GB2463878A

GB2463878A - Ionic catalyst capture of carbon oxides

Info

Publication number: GB2463878A
Application number: GB0817567A
Authority: GB
Inventors: David Dorab Jamshed Antia
Original assignee: DCA CONSULTANTS Ltd
Current assignee: DCA CONSULTANTS Ltd
Priority date: 2008-09-25
Filing date: 2008-09-25
Publication date: 2010-03-31
Anticipated expiration: 2028-09-25
Also published as: GB0817567D0; GB2463878B

Abstract

Ionic catalysts, such as sodium chloride, are used for the capture of carbon oxides, such as CO and CO2contained in a flowing feed gas. The feed gas contains one or more of CO and CO2and one or more of H2, CH4, CxHy, CxHyOz. The catalyst is not reduced in CO or H2prior to use. The feed gas can additionally contain sulphides, halides, ammonia, ionic substances, organic chemicals, nitrogen, water/steam, particulates, air, and oxygen. The catalysts operate at a gas hourly space velocity of less than 150,000 M3/hour per m3catalyst at a temperature of less than 650°C (923 K) and a pressure of less than 107Pa (100 bar). Also disclosed are 15 different embodiments which remove CO and CO2from a feed gas at temperature of between 16°C to greater than 35°C and at atmospheric pressure.

Description

Capture of Carbon Oxides

DOCUMENTS CITED

US Patent Documents US Patent 1,924,757 29 August 1933 Carpenter US Patent 1,924,769 29 August 1933 Carpenter US Patent 2,135,453 1 November 1938 Loder US Patent 2,526,651 24 October 1950 Garbo US Patent 4,377,503 22 March 1983 Dessau US Patent 4,539,334 3 September, 1985 Murchison US Patent 4,549,396 29 October 1985 Garwood et al US Patent 4,704,495 3 November, 1987 Dessau US Patent 6,682,711 27 January, 2004 Motal et al US Patent 6,716,886 6 April, 2004 Krylova et al US Patent 6,774,149 BI 10 August, 2004 Gagnon US Patent 6,987,134 Bi 17 January, 2006 Gagnon US Patent 7,192,987 20 March 2007 Van Egmond et al UD Patent 7,361,626 22 April 2008 Baijense et al US Patent 7, 396,972 8 July, 2008 Van Egmond et al US Patent 7,396,978 8 July, 2008 Ma et al US Patent Application 2004/0002622 Al, 1 January, 2004 Gagnon Other Patent Documents EP0958237, Process for the removal of hydrogen cyanide from synthesis gas, 26 June 2002 Koveal et al EP 1920836 Al Process for regenerating a cobalt catalyst, 14 May 2008 Reynhout French Patent 689,342 Perfectionnements a Ia fabrication de composes organiques oxygenes, 4 September 1930, Dreyfus WO/2003/090925, Fischer-Tropsch Catalyst, filed 6 November 2003, Baljense and Rekker Other References Storch, H.H., Golumbic, N., Anderson, R.B., 1951. The Fischer-Tropscli and Related Synthesis Including a Summary of Theoretical and Applied Contact Catalysis. John Wiley & Sons Inc., New York; Chapman & Hall Ltd, New York.

Sheldon, R.A., 1983 Chemicals from synthesis gas: catalytic reactions of CO and H2: (catalysis by metal complexes). Kluwer. ISBN-13: 978-9027714893 Coats, J.S., Shaw, M.H,, Gallagher, M.J., Armstrong, M., Greenwood, P.G., Chacksfield, B.C., Williamson, J.P., Fortey, N.J., 1991. Gold in the Ochil Hills, Scotland. MRP Report 116. Technical Report WF/91/1. British Geological Survey Kreith, F. et al, 2004. CRC handbook of mechanical engineering. CRC Press. ISBN-13: 978- Higman, C. and van der Burgt, M. 2008. Gassification. Gulf Professional Publishing. ISBN-13: 978-

FJELD OF INVENTION

The present invention relates to a new catalytic process for the removal of one or more of the greenhouse gases, CO and CO2 from a flowing gas. The invention uses ionic substances to catalyse the formation of organic compounds with a carbon number of at least one. The invention provides a new catalytic process for the low cost removal of large volumes of carbon oxides from flowing flue gas, specific product gas, and natural gas. The invention also provides a new low cost catalytic process for the conversion of carbon oxides and methane in a natural gas containing significant quantities of carbon oxides (for example between <5% to >60% C02) to organic compounds. This new catalytic process is designed to be able to remove carbon oxides from gases flowing at rates of between less than m3 per day and more than 100,000,000 m3 per day.

BACKGROUND TO THE INVENTION

There is a requirement for a process which allows the greenhouse gases (methane, carbon monoxide, carbon dioxide) to be removed directly from flowing flue gases (for example, flue or exhaust or product gases produced by combustion processes, distillation, heating, pyrolysis, carbonisation, chemical processes, separation processes or biological processes), or specific product gases, (for example, synthesis gas, or water gas, or producer gas, or town gas) or natural gas (for example, a gas containing a high nitrogen content or a high carbon dioxide content) or gases containing conventional catalyst poisons or corrosive chemicals (for example, a high sulphur content or a high chlorine content), or a combination thereof. Gases from these sources are typically available at temperatures of between -50°C and 650° C and at pressures of between atmospheric pressure and 100 bar. There is also a requirement for a process and catalyst which is able to convert the greenhouse gases CO and CO2 contained in a gas to products when the gas is delivered to the reactor at a temperature of less than 6500 C and a pressure of less than 100 bar.

The prior art (e.g. Storch et al, 1951; Sheldon, 1983, .34 US Patent 7,361,626; WO/2003/090925) has established that some metals (e.g. Co, Fe, Ni), following reduction in carbon monoxide or hydrogen or a combination thereof, to a pure metal form or a polynuclear carbide structure (e.g. Fe5C(CO)15), can catalyse the conversion of carbon monoxide and carbon dioxide in the presence of hydrogen to alkanes, alkenes, alcohols and various carbonyls at temperatures of between 180°C -450° C and pressures of between I ->30 bar. Commercial plants currently operate at temperatures of between 220°C -450° C and pressures of between 2.5 -4.5 MPa using catalysts based on reduced Fe or Co (e.g. Kreith et at, 2004, page 7-42). This prior art considers that many of the constituents of the ionic catalysts used in this invention such as sodium salts (e.g. WO/20031090925), ammonia/ammoniumlnitrates/cyanides (e.g. US Patent 2,526,651,4,549,396), halides/halogens (e.g. chlorides (Storch et al, 1951 p. 256;Higman and van der Burgt, 2008, p.66,236; US Patent 2,526,651)), sulphur containing chemicals (e.g. Storch et al, 1951, p.312-315; Higman and van der Burgt, 2008, p. 15, 233; US Patent 6,682,711; 7,192,987, 7,396,972; EP 1920836 Al)), phosphorous/phosphates/phosphines (US Patent 4,377,503; 4,539,334; 4,704,495), potassium sulphate (e.g. Storch et al, 1951, p. 226), carbonyls (e.g. US Patent 2,526,651), thiophene (US Patent 2,526,651), oxygen (e.g. Higman and van der Burgt, 2008, p. 237), arsenic (e.g. [-ligman and van der Burgt, 2008, p.243), charcoal (e.g. US Patent 7,396,798), and ionic forms of chlorine, bromine and sulphur (US Patent 6,716,886) are Fisher-Tropsch catalyst poisons. The prior art requires that the feed gas (CO + C0H + H2) should be purified to remove sulphur compounds, nitrogen compounds, particulate matter, other condensables and other catalyst poisons prior to the gas passing through the catalyst (e.g. US Patent 7,192,987; 7,396,972).

Unlike the prior art, the current invention is able to use halides and other ionic substances in the reactor to produce organic products from gases containing carbon dioxide and does not require the catalyst to be reduced in CO or H2 prior to use.

It has also been established (e.g. US Patent 1,924,762; 1,924,769; 2,135,453) that the formation of specific carboxylic acids, esters and alcohols can be undertaken at pressures of 25 -900 atmospheres (about 25 to 912 bar) and temperatures of 100° C to 400° C from a mixture of steam and CO, using the halides of Li, Na, K, Cs, Ca, Ru, Nb, Hf, Zr, Sb, Sr, Mg, Ba, Sn, Fe, Co, Ni, Bi, Mn, Mo, Pb, Te, W, V, Cr, Ta, P, Si, S, Zn, Cd supported on charcoal, Fullers Earth or kieselguhr (i.e. diatomite), or from a mixture of CO and H2 using Zn, Cu, Pb and Cd sulphides and mixtures of these sulphides with a chromium oxide (e.g. French Patent 689,342). Unlike the prior art, this invention is able to produce carboxylic acids, esters, alcohols and other organic chemicals using one or more ionic substances, without requiring the presence of H20 in the feed gas, is able to use CO2 or a mixture of CO and C02, or CO to produce the products and is able to operate over wider temperature and pressure ranges including being able to produce products at atmospheric pressures and temperatures of less than 100°C.

US Patent 6,774,149 B1 and US Patent 6,987,134 Bi claim that when NaCl is mixed with a Fischer Tropsch catalyst and operated at a pressure of 2300 -3500 psi (about 158 -241 Bar), then the Fisher Tropsch catalyst uses the carbon and hydrogen to produce the hydrocarbon while the NaCI prevents oxidation of the Fischer Tropsch catalyst by removing water. Application 2004/0002622 Al claims that when NaCI is mixed with a FeO-iron catalyst and solid organic waste in a batch reactor operated in the absence of oxygen in a stream of hydrogen at a temperature of 400° C and a pressure of 1850 psi (about 127 bar) that the NaCI prevents oxidation of the FeO catalyst by removing water. Unlike the prior art and contrary to the teachings of US Patents 6,774,149 B 1; 6,987,134 B 1; 2,526,651; US Patent Application 2004/0002622 Al this invention found that when a continuous flow of feed gas containing carbon oxides was passed through NaCI at atmospheric pressure that the carbon oxides were converted to products.

The current requirement to reduce greenhouse gas emissions (CO2 + CH4) from flue gases has created a need for a low cost, low energy requirement, small footprint, catalytic process which can convert one or more of the carbon oxides (CO + C02) contained in a feed gas into products without requiring the feed gas to be processed into a purified synthesis gas prior to use and without requiring the catalysts to be reduced in either CO or hydrogen prior to use. This invention meets these requirements and provides a low cost, low energy requirement, alternative to the current technologies.

Definitions All references to the periodic table refer to the IUPAC definition of the periodic table as outlined in CRC Handbook of Chemistry and Physics, 2008-2009, 89 Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, JSBN-13 978-1-4200-6679-1. All references to the global warming potential of CO, CO2 CH4 refer to pages 14-34 and 14-35 of CRC Handbook of Chemistry and Physics, 2008-2009, 89th Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, ISBN-l3 978-1-4200-6679-1.

TheAnions used to construct the catalyst include one or more of H, F, CI, Br, I, At, 0, S, Se, Te, N, P, As, Sb, C, Si, Ge, B held in a monoatomic or polyatomic form. They can be a halide (selected from Cl, F, Br, 1, At) or a sulphate (SO42') or a hydroxide (OH') or a carbonate (C032') or a phosphate (P043') or a sulphide (S2') or a nitrate (NO3') or a bicarbonate (HCO3') or a hydrogen phosphate (HP042') or a dihydrogen phosphate (H2P04') or a nitrite (NO2') or N2O22, or a suiphite (SO32') or a thiosulphate (S2032) or S2062, or S2082, or S4062, or HS204, or an oxide (02') or a chromate (Cr042') or a dichromate (Cr2072') or a peroxide (022') or an arsenate (As043') or an acetate (C2H302') or a perchlorate (ClOg) or perrnanganate (Mn04') or a thiocyanate (CNS') or cyanide (CN) or oxalate (C2042) or hypochlorite (ClO') or chlorite (dO2') or chlorate (CIO3) or perchiorate (CIO4) or M1][0] (where Ml is one or more elements) or another inorganic anion or another organic anion or a combination thereof. The anions can contain attached metals or other elements. Examples of cations and anions are provided on pages 8-20 to 8-31 of CRC Handbook of Chemistry and Physics, 2008- 2009, 89th Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, ISBN-13 978-1-4200-6679-1. The catalyst can contain more than one type of anion. The anions can be inorganic or organic or a combination thereof. The illustrative lists of ionic substances provided in the CRC Handbook of Chemistry and Physics, 2008-2009, 89th Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, ISBN-13 978-1-4200-6679-1 are not inclusive and other ionic relationships occur and are specifically incorporated.

Ash is any solid residue from a combustion processes, carbonisation process, or thermal process or an industrial process. The ash may contain no organic matter, but can contain organic matter, fullerenes, char, charcoal, semi-coke, coke, petro-coke, activated carbon.

Catalytic reactor types which can be used to undertake the process claimed in Claim I include, but are not limited to, a flow line reactor, a monolith reactor, a microchannel reactor, a nanochannel reactor, a tubular reactor, a nano-tube reactor, a mono-tubular reactor, a multitubular reactor, a shell and tube reactor, a fixed bed reactor, a moving bed reactor, a tubular membrane reactor, a membrane reactor, a fluidised bed reactor, a transport fluidised bed reactor, a multi-hearth reactor, a gas-liquid reactor, a tray tower reactor, a packed reactor, a packed counter current reactor, a packed co-current reactor, a stirred tank reactor, a slurry reactor, a bubble reactor, a bubble column reactor, a spray tower reactor, a trickle bed reactor, an electrolytic reactor. The catalyst can be contained within an electromagnetic or magnetic field. Gaseous catalyst can be mixed with the feed gas in the reactor, and is removed from the product gas, either within the reactor or downstream of the reactor or a combination thereof. When more than one reactor is present, each reactor can be the same type or are from two or more types. In some embodiments a reactor type may be a hybrid including elements from several reactor types. In other embodiments a reactors mode of operation may change the effective reactor type over time.

