especially nano carbon, and it is characterized by composite carbon-containing material being placed in a chamber and exposed to microwaves in order to produce plasma to then separate CO₂ from plasma, as CO₂-containing gases are fed to the chamber and led through the plasma zone, after which split elementary C and O are led out of the plasma zone directly to cooled surroundings where the temperature is below the threshold value for re-binding between carbon and oxygen (C and O). The invention relates to low temperature separation and thereby energy efficient cooling of separated elements produced in plasma, so that atomic carbon and oxygen (C and O) do not reconfigure outside of the plasma zone. The invention also relates to a composite material as well as the production of this, as well as a number of uses of the methods and the material. The invention is especially used in a process for removal of CO₂, with simultaneous production of fine particular nano coal, as well as use for CO₂-free hydrogen production of natural gas.

Description

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

The present invention concerns a method for separating (splitting) CO₂ gas and simultaneously producing nano coal, as evident from the introduction to claim 1. The invention also concerns a composite material for use in the abovementioned method, as well as a method for producing this. The invention also concerns different uses.

The invention is particularly concerned with the production of carbon-containing or carbon- based composite material which, when subjected to microwave radiation, forms plasma, whereby the formed plasma has a very low starting temperature as indicated in the introduction to the following patent claim 6.

The invention aims for different utilizations of plasma formed by microwaves applied to such composite material according to the invention.

The invention relates to the technology that concerns an energy efficient way of producing plasma with a high internal plasma temperature in the size order of 3-9000⁰C (degrees Celsius) whereby this may be used to separate or split organic material and especially to split gases such as CO₂ with very low surrounding temperature in a microwave chamber.

Organic material which can be treated using the method according to the present invention is a material which on its own can be incinerated at contact with air. Examples may be organic waste materials, wood, charcoal, fossil coal, peat, peat moss and cellulose.

The invention further relates to the technology that concerns separation of organic materials/gases into plasma and converting the separated products H, C and O into the singular components H₂O and/or C and O₂.

Known methods used today. When it comes to incinerating organic material in order to produce energy, there are two main principles used today for combustion of plasma. These are the "Plasma Arc" method and the "Plasma Torch" method. Both have the starting point of inducing plasma by impressing very high voltage on an anode and a cathode with a certain distance. The "Plasma Arc" method incinerates using a "welding" principle, where a plasma arc forms very high temperatures over time in the combustion chamber and thermally oxidizes the combustion material; simultaneously, the cathode of carbon is used in a manner corresponding to a welding stick during welding. This reaction may take place with the anode/cathode being placed in pollution. The "Plasma Torch" method induces plasma in the gas between the anode and the cathode, either directly between the anode/cathode or by leading the cathode into a sludge mixture with pollution to be separated so that gas in plasma form and with plasma temperature is brought into contact with organic/inorganic material which is to be separated under plasma temperature. Both of these methods result in complete combustion of the organic material, with CO₂ and H₂O as the main residual product. In both methods, it is known that the residual product may be used for production of synthesis gas, as well as CO gases and H₂ in further process steps.

It is also known that microwave technology can be used to induce plasma from a carbon source for coating on a substratum liner 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 gases and conditions such as pressure and temperature control the coating process in the inert atmosphere where there is no combustion. The known features of this method are unsuitable for generating plasma in energy production which the present invention aims for, as it is developed for completely different purposes. The entire process differs significantly from the present invention.

Microwaves are electromagnetic waves whose wave lengths are longer than the wavelengths of infrared light, but shorter than those of radio waves. The wavelengths of microwaves is in the area of 30 centimeters (frequency: 1 GHz) to 1 millimeter (frequency: 300 GHz). The microwave area comprises "ultra-high frequency" (UHF, 0.3-3 GHz), "super-high 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 supplied heating effect, which is used in the following tests, is typically 300 watt and up. The last-mentioned parameters are applicable to the present invention, but in industrial plants one could also move outside the distinct microwave area and still achieve the same effect.

