WO2016162866A1 - Catalyst composition and catalytic processes for producing liquid hydrocarbons - Google Patents
Catalyst composition and catalytic processes for producing liquid hydrocarbons Download PDFInfo
- Publication number
- WO2016162866A1 WO2016162866A1 PCT/IL2016/050364 IL2016050364W WO2016162866A1 WO 2016162866 A1 WO2016162866 A1 WO 2016162866A1 IL 2016050364 W IL2016050364 W IL 2016050364W WO 2016162866 A1 WO2016162866 A1 WO 2016162866A1
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- WO
- WIPO (PCT)
- Prior art keywords
- extrudates
- hydrocarbons
- silica
- potassium
- pellets
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 84
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 52
- 230000003197 catalytic effect Effects 0.000 title description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 239000008119 colloidal silica Substances 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 164
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 76
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 66
- 239000008188 pellet Substances 0.000 claims description 57
- 229910001868 water Inorganic materials 0.000 claims description 49
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 44
- 239000001569 carbon dioxide Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002407 reforming Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 229910052596 spinel Inorganic materials 0.000 claims description 21
- 239000011029 spinel Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 15
- 239000011591 potassium Substances 0.000 claims description 15
- 239000003345 natural gas Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 238000001879 gelation Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001960 metal nitrate Inorganic materials 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000000629 steam reforming Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 229910052595 hematite Inorganic materials 0.000 description 4
- 239000011019 hematite Substances 0.000 description 4
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 101100007418 Caenorhabditis elegans cox-5A gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- pellets are rarely used as powders; they are usually employed as entities of larger size and/or better defined shapes, e.g., in the form of pellets, to prevent an unacceptably high pressure drop in gas-phase reactions in packed beds.
- pellet is used herein to indicate any discrete solid form created from powdered material by means of forming operations, typically through the application of pressure or compaction, for example, using an extruder to form extrudates, or a press to produce tablets or by granulation methods .
- the alumina-containing pellets are mechanically stronger, but in their presence, the selectivity of the reaction to the valuable C5+ hydrocarbons, and especially to C7+ hydrocarbons is unfortunately lower than the activity measured for a parallel reaction using the binder-free pellets.
- silica as a binder in place of alumina, it is possible to produce via carefully chosen conditions potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica-containing pellets, in particular extrudates, which are not only mechanically strong, but also display high catalytic activity, surpassing that of the binder-free pellets.
- an extrudable mass was achieved on combining the catalyst Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4 with colloidal silica as the sole silica source, in a specific pH environment, more precisely, around neutral pH values.
- Extrusion of silica-rich solids, consisting of silica, zeolite or a mixture thereof to form extrudates with an acceptable physical strength is described in US 4,582,815 and US 5,053,374.
- the preparation method according to the invention involves the gelation of a colloidal silica in the presence of Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4 particles at a suitable pH, preferably in the range from 6.5 to 7.5, more preferably from 6.8 to 7.2.
- the so-formed gelled material is optionally dried, to give an extrudable mass with an acceptable moisture content, preferably from 40 to 45% (by weight) , which is then formed into pellets (extrudates) .
- the resultant extrudates after aging and drying, undergo a first calcination, followed by impregnation with potassium solution, and are then dried and calcined again, to give potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4 silica-containing extrudates with high mechanical strength and greatly improved catalytic activity which can find utility in a variety of processes of hydrocarbons production from carbon dioxide, that is, the reaction of carbon dioxide with hydrogen (produced by water splitting or by steam reforming of natural gas or other sources) to produce hydrocarbons, the reaction of carbon monoxide (produced by carbon dioxide splitting or other sources) with steam to produce hydrocarbons and conversion of H2 ⁇ lean syngas (obtainable by dry reforming of natural gas or other sources) to hydrocarbons.
- the features of these processes are set out in detail below.
- a first aspect of the invention is a process for preparing potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica- containing pellets [0.3 ⁇ y ⁇ 0.7, preferably 0.4 ⁇ y ⁇ 0.6], comprising subjecting colloidal silica to gelation in the presence of Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4 spinel particles, converting the gelled material into pellets and adding potassium to said pellets.
- the weight ratio Fe:Al:K in the catalyst preferably varies from 100:20:3 to 100:30:20.
- the active catalytic material Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4 is prepared by a co-precipitation technique described in detail in WO 2014/111919.