The Cations used to construct the catalyst can be monoatomic or polyatomic and includes one or more metals selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ic, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Sn, Pb, Bi, Po, Ce, Th, U, or an organic ion or an ammonium ion ((NH4) or l-l or a hydrogen containing ion or a combination thereof.

Carbon oxide insertion refers to the addition of a carbon oxide from any source to an organic compound.

Layered silicates are one or more of muscovite, hydromuscovite, paragonite, glauconite, margarite, phiogopite, biotite, zinnwaldite, lepidolite, clintonite, xanthophyllite, stilophnomelane, pyrophyllite, talc, chlorite, septechlorite, chamosite, serpentine, kaolinite, dickite, nacrite, halloysite, illite, kandite, smectite, montmorillonite, bentonite, phengite, nontronite, beidellite, saponite, hectorite, sauconite, vermiculite, apophyllite, prehnite, sericite, phengite, hydromuscovite, fluromuscovite and derivatives and variants of these layered silicates. The layered silicate can be a clay, shale, mud, ooze or silt. The layered silicate can be in rock, sediment or mineral form. The layered silicate can contain a mixture of layered silicates and other minerals.

Fullerenes include buckyballs, buckminsterfullerene, carbon nanotubes (including but not limited to, single walled and multi walled nanotubes, nanoribbon, chiral, zigzag, vectorial, scroll, nested layer, nanotorus, nanoflower forms), carbon nanobuds, carbon nanofibres, carbon megatubes, carbon polymer structures, carbon nano-onions, fullerene rings, carbon ball and chain diamirs, aggregated diamond nanorods, lonsdaleite, poly(hydridiocarbyne), fullerite, glassy carbon, carbon nanofoam, active carbon, carbon black, and linear acetylenic carbon (carynes and polyynes) and derivatives and variants of these fullerenes.

Gas Hourly Space Velocity is calculated as the volume (CO + C02), m3 in the feed gas per hour passed through one m3 of ionic substance contained in the catalyst (e.g. NaCl, KCI, FeSO4, etc.).

Hydrated Ionic Solids include, but are not limited to, kainite (MgSO4 KCI 1-120), schonite (K2S04 MgSO4 6H20), leonite (K2S04 MgSO4 4H20), langbeinite (K2S04 2MgSO4), glaserite (K3Na(S04)2), polyhalite (K2S04 MgSO4 2CaSO4 2H20), epsom salts (heptahydrate (MgSO4 7H20)), alpersite ((Mg, Cu)S04 71-120), meridianite (MgSO4 11 H20), pentahydrate (MgSO4 51-120), starkeyite (MgSO4 4H20), sanderite (MgSO4 2H20), kieserite (MgSO4 H20), szomolnokite (FeSO4 H20), rozenite (FeSO4 2H20), siderotil (FeSO4 5H20), ferrohexahydrate (FeSO4 6H20), melanterite (FeSO4 71120), Mohrs salt (ammonium iron sulphate ([NJ-L1]2[FeJ[S04]2 61-120; FeF120N2O14S2)), iron(IlI) sulphate hydrates, (general form Fe2(504), xH2O, examples include paracoquimbite (x=9), coquimbite (x9), komelite (x'7), quenstedtite (x'=lO), lausenite (x"5 and x=6)), hemihydrates (CaSO4 O.5H20), dehydrate ((gypsum) CaSO4 2H20), COSO4 7H20, NiSO4 6H20, tetrahydrate (MnSO4 4H20)), Fe(OH)2, FeO(OH) n1120 (including goethite (FeO2H), akaganeite (FeO2H), lepidocrocite (FeO2H), feroxyhyte (FeO2H), siderogel, limonite, ferrihydrite (Fe5(OH)3 4H20) , FeS0 H20, FeSO4 4H20, PeSO4 5H20, FeSO4 5H20, FeSO4 nH2O, Fe2(SO4)3, Fe2(S04)3 5H20, Fe2(S04)3 nH2O, FeO(OH), FeO(OH) nH2O, FeO(OH)3, FeO(OH)3 nl-120, Fe(N03)3, Fe(N03)3 nH2O, Fe(N03)3 9H20, FePO4, FePO4 nH2O, Fe3(P04)2, Fe3(P04)2 nH2O, NiSO4 6H20, NiSO4 nH2O, Ni(N03)2 6H20, Ni(N03)2 nH2O, Ni(OH)2, Ni3(P04)2 7H20, Ni3(P04)2 nI-120. n = 0 for an anhydrous substance. n is greater than 0 for a hydrated substance.

Hydrated silicates include, but are not limited to, one or more of artificial zeolites (for example ZSM5 and variants thereof), zeolites, natrolite, mesolite, scolecite, thompsonite, gonnardite, edingtonite, phillipsite, harmotome, gismonine, garronite, chabazite, gmelinite, levyne, erionite, faujasite, heulandite, stilbite, epistilbite, ferrierite, brewsterite, mordenite, dachiardite, laumontite, ashcroftine, yugawaralite and derivatives and variants of these hydrated silicates.

Hydrogenation refers to the addition of hydrogen from any source to a carbon oxide or an organic compound.

Ionic liquids: Organic ionic liquids may optionally include one or more components selected from choline, ammonium, ethylammonium, izidazolium, phosphonium, pyrazolium, pyridinium, pyrrolidinium, sulfonium,, limidazolium, morpholinium, piperidinium, aminium, hexaflurophosphate, tetrafluroborate, bistriflimide, triflate, tosylate, halide, nitrile, bis(trifluromethylsulfonyl)imide.

Examples of organic ionic liquids are provided on pages 6-141 to 6-144 of CRC Handbook of Chemistry and Physics, 2008-2009, 89th Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, ISBN-13 978-1-4200-6679-I. Ionic liquids used as a catalyst or in constructing a catalyst can be inorganic or organic or a combination thereof.

Ionic Substances include ionic solids, ionic liquids and ionic gases. An ionic substance is constructed from one or more cations and one or more anions.

Macroporous, mesoporous, microporous, nano-porous material includes one or more of particulate matter and support material.

Meihanation refers to the incorporation of a methane molecule or a fragment of a methane molecule into a carbon oxide or an organic compound.

Organic mailer is one or more of coal, lignite, peat, cellulose, hemi-cellulose, lignin, cellulose/lignin, soil improvers, fertilisers, organic products (including textiles), kerogen, activated carbon, char, coke, charcoal, semi-coke, petro-coke, organic chemicals, waste petrochemicals, compost, manure, agricultural waste, agricultural slurry, foul sewerage, dung, activated carbon, oil shale, carbonaceous shale, oil, carbonaceous rocks, bitumen, biomass, organic waste containing biomass, bituminous clay (defmed as clay or shale or silt or sand or limestone, or muds or oozes or a combination thereof in a consolidated or unconsolidated form containing more than 1% by weight of organic compounds or substances).

Particulate material includes all forms of natural and artificial solid material which is present in particulate form, for example, nano-particles, powder, granules, crystals, grains. Particles can assume any shape and have dimensions between 10b0 m and 1 in. Particulates can have a multimodal distribution. Different catalysts or types of catalyst within the catalyst bed can have the same or different particle sizes or a combination thereof. In a fluidised bed reactor or slurry reactor or bubble reactor containing particles and liquids, some or all of the particles may fluidise when the feed gas flow rate exceeds the minimum fluidising velocity. The catalyst bed can be structured to (i) allow the particles to remain static, or (ii) allow macropores or natural pipes to develop within the catalyst bed, or (iii) allow expansion of the porosity of the catalyst bed where the particles act as moving "stationary particulates", where the downward gravitational force acting on the particles is matched by the "upward force" applied by the feed gas, or (iv) allow expansion of the porosity of the catalyst bed and the development of a "conveyor within the reactor" where the force associated with the flowing gas carries a stream of particles within the feed gas until the flow rate of the gas drops, resulting in a settling of the particles. In a vertical or inclined tubular reactor structure gravitational forces return the settling particles to the catalyst bed. In some embodiments the particles will be collected outside the reactor and may be returned to the catalyst bed by mechanical or gravitational forces or by some other method, or (v) a combination thereof Physical Processes: A physical process is any process which is used to formulate a catalyst before it is entered into the reactor which does not involve a chemical reaction. A chemical reaction results in the formation of a new covalent chemical. Physical processes include all processes designed to 1. create hydrated structures, crystals, solutions, solutes, precipitation from a solution, condensation from a gas, changes in substance phase (liquid, gas, solid), changes in substance viscosity, plasticity, liquid limit.

2. impregnate solid material.

3. coat solid material.

4. use foam or another substance (which is made from the catalyst and can include solid material) to produce a monolith or membrane or particle or a moulded structure or a combination thereof 5. produce a particulate catalyst. Processes include, but are not limited to, those designed to produce a particle of the appropriate shape, size, roughness, hardness, density, surface area, porosity, permeability, pore throat/inter layer laminae size. Support material and particulate material can be coated with a material which is designed to increase its hardness and/or reduce its attrition within the reactor, Physical processes include, but are not limited to, heating, cooling, moulding, crushing, vibrating, shaking, plating, pressurising, depressurising, blowing, foaming, mixing, stirring. Physical mixing which results in the temporary or permanent exchange of anions or cations between one or more ionic substances and one or more types of solid material, or between ionic substances or a combination thereof is defined here as a physical process. Both hydration and dehydration are defined as physical processes.

Polyaddition is the addition of two or more organic molecules to form a single organic molecule.

Pyroclastics include ash and tuffs from volcanic eruptions, and all pyroclastic sediments and rocks.

Solid material includes one or more of organic matter, layered silicates, hydrated silicates, fullerines, ash, suiphides, silicates, ortho-silicates, ring-silicates, chain silicates, sheet silicates, framework silicates, suiphides, sulphates, carbonates, hydroxides, oxides, phosphates, halides, pyroclastic material, hydrated silicates, hydrated carbon oxides, methane hydrates, support material, particulate material, macroporous, mesoporous, microporous, nano-porous material, metals.

Support material includes, but is not limited to, artificial membranes, monoliths, wire, gauze, rods, particles, metal skeletons, calcareous algal skeletons, silica skeletons, phosphatic skeletons, carbonate skeletons, sulphate skeletons, sulphide skeletons, carbon skeletons, strontium skeletons, calcium skeletons, chitin skeletons, lignin skeletons, kerogen skeletons, cellulose skeletons, hemi-cellujose skeletons, maerl, diatoms, coral, sponges, bryozoans, molluscs, crinoids, brachiopods, algal skeletons, radiolarian skeletons, porous sediments and rocks (for example clays, sands, silts, limestones, radiolarite, diatomite, bone-beds and variants and derivatives thereof) and minerals (for example hydrothermal minerals, secondary porosity created through diagenetic activity and variants and derivatives thereof). The artificial membranes include polymers (including, but not limited to, polypropylene, polycarbonate, polysulfone, polybutylene, polystyrene, polyvinylalcohol, polyacrylonitrile, polyvinylchioride, polymethacryate, polyvinylpyrrolidone, polyethylene, isoprene, polyisoprene, polypyrrone, polybenzimidazoles, polyimide, polyether, polyacetylene, polyoxadiazole, polybutadiene, polyamide, polyoxymethylene and other organic synthetic membranes), metal membranes, fabrics, ceramic membrane (including, but not limited to, alumina, zirconia, titania and silicon carbide forms), natural fibres (including, but not limited to, fibrous mineral, rock fibres, wool, cotton, textiles), other artificial membranes (for example cement, lime, silicates, carbonates, sulphates, hydroxides, mineral fibre, glass fibre, monoliths) and metals (including but not limited to wire wool, gauze, wire, rods, tubes, flakes, filings, pellets, chips, structures), The support material can be an igneous rock (including, but not limited to, vesicular basalt or andesite or similar volcanic rock), a pyroclastic rock (including, but not limited to, pumice, ash, agglomerate, tuft), a hydrothermal rock (including, but not limited to, a hydrothermal breccia, silicate, or carbonate), a sedimentary rock (including, but not limited to, a limestone or sandstone) or a metamorphic rock.

BRIEF DESCRIPTION OF FIGURES

All the figures pertain to the non-limiting example. The figures show different compositional ratios associated with the feed gas entering the catalysts (Figures I to 4) and the product gas leaving the catalysts (Figures 5 to 82) for the non-limiting example. The ratios shown in the figures are:- 1) Ratio A: CO:C02 Ratio in feed gas ii) Ratio B: (CO+C02): (CH4 + H2 + H20 + CH + CXHYOZ) Ratio in the feed gas iii) Ratio C: C02: (CH4 + H2 + H20 + CH + CHYOZ) Ratio in the feed gas iv) Ratio D: CO2 per 100 moles product gas/CO2 per 100 moles feed gas v) Ratio E: CO per 100 moles product gas/CO per 100 moles feed gas vi) Ratio F: (CO+C02) per 100 moles product gas/COy per 100 moles feed gas vii) Ratio G: CO:C02 Ratio in product gas viii) Ratio H: Number of moles of nitrogen present in 100 moles of product gas ix) Ratio 1: Number of moles of nitrogen present in 100 moles of feed gas x) Ratio J: Number of moles of CO + CO2 per 100 moles of feed gas converted to products/Number of moles CO + CO2 per 100 moles of feed gas xi) Ratio K: Number of moles of(CH4 + H2 + H20 + CH + CXHYOZ) per 100 moles of feed gas converted to products/Number of moles of(CH4 + F-I2 + H20 + CH + CXHYOZ) per moles of feed gas Molar volumes are referenced to a pressure of I atmosphere and 00 C (273.15 K) using the Ideal Gas Equation. The Ideal Gas Equation is calculated as V nRTIP, where V = gas volume, litres, n number of moles of gas component, R = gas constant of 0.08206 L-atm/mol-K, I = temperature, K, P = pressure (atmospheres), where 1 mol of an ideal gas occupies 22.41 litres. The Ideal Gas Equation is taken from page 363 of Brown, L., Le May Jr, H.E., Bursten, B.E., 2000. Chemistry the Central Science. Prentice Hall, ISBN: 0-13-010310-1.