It is known from US-patent document that by using the "Plasma Arc" method to produce plasma, with a subsequent stream of CO₂ gas through induced plasma, where charcoal powder was added to CO₂ gas and followed the CO₂ stream through the plasma zone, as much as 99 % CO₂ conversion into CO was achieved, from the reaction CO₂ + C -> 2CO reacted with plasma arc.

It can be calculated theoretically and is also referred to in the aforementioned patent that the optimal carbon/coal input is 0.54 g/l CO₂. From tests using "Plasma Arc" it became apparent 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 a 1000 degrees Celsius.

Reference is made to the documents US 2007/0084308, US -3.850.588, US-5.266.175 and WO 2005/007565. For example, US-3.850.588 discloses to produce synthesis gases which are enriched in in carbonmono oxide. It is produced by feeding a mixture of carbon dioxide and an organic material into the reeaction zone thar is kept at a temperature of 1000 to 3000 degrees F (that is ca 600 to 1700 degress centigrade).

Carbon, hydrogen and oxygen having an oxygen content of at least 10% by weight are suitable materials. Alkaline metal carbonates catalyst the reaction. However, at this process no plasma is formed, which is necessary for using the present invention. The process is forced by temperature. Added alkaline metal carbonates improves the process when adding oxygen, and further the alkaline metal by said temperatures reduces the treshold value for bonding strength between the single and in particular the double bonding of the elements of H, C and O that are included in the process as disclosed in US.3.850.588. In the present invention the alkaline metal iones are brought directly into plasma, on to an internal plasma temperature of 3500 degree centigrade, which is directly caused by the micro wave energy that is added, directly excites the electron(es) of the alkaline metal, so that the decomposing of (COOH)_n immediately occurs at a very low ambient temperaturem due to the influence of the alkaline metal in the plasma state. The two abovementioned reactions are further catalysed by the internal temperature in C due to the high ability of C to absorb the exposed micro wave radiation, in that all kinetic reactions proceeds more easily at higher temperatures.

For producing synthesis gases (syngas) for energy production from an incineration process it is known that this appears at C + O₂ -> CO₂ CO₂ + C ^ 2CO C + H₂O -> CO + H₂

It is further known that for fuel cells the following reaction takes place, where hydrocarbon, generally CnHm, is converted with H₂O water with the following reaction pattern: CnHm + n H₂O -> n CO + (m/2 + n) H₂ CO + H₂O ^■» CO₂ + H₂

It is further known that CO fed with water steam H₂O (g) can produce additional H₂ from the water split reaction:

CO + H₂O - CO₂ + H₂ The end product in all aforementioned processes will be CO₂ if carbon C has participated in the process. Carbon dioxide emissions in flue gases is a considerable environmental problem, and a number of methods are developing for the capturing, controlled dumping or utilization of CO₂. Of these methods, the most well-known are capturing CO₂ with amine, and reforming to carbonate or to high-value oxides. The method for capturing as well as the handling of the residual product represents a considerable logistical problem and is a particularly cost driving element in energy production.

It is known that methane CH₄ 4 can be gasified by adding small amounts of air at a high temperature (approx. 4000 ⁰C), whereupon it will, if quickly cooled, produce a large amount of elementary carbon C hydrogen gas and H₂, and where C is removed as nano coal. In this context, nano coal means very fine powder of carbon (coal) with particle sizes of <1 μm (micrometer) while a typical particle size is about 25 nm.

Emissions of CO₂ are low as a result of the cooling reducing the ability of C^'and 0^Λ to form CO, and thereby C falls out as nano coal powder and H^' is formed and O^' reacts with H or to 0\ forming, respectively, H₂O or O₂. In the known processes, cooling is therefore inserted as a factor with a secondary job of reducing CO₂ emissions, and the primary object of forming high-value nano coal from an energy producing process.