- the co-precipitation of the metals takes place to give the corresponding mixed hydroxides which on drying undergo dehydration whereby a spinel compound is formed, which is preferably free of a hematite or magnetite phases after calcination.
- Suitable starting materials for use in the preparation of the Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4 catalyst are water-soluble ferric and aluminum salts, such as the nitrate salts.
- the two metal nitrates exist in hydrated forms: Fe (NO3) 3 ⁇ 93 ⁇ 40 and Al (NO3) 3 ⁇ 9H2O .
- the preferred concentrations of the ferric and aluminum salts in the aqueous solution are from 400 to 1200 g/liter and 200-600 g/liter and, respectively, with the relative amounts of the salts being adjusted to form the desired composition of the catalyst.
- the water-soluble metal salts e.g., the nitrates
- the weight ratio Al : Fe in the solution is not less than 20:100, e.g., from 20:100 to 30:100.
- the adjustment of the pH of the aqueous solution to the range from 6.0 to 8.5, especially between 7.5 and 8.5, e.g., around 8.0, in order to induce the co-precipitation of the metal hydroxides, is preferably accomplished by the gradual addition of an aqueous base solution, such as ammonium hydroxide solution, which solution is preferably applied in a dilute form, with concentration of not more than 5% by weight.
- an aqueous base solution such as ammonium hydroxide solution
- the precipitate formed is separated from the mother liquor, e.g., by filtration or any other solid/liquid separation technique, optionally washed with water and then dried at temperature in the range of 100-140°C for period of at least 3 hours, e.g., at least 6 hours.
- the spinel compound is combined with a suitable silica precursor.
- a reduced-particle size form of the spinel material is preferably employed. Particle size reduction could be achieved using conventional methods, e.g., with the aid of a milling device such as a ball mill.
- the Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4 compound is milled to produce a population of particles (nanocrystalline aggregates) with particle size of less than 250 ⁇ , preferably from 20 to 200 ⁇ , as determined, for example, by laser light scattering (laser diffraction) method.
- a silica precursor useful as a starting material in the preparation of the pellets is an aqueous alkali-stabilized colloidal silica with amorphous silica particle size of up to lOOnm, preferably up to 50 nm, e.g., from about 10 to 20 nm (nominal size) , with the content of the silica in the dispersion varying from 20 to 40% by weight.
- Suitable colloidal silica are commercially available (for example, Ludox® HS originally from E I Du Pont de Nemours & Co and now from Grace & Co; two preferred grades are Ludox® HS-30 and Ludox® HS-40 which contain 30% and 40% silica, respectively) .
- the amount of colloidal silica is from 90 to 100% weight percent of the total amount of silica used in the process; preferably, only colloidal silica is used as a silica source in forming the extrudates of this invention .
- the pH of the colloidal silica is reduced by the addition of a mineral acid, such as concentrated nitric acid, although other acids may also be used.
- a mineral acid such as concentrated nitric acid
- the pH of the system is reduced to within the range of below the alkaline pH threshold necessary to stabilize the colloidal silica starting material.
- setting the pH of the colloidal silica too low within the acidic regime can damage the structure of the spinel powder (the spinel is incompatible with either highly basic or acidic environment) .
- a suitable pH window exists around neutral pH, e.g., from about 6.5 to 7.5, preferably from 6.8 to 7.2.
- the Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4 powder is combined with the silica dispersion.
- the weight ratio Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2O4/S1O2 in the mixture is preferably from 50:50 to 80:20, e.g., 55:45 to 75:25, more preferably from 65:35 to 75:25.
- a gel is formed on maintaining the mixture under mixing/kneading at temperature of 20-80°C for at least three hours (preferably 3-6 hours at elevated temperatures and 20-24 hours at room temperature) .
- the Fe 2+ ( Fe 3+ y Al 3+ i- y ) 204/Si02-containing gel is optionally dried under kneading to adjust the consistency of the mass (e.g., to achieve water content of about 40-45 wt%), taken out from the vessel ( kneader) and formed into pellets using conventional methods, including extrusion to produce extrudates or inserting in a perforated plate.
- the extrudates may be produced in different shapes and sizes; for example, cylindrical extrudates with diameter of 1.5-2.5 mm and length in the range from 3 to 15 mm.
- the invention provides extrudates, using an apparatus customary for this purpose, that is, extruders including single-screw or twin-screw extruders which can be co-rotating or counter-rotating.