1. Figure 1 Composition of the feed gas: Ratio A vs. Ratio B: Range of Ratio A is <0.01 to >1.0 2. Figure 2 Composition of the feed gas: Ratio A vs. Ratio I 3. Figure 3 Composition of the feed gas: Ratio C vs. Ratio I 4. Figure 4 Composition of the feed gas: Ratio B vs. Ratio I 5. Figure 5 Catalyst A: Ratio D vs. Feed Gas Temperature, C 6. Figure 6 Catalyst A: Ratio E vs. Feed Gas Temperature, C 7. Figure 7 Catalyst A: Ratio F vs. Ratio B 8. Figure 8 Catalyst A: Ratio 0 vs. Ratio A 9. Figure 9 Catalyst B: Ratio D vs. Feed Gas Temperature, C 10. Figure 10 Catalyst B: Ratio E vs. Feed Gas Temperature, C II. Figure 11 Catalyst B: Ratio F vs. Ratio B 12. Figure 12 Catalyst B: Ratio 0 vs. Ratio A 13. Figure 13 Catalyst C: Ratio ID vs. Feed Gas Temperature, C 14. Figure 14 Catalyst C: Ratio E vs. Feed Gas Temperature, C 15. Figure 15 Catalyst C: Ratio F vs. Ratio B 16. Figure 16 Catalyst C: Ratio G vs. Ratio A 17. Figure 17 Catalyst D: Ratio ID vs. Feed Gas Temperature, C 18. Figure 18 Catalyst ID: Ratio E vs. Feed Gas Temperature, C 19. Figure 19 Catalyst ID: Ratio F vs. Ratio B 20. Figure 20 Catalyst D: Ratio G vs. Ratio A 21. Figure 21 Catalyst E: Ratio ID vs. Feed Gas Temperature, C 22. Figure 22 Catalyst E: Ratio E vs. Feed Gas Temperature, C 23. Figure 23 Catalyst B: Ratio F vs. Ratio B 24. Figure 24 Catalyst E: Ratio G vs. Ratio A 25. Figure 25 Catalyst F: Ratio D vs. Feed Gas Temperature, C 26. Figure 26 Catalyst F: Ratio E vs. Feed Gas Temperature, C 27. Figure 27 Catalyst F: Ratio F vs. Ratio B 28. Figure 28 Catalyst F: Ratio C vs. Ratio A 29. Figure 29 Catalyst G: Ratio D vs. Feed Gas Temperature, C 30. Figure 30 Catalyst G: Ratio E vs. Feed Gas Temperature, C 31. Figure 31 Catalyst 0: Ratio F vs. Ratio B 32. Figure 32 Catalyst G: Ratio G vs. Ratio A 33. Figure 33 Catalyst H: Ratio D vs. Feed Gas Temperature, C 34. Figure 34 Catalyst H: Ratio E vs. Feed Gas Temperature, C 35. Figure 35 Catalyst H: Ratio F vs. Ratio B 36. Figure 36 Catalyst H: Ratio 0 vs. Ratio A 37. Figure 37 Catalyst 1: Ratio D vs. Feed Gas Temperature, C 38. Figure 38 Catalyst I: Ratio E vs. Feed Gas Temperature, C 39. Figure 39 Catalyst I: Ratio F vs. Ratio B 40. Figure 40 Catalyst I: Ratio G vs. Ratio A 41. Figure 41 Catalyst J: Ratio D vs. Feed Gas Temperature, C 42. Figure 42 Catalyst J: Ratio E vs. Feed Gas Temperature, C 43. Figure 43 Catalyst J: Ratio F vs. Ratio B 44. Figure 44 Catalyst J: Ratio 0 vs. Ratio A 45. Figure 45 Catalyst K: Ratio D vs. Feed Gas Temperature, C 46. Figure 46 Catalyst K: Ratio E vs. Feed Gas Temperature, C 47. Figure 47 Catalyst K: Ratio F vs. Ratio B 48. Figure 48 Catalyst K: Ratio 0 vs. Ratio A 49. Figure 49 Catalyst L: Ratio D vs. Feed Gas Temperature, C 50. Figure 50 Catalyst L: Ratio E vs. Feed Gas Temperature, C 51. Figure 51 Catalyst L: Ratio F vs. Ratio B 52. Figure 52 Catalyst L: Ratio 0 vs. Ratio A 53. Figure 53 Catalyst M: Ratio D vs. Feed Gas Temperature, C 54. Figure 54 Catalyst M: Ratio E vs. Feed Gas Temperature, C 55. Figure 55 Catalyst M: Ratio F vs. Ratio B 56. Figure 56 Catalyst M: Ratio G vs. Ratio A 57. Figure 57 Catalyst N: Ratio D vs. Feed Gas Temperature, C 58. Figure 58 Catalyst N: Ratio E vs. Feed Gas Temperature, C 59. Figure 59 Catalyst N: Ratio F vs. Ratio B 60. Figure 60 Catalyst N: Ratio G vs. Ratio A 61. Figure 61 Catalyst 0: Ratio D vs. Feed Gas Temperature, C 62. Figure 62 Catalyst 0: Ratio E vs. Feed Gas Temperature, C 63. Figure 63 Catalyst 0: Ratio F vs. Ratio B 64. Figure 64 Catalyst 0: Ratio G vs. Ratio A 65. Figure 65 Catalyst A, Catalyst B, Catalyst C, Catalyst D, Catalyst E: Ratio H vs. Ratio I 66. Figure 66 Catalyst F, Catalyst G, Catalyst H, Catalyst 1, Catalyst J: Ratio H vs. Ratio I 67. Figure 67 Catalyst K, Catalyst L, Catalyst M, Catalyst N, Catalyst 0: Ratio H vs. Ratio I 68. Figure 68 Catalyst A: Ratio J vs. Ratio K 69. Figure 69 Catalyst B: Ratio J vs. Ratio K 70. Figure 70 Catalyst C: Ratio J vs. Ratio K 71. Figure 71 Catalyst D: Ratio J vs. Ratio K 72. Figure 72 Catalyst E: Ratio J vs. Ratio K 73. Figure 73 Catalyst F: Ratio J vs. Ratio K 74. Figure 74 Catalyst C: Ratio J vs. Ratio K 75. Figure 75 Catalyst H: Ratio J vs. Ratio K 76. Figure 76 Catalyst 1: Ratio J vs. Ratio K 77. Figure 77 Catalyst J: Ratio J vs. Ratio K 78. Figure 78 Catalyst K: Ratio J vs. Ratio K 79. Figure 79 Catalyst L: Ratio J vs. Ratio K 80. Figure 80 Catalyst M: Ratio J vs. Ratio K 81. Figure 81 Catalyst N: Ratio J vs. Ratio K 82. Figure 82 Catalyst 0: Ratio J vs. Ratio K

BRIEF DESCRIPTION OF TABLES

The tables (Tables Ito 30) provide compositional data pertaining to 100 moles of feed gas and 100 moles of product gas for the non-limiting example (catalysts A to 0).

DESCRIPTION OF THE INVENTION

The invention comprises a process and an associated group of ionic catalysts where the ionic catalyst removes all or part of one or more of carbon dioxide and carbon monoxide contained in a flowing gas by converting one or more of carbon dioxide and carbon monoxide into products. The flowing gas includes one or more carbon containing gases (selected from CO and C02) and one or more hydrogen containing gases (selected from H2, gaseous hydrocarbons and organic chemicals). The products are organic chemicals containing one or more carbon atoms. The process removes carbon oxides from the feed gas by one or more of methanation, carbon oxide insertion, polyaddition and hydrogenation.

Products include, but are not limited to, one or more of alkanes, atkenes, alkynes, aldehydes, ketones, alcohols, arenes, amines, amides, ethers, esters, carbonyls, nitriles, carboxylic acids, aromatics, cyclic organic compounds, vinyl monomers, vinyl polymers, polymers, copolymers, addition polymers, condensation polymers, polyamides, organic halogen compounds, organic compounds containing sulphur, organic compounds containing phosphorous, organic compounds containing nitrogen, organic compounds containing a metal. The overall catalytic process results in one mole of feed gas producing less than one mole of product gas (including unreacted feed gas).

Catalyst This invention uses ionic solids or ionic liquids or ionic gases or a combination thereof, to catalyse the conversion of one or more of carbon monoxide and carbon dioxide to products. This is demonstrated in the examples described by Tables I to 30 and Figures 1 to 82 at atmospheric pressure and a temperature of 16° C -35° C. The ionic solids, ionic liquids and ionic gases can contain I12O and include one or more ionic forms of metals, carbon, hydrogen, halogens, nitrogen, phosphorous, and sulphur. This invention achieves the conversion without first reducing the catalyst in l2 or reducing the catalyst in CO to manufacture a polynuclear carbide structure (e.g. Fe5C(CO)15). This invention can use gases which have not been purified.

The use of ionic catalysts for the purpose of removing one or more of carbon dioxide and carbon monoxide contained in a flowing gas, for example, a flue gas, an exhaust gas, a waste gas, a process gas, or natural gas, by converting one or more of carbon dioxide and carbon monoxide into products using an ionic catalyst is novel and contrary to the prior art. It involves an inventive step, does not form part of the current state of the art (e.g. Storch et al, 1951; Sheldon, 1983) and is designed specifically for industrial applications.

Ionic Processes used in the Catalytic Reaction The ionic catalyst uses a process of one or more of hydrogenation, carbon oxide insertion, methanation and polyaddition to convert CO, CO2 and CH4 to organic chemicals. Examples of ionic relationships for the hydrogenation of C02, CO and CH4 used in the invention include:-CO2+e=CO2 (1) 2C02 + 2& CO + CO32 (2) 2C02 + 2H + 2e H2C204 (3) CO2 + 2H + 2e HCOOH (4) CO2+2H+2e=CO+H2O (5) CO2 + 4H + 4e HCHO + H20 (6) CO2 + 6H4 + 6e = CH3OH + H20 (7) CO2+8l-['+8eCH4+2fl2O (8) CO2 + 7l{ = CH3 + 2H20 (9) CO2 + 6H = CH22 + 2H20 (10) CO2+5H=CH3+2I-f2O (11) CO2+4H=C4+21-I2O (12) CH4=CH3+J-1 (13) Cl-L4=CH22+2j-I (14) CH4=CH3+3H (15) (16) CO+5H=CH3+l-I2O (17) CO+41{F=CH22+H20 (18) C0+3F[CH3+H2O (19) CO+2H=C4+H2O (20) 2CO+2H=H2C2O2 (21) Co + 21{' HCHO (22) Co + H20 = CO2 + 2H (23) CO + 4H4 CH3OH (24) CO + 6H4 Cl-I4 + H20 (25) 2H20 + 2& = H2 + 20H (E(V) -0.83 Volts) (26) electron; E(V) = standard reduction potential in water at 298 K (25° C); By definition (Brown et al, 2000, Table 1, p. 766), E(V) 0 volts for H2 = 2H. E(V) for Equation 26 is taken from Table 1, page 766 of Brown, L., Le May Jr, H.E., Bursten, B.E., 2000. Chemistry the Central Science. Prentice Hall, ISBN: 0-13-010310-1.

This list of equations is not inclusive and other ionic relationships occur and they are specifically incorporated.

Adsorpiton onto the Catalyst The catalyst creates an electrochemical environment within the catalyst bed which forces the carbon oxides and organic chemicals in the feed gas passing through the catalyst bed to act as weakly associated anions and cations. These anions (e.g. Equations 1 to 40) flow in a gas phase through the catalyst bed or are temporarily captured and form a loose association with the cation of the catalyst.

These anions either (a) capture the H cations (e.g. Equations I to 51) to produce a covalent organic product, or (b) capture a carbon oxide (or an organic chemical) to produce an enlarged anion, or (c) a combination thereof. The principal inorganic by-products from this ionic process are one or more of H2 and H20.

The reaction is catalysed by the ionic catalyst in the gas phase and on the catalyst surface, where chain growth from an initial organic nucleus (Equations I to 40) is by one or more of polymerisation, hydrogenation, methanation, carbon oxide insertion and polyaddition with species (reactants and products) contained within the catalyst bed (Equations 41 to 51). This is a major difference from the Fischer Tropsch and related processes which polymerises hydrocarbons (and organic chemicals) in a complex Langmuir-Hinshelwood surface reaction where the reactants are equilibrated to the reduced reaction surface prior to the reaction occurring. Polymerisation occurs in the Fischer Tropsch and related processes by (a) methylene insertion, (b) methylene insertion onto an adsorbed ethylidene, (c) carbon oxide adsorption following hydrogenation, (d) alkenyl insertion and (e) oxide bond insertion.

The principal by-products associated with the Fischer Tropsch and related processes are CO2 and H20.

The Fischer Tropsch and related processes are operated under conditions where the feed gas composition is constant, the feed gas flow rate is constant, the operating temperature is constant and the operating pressure is constant.