It is also generally known in chemistry and physics that elementary C and O do not bind with each other under threshold temperature 180 ⁰C at standard pressure.

It is an object of the invention to produce a new carbon-containing composite material, where the material under microwave influence produces plasma at very low surrounding temperature, where the internal plasma temperature is sufficient for the CO₂ to separate into atomic C + O^* + 0\ It is furthermore an aim of the invention to produce a new carbon-containing composite material where a carboxyll compound is also included.

It is furthermore an aim of the invention to produce a carbon-containing composite material where an alkaline metal from main group I or Il of the periodic table is also included.

It is furthermore an aim of the invention to produce a new carbon-containing composite material where the plasma reaction as a consequence of microwave influence takes place in a stream of mainly pure CO₂ atmosphere, whereby reacted carbon is included as an addition in the reaction:

CO₂ + C ^ 2CO in an optimal mixture so that the CO₂ in plasma with internal temperature of 3000⁰C aims at the mixture C + C + O + O.

It is furthermore an aim of the invention to produce the mentioned composite material in the form of powder for dosing to the processed stream of CO₂ through a microwave chamber in order to form plasma as a result of the dosed composite material.

It is also an aim of the invention to produce carbon-containing composite material with a carboxyl compound included, and alkaline metal included, in which case the material may be in dry or dried solid form, flakes, granulated material or as powder. It is also an aim of the invention to include water and/or liquid in the carbon-containing composite material so that hydrogen gas, H₂, may be formed in the plasma chamber from the following reaction:

H₂O + C -» H₂ + CO where atomic materials H^* + H^* + σ and O^{^} are created internally in the plasma zone, and where thereby added carbon dioxide, CO₂, in plasma additionally gives atomic carbon and oxygen, like this: C" + C^Λ + O' + O\ and where thereby added (COOH)_n in plasma additionally gives (C + O^' + O' + H^Λ)_n.

It is an aim of the invention to be able to add to the composite material a slurry of carbon- containing material, carboxyl-containing compound and liquid and dissolved alkaline metal, and also a slurry where alkaline metal formate is added to carbon-containing materials.

It is also an aim of the invention to be able to produce plasma from the composite material in very low surrounding temperature at input of the composite material, to then use plasma to separate CO₂ as sufficient cooling of the atmosphere outside the plasma zone is maintained by refrigeration, where the preferred temperature is lower than 18O⁰C, and where cooling is preferably carried out using a heat exchange medium, but where cryogenic cooling (refrigeration by condensation of gas) may also be used.

It is also an aim of the invention to be able to destroy captured CO₂ from other energy production by processing such CO₂ to plasma formed by the composite material in a microwave chamber according to the invention, in a preferred surrounding temperature below 180 ⁰C outside the plasma zone, and thereby convert CO₂ to high-value nano coal, oxygen and possibly water from an H₂ fraction present in the mixture.

It is an aim of the invention to utilize produced C repeatedly in the composite material. It is also an aim of the invention that the alkaline metals remaining in the ash residue after separation of organic material may be regenerated and used again.

The method in claim 1 is characterized by the organic material being placed in a chamber and exposed to microwave radiation in order to produce plasma separation of the material. The preferred executions are evident from claims 2-5. The method in claim 6 is characterized by one or more alkaline metals from main group I or Il of the periodic table being added to carbon-containing material, preferably cesium, sodium, potassium preferably as hydroxide or carbonates or bicarbonates, but where Si as the only element not in main group I or Il may also be included. Preferred executions are evident from claims 8-12. The composite material is characterized by a mixture of a compound of one or more alkaline metals from main group I or Il of 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 in a compound as hydroxide or carbonates or bicarbonates, while Si may also be used as the only element not in main group I or II. Preferred executions in claims 14-20.