- extruders including single-screw or twin-screw extruders which can be co-rotating or counter-rotating.
- the mass is fed through the feed inlet of an extruder and extruded through a die plate containing 2-4 mm diameter holes.
- the pellets are aged in air at room temperature for period of not less than 5 h, e.g., not less than 15 h, dried, e.g., in air at a temperature of not less than 100°C for a period of time of not less than 3 hours, e.g., not less than 6 hours, and then calcined in air at a temperature in the range from 300 to 400°C for not less than 3 hours.
- the catalytically active material Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4 distributed within the pellet is essentially free of hematite or magnetite phases .
- potassium is loaded onto the pellets (e.g., extrudates) .
- the potassium promoter may also be added to the catalyst at one of the early stages of the process, e.g., a portion of the desired amount of the promoter may be added to the Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4 powder or to the Fe 2+ ( Fe 3+ y Al 3+ i-y) 204/Si02-containing gel.
- the impregnation-drying cycle may be repeated several times.
- the weight ratio Fe : K is in the range from 100:3 to 100:20, for example, more than 100:10 and up to 100:18.
- the potassium-containing pellets are subjected to drying in air at a temperature in the range of 100-140°C for period of at least 3 hours, e.g., at least 6 hours followed by calcination in air at a temperature in the range from 400 to 500°C for period of at least 3 hours, e.g., at least 6 hours.
- the invention specifically relates to a process for preparing potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica- containing extrudates, comprising the following steps:
- step (iii) allowing the mixture resulting from step (ii) to transform into a gel
- step (x) calcining the extrudates resulting from step (ix) .
- the resultant potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica- containing pellets (e.g., extrudates) form another aspect of the invention.
- the pellets e.g., extrudates
- the extrudates comprise 45 to 85% by weight Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 0 4 , 10-50% by weight S1O2 and 3 to 10% by weight potassium.
- the extrudates comprise 60 to 80% by weight Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, 15- 40% by weight S1O2 and 4 to 8% by weight potassium.
- the extrudates of the invention exhibit surface area of not less than 130 m 2 /gram, e.g., between 150 and 220 m 2 /gram; pore volume of not less than 0.23 cm 3 /gram, e.g. between 0.25 and 0.40 cm 3 /gram, and average pore diameter between 6.0 and 8.0 nm. Elemental analysis by means of energy dispersive X-ray spectroscopy of the catalyst indicates that the weight ratio Fe:Al is in the range from 100:20 to 100:30. Analytical techniques and instruments used for the measurements reported herein are as described in WO 2014/111919.
- Extrudates of 1.6 mm diameter prepared according to the invention display good mechanical properties, that is, a crush strength measured by Quantachrome Crush Strength Analyzer CSA- 2 ranged from 11 to 26 N/mm, e.g., from 15 to 22 N/mm, and crushing force/circumference from 5 to 8 N/mm.
- the pellets e.g., extrudates
- a suitable reactor e.g., a continuous fixed bed reactor.
- the thickness of the catalyst layer packed in the reactor may vary within the range of 7 cm to 12 m, typically from 1 m to 12 m, provided the size of the pellets is chosen so as to avoid a significant pressure drop.
- the extrudates of the invention finds utility in a wide range of processes for preparing hydrocarbons from different feedstock materials, and in particular, the extrudates can effectively advance the conversion of carbon dioxide by hydrogenation to hydrocarbons, the conversion of carbon monoxide by reaction with steam to hydrocarbons and the conversion of 3 ⁇ 4-lean syngas (the product of dry reforming of natural gas) into hydrocarbons.
- the extrudates need first to undergo activation.
- the activation of the extrudates is carried out in-situ, by either reduction (hydrogenation) or carburization .
- Reduction involves the flow of hydrogen stream through the reactor in which the extrudates are placed at a temperature of not less than 400°C.
- the flow rate of the hydrogen stream is not less than 20cm 3 /min per gram of extrudates.
- the reduction is continued at atmospheric pressure for not less than 3 hours .
- Carburization involves the exposure of extrudates to a carbon-containing atmosphere. To this end, streams of carbon monoxide, hydrogen and an inert gas carrier are caused to flow through the reactor in which extrudates are placed at a temperature of not less than 300°C.
- the flow rates of the three gaseous components (CO, 3 ⁇ 4 and inert gas (N2, He, Ar) ) are at least 30:30:150 cm 3 /min per one gram of the extrudates, respectively.