One application for the ionic catalyst is to remove carbon oxides from the flue gases associated with a combustion, incineration, electricity generating, or carbonisation plant. The flue gas from these sources will vary in composition, flow rate and temperature over time. The flue gas will contain oxygen when it is derived from a fuel which has been burnt in an excess of air or oxygen. The flue gas may also contain substantial quantities of nitrogen. The presence of oxygen, delivery variability, and flue gas composition variability renders this gas source unsuitable for processing using a Fischer Tropsch catalyst. This flue gas is suitable for use with an ionic catalyst as defined in this invention.

The presence of oxygen in the flue gas will poison the Fischer Tropsch catalyst by oxidising its surface.

Oxygen does not poison the ionic catalyst. The oxygen may combine with H2 or CO within the catalyst bed to produce H20 and CO2 (e.g. 02 + 2H2 2H20; 02 + 2C0 = 2CO2). Some or all of these products (CO2 + H20) will be disassociated (Equations I to 12, 26) within the catalyst bed and incorporated into organic products. Consequently, the presence of oxygen will either (a) enhance the organic product yield, or(b) increase the amount of water product or(c) alter the CO:C02 ratio of the product gas relative to the CO:C02 ratio in the feed gas or (d) a combination thereof. The Example demonstrates (Tables I to 30) that variability in feed gas composition and associated delivery parameters will be reflected in the product composition.

C1-L-(cation + anion) = CH3 + H + (cation + anion) (27) Cl-Lg-(cation + anion) = CH2 + H2 + (cation + anion) (28) CH4-(cation + anion) = CH + H3 + (cation + anion) (29) CH4-(cation + anion) C + H4 --(cation + anion) (30) H2C204-(cation + anion) l-1C204+ H + (cation + anion) (31) H2C,04-(cation + anion) = C2042+ 2H + (cation + anion) (32) HCOOH-(cation + anion) HCOC + H + (cation + anion) (33) HCOOH-(cation + anion) C002+ 2H + (cation + anion) (34) HCIIO-(catjon + anion) CHO+ H + (cation + anion) (35) HCHO-(cat ion + anion) C02+ 2l{ + (cation + anion) (36) CH3OI-l-(cation + anion) = CH2OH+ H + (cation + anion) (37) CH3OH-(cation + anion) = CHOH2+ 2H + (cation + anion) (38) CH3OH-(cation + anion) C0H3 + 3H + (cation + anion) (39) CH3OH-(catjon + anion) C04 + 4H + (cation + anion) (40) This list of equations is not inclusive and other ionic relationships occur and they are specifically incorporated. Similar ionic relations occur for CH and CXHYOX and these are also specifically incorporated.

Formation of Larger Covalent Organic Molecules The product can be an organic chemical containing a single carbon atom. However, the organic anion can act as a nucleus for subsequent chain growth resulting from insertion of one or more of Cl-I4, CO, C02, CI-IO, CH3, CH22, CH3, C4, H2C202, HCHO, CH3OH, I-ICOOH, H2C204 and so forth, and by polyaddition of individual nucleated chains, and by the capture of organic molecules, or a combination thereof. For example, chain growth from a nucleating centre through the insertion or addition of one or more of H2, CO, CO2 and CH4 includes, but is not limited to:-CH4-(cation + anion) + CH4 = C2H3-(cation + anion) + 2H (41) HCHO-(catjon + anion) + CH4 = CH3CHO-(cat ion + anion) + 2H (42) HCOOI-I-(catjon + anion) + CH4 CH3COOH-(cation + anion) + 2H' (43) CH3OH-(cation + anion) + Cl-I4 = CH3CH2OFJ-(catjon + anion) + 2H (44) H2C204-(catjon --anion) + CH4 CO2HCH2CO2H-(cation + anion) + 2H (45) CH4-(catjon + anion) + CO2 = CH3COOH -(cation + anion) (46) CH4-(cation + anion) + CO = CH3CHO -(cation + anion) (47) CH4-(cation + anion) + CO + 2H2 = C2H6 -(cation + anion) + H20 (48) CH.1-(cation + anion) + CO2 + 3H2 = C2H6 -(cation + anion) + 2H20 (49) This list of equations is not inclusive and other ionic relationships occur and they are specifically incorporated.

The generic reaction equation is:-aCH4 + bCO + cCO2 + dH2 + eH2O + fCXHY + gCHO = Organic chemicals. (50) a, b, c, d, e, f, g signify relative molar abundances. Each of a, b, c, d, e, f, g can be zero. Each of a, b, c, d, e, f, g can fall within the range 0 and 1. The sum ofa+ b+c + d + e + f+ g= 1.0. fCH refers to a single chemical species or a collection of different chemical species with this generic equation, for example, ethane, propane, ethene, propene, hexane, benzene, and so forth. gCHO refers to a single chemical species or a collection of different chemical species with this generic equation, for example, acetone, formaldehyde (methanal), methanol, ethanol, formic acid, acetic acid, oxalic acid, ethanoic anhydride, methyl methanoate, furan, phenol, and so forth. Products by this process can include alcohols, aldehydes, ketones, alkanes, alkenes, aromatics, carboxylic acids, esters and carbonyls. For example, for an alkane or alkene:- (n-x)C02 + (3n+a-4x)H2 + xCH4 CH2�2 + 2(n-x)H20 (51) a I for alkanes, a 0 for alkenes.

Similar equations can be constructed for the large number of aromatics and different compounds of the general form gCHO and these are specifically incorporated. The reactions described by Equations 1 to 49 and 51, and variations of these equations fall within the scope of the generic reaction described in Equation 50.

Catalyst Construction The catalysts claimed include one or more ionic solids or ionic liquids or ionic gases, or a combination thereof and are constructed from:-i) a single ionic substance (for example NaCI, KCI), where an ionic substance has one or more cations and one or more anions, or ii) a mixture of two or more ionic substances (for example NaCI plus K2S04), or iii) a mixture of one or more ionic substances with one or more non-ionic catalysts or metals or metal oxides or metal carbides or carbon or a combination thereof or iv) a mixture of one or more ionic substances with one or more types of solid material selected from one or more of organic matter, layered silicates (for example clays and micas), hydrated silicates, fullerines, ash, sulphides, silicates, ortho-silicates, ring-silicates, chain silicates, sheet silicates, framework silicates, suiphides, suiphates, carbonates, hydroxides, oxides, phosphates, halides, pyroclastic material, hydrated silicates, hydrated carbon oxides, methane hydrates, support material, macroporous, mesoporous, microporous, nano-porous material, particulate material, or v) a combination thereof of(i) to (iv) The substances referred to in (i) to (v) are mixed at atmospheric pressure and at a temperature of less than 650° C. The substances can be mixed in the presence of air or nitrogen. The ionic substance can be coated onto solid material or impregnated into solid material or a combination thereof. The substances referred to in (i) to (v) are mixed together without additional chemical processing. The mixed substances can undergo additional physical processing designed to produce a finished catalyst.

Processing can be used to impregnate or coat solid material (including support material) with the catalyst. The catalyst is not reduced in CO or H2 prior to use.

The ionic solid is anhydrous or hydrated or held in a liquid or dissolved into one or more of an aqueous solution, a polar solvent, an ionic liquid, a deep eutectic liquid, a non-polar liquid or a combination thereof. The ionic liquid is a room temperature ionic liquid or an ionic liquid with a melting point below 100° C, or a deep eutectic solvent or an ionic solid which is liquid at the reactor operating temperature or a combination thereof; the ionic liquid can be water or can be insoluble in water or can contain water or can be soluble in water or a combination thereof; the ionic liquid can be a mixture of ionic liquids or a combination of the ionic substance or ionic substances with one or more non-ionic substances or polar substances or a combination thereof. The catalyst either has no promoters or is mixed with one or more promoters selected from one or more of organic compounds, organo-rnetallic compounds, metals, metal oxides, metal sulphides, metal phosphates, metal carbonates, metal hydroxideswherethemetalsareselectedfromcjroups 1,2,3,4,5,6,7,8,9, 10,11,1213,14,15,16 and the lanthanide and actinide series of the Periodic Table. Promoters when present are added at atmospheric pressure and mixed with the catalyst at a temperature of less than 650° C. The non-limiting example (Catalysts D, E, F, and 0) includes promoters which formed part of the solid material which was mixed with the ionic substance.

The non-limiting example experiment demonstrates that (i) the presence of a micro-porous or nano-porous support can enhance catalytic activity (e.g. Catalyst F), (ii) relatively small changes in the concentration of one or more ionic compounds contained in the catalyst (e.g. Catalyst G, H) or changes in the type of support material or changes in the type of solid material can have an effect on the proportion of carbon oxides in the feed gas which are removed by the invention.

Product Suite The composition of the product suite produced by the catalyst and the conversion efficiency may change with temperature, pressure, feed gas flow rate, feed gas composition, composition of the catalyst, structure of the catalyst, reactor type, and reaction time. The product suite produced by the catalyst may change with time as the catalyst ages. The catalysts operate at a temperature of less than 650°C and pressure of less than Pa (100 bar), where a pressure of I bar equals iO Pa, and at a feed gas hourly space velocity of less than 150,000 m3 hr' per m3 catalyst.

Feed Gas Composition The feed gas contains one or more of nitrogen, nitrogenous compounds, air, oxygen, oxygen containing gases, sulphur compounds (including, but not limited to sulphides, sulphur oxides, sulphates, etc.), halogen compounds (including but not limited to halides, hydrated halogenated compounds, organic compounds containing halogens, etc.), phosphorous compounds, ammonia compounds, amine compounds, H20, acids, metal contaminants (including, but not limited to, Hg), entrained soot, entrained particulate matter, entrained solid organic chemicals, entrained inorganic matter, entrained liquid organic chemicals and entrained hydrocarbon liquids.

The non-limiting example demonstrates that the invention can be flexibly operated (i) with a nitrogen content in the feed gas of between <5% and> 70% (Figures 65, 66, 67), (ii) when carbon oxides form from <2% to >15% of a feed gas containing nitrogen, and (iii) when carbon oxides form between <2% and >50% of the feed gas constituents, excluding nitrogen, (Tables Ito 30; Figures 5 to 82). The non-limiting example demonstrates that CO removal is independent of the CO:C02 ratio in the feed gas, and that some embodiments of the invention will be able to remove CO when CO2 is absent and vice versa.

The catalytic process can be used to concentrate nitrogen in a product gas when nitrogen is a constituent in the feed gas as illustrated in the example (Figures 65, 66 and 67).

Process Constraints The non-limiting example demonstrates (Tables I to 30, Figures 1 to 82) that the invention is effective when (a) the feed gas temperature is constant or varies over time; (b) the feed gas flow rate is constant or varies over time; (c) the feed gas composition is constant or varies over time; (d) the feed gas pressure is constant or varies over time.

Reactor Required The catalyst is placed in a fixed bed reactor, membrane reactor, bubble reactor, fluidised reactor, slurry reactor, insert reactor, coated wall reactor, tube wall reactor, nano-tube reactor, micro-channel reactor, nano-channel reactor, multitubular reactor, stirred reactor, or any other type of reactor which is able to contain the catalyst. The reactor can be made from any suitable material.

The catalyst can be placed in one or more reactors. When two or more reactors are present they can be arranged in parallel or in series or a combination thereof. Each reactor may operate at the same or different gas hourly space velocities. Different reactors may contain different catalysts, or the same catalyst or variations of one or more catalyst. The catalyst composition within a single reactor may be constant or may be variable. Different catalysts or variations of the same catalyst may be placed in different parts of the same reactor or mixed together within the same catalyst bed.

The catalyst is held in the reactor as particulate material or as a coating on solid material or as impregnated solid material or as liquid or as slurry or within slurry, or a combination thereof.

Recycling all or part of the product gas into the catalyst bed may alter the proportion of carbon oxides converted to products. Recycling may result in a change in the composition of the products produced.

The process and catalyst described above will be further understood by reference to the following non-

limiting examples.

EXAMPLES

Example Apparatus

A vertical internally heated carbonisation reactor was used to generate a flue gas (the feed gas). The particulate catalyst was held in place by a porous membrane/porous sleeve in a flow line. Flow line gas composition and temperature measurements were made on the gas immediately before and after it entered the catalyst bed. The reactor and flow lines were maintained at atmospheric pressure. The feedstock used in the carbonisation reactor was a mixture of municipal waste (plastics, cardboard, paper, food waste, polystyrene packaging, etc.) and biomass (green and brown garden waste). The temperature in the combustion chamber was allowed to vary between <1500 C and >4500 C. Air was used as the oxygen containing gas. The feed gas entering the catalyst bed contained some entrained particulates.