The applications are evident from claims 21-27. According to the present invention, a carbon/carboxyl/alkaline metal composite material has been produced, which is suitable for exposure to microwaves in order to form plasma with very low energy input, and for plasma formation at very low starting temperature, where the main components are carbon, wherein one or more alkaline metals is added, as well as carboxyl, and wherein also water/liquid or a binding agent may be included so that the material may be in the form of powder, granulated material, flakes, solid form or as a slurry, with the purpose of having the material form plasma under the influence of microwaves in an atmosphere or in a slurry of CO₂, whereby carbon may also be added from the composite material and C thereby forms the desired C" + C^* + O^' + O^' in the generated plasma.

According to the present invention a utilization has been brought forth, according to the invention, by reacting the produced plasma at a very low temperature, so that the cooling to keep the temperature in the reaction area outside the plasma area is preferably below temperature limit value (18O⁰C) where C + O can reform CO, and thereby produce high- value nano coal, and also destroy CO₂.

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 charcoal or mineral coal are preferable, but most other materials that are rich in carbon can also be used. Recycling of technical pure recovered carbon is preferred.

Furthermore, the invention is characterized by mixing the carbon material with a carboxyl- containing compound. Typically, this can be carboxyl acid, organic material high in carboxyl as well as hydrocolloid, pectin from fruit waste production, or that the material has a high enough content of both carbon and carboxyl to begin with, so that it can be used as it is without further additives.

The invention is further characterized by having the alkaline metal and carboxyl represented by hydrocolloid as well as CMC (carboxyl methyl cellulose), pectin, alginate carrageenan or similar where alkaline metal is included as for example in Na-Alginate, K- Alginate or Na-CMC. The invention is further characterized by dosing one or more alkaline metal compounds, preferably as hydroxide dissolved in liquid or dry. Typically, the most reactive metals with the lowest electron binding such as cesium, sodium and potassium are preferred, but, in principle, all alkaline metals will make the process work. Also here carboxyl and alkaline metal can be mixed in advance. Especially preferable in this case are formate of sodium, cesium and potassium, which is formic acid neutralized to an alkaline solution with an alkaline metal.

The invention is characterized by the composite material as described above for use as powder, granulate, flakes, slurry or solid form.

The invention is characterized by the composite material as described above being in dry form or having a liquid/water content varying up to 95 weight %, where the preferred content of dry material is 0-40 weight %.

The invention is further characterized by the composite material being placed in a chamber wherein it is exposed to microwaves, whereon these set the alkaline metal electrons in motion, with very low energy input. Simultaneously, carbon absorbs microwaves very easily, and is heated. The heat further escalates the electrons in the alkaline metal. Thus the alkaline metal is easily brought to a state of plasma. While glowing temperature for alkaline metal is much lower than for carbon, carbon also contributes to this temperature being reached more quickly in the alkaline metal. As plasma begins at a very low temperature in alkaline metal, this triggers the compounds in the carboxyl groups 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 room temperature. Alkaline metals function as a starter (catalyst) for the plasma process, after which carboxyl separates and triggers carbon to separate. Plasma is formed and the energy input can be reduced as long as the process proceeds continuously.

The invention is further characterized by the produced plasma converting CO₂ into CO, and very small amounts of H₂ appearing from added CH_n or H₂O in the composite material.

The invention is further characterized by separating CO₂ which is injected through plasma, as plasma in the process is at 3-5000 degrees Celsius.

The invention is further characterized by the composite material, exposed to microwave energy and CO₂, being sufficient for maintaining plasma and forming C + C^* + O^' + O^' from added CO₂.

The invention is also characterized by C + C^Λ + O^' + O^' in plasma being maintained and cooled to plasma surrounding temperature low enough that the elements will not collapse into CO when they leave the plasma zone, and the carbon falling out as fine powder in the form of nano coal. Advantages of the present new method

The present invention distinguishes itself from existing plasma technologies by using very little energy. It takes a very low energy input for the alkaline metals to become plasma, especially with the help of the surrounding heat from carbon. The accelerating help caused by the carboxyl content causes the whole composite material to become plasma using much less energy than other technologies are capable of.