- the carburization is continued at atmospheric pressure for not less than 3 hours.
- the carbon dioxide hydrogenation reaction is allowed to start.
- carbon dioxide-containing gaseous stream and hydrogen stream are continuously fed to the reactor at H2/CO2 of not less than 1, e.g., not less than 2, and weight hourly space velocity (WHSV) not less than 0.1 hr 1 , preferably not less than 0.5 hr 1 and more preferably not less than 1 hr 1 .
- the reaction is carried out at a temperature in the range from 250 to 360°C at pressure of not less than 5, e.g., not less 10 atmospheres, e.g., from 20 to 40.
- Another aspect of the invention is therefore a process for producing hydrocarbons comprising hydrogenation of carbon dioxide-containing gas stream in the presence of the potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica-containing pellets (e.g., extrudates) that were described above.
- carbon dioxide-containing gas stream used in the present invention may be neat carbon dioxide and also any gas mixture which contains carbon dioxide, for example, a mixture of carbon dioxide and carbon monoxide, with the molar fraction of carbon dioxide being not less than 0.25.
- the hydrogenation of carbon dioxide-containing gas stream may be carried out in the apparatus illustrated in Figure 4 of WO 2014/111919, where the reactor configuration is based on a plurality of fixed bed reactors arranged in series.
- This figure is reproduced below as Figure 1.
- the serially-positioned reactors are designated by numerals (1) , (2) and (3) .
- Each reactor is provided with a suitable amount of pellets (extrudates) loaded therein.
- the amount of pellets in each reactor is adjusted to improve conversion and productivity. Alternatively, the total amount of the pellets used in the process may be equally divided between the set of reactors.
- Each reactor is provided with a discharge line (4) , with a cooler (5) , a gas-liquid separator (6) and a liquid-liquid separator (7) positioned successively along said discharge line.
- Each liquid-liquid separator (7) is connected to two tanks, (8) and (9) , for collecting organic and aqueous phases, respectively.
- the gas-liquid separator is connected by means of a feed line (10) to the consecutive reactor.
- Carbon dioxide, hydrogen and optionally carbon monoxide required for the process are supplied through feed lines (11) , (12) and (13) , respectively.
- Hydrogen may be produced by the electrolysis of water in an electrolysis unit (not shown) and carbon dioxide may be recovered from industrial processes such as the combustion of fossil fuels in power generating plants, cement or steel plants.
- Another useful source of the reactans required for the process is carbon dioxide-rich syngas, i.e., a gas mixture comprising CO2, 3 ⁇ 4 and CO where the concentration of CO2 is greater than the normal concentration in conventional syngas, i.e., the molar fraction of carbon dioxide in the syngas is not less than 0.25 and preferably not less than 0.5.
- carbon dioxide (11) and hydrogen (12) , and optionally carbon monoxide (13) streams are fed to the first of said serially arranged reactors, with their relative amounts being adjusted by means of flow controllers (14) .
- hydrogen may be directly fed also to each of the successive reactors by means of feed lines (15, 16) equipped with flow controllers (14) , so as to maintain an optimal ratio between the gaseous reactants.
- CO2, H2 and CO may be fed at molar ratios 1:5:1.
- the temperature and pressure maintained within each of the serially-placed reactors are as set forth above, and the preferred WHSV is not less than 0.5 hr 1 .
- the gaseous mixture produced at each reactor is discharged (4), and subjected to cooling and condensation (5) whereby a liquid-gas mixture is obtained.
- This mixture is separated into its liquid and gaseous components in a gas-liquid separator (6) .
- the gaseous, non-condensable component which consists of non-reacted CO2, 3 ⁇ 4 and CO with light organic compounds is removed from the liquid component and fed directly to the next reactor via line (10) .
- the liquid component is fed to a liquid-liquid separator (7) , where it is separated into organic and aqueous phases, which are collected in two distinct tanks.
- the organic product (8) (containing mainly alkanes and alkenes with 6-20 carbon atoms in their molecules) is further processed to produce high-quality liquid fuels and chemicals by methods known in the art. As shown in Figure 1, a further separation may be conducted after the third stage, to separate liquids from non- condensable products.