Catalysts The ionic catalysts tested in the experiment were:- 1. Catalyst A 0.125 kg of granulated NaCI (<1 ->5mm). Tables 1,2; Figures 5,6, 7, 8, 65, 68 2. Catalyst B 0.125 kg of granulated NaCl (<1 ->5 mm) + 0.125 kg of bituminous coal dust powder (<1 mm). Tables 3, 4; Figures 9, 10, 11, 12, 65, 69 3. Catalyst C 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of powdered FeSO4 Tables 5, 6; Figures 13, 14, 15, 16, 65, 70 4. Catalyst D 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of powdered lime (CaO + Ca(OH)2 + traces of MgO, Si02, A1203, Fe203) + 0.125 kg (<1 ->2 mm) granular quartz sand, Tables 7, 8; Figures 17, 18, 19, 20, 65, 71 5. Catalyst E = 0.125 kg of granulated NaCl (<1 ->5 mm) + 0.125 kg of granulated (0.5 3 mm) lodgement till ((boulder clay) swelling clay containing a layered silicate (illite, smectite.

chlorite, etc.), from Greenloaning, Scotland). Tables 9, 10; Figures 21, 22, 23, 24, 65, 72. XRF analysis of tills from this area (Coats et al, 1991, p. 5,6, 9,10) indicate the presence ofCa, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Hg, As, Rb, Sr, Y, Nb, Mo, Ag, Au, Sb, Ba, La, Ce, W, Pb, Bi, Th, U. 6. Catalyst F 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of particulate calcified seaweed (<1 ->5 mm), CaCO3, ((Maerl) coralline algae (Lirhothamn ion coraliioides, Lithothainnion glaciale, Lithothamn ion calcareum, Phymazolithon calcareum and similar coralline algae species)). The maerl contains Ca, Mg, Mn, Co, Zn, Cu, Na, Cl, S, Fe, I, Bo, Sr and has a porous microstructure. Tables 11, 12; Figures 25, 26, 27,28,66, 73 7. Catalyst G = 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of granulated (<1 ->3 mm) fertiliser, Type A: 45% organic matter + 6% N (as ammonium salts and nitrates) + 5% P (as Phosphates, phosphenes) + 7% K + 4% Mg. Tables 13, 14; Figures 29, 30, 31, 32, 66, 74 8. Catalyst H = 0.125 kg of granulated NaCI (<I ->5 mm) + 0.125 kg of pelleted (5 -20 mm) fertiliser, Type B: Organic matter (chicken manure) + 4.5% N (as ammonium salts and nitrates) + 3.5% P (as Phosphates, phosphenes) + 2.5% K + 1% Mg + 0.5% S (as SO4) + 9.0% Ca + trace Fe, Mn, Mo, Cu, Zn. Tables 15, 16; Figures 33, 34, 35, 36, 66, 75 9. Catalyst I = 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of Sphagnum Peat. Tables 17, 18; Figures 37, 38, 39, 40,66, 76 10. Catalyst J = 0.125 kg of granulated NaCl (<I ->5 mm) + 0.125 kg of commercial compost/soil improver. Tables 19, 20; Figures 41, 42, 43, 44, 66, 77 11. Catalyst K 0.125 kg of granulated NaCI(<1 ->5 mm) + 0.125 kg of Ammonium sulphate powder (NH4)2S04. Tables 21, 22; Figures 45, 46, 47, 48, 67, 78 12. Catalyst L = 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of Magnesium sulphate granules (0.5 -2 mm) (MgSO4:7H20) -Hydrate form (Epsom Salt). Tables 23, 24; Figures 49, 50, 51, 52, 67, 79 13. Catalyst M 0.125 kg of granulated NaCI (<I ->5 mm)+ 0.125 kg of Potassium sulphate powder (potash of sulphur) (K2S04). Tables 25, 26; Figures 53, 54, 55, 56, 67, 80 14. Catalyst N = 0.125 kg of granulated NaCI (<1 ->5 mm) + 0.125 kg of ash (l ->5 mm) from a carbonisation reactor. The ash includes char/charcoal/semicoke Tables 27, 28; Figures 57, 58, 59, 60, 67, 81 15. Catalyst 0 = 0.125 kg of granulated NaCI (<I ->5 mm) + 0.125 kg of granulated (<1 ->5 mm) Lower Old Red Sandstone, pyroclastic ash (tuff) from Dunning Glen, Dunning, Scotland.

Tables 29, 30; Figures 61, 62, 63, 64, 67, 82 The tuff is an andesitic tuff which has undergone extensive alteration containing quartz, sericite (mica), chlorite, pyrite, goethite, limonite, plagioclase, hematite, clay (illite, hydromuscovite, montmorjllonite, kaolinite). XRF analysis (Coats et al, 1991, p. 56, 68, 69) indicate the presence of Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Hg, As, Rb, Sr, Y, Nb, Mo, Sb, Ba, La, Ce, W, Pb, Th, U, Au, Bi In each case the catalyst was mixed at a temperature of between 10°C and 30°C. The NaCI used was in a ciystalline/rock salt/halite form. Individual catalysts were left in the reactor for time durations of between 8 and 72 hours online with no apparent loss of activity. Removing the catalyst from the reactor, leaving it exposed to air and then inserting it into the reactor gave no apparent loss of activity.

The groups of solid ionic catalyst evaluated by the example experiment include:-I. A transition metal plus a halide (Catalyst A through toO) 2. A transition metal plus a sulphate (Catalyst L, M) 3. A metal plus a sulphate (Catalyst C) 4. A nitrogenous compound plus a sulphate (Catalyst K) S. A metal plus a nitrate or a nitrogenous compound plus a nitrate (Catalyst C, H) 6. A transition metal plus a hydroxide or a metal plus a hydroxide (Catalyst D) 7. A transition metal plus a carbonate or a metai plus a carbonate (Catalyst F) 8. Mixture of organic material, metals, chlorides, phosphates and suiphates (Catalyst G, H) 9. Combinations of organic matter with an ionic catalyst (Catalyst B, C, H, I, J, N) 10. Clay (including a range of Fe-oxides and trace metals) plus an ionic catalyst (Catalyst E) 11. Microporous or nanoporous support plus an ionic catalyst (Catalyst B, F, G, H, 1, J, N) 12. Ionic catalyst plus an inert support (Catalyst C) 13. Ionic catalyst plus a pyroclastic including sulphides and a range of trace metals (Catalyst 0) 14. Ionic catalyst plus ash, including char, charcoal, semi-coke (Catalyst N) 15. Ionic catalyst plus trace metals (Catalyst E, F, 0) 16. Ionic catalyst including an ammonium cation (Catalyst K) 17. Ionic catalyst including sulphides (Catalyst 0) 18. Ionic catalyst mixed with material containing fullerines (Catalyst N) 19. Ionic catalyst containing promoters (Catalyst E, F, H, 0) Example Flue (Feed) Gas Composition The flue gas (feed) comprises N2 + CO + CO2 + CH4 where CH4 comprises aCH4 + dH2 + eH2O + + gCHO (Equation 50). The molar proportions of CO, C02, CH4, and N2 per 100 moles flue gas are provided in Figures Ito 4,65, 66, and 67 and Tables 1, 3,5, 7,9, 11, 13, 15, 17, 19, 21, 23, 25, 27 and 29. The CO:CO2 ratio in the flue gas is a function of combustion temperature and organic feedstock type (Figure 1). The CO:CH4 ratio in the feed gas (Figure 1) was between 1:100 and 10,000:1(0.01 to 10,000). The N2 range in the flue gas was between <5% and >80% (Fiure 2, 3, 4).

The feed gas flow rates entering the catalyst bed were varied between <700 ->60,000 m hr' flue gas per m3 catalyst. Feed gas temperatures entering the catalyst bed were varied between 16° C and 350 C. Example Product Gas Composition The product gas comprises unreacted feed gas + gaseous products. The molar proportions of CO and CO2 in 100 moles of product gas are provided in Figures 5 to 64 and Tables I to 30 for the 15 example catalysts, Catalyst A to 0. Figures 5, 9, 13, 17, 21, 25, 29, 33, 37,41,45,49, 53, 57, 61 show examples where the presence of the ionic catalyst has resulted in the CO2 content of 100 moles product gas being reduced to <30% of the CO2 content of 100 moles of feed gas. Figures 6, 10, 14, 18, 22, 26, 30, 34, 38, 42, 46, 50, 54, 58, 62 show examples where the presence of the ionic catalyst has resulted in the CO content of 100 moles product gas being reduced to <30% of the CO content of 100 moles of feed gas.

Figures 7, 11, 15, 19, 23, 27, 31, 35, 39, 43, 47, 51, 55, 59, 63 illustrate the relationship between Ratio F and Ratio B. They show that different catalysts may provide a different response to decreasing the relative proportion of carbon oxides to hydrogen containing compounds in the feed gas. Figures 8, 12, 16, 20, 24, 28, 32, 36, 40, 44,48, 52, 56, 60, 64 illustrate the relationship between Ratio G and Ratio A. They demonstrate that some catalysts result in preferential removal of CO relative to CO2 and vice versa, and that this relationship can change as Ratio A changes.

The tabulated data for each set of measurements (Tables I to 30) illustrate that the catalyst can change one or more of the molar mean abundance, standard deviation, skewness and kurtosis of the CO and CO2 components of the product gas when compared with the feed gas.

Example CO, CO2 and CH4 Conversion The catalytic reaction results in 100 moles of feed gas producing less than 100 moles of product gas (including unreacted feed gas). In the example experiments the volume of product gas produced ranged between 40 and 99 moles product gas (including unreacted feed gas) for each 100 moles of feed gas.

This reduction in gas volume resulted in the N2 concentration in the product gas increasing relative to the N2 concentration in the feed gas (Figures 65, 66, 67). Each catalyst provided a value for Ratio J and Ratio K (see Figures 68 -82) which was between 0% and 100%. The non-limiting examples (Figures 68-82) identif,' that, typically, between <10% and >80% of the (bCO + cCO2) and (aCI-L1 + dH2 + eH2O + fCXHY + gCHO) was removed from the feed gas during the catalytic reaction (Equation 50).

Figures 5 to 82 demonstrate that catalysts can be constructed by mixing ionic substances or mixing ionic substances with other materials. The conversion of CO2 to products resulted in the global warming potential of the product gas being less than the global warming potential of the feed gas (where the global warming potential of CO2 and CH4 is defined on pages 14-34 and 14-35 of CRC Handbook of Chemistry and Physics, 2008-2009, 89th Edition, dated 2008, Lide, D.R. (editor) published by CRC Press, Taylor and Francis Group, ISBN-l3 978-1-4200-6679-I).

Thus the present invention comprises a combination of features and advantages that provide it with flexibility, allow it to be constructed to accommodate a wide range of feed stocks and operating conditions and allow it to produce a range of products. Products can refer to financial products or financial benefits (for example tax credits resulting from a reduction in greenhouse gas emissions), or products can refer to a range of marketable products produced from the feedstock, or products can refer to the production of a fuel or a chemical ingredient for a process, or a combination thereof. Some embodiments of the invention will produce a gaseous fuel with a calorific value of>4.4 MJ/m3. Some embodiments of the invention will produce a liquid fuel with a calorific value of> 10 MJ/kg.

These and various other characteristics and advantages of the present invention will be readily apparent to those skilled in the art upon reading the detailed description of the preferred embodiments of the invention and by referring to the accompanying figures and tables. Publications cited herein and the materials for which they are cited, including any reference to the periodic table, ionic solids, ionic liquids, ionic gases, and ionic reactions are specifically incorporated by reference. It is to be understood that the present invention is not limited by the examples set forth which have been provided merely to demonstrate operability, Modifications and variations of the process, methods, catalysts and apparatus described herein will be obvious to those skilled in the art from the foregoing detailed descriptions.

Such modifications and variations are intended to come within the scope of the attached claims.