The alkaline metal remains in the carbon composite and now has a temperature high enough that carbon receives explosive plasma separation. Thus, very little energy is required to keep the process going. It actually does not take much more than to keep the alkaline metal electrons in an energized state, and they will drive the process forward. Thus the energy balance can be calculated to a starting temperature like room temperature versus normal plasma starting temperature for carbon of 3000 degrees Celsius.

The present invention distinguishes itself from existing plasma technologies in that its purpose is separating CO₂ and producing carbon.

The invention further distinguishes itself in that CO₂ can be separated into C + O + O in the temperature area below 18O⁰C in cold surroundings with no need for reducing surrounding temperature outside the plasma zone from several 1000⁰C in order to reach below the threshold temperature which prohibits CO to form as the elements leave the plasma zone.

CO usually appears in elementary form above 3000⁰C. Rapid cooling of such gas to a temperature below 18O⁰C has until now not been possible. The present invention makes it possible to maintain the surrounding temperature constantly below the threshold temperature, while CO₂ simultaneously appears in elementary components in the plasma zone.

The reaction CO₂ + C -> 2CO requires the energy ΔH1 0 +172 kJ/mol at plasma temperature 3000⁰C. Additionally, ΔH₂ = +141 kJ/mol at plasma temp 3000⁰C is required to separate organic material to C and CO₂. Total necessary energy input would then be ΔH1 + ΔH2 0 312 kJ/mol. This would normally destroy the energy balance of the process, but since the invention in principle only uses energy input to microwave induced alkaline metal plasma and maintains this at 20⁰C, the energy input required will only be 3-4 kJ/mol. Alkaline metal plasma temperature will then be in the area of 4-5000⁰C, and the COOH groups in the carboxyl, as well as C, is by this driven to plasma with positive input on the energy balance so that negative contributions from reforming added CO₂ to CO are cancelled or brought to plus in the context if cryogenic cooling is not used and one can heat exchange the cooling medium and retrieve this energy.

The present invention uses alkaline metals as an aid to make low microwave energy drive the process by having the electrons of the alkaline metals put in the necessary motion in order to easily go to energized state.

Alkaline metals are easily recycled as there is complete combustion of organic material in the composite material.

By using hydrocolloid reacted with alkaline metal, the feeded form of the composite material can be adjusted to the process. The composite material may be used dry or moist.

The composite material of the plasma process supplies the necessary carbon to added CO₂ as this is reproduced as it passes through the plasma field.

The invention enables nano coal production of CO₂ and permanent destruction of CO₂ emission from energy producing combustion processes. The use of the invention includes the destruction of CO₂ from energy production from combustion gases as well as flue gas from engines and machinery.

The present invention is characterized by CO₂ being processed through a plasma field for conversion and splitting into CO, where the plasma field is generated by microwaves which are applied to a composite material of carbon-containing organic material, carboxyl- and alkaline metal-containing compounds, in the plasma zone all inset components are brought to elementary condition, whereby they in this condition are taken out of the plasma zone into a cooled surrounding temperature lower than the threshold temperature where C and O can form CO or CO₂.

The device according to the invention shall be explained in closer detail in the following description with reference to the corresponding figures, tests and examples, wherein:

Figure 1 shows a principle sketch for use of the composite material in the microwave plasma process.

1 ) Shows an inlet through which CO₂ is fed. (If the composite material is dosed as powder, it will be dosed through this inlet with the CO₂ gas). 2) Shows feed of the carbon-containing composite material. In theory, it takes 54 kg material per 1000 m³ CO₂ to balance the carbon required for approximately 100 % conversion of all CO₂ to CO. 3) Schematically shows a source for feeding microwave energy to the reaction chamber.

4) illustrates the reaction chamber.

5) Shows an outlet where oxygen O₂ and possibly water and nano coal are drawn out. (H₂O can also be included in the plasma chamber.) 6) Indicates refrigeration of chamber and outlet at below 18O⁰C.