Table 1: Molar Flue Gas Composition (%) entering Catalyst A STD Standard Deviation. T = Temperature, C Number of CO2 CO lest Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 7 8.40 1.21 0.07 -1.53 1.44 0.42 1.02 0.09 33 2 24 4.15 3.46 3.11 1.79 0.89 0.76 2.13 1.57 21 3 9 2.93 0.78 -2.24 5.63 0.54 0.19 0.15 1.15 23 4 10 9.23 3.74 -1.46 1.03 2.45 1.01.0.95 -0.45 23 29 2.39 0.16 -3.01 11.48 0.43 0.07 -2.59 6.03 26 6 27 3.30 0.15 -2.92 10.16 0.66 0.13 -2.09 3.16 26 7 23 2.28 0.26 -3.05 9.47 0.47 0.11 -2.10 3.49 27 8 29 3.54 0.28 -2.89 9.46 0.80 0.19 -1.03 1.48 27 9 26 1.39 0.16 -0.90 0.13 0.26 0.06 -0.43 -0.96 30 22 1.04 0.09 -0.54 -0.90 0.14 0.03 -0.81 0.19 19 11 19 1.61 0.11 -3.03 11.67 0.24 0.03 -2.02 3.37 21 12 25 8.20 0.97 -2.98 10.25 1.63 0.30 -0.92 0.40 19 13 25 4.42 0.11 -2.59 9.16 0.70 0.11 -2.48 6.04 19 14 18 11.30 0.27 -1.08 0.94 1.73 0.19 -1.87 4.06 21 25 6.15 2.35 -0.02 -1,07 1.31 0.55 -0.75 -0.37 28 16 23 5.66 0.58 -1.12 0,54 1.25 0.43 -0.45 -0.72 23 17 10 6.62 2.08 -0.83 -0.88 0.82 0.59 0.15 -1.61 22 Table 2: Molar Product Gas Composition (%) leaving Catalyst A STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 8 3.53 2.27 0.83 -0.79 0.48 0.20 -0.90 1.11 33 2 33 4.62 3.33 1.03 -0.27 0.96 3.33 1.03 -0.27 21 3 7 2.53 0.66 -2.16 4.91 0.44 0.12 -0.77 0.42 23 4 6 10.40 6.47 -0.57 -1.90 1.69 1.69 1.69 1.69 23 32 2.83 0.15 -2.34 5.17 0.54 0.10 -2.25 4.23 26 6 30 1.95 0.51 0.18 -0.56 0.35 0.12 0.12 -0.30 26 7 28 2.62 0.11 -2.23 7.06 0.67 0.17 0.36 1.76 27 8 23 2.93 0.84 -0.92 -0.53 0.72 0.31 -0.53 -1.14 27 9 26 1.04 0.06 -0.53 -0.52 0.20 0.03 -2.11 4.03 30 33 1.19 0.04 -5.57 31.00 0.16 0.02 -3.18 11.43 19 11 32 1.57 0.06 -2.01 3.19 0.23 0.02 -2.98 10.29 21 12 19 5.83 0.76 -2.03 2.46 1.55 0.50 -1.17 -0.11 19 13 19 4.68 0.07 -0.69 1.26 0.72 0.06 -3.13 10.82 19 14 16 11.09 0.70 -2.61 7.65 1.51 0.37 -1.09 0.65 21 49 2.75 0.53 -1.65 1.95 0.63 0.14 -0.57 0.80 28 16 44 4.18 1.31 -1.43 0.64 0.95 0.46 -0.72 -1.12 23 17 22 5.76 1.73 -1.97 3.05 0.85 0.28 -1.37 093 22 Table 3: Molar Flue Gas Composition (%) entering Catalyst B STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 16 12.26 0.45 -3.93 16.29 1.88 0.05 -4.48 21.70 27 2 14 4.52 0.20 1.72 1.87 0.99 0.09 3.19 11.19 27 3 33 3.38 2.12 0.70 -0.87 0.55 0.29 0.98 -0.08 25 4 13 7.03 0.86 -0.65 -0.11 1.46 0.44 -0.55 -0.97 22 13 1.45 0.41 0.05 -1.96 0.38 0.19 0.91 0.41 28 6 7 1.87 0.43 -0.62 -1.51 0.37 0.14 -0.36 -1.37 23 7 20 8.36 0.92 -0.55 -1.42 1.13 0.34 0.05 -1.93 23 8 23 9.18 1.50 -2.68 6.79 1.63 0.48 -1.63 1.36 23 9 16 2.99 0,84 0.13 -0.59 0.79 0.28 0.41 -1.24 21 14 10.36 1.10 -2.58 7.14 1.32 0.24 -1.23 0.61 18 Table 4: Molar Product Gas Composition (%) leaving Catalyst B STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean SID Skewness Kurtosis T 1 23 12.88 0.34 -2.01 3.76 1.89 0.05 3.36 13.30 27 2 23 4.78 1.15 -0.27 -0.85 0.91 0.35 -0.33 -1.02 27 3 20 3.39 1.10 0.49 -0.27 0.69 0.34 0.80 1.41 25 4 24 2.43 0.50 -0.06 -1.16 0.59 0.21 -0.12 -0.52 22 21 1.49 0.47 -1.05 2.28 0.44 0.29 2.07 7.19 28 6 5 0.31 0.08 0.22 -2.75 0.05 0.01 -0.52 -0.48 23 7 15 4.54 2.13 0.29 -1.62 0.78 0.32 -0.57 -1.18 23 8 26 2.07 0.57 -0.22 -0.75 0.42 0.16 0.03 -1.18 23 9 16 2.21 1.05 1.09 -0.10 0.37 0.19 0.90 0.36 21 15 3.71 1.42 0.17 -0.98 0.68 0.44 0.85 -0.55 18 Table 5: Molar Flue Gas Composition (%) entering Catalyst C STD Standard Deviation, T Temperature C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STO Skewness Kurtosis T 1 14 10.36 1.10 -2.58 7.14 1.32 0.24 -1.23 0.61 18 2 16 2.99 0.84 0.13 -0.59 0.79 0.28 0.41 -1,24 21 3 23 9.18 1.50 -2.68 6.79 1.63 0.48 -1.63 1,36 23 4 20 8.36 0.92 -0.55 -1.42 1.13 0.34 0.05 -1.93 23 33 3.38 2.12 0.70 -0.87 0.55 0.29 0.98 -0.08 25 6 14 4.52 0.20 1.72 1.87 0.99 0.09 3.19 11.19 27 7 25 12.26 0.45 -3.93 16.29 1.88 0.05 -4.48 21.70 27 8 26 8.87 0.67 -3.98 16.84 1.79 0.32 -2.90 8.08 24 9 28 6.29 0.33 -4.41 20.69 1.03 0.13 -2.92 10.38 24 35 7.56 0.98 -3.55 12.90 1.13 0.24 -2.08 3.59 25 11 30 4.08 0.26 -3.03 10.12 0.55 0.10 -1.84 2.84 27 12 38 3.05 0.38 -0.95 0.48 0.44 0.09 -1.07 0.61 29 13 39 3.39 0.93 -1.01 -0.54 0.42 0.13 -0.85 -0.78 30 14 25 2.78 0.49 -1.77 3.33 0.33 0.06 -0.75 -0.82 27 Table 6: Molar Product Gas Composition (%) leaving Catalyst C STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STO Skewness Kurtosis Mean STD Skewness Kurtosis T 1 17 5.81 2.00 -0.04 -1.18 0.68 0.27 0.14 -1.36 18 2 12 3.34 0.82 -0.90 0.91 0.62 0.21 -0.26 -1.15 21 3 25 5.61 1.99 -0.37 -1.10 0.96 0.40 0.19 -0.89 23 4 22 6.82 0.87 -1.09 0.03 1.05 0.25 -0.70 -0.94 23 14 2.59 0.71 -0.35 -0.90 0.49 0.26 0.99 0.94 25 6 16 4.99 0.28 -0.35 -1.38 0.62 0.14 1.70 2.77 27 7 27 11.29 0.83 -1.04 1.54 1.84 0.20 -3.69 15.44 27 8 38 4.08 1.08 0.42 -1.31 0.89 0.30 0.28 -0.63 24 9 27 7.30 0.64 -2.99 9.32 1.34 0.26 -2.08 3.75 24 37 2.12 0.54 0.05 -0.38 0.32 0.08 -0.21 -1.26 25 11 30 4.02 0.35 -1.80 2.17 0.62 0.10 -1.39 3.00 27 12 30 2.56 0.58 -0.34 -0.66 0.33 0.09 -0.59 -0.20 29 13 34 3.49 0.45 -1.23 1.68 0.45 0.05 -0.43 -0.49 30 14 31 2.26 0.61 -0.82 -0.76 0.27 0.09 -0.50 -1.24 27 Table 7: Molar Flue Gas Composition (%) entering Catalyst D STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STO Skewness Kurtosis Mean STO Skewness Kurtosis T 1 17 4.64 0.33 -1.86 3.29 0.65 0.13 -0.72 -0.95 21 2 22 8.57 1.07 -2.01 4.41 1.65 0.41 -1.71 1.84 24 3 22 6.83 0.84 -2.20 4.68 0.93 0.21 -1.19 0.35 26 4 13 8.77 0.44 -1.08 0.86 1.21 0.21 -0.69 -0.90 19 20 9.72 0.18 -2.82 8.29 1.90 0.14 -3.52 12.68 16 6 18 7.13 0.16 -2.67 6.81 1.35 0.21 -2.37 5.18 18 7 22 8.68 0.54 -2.97 9.01 1.62 0.34 -1.73 2.12 24 8 19 11.08 0.48 -2.66 7.02 1.85 0.13 -3.69 14.51 24 9 17 8.41 0.59 -2.38 5.44 1.29 0.28 -1.22 -0.08 27 Table 8: Molar Product Gas Composition (%) leaving Catalyst D STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STO Skewness Kurtosis T 1 12 4.06 0.39 -0.84 1.06 0.54 0.11 -0.52 -1.12 21 2 36 1.99 0.18 0.12 -0.48 0.28 0.04 -0.94 0.97 24 3 25 1.82 0.42 -1.25 0.07 0.26 0.07 -0.65 -1.41 26 4 16 7.89 0.80 -0.88 -0.66 1.20 0.10 -0.35 -1.62 19 19 10.39 0.72 -2.68 7.81 1.88 0.18 -2.41 4.91 16 6 19 7.14 0.36 -2.44 8.11 1,39 0.27 -2.02 3.24 18 7 14 10.17 0.87 -1.84 2.79 1.60 0.40 -1.07 -0.40 24 8 14 10.19 0.64 -2.04 4.38 1.82 0.19 -3.17 10.36 24 9 21 6.87 1.50 -0.68 -0.81 1.14 0,30 -0.19 -1.29 27 Table 9: Molar Flue Gas Composition (%) entering Catalyst E STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 13 5.00 0.89 -1.98 3.92 0.59 0.25 -0.47 -0.98 25 2 35 3.37 0.13 -2.52 9.23 0.52 0.08 -2.75 7.24 29 3 23 13.31 0.43 -2.91 9.16 1.80 0.16 -2.10 2.92 26 4 18 6.27 0.48 0.54 -0.83 0.80 0.09 0.11 -0.75 23 38 3.54 0.40 -1.89 3.07 0.49 0.14 -1.37 0.28 26 6 37 4.00 0.41 -1.04 0.55 0.67 0.21 -0.70 -0.83 24 7 33 6.67 0.71 -0.05 -1.30 1.01 0.14 -0.49 1.01 27 8 18 10.48 0.71 -1.15 0.79 1.32 0.27 -1.37 1.39 26 9 26 1.39 0.16 -0.90 0.13 0.26 0.06 -0.43 -0.96 30 29 3.54 0.28 -2.89 9.46 0.80 0.19 -1.03 1.48 27 11 23 2.28 0.26 -3.05 9.47 0.47 0.11 -2.10 3.49 27 12 27 3.30 0.15 -2.92 10.16 0.66 0.13 -2.09 3.16 26 13 29 2.39 0.16 -3.01 11.48 0.43 0.07 -2.59 6.03 26 14 25 12.26 0.45 -3.93 16.29 1.88 0.05 -4.48 21.70 27 26 8.87 0.67 -3.98 16.84 1.79 0.32 -2.90 8.08 24 16 19 9.37 0.77 -0.69 6.55 1.82 0.13 -3.77 14.79 24 17 29 8,65 1.07 -0.90 1.29 1.81 0.31 -3.15 9.87 25 Table 10: Molar Product Gas Composition (%) leaving Catalyst E STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 7 0.29 0.06 0.18 -0.68 0.03 0.01 0.18 -0.68 25 2 38 2.56 0.29 -2.90 8.81 0.38 0.06 -1.55 1.46 29 3 53 6.68 2.79 -0.78 -0.95 0.74 0.33 -0.55 -1.13 26 4 41 2.48 0.90 -0.45 -1.24 0.26 0.10 -0.27 -1.37 23 25 1.74 0.50 -0.22 -1.63 0.24 0.09 0.01 -1.46 26 6 34 2.09 0.59 -0.10 -0.78 0.38 0.13 -0.12 -0.95 24 7 11 2.24 0.45 -1.30 1.76 0.20 0.07 -1.84 3.62 27 8 42 5.06 1.25 0.35 -1.39 0.72 0.14 0.19 -1.11 26 9 24 1.43 0.19 -0.84 -0.65 0.27 0.07 -0.61 -1.11 30 24 1.63 0.32 0.23 -0.14 0.32 0.12 0.40 -0.22 27 11 26 1.86 0.20 -0.23 -0.40 0.38 0.10 -0.87 -0.13 27 12 30 1.66 0.37 0.42 -0.81 0.30 0.08 -0.13 -0.25 26 13 30 1.88 0.26 -1.03 0.08 0.32 0.08 -1.03 -0.18 26 14 38 5.68 0.91 -0.95 0.21 1.33 0.32 -1.17 1.19 27 28 3.77 0.73 0.39 -0.35 0.69 0.18 -0.81 0.32 24 16 19 8.78 1.02 -2.05 5.42 1.72 0.32 -2.58 7.26 24 17 29 5.10 1.57 -0.32 -1.48 1.22 0.43 -0.11 -1.38 25 Table 11: Molar Flue Gas Composition (%) entering Catalyst F STD = Standard Deviation, I = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 13 5.00 0.89 -1.98 3.92 0.59 0.25 -0.47 -0.98 25 2 35 3.37 0,13 -2.52 9.23 0.52 0.08 -2.75 7.24 29 3 25 13.31 0.43 -2.91 9.16 1.80 0.16 -2.10 2.92 26 4 18 6.27 0.48 0.54 -0.83 0.80 0.09 0.11 -0.75 23 28 6.29 0.33 -4.41 20.69 1.03 0.13 -2.92 10.38 24 6 35 7.56 0.98 -3.55 12.90 1.13 0.24 -2.08 3.59 25 7 30 4.08 0.26 -3.03 10.12 0.55 0.10 -1.84 2.84 27 8 38 3.05 0.38 -0.95 0.48 0.44 0.09 -1.07 0.61 29 9 39 3.39 0.93 -1.01 -0.54 0.42 0.13 -0.85 -0.78 30 25 2.78 0.49 -1.77 3.33 0.33 0.06 -0.75 -0.82 27 11 19 9.94 0.48 -1.13 4.04 1.82 0.28 -2.63 7.06 21 Table 12: Molar Product Gas Composition (%) leaving Catalyst F STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STO Skewness Kurtosis Mean STO Skewness Kurtosis T 1 7 3.96 1.08 -0.69 -1.30 0.41 0.19 0.17 -1.59 25 2 63 1.84 0.59 -0.29 -1.42 0.28 0.11 0.03 -0.96 29 3 38 9.46 1.69 -0.64 -0.37 1.35 0.36 -0.92 0.25 26 4 41 4.74 1.90 -0.42 -1.26 0.76 0.34 -0.41 -1.17 23 28 3.42 1.11 -0.18 -0.72 0.56 0.23 -0.04 -0.64 24 6 33 1.78 0.35 0.21 -0.57 0.27 0.07 0.42 1.61 25 7 26 2.59 0.40 -0.60 -0.23 0.37 0.08 -1.02 0.54 27 8 34 1.96 0.15 -1.53 2.55 0.27 0.04 -1.30 1.01 29 9 29 3.29 0.51 -1.19 2.19 0.40 0.08 -0.91 1.05 30 26 1.71 0.62 0.59 -0.99 0.21 0.09 0.69 -0.76 27 11 27 5.12 1.60 0.08 -0.77 1.01 0.37 0.15 -0.62 21 Table 13: Molar Flue Gas Composition (%) entering Catalyst G STD Standard Deviation, T = Temperature, C Number of CO2 Co _Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 21 4.37 0.45 -3.15 10.18 0.61 0.13 -1.53 1.47 21 2 22 8.57 1.07 -2.01 4.41 1.65 0.41 -1.71 1.84 24 3 22 6.83 0.84 -2.20 4.68 0.93 0.21 -1.19 0.35 26 4 13 8.77 0.44 -1.08 0.86 1.21 0.21 -0.69 -0.90 19 20 9.72 0.18 -2.82 8.29 1.90 0.14 -3.52 12.68 16 6 18 7.13 0.16 -2.67 6.81 1.35 0.21 -2.37 5.18 18 7 22 8.68 0.54 -2.97 9.01 1.62 0.34 -1.73 2.12 24 8 19 11.08 0.48 -2.66 7.02 1.85 0.13 -3.69 14.51 24 9 17 8.41 0.59 -2.38 5.44 1.29 0.28 -1.22 -0.08 27 28 2.42 0.69 -0.55 -0.77 0.26 0.07 -0.33 -1.16 23 11 28 9.79 1.51 -2.67 8.18 1.66 0.41 -1.81 2.56 26 12 27 2.57 0.37 -2.39 5.34 0.42 0.07 -1.12 -021 27 13 29 4.91 1.49 -1.53 1.03 0.92 0.39 -0.68 -1.07 35 Table 14: Molar Product Gas Composition (%) leaving Catalyst G STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 25 1.98 0.70 0.21 -1.43 0.26 0.11 0.58 -0.85 21 2 23 4.94 1.77 -0.67 -072 0.79 0.38 -0.40 -1.37 24 3 24 6.57 1.03 -1.44 0.83 0.97 0.24 -0.97 -0.59 26 4 17 6.26 0.80 -1.70 2.08 0.85 0.20 -0.95 -0.56 19 34 3.38 1.33 -0.11 -1.67 0.69 0.29 0.08 -1.58 16 6 23 5.42 0.92 -1.01 0.22 1.00 0.27 -1.24 0.86 18 7 26 7.15 0.80 -2.75 7.15 1.39 0.37 -1.67 1.56 24 8 28 6.07 2.91 -0.40 -1.33 1.22 0.63 -0.34 -1.56 24 9 31 5.74 1.14 -0.88 0.06 0.97 0.30 -0.78 -0.51 27 24 2.06 0.17 -0.97 0.49 0.23 0.03 0.39 1.32 23 11 29 1.67 0.13 -0.92 0.74 0.14 0.02 -1.81 3.87 26 12 29 1.97 0.26 -0.46 0.02 0.28 0.26 -0.46 0.02 27 13 33 2.16 0.57 0.47 -0.15 0.39 0.15 0.19 -0.51 35 Table 15: Molar Flue Gas Composition (%) entering Catalyst H STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 18 13.10 0.95 -3.43 12.06 1.91 0.05 -2.97 9.08 24 2 21 10.86 1.98 -1.97 3.45 1.78 0.47 -0.93 1.14 22 3 27 9.15 0.60 -4.87 24.60 1.24 0.17 -2.35 5.24 20 4 22 15.86 0.73 -3.62 13.74 1.89 0.13 -4.67 21.87 20 26 4.04 1.42 -1.02 -0.51 1.03 0,51 -0.77 -1.22 25 6 30 4,53 1.14 -1.58 1.52 0.73 0.28 -0.89 -0.62 29 7 28 3.04 0.73 2.20 5.30 0.74 0.22 1.70 5.48 24 8 22 9.96 1.36 -1.91 3.49 1.82 0.36 -2.98 9.07 23 9 23 12.18 1.33 -2.36 6.66 1.87 0.04 -3.88 16.14 23 21 15.99 1.11 -2,83 7.03 1.88 0.06 -4.29 19.11 22 11 18 10.72 0.62 -2.73 7.06 1.69 0.33 -1.42 0.66 21 Table 16: Molar Product Gas Composition (%) leaving Catalyst H STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 19 12.17 1.34 -2.07 3.46 1.78 0.29 -2.77 6.39 24 2 19 12.87 0.06 -1.77 2.54 1.91 0.01 -0.82 1.12 22 3 28 8.43 0.34 -3.45 12.85 1.11 0.13 -1.73 2.11 20 4 19 15.32 0.60 -3.70 14.13 1.89 0.14 -4.23 18.17 20 21 4.47 0.80 -1.87 2.31 0.96 0.31 -1.50 0.79 25 6 35 3.89 0.43 -3.68 14.67 0.91 0.21 -1.99 3.35 29 7 31 4.00 0.14 -1.75 4.57 0.96 0.13 -2.53 6.58 24 8 24 8.79 3.21 -0.86 -0.42 1.56 0.54 -1.61 1.22 23 9 25 11.86 0.46 -4.16 18.19 1.82 0.22 -4.21 18.45 23 27 14.79 0.94 -2.78 8.84 1.83 0.17 -3.89 16.58 22 11 13 10.48 0.99 -0.77 0.46 1.73 0.26 -1.14 1.25 21 Table 17: Molar Flue Gas Composition (%) entering Catalyst I STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 18 13.10 0.95 -3.43 12.06 1.91 0.05 -2.97 9.08 24 2 17 11.55 0.63 -4.12 17.00 1.56 0.15 -3.99 16.22 27 3 22 10.86 1.98 -1.97 3.45 1.78 0.47 -0.93 1.14 21 4 27 9.15 0.60 -4,87 24.60 1.24 0.17 -2.35 5.24 20 22 15.86 0.73 -3.62 13.74 1.89 0,13 -4.67 21.87 20 6 26 4.04 1.42 -1.02 -0.51 1.03 0.51 -0.77 -1.22 25 Table 18: Molar Product Gas Composition (%) leaving Catalyst I STD = Standard Deviation, I = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 22 3.28 0.57 -1.45 1.53 0.94 0.29 -1.17 0.51 24 2 14 9.01 1.34 -0.64 0.75 1.72 0.39 -2.16 4.01 27 3 26 8.85 0.70 -3.39 12.83 1.35 0.26 -1.75 2.02 21 4 25 8.92 0.45 -0.03 -1.66 1.29 0.13 -2.07 3.98 20 24 10.41 1.40 -0.41 -1.40 1.76 0.39 -1,31 0.24 20 6 23 2.24 0.56 -0.16 -1.65 0.50 0.12 -0.26 -0.55 25 Table 19: Molar Flue Gas Composition (%) entering Catalyst J STD = Standard Deviation, I = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 28 2.42 0.69 -0.55 -0,77 0.26 0.07 -0.33 -1.16 23 2 28 9.79 1.51 -2.67 8,18 1.66 0.41 -1.81 2.56 26 3 27 2.57 0.37 -2.39 5.34 0.42 0.07 -1.12 -0.21 27 4 29 4.91 1.49 -1.53 1.03 0.92 0.39 -0.68 -1.07 35 19 9.37 0.77 -0.69 6.55 1.82 0.13 -3.77 14.79 25 6 29 8.65 1.07 -0.90 1.29 1,81 0.31 -3.15 9.87 24 7 22 9.94 0.48 -1.13 4.04 1.82 0.28 -2.63 7.06 21 Table 20: Molar Product Gas Composition (%) leaving Catalyst J STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 31 4.18 0.19 -3.06 10.19 0.60 0.08 -2.20 3.83 23 2 27 6.25 1.25 -1.66 2.60 0,99 0.29 -1.32 0.72 26 3 24 3.05 0.81 -1.18 0.11 0.44 0.14 -0.96 -0.44 27 4 29 2.94 1.30 -0.48 -1.40 0.63 0.31 -0.24 -1.67 35 17 11.03 0.57 -2.40 6.40 1.81 0.15 -4.09 16.79 25 6 23 6.81 1.55 -1.05 0.55 1.64 0.43 -1.73 1.99 24 7 22 11.24 0.41 -3.09 9.77 1.86 0.14 -3.46 12.37 I 21 Table 21: Molar Flue Gas Composition (%) entering Catalyst K STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 29 4.29 0.43 -2.61 6.97 0.50 0.07 -2.02 3.76 23 2 40 2.02 1.23 1.41 0.24 0.30 0.16 1.47 0.33 19 3 30 3.85 0.43 -1.47 1.71 0.18 0.02 -2.88 9.57 21 4 33 11.60 0.85 -3.50 13.56 1.77 0.28 -2.36 5.00 24 31 10.74 0.58 -3.07 12.35 1.85 0.21 -3.52 12.54 24 6 27 11.24 1.10 -4.00 16.78 1.89 0.05 -4.13 17.76 25 7 31 13.24 0.29 -3.45 12.53 1.90 0.01 -3.00 8.97 23 8 34 9.79 0.30 -1.70 6.09 1.91 0.12 -2.60 17.94 24 9 43 1.98 0.14 -1.36 1.64 0.36 0.07 -1.04 2.47 24 44 2.30 0.29 -0.73 -0.16 0.47 0.09 -1.87 3.57 24 11 31 2.40 0.49 -1.18 0.17 0.41 0.11 -1.12 0.19 25 12 35 2.01 0.19 -2.69 8.27 0.31 0.06 -2.09 3.71 25 13 19 2.39 0.77 0.03 -0.90 0.41 0.18 -0.05 -1.20 24 14 28 4.22 0.21 -0.70 1.04 0.69 0.09 -2.47 6.07 25 Table 22: Molar Product Gas Composition (%) leaving Catalyst K STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 33 4.13 0.48 -2.67 7.28 0.41 0.10 -1.86 2.90 23 2 38 1.02 0.07 -0.26 -0.82 0.20 0.02 -0.86 0.30 19 3 35 4.65 0.14 -2.02 6.75 0.16 0.01 -3.42 12.98 21 4 28 9.80 0.64 -1.75 3.34 1.12 0.24 -1.49 1.90 24 36 9.48 1.04 -3.29 11.61 1.80 0.36 -2.56 5.87 24 6 29 10.18 0.38 -2.80 8.43 1.87 0.10 -3.46 11.02 25 7 29 10.04 1.03 -2.80 8.53 1.85 0.18 -4.25 18.96 23 8 29 10.67 0.27 -2.85 12.87 1.74 0.13 -4.97 26.24 24 9 39 1.73 0.17 -3.06 9.59 0.31 0.06 -2.33 5.11 24 54 1.42 0.18 -1.39 1.47 0.31 0.07 -1.09 0.28 24 11 44 2.33 0.44 -1.18 0.48 0.40 0.11 -1.15 0.32 25 12 32 2.36 0.12 -1.24 1.70 0.39 0.04 -1.39 2.99 25 13 30 3.76 0.47 -1.66 3.26 0.71 0.15 -2.05 4.01 24 14 29 2.81 0.44 -0.80 1.55 0.45 0.11 -0.67 1.37 25 Table 23: Molar Flue Gas Composition (%) entering Catalyst L STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STO Skewness Kurtosis Mean STD Skewness Kurtosis T 1 25 8.39 1.05 -2.45 6.01 1.43 0.36 -1.60 1.54 22 2 24 9.45 1.10 -1.34 1.16 1.70 0.34 -2.06 3.43 22 3 24 14.25 1.04 -3.70 14.51 1.78 0.26 -2.66 6.87 21 4 26 10.22 0.53 -4.71 23.03 1.59 0.25 -1.93 3.43 20 23 12.20 0.50 -2.87 7.53 1.90 0.04 -4.55 21.37 19 6 20 5.89 0.19 -1.40 3.57 0.99 0.14 -2.21 4.51 18 7 29 4.29 0.43 -2.61 6.97 0.50 0.07 -2.02 3.76 23 8 40 2.02 1.23 1.41 0.24 0.30 0.16 1.47 0.33 19 9 30 3.85 0.43 -1.47 1.71 0.18 0.02 -2.88 9.57 21 33 11.60 0.85 -3.50 13.56 1.77 0.28 -2.36 5.00 24 11 31 10.74 0.58 -3.07 12.35 1.85 0.21 -3.52 12.54 24 12 27 11.24 1.10 -4.00 16.78 1.89 0.05 -4.13 17.76 25 13 31 13.24 0.29 -3.45 12.53 1.90 0.01 -3.00 8.97 23 14 34 9.79 0.30 -1.70 6.09 1.91 0.12 -2.60 17.94 24 43 1.98 0.14 -1.36 1.64 0.36 0.07 -1.04 2.47 24 16 44 2.30 0.29 -0.73 -0.16 0.47 0.09 -1.87 3.57 24 Table 24: Molar Product Gas Composition (%) leaving Catalyst L STD = Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 30 4.33 0.27 -1.91 3.89 0.69 0.11 -1.70 2.71 22 2 19 10.89 1.02 -1.96 3.58 1.34 0.24 -1.45 0.97 22 3 26 12.48 1.35 -1.49 1.98 1.57 0.29 -1.18 2,40 21 4 31 8.35 0.41 -4.15 18.98 0.97 0.13 -1.01 0.77 20 28 10.37 1.00 -1.28 0.35 1.52 0.21 -2.86 8.15 19 6 24 4.20 0.51 -2.49 6.64 0.58 0.13 -1.49 1.25 18 7 30 1.91 0.82 2.06 5.33 0.23 0.14 3.17 10.01 23 8 35 1.81 0.18 -2.79 8.09 0.26 0.08 -0.59 -1.47 19 9 35 2.40 0.15 -3.29 13.87 0.20 0.03 -3.49 13.86 21 25 11.04 2.33 -2.36 5.21 1.44 0.40 -1.85 2.30 24 11 26 11.21 1.74 -2.07 3.94 1.47 0.31 -1.99 3.94 24 12 29 11.87 1.45 -2.41 6.77 1.60 0.13 -4.59 22.36 25 13 31 12.47 1.04 -1.63 2.61 1.62 0.08 -4.05 18.38 23 14 47 10.67 0.27 -2.85 12.87 1.74 0.13 -4.97 26.24 24 38 1.73 0.17 -3.06 9.59 0.31 0.06 -2.33 5.11 24 16 35 2.60 0.22 -3.25 12.15 0.51 0.10 -2.18 4.50 24 Table 25: Molar Flue Gas Composition (%) entering Catalyst M STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 28 304 0.73 2.20 5.30 0.74 0.22 1.70 5.48 24 2 22 9.96 1.36 -1.91 3.49 1.82 0.36 -2.98 9.07 23 3 23 12.18 1.33 -2.36 6.66 1.87 0.04 -3.88 16.14 23 4 21 15.99 1.11 -2.83 7.03 1.88 0.06 -4.29 19.11 22 18 10.72 0.62 -2.73 7.06 1.69 0.33 -1.42 0.66 21 6 25 8.39 1.05 -2.45 6.01 1.43 0.36 -1.60 1.54 22 7 24 9.45 1.10 -1.34 1.16 1.70 0.34 -2.06 3.43 22 8 24 14.25 1.04 -3.70 14.51 1.78 0.26 -2.66 6.87 21 9 26 10.22 0.53 -4.71 23.03 1.59 0.25 -1.93 3.43 20 23 12.20 0.50 -2.87 7.53 1.90 0.04 -4.55 21.37 19 11 20 5.89 0.19 -1.40 3.57 0.99 0.14 -2.21 4.51 18 12 31 2.40 0.49 -1.18 0.17 0.41 0.11 -1.12 0.19 25 Table 26: Molar Product Gas Composition (%) leaving Catalyst M STD Standard Deviation, T = Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 37 3.02 1.20 0.61 -0.88 0.72 0.33 0.51 -0.75 24 2 31 3.43 2.34 0.06 -2.12 0.81 0.58 0.06 -2.11 23 3 33 2.54 0.19 -3.07 12.79 0.53 0.08 -2.67 6.93 23 4 21 10.59 1.22 -1.79 4.28 1.75 0.33 -3.04 9.03 22 12 4.82 1.28 -1.08 1.02 0.95 0.23 -0.68 -0.66 21 6 28 3.53 0.97 -0.70 -0.53 0.60 0.23 -0.55 -0.96 22 7 24 3.94 0.44 -2.25 4.91 0.78 0.18 -1.49 1.46 22 8 24 6.34 1.68 -1.04 0.20 0.90 0.32 -0.81 -0.78 21 9 27 8.87 1.76 -0.48 -1.03 1.07 0.23 -0.25 -0.77 20 23 3.55 0.32 -0.03 -0.55 1.01 0.21 -2.19 4.65 19 11 25 5.66 0.09 -3.00 10.11 1.21 0.13 -2.39 5.78 18 12 35 1.00 0.08 0.05 -1.35 0.19 0.02 -0.26 -1.49 25 Table 27: Molar Flue Gas Composition (%) entering Catalyst N STD = Standard Deviation, I Temperature, C Number of C02 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis I 1 24 1.90 0.55 -0.03 -1.01 0.50 0.20 0.28 -0.23 25 2 29 2.69 0.57 -0.39 -0.72 0.53 022 3.11 13.47 24 3 30 2.49 0.62 -0.85 -0.60 0.64 0.19 -0.91 -0.30 27 4 29 9.13 0.74 -3.59 13.09 1.79 0.33 -3.29 10.75 25 34 1.55 0.28 -0.81 0.15 0.32 0.06 -0.67 -0.44 22 6 23 5.97 2.61 -0.49 -1.25 1.52 0.76 -0.47 -1.40 22 7 44 2.40 0.27 -3.41 12.44 0,33 0.06 -2.03 3.51 20 8 27 1.31 0.06 -1.28 6.65 0.16 0.01 -2.73 8.11 22 9 37 4.65 1.72 -0.30 -0.85 0,99 0.33 -0.84 -0.12 20 19 13.49 0.87 -3.49 12.80 1.85 0.23 -2.83 7.30 17 11 25 7.02 0.86 -3.83 15.56 1.04 0.19 -2.47 6.63 16 Table 28: Molar Product Gas Composition (%) leaving Catalyst N STD -Standard Deviation, T = Temperature, C Number of CO2 CO Test Samptes Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 36 1.84 0.40 -0.57 -0.68 0.42 0.14 -0.31 -0.22 25 2 46 1.73 0.31 0.01 -0.84 0.33 0.06 0.02 0.19 24 3 19 2.48 0.98 0.48 -0.23 0.44 0.21 0.52 -0.34 27 4 29 6.42 1.09 -1.84 3.78 1.40 0.40 -0.96 0.20 25 9 1.10 0.12 -1.05 -0.29 0.18 0.02 -0.32 -0.86 22 6 9 9.19 1.12 -2.15 4.50 1.61 0.46 -1.27 0.23 22 7 29 1.60 0.34 -0.85 -0.58 0.21 0.05 0.48 -0.26 20 8 29 1.73 0.11 -2.50 7.83 0.21 0.03 -0.53 1.22 22 9 19 6.21 1.49 -1.77 2.89 0.94 0.33 -1.05 -0.09 20 14 12.58 1.42 -2.61 6.71 1.78 0.33 -2.35 4.47 17 11 24 3.58 0.64 -0.51 -0.67 0.54 0.14 -0.09 -0.57 16 Table 29: Molar Flue Gas Composition (%) entering Catalyst 0 STD = Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 24 1.90 0.55 -0.03 -1.01 0.50 0.20 0.28 -0.23 25 2 29 2.69 0.57 -0.39 -0.72 0.53 0.22 3.11 13.47 24 3 38 1.51 0.44 0.05 -1.33 0.39 0.16 0.21 -1.31 27 4 15 2.27 0.96 0.70 -0.07 0.25 0.13 0.27 -1.08 25 30 2.49 0.62 -0.85 -0.60 0.64 0.19 -0.91 -0.30 27 6 29 9.13 0.74 -3.59 13.09 1.79 0.33 -3.29 10.75 25 7 34 1.55 0.28 -0.81 0.15 0.32 0.06 -0.67 -0.44 22 8 23 5.97 2.61 -0.49 -1.25 1.52 0.76 -0.47 -1.40 22 9 14 2.81 0.85 -0.88 -0.24 0.46 0.20 0.54 0.10 22 44 2.40 027 -3.41 12.44 0.33 0.06 -2.03 3.51 20 11 27 1.31 0.06 -1.28 6.65 0.16 0.01 -2.73 8.11 22 12 37 4.65 1.72 -0.30 -0.85 0.99 0.33 -0.84 -0.12 20 13 19 13.49 0.87 -3.49 12.80 1.85 0.23 -2.83 7.30 17 14 25 7.02 0.86 -3.83 15.56 1.04 0.19 -2.47 6.63 16 Table 30: Molar Product Gas Composition (%) leaving Catalyst 0 STD Standard Deviation, T Temperature, C Number of CO2 CO Test Samples Mean STD Skewness Kurtosis Mean STD Skewness Kurtosis T 1 28 1.91 0.34 -0.40 -1.03 0.46 0.13 -0.11 -0.38 25 2 38 1.64 0.35 -0.05 -1.23 0.30 0.07 -0.41 -0.12 24 3 17 1.42 0.37 0.20 -0.99 0.36 0.12 0.13 -1.20 27 4 20 3.05 1.29 0.07 -1.10 0.56 0.28 0.66 -0.42 25 27 1.07 0.12 -0.54 -1.33 0.32 0.04 -0.62 -1.28 27 6 33 3.88 1.52 -0.38 -1.00 0.70 0.32 0.13 -1.10 25 7 31 1.25 0.18 -0.36 -1.07 0.24 0.06 -0.01 1.28 22 8 15 6.39 1.70 -1.59 1.63 1.25 0.49 -1.11 1.63 22 9 20 4.99 0.83 -0.85 0.08 0.95 0.25 -1.08 0.67 22 34 2.65 0.12 -1.99 3.41 0.38 0.04 -1.74 2.63 20 11 26 1.14 0.08 -1.45 1.91 0.13 0.02 -1.25 1.18 22 12 16 6.44 1.35 -2.01 4.12 1.09 0.39 -1.00 -0.40 20 13 20 13.11 1.64 -2.66 7.22 1.78 0.34 -2.22 3.88 17 14 25 I 6.51 0.77 -2.01 4.01 0.90 0.18 -1.38 1.15 16