Example 1 :

The energy balance for separating carbon and CO₂ to 2CO will be

Process 1 : C + CO₂ -> 2CO Delta H = +172 kJ/mol

Normal energy input to achieve plasma temperature (set at 3000⁰C (3273⁰K)) where

E = C.m (T2— T1)

Where C= Specific heat capacity

M= mass

T2= plasma temperature

T1= surrounding temperature (2O⁰C (293⁰K))

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 theoretical energy input of E_in=312.826 kJ/mol

Example 2:

Energy profit by using 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, whereby the catalytic effect from alkaline metal drives carboxyl to plasma with large catalytic effect, whereby the two components drive carbon to bind with O split from CO₂ plasma or with O separated from^' carboxyl or carbon- containing organic material or added O. Input to make plasma work is the energy required to bring alkaline metal electrons to an energized state, meaning that the plasma temperature in the energy estimate must be calculated from 100 degrees Celsius as this is the starting temperature that drives the 3 step catalysis process alkaline metal, carboxyl, carbon to plasma by adding microwave energy. Energy estimate will then be as follows:

Process 1 :

C + CO₂ -> 2Co 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 (100-20)=0,808 kJ/mol

According to the invention, this gives a total theoretical energy input of 175,784 kJ/mol versus 312,826 kJ/mol without the catalysis effect according to the invention. Meaning a reduction of energy input of 56.19 % as a consequence of the catalysis effect achieved by the composite material according to the invention. By recycling the heat from the cooling process from the plasma zone to the surrounding atmosphere, the energy accounts will be approximately balanced.

Figure 2 shows a sketch of how a reactor which can be used for the process of the present invention may be designed. The reactor is shown at 10 as a closed container. A generator unit which can impress microwaves on the carbon/metal ion-containing material is shown at 30, enveloping the reactor container.

Inlets 12, 14 show where carbon/metal ion-containing material and carbon dioxide are fed to the container. At the top of the reactor is an outlet wire [/transmission] for the outtake of gases and coal dust (nano coal). At the bottom of the container is outlet 24 for extracting effluent, meaning ashes in the form of metal oxides of alkaline and earth alkaline metals (and possibly) silica SiO₂.

A cooling spiral is placed inside, the reactor chamber to contribute to the cooling of gases to temperatures lower than the re-reaction temperatures. When the reactants carbon-containing material, alkaline/earth alkaline metal-containing material (or silicon-containing material) are fed into the chamber and exposed to microwaves from the generator 30, plasma is formed with very high point-temperatures in the area shown at 20, i.e. centrally inside the reactor. This is the area where the mentioned splitting of elements into atomic elements takes place, and with a quick cooling adjacent to the plasma area, re-reactions are avoided, and there is an adequate window for extraction of for example atomic carbon (nano coal) from the reactor area, for example through outlet 18.

The tests described below were carried out in a reactor similar to the one shown in figure 2.

Test 1

A slurry of sludge with 40 % water precipitated from a water cleansing process consisting of charcoal, humus where Na-alginate (Na-C₆H₉O₇) and supplied Ca(OH)₂ had been used for precipitation of pollution (charcoal/humus) from a water phase, was placed in a microwave oven for quick dehydration in an air atmosphere. The microwave was switched on, and, surprisingly, plasma was immediately formed in the oven, and all organic material separated by combustion/plasma. Only inorganic material remained as ash residue.

Test 2 Coal powder, 40 % water, and material containing sodium alginate, and Ca++ was then attempted to be brought to plasma under the same conditions, with the same result. The components were then removed one by one prior to microwave processing. It was found that only the following input elements led to conditions that formed plasma:

Coal, water, sodium alginate. Coal and sodium alginate.

No other combinations with one or more components removed gave conditions which led to plasma in the reactor.

Test 3 Na-alginate from test 1 and 2 were replaced with NaOH, then Na carbonate and then bicarbonate. It was not possible to bring the composite materials to stable plasma in the microwave oven. Test 4

Coal and sodium formate (formic acid neutralized with NaOH with a total water content of 40 %) was mixed, and immediate plasma formation was observed, with very little dosing of formate. Test 5

Coal and cesium formate (formic acid neutralized with CeCo₃) was mixed, and immediate plasma formation was observed, with very little dosing of formate.

Test 6

The formate-containing compound from tests 4 and 6 were replaced with citric acid which was neutralized with NaOH, and again mixed with charcoal, plasma was immediately formed in the microwave.

Test 7

Charcoal from previous tests was replaced with dried peat moss, which resulted in corresponding complete combustion and plasma formation by using a solution of alkaline formate, alkaline metal/citric acid.

Test 8

As peat moss contains large amounts of humic acids and thereby carboxyl compounds, an attempt was made to add sodium lye (NaOH) dissolved to saturation in water, and plasma was achieved, but it was noted that it took a while before the process started. However, when small amounts of coal dust were dosed in order to have a temperature contributor in the composite material, plasma was immediately formed as in the previously mentioned successful tests. It was determined that compounds containing carbon, carboxyl and alkaline metal are ideal, and that alkaline metal and carboxyl compounds need a certain amount of heat in order for the process to take place with low microwave influence.

Test 9

Soy bean flour and NA-formate was mixed to a paste, which was then exposed to microwaves. This immediately became plasma and was completely incinerated.

Test 10 Peat moss and sodium lye (NaOH) saturated water were completely incinerated under microwave exposure, after which ash residue was added to water, and peat moss brought to absorption by the solution. Again, full combustion was achieved, as well as plasma formation, from exposure to microwaves. The test shows that alkaline metal can be recycled.

Test 11 A microwave oven with a wavelength of 2,45 GHz and with a controlled feed of CO₂ atmosphere for combustion was used in further tests with charcoal and alkaline metal and carboxyl and varying amounts of water content. The temperature feeler in the chamber could be read continuously and a GC gas chromatograph was connected to the flue gas outlet 18 for detection of the concentration progress in the flue gases, to determine gas peaks, among other things, i.e. the concentration progress in the gas outlet when it comes to H₂ and CO. The tests were carried out with control of the weight of the carbon- containing composite material prior to and after the process. The tests were done with surrounding temperature (approx. 25 degrees C) to 450 degrees Celsius whereon the process was stopped. Gas peak occured in all instances where Na was present as alkaline metal compound at a temperature between 50 and 100 degrees. All tests showed immediate plasma formation in CO₂ atmosphere at room temperature as the oven was switched on. Using a cesium compound as alkaline metal, gas peak in the outlet 18 was read at below 60 degrees. The flue gases H₂ and CO and with approximately no CO₂, and thereby the reforming in plasma was confirmed with help from multistep catalysis effect from the components in the composite material.

Measurements of gas flow and composition showed approximately complete reforming with up to 90 % synthesis gas at temperature below 180 degrees Celsius in the preliminary tests.

Claims

P A T E N T C L A I M S.

1. Method for handling and removal of CO₂ and/or production of carbon in powder form, particularly nano carbon, characterized by placing the composite carbon-containing material in a chamber and subjecting it to microwaves in order to produce plasma to then separate plasma from CO₂ as CO₂-containing gases are fed into the chamber and led through the plasma zone, whereby split elementary C and O are led out of the plasma zone directly to cooled surroundings where the temperature is below threshold value for re-binding of carbon and oxygen (C and O).

2. Method according to claim 1, characterized by using an organic composite material of a carbon- and/or carboxyl-containing and an alkaline metal-containing material, in dry form or with a liquid.

3. Method according to one of the previous claims, characterized by the production taking place in an atmosphere where CO₂-containing gas is fed and/or exists and/or is produced in a plasma chamber.