Claims

CLAIMSWhat is claimed is:- 1. A catalytic process and catalysts for the removal from a flowing gas of one or more carbon oxides, selected from carbon monoxide and carbon dioxide and one or more hydrogen containing gases selected from hydrogen, methane, other hydrocarbon gases, and gaseous organic chemicals wherein:-I) the ionic catalytic process removes carbon oxides from a feed gas by one or more of methanation, carbon oxide insertion, polymerisation, polyaddition and hydrogenation to produce organic products containing one or more carbon atoms selected from one or more of alkanes, alkenes, alkynes, aldehydes, ketones, alcohols, arenes, amines, amides, ethers, esters, carbonyls, nitriles, carboxylic acids, aromatics, cyclic organic compounds, vinyl monomers, vinyl polymers, polymers, copolymers, addition polymers, condensation polymers, polyamides, organic halogen compounds, organic compounds containing sulphur, organic compounds containing phosphorous, organic compounds containing a metal, ii) the process is undertaken at an operating pressure of less than i07 Pa (100 bar) and at a gas flow line temperature of less than 65 0°C (823 K) and at a gas hourly space velocity entering the catalytic reactor of less than 150,000 m3 hf' per m3 catalyst, iii) the process is undertaken when (a) the feed gas temperature is constant or varies over time; (b) the feed gas pressure is constant or varies over time; (c) the feed gas flow rate is constant or varies over time; (d) the feed gas composition is constant or varies over time, iv) the feed gas is a flue gas or an exhaust gas or a specific product gas or a waste gas or a natural gas, or a gas from any other source which contains one or more carbon oxides selected from carbon monoxide and carbon dioxide, or a combination thereof, v) feed gases from different sources can be mixed prior to arriving in the catalyst containing reactor or mixed in the catalyst containing reactor or a combination thereof, vi) the feed gas can additionally contain one or more of nitrogen, nitrogenous compounds, air, oxygen, oxygen containing gases, sulphur compounds, halogen compounds, phosphorous compounds, ammonia compounds, amine compounds, H20, acids, metal contaminants, entrained soot, entrained particulate matter, entrained solid organic chemicals, entrained inorganic matter, entrained liquid organic chemicals and entrained hydrocarbon liquids.
2. The catalysts according to Claim 1 include one or more ionic solids or ionic liquids or ionic gases or a combination thereof where the ionic catalyst is constructed from either a single ionic substance or a mixture of two or more ionic substances or a mixture of one or more ionic substances and solid material wherein:-i) the catalyst is organic or inorganic or a combination thereof, ii) the ionic solid is anhydrous or hydrated or held in a liquid or dissolved into one or more of an aqueous solution, a polar solvent, an ionic liquid, a deep eutectic liquid, a non-polar liquid or a combination thereof, iii) the ionic liquid is a room temperature ionic liquid or an ionic liquid with a melting point below 100° C, or a deep eutectic solvent or an ionic solid which is liquid at the reactor operating temperature or a combination thereof; the ionic liquid can be water or can be insoluble in water or can contain water or can be soluble in water or a combination thereof; the ionic liquid can be a mixture of ionic liquids or a combination of the ionic substance or ionic substances with one or more non-ionic substances or polar substances or a combination thereof, iv) the catalyst either has no promoters or is mixed with one or more promoters selected from one or more of organic compounds, organo-metallic compounds, metals, metal oxides, metal sulphides, metal phosphates, metal carbonates, metal hydroxides where the metals are selected from Groups 1, 2, 3,4, 5,6,7,8, 9, 10, 11, 12 13, 14, 15, 16 and the lanthanide and actinide series of the Periodic Table, v) the anion includes one or more metalloids or non-metals selected from H, F, Cl, Br, I, At, 0, S, Se, Te, N, P, As, Sb, C, Si, Ge, B held in a monoatomic or polyatomic form; the catalyst can contain more than one type of anion; the anions can be inorganic or organic or a combination thereof, vi) the cation includes one or more metals selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Sn, Pb, Bi, Po, Ce, Th, U, or an organic ion or an ammonium ion ((NH4) or H or a hydrogen containing ion or a combination thereof where the cations are held in a monoatomic or polyatomic form, vii) when one or more ionic solids or ionic liquids or ionic gases or a combination thereof are mixed with solid material then the solid material is selected from one or more of organic matter, layered silicates, hydrated silicates, fullerines, ash, sulphides, silicates, ortho-silicates, ring-silicates, chain silicates, sheet silicates, framework silicates, sulphides, sulphates, carbonates, hydroxides, oxides, phosphates, halides, pyroclastic material, hydrated silicates, hydrated carbon oxides, methane hydrates, support material, particulate material, macroporous, mesoporous, microporous, nano-porous material, viii) mixtures of one or more of ionic substances with one or more of promoters and solid material are mixed together at atmospheric pressure and at a temperature of less than 6500 C, ix) the catalyst is held in the reactor as particulate material or as liquid or as slurry or as coatings on solid material or as impregnated solid material or a combination thereof, x) the catalyst does not require to be reduced in either CO or H2 prior to use