4. Method according to one of the previous claims, characterized by the atmosphere and/or the surroundings of the plasma zone being cooled to temperatures below the threshold value for re-binding between atomic carbon and oxygen (C and O), preferably below 180 degrees Celsius, but higher temperatures may also be used, wherein a stream of C and O is extracted from the plasma zone.

5. Method according to one of the previous claims, characterized by the option of carrying out cooling using cryogenic cooling or by recycling heat energy, wherein charcoal powder (nano coal) C is recycled from the cooled zone, and atomic oxygen O is reacted to O₂ or water.

6. Method for producing a composite material, characterized by adding to carbon- containing material one or more metal compounds from main group I (alkaline metal) or Il (earth alkaline metal) of the periodic table, preferably cesium, sodium, potassium preferably as hydroxide or carbonates or bicarbonates, but where also compounds of Si may be included as the only element not in main group I or II.

7. Method according to claim 6, characterized by adding to the material a carboxyl compound, preferably carboxyl acid, acetate or organic material with a high carboxyl content.

8. Method according to one of the previous claims 6-7, characterized by adding to the material carboxyl and alkaline metal 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 un-dissolved alkaline-based hydrocolloid, preferably Na and/or K and/or Cs alginate and/or pectin and/or carrageenan and/or carboxyl methyl cellulose.

10. Method according to one of the previous claims 6-9, characterized by the main component of the material consisting of carbon, preferably recycled carbon from the process, charcoal, fossil coal, peat, peat moss, cellulose or wood chippings.

11. Method according to one of the previous claims 6-10, characterized by the composite material containing/being fed 0-95 % water, where the preferred moisture of the material is less than 40 %, wherein the concentration of alkaline metals is sufficiently high to start and maintain plasma formation with low microwave feed and low temperature.

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 the composite material or partial components thereof being suspended 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 into 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 cesium, sodium, potassium preferably as hydroxide or carbonates or bicarbonates, while also Si may be included as the only element not in main group I or II.

15. Composite material according to claims 13-14, characterized by adding carboxyl to the material, preferably carboxyl acid, acetate or organic material with a high carboxyl content.

16. Composite material according to claims 13-15, characterized by the material including 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 un-dissolved alkaline-based hydrocolloid, preferably Na and/or K and/or Cs alginate and/or pectin and/or carrageenan and/or carboxyl methyl cellulose.

18. Composite material according to claims 13-17, characterized by the main component of the material being carbon, preferably recycled carbon from the process, charcoal, fossil coal, peat, peat moss, cellulose or wood chippings.

19. Composite material according to claims 13-18, characterized by the composite material containing/being fed 0-95 % water, where the preferred moisture of the material is below 40 %, wherein the concentration of alkaline metals is sufficiently high to start and maintain plasma formation with low microwave feed.

20. Composite material according to claims 13-19, characterized by the composite material being a mixture of the materials, or that the composite material, or partial components thereof, is suspended 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 shaped and/or dried into powder, granulate, flakes or solid shape.

21. Use of the composite material according to the previous claims, for the processing of plasma using microwave energy for destruction of CO₂ and production of nano coal.

22. Use of the composite material according to the previous claims, for the processing of plasma using microwave energy to separate and/or incinerate organic material and simultaneous destruction of CO₂ and production of nano coal.

23. Use of the composite material according to the previous claims, for processing plasma using microwave energy to recycle carbon and O₂ in an energy production which includes gasification and/or use of synthesis gas.

24. Use of the composite material according to the previous claims, for processing plasma using microwave energy for further utilization for destruction of CO₂ from coal generating plants and/or gas generating plants.

25. Use of the composite material according to the previous claims, for processing plasma for further utilization for destruction of CO₂ from waste gas from propulsion of turbines, motors and machinery.

26. Use of the composite material according to the previous claims, for processing plasma for reforming natural gas to hydrogen and carbon without forming CO₂.

27. Use of the composite material according to the previous claims, for processing plasma for further utilization for destruction of CO₂ from waste gas from fuel cells.