- the so-formed product consists of a mixture of aliphatics, olefins and monoaromatics , with a distribution dependant on the CO/H2O ratio at the reactor inlet. With the aid of Fe203 powder catalyst, it was possible to reach 67.5% CO conversion at 300°C and CO/H 2 0 ratio of 3
- the extrudates of the invention undergo activation.
- the activation of the extrudates is carried out in-situ, by reduction (hydrogenation) .
- Reduction involves the flow of hydrogen stream through the reactor in which extrudates are placed at a temperature of not less than 400°C.
- the flow rate of the hydrogen stream is as high as 20 cm 3 /min per gram of extrudates.
- the reduction is continued at atmospheric pressure for not less than 3 hours.
- temperature is adjusted according to the reaction conditions and a CO/H2O mixture is fed to the reactor.
- Streams of carbon monoxide and steam are continuously fed to the reactor at H20:CO molar ratio of not less than 0.2:1, e.g., preferably from 0.3:1 to 0.4:1, and weight hourly space velocity (WHSV) of not less than 0.1 hr 1 , preferably from 0.4 to 2 hr 1 .
- the reaction is carried out at a temperature in the range from 250 to 340°C (for example, 250 to 290°C) , at pressure of not less than 15 atmospheres, e.g., from 20 to 50 atm at the reactor inlet.
- the apparatus includes at least one reactor (30) with a configuration suitable for heterogeneous solid-catalyzed reactions.
- Carbon monoxide (31) and steam (32) required for the process are supplied to the reactor via feed lines equipped with flow controllers.
- the outlet of the reactor is connected to a discharge line provided with at least one cooler (34) and one gas-liquid separator (35) coupled to said cooler.
- the apparatus comprises an array of n successively positioned coolers (cooleri, cooler, cooler n ) each associated with a gas-liquid separator (gas-liquid separatori, gas-liquid separator, gas-liquid separator n , respectively) .
- a gas-liquid separator gas-liquid separatori, gas-liquid separator, gas-liquid separator n , respectively.
- Non- condensable matter withdrawn from a gas-liquid separator is passed via a conduit to a cooler placed downstream to said gas-liquid separator (namely, cooleri + i receives non- condensable materials from gas-liquid separatori) .
- Each of the gas-liquid separators is either directly or indirectly in fluid communication with a vessel for collecting an organic liquid, with at least one of the gas-liquid separators being connected to a liquid-liquid separator for carrying out a separation of a liquid mixture into its organic and aqueous components .
- the apparatus of Figure 7 comprises a first cooler (34) and a second cooler (36) , each coupled to a gas- liquid separator, i.e., to a first gas-liquid separator (35) and a second gas-liquid separator (37) , respectively, with either the first gas-liquid separator (35) , the second gas- liquid separator (37) or both, being in fluid communication with a liquid-liquid separator (38) to enable the separation of a liquid mixture into organic and aqueous phases.
- a gas- liquid separator i.e., to a first gas-liquid separator (35) and a second gas-liquid separator (37)
- a liquid-liquid separator i.e., to a first gas-liquid separator (35) and a second gas-liquid separator (37)
- the gaseous mixture produced at the reactor (30) is discharged.
- a first cooler (34) On cooling the mixture with the aid of a first cooler (34) to a temperature Ti (Ti>100°C) and condensation, a first gas-liquid mixture is formed, which is separated in (35) into a first liquid component and a first gaseous component.
- the first liquid component may consist of both aqueous and organic phases.
- the first liquid undergoes separation in a liquid-liquid separator (38) into organic and aqueous phases, following which the heavy organic compounds produced by the process are collected (39), e.g., linear alkanes and alkenes with 7-40 carbon atoms.
- This organic liquid constitutes the major product of the process and can be processed to give high-quality liquid fuels or chemicals by methods known in the art. Water may be also collected (in vessel (40)) .
- the first gaseous component discharged from (35) contains non- reacted CO, 3 ⁇ 4, and CO2 with light organic compounds. It flows to a successively placed cooler (36) . On further cooling to a temperature T2 (T2 ⁇ 10°C) in said second cooler (36) , a second gas-liquid mixture is formed, which is separated in a second gas-liquid separator (37) into a second liquid component and a second gaseous component.
- the liquid component consists of an organic phase to be collected (in vessel (41)) .
- another aspect of the invention comprises a process for preparing liquid hydrocarbons, comprising contacting carbon monoxide-containing gas stream with steam in the presence of the potassium-promoted Fe 2+ ( Fe 3+ y Al 3+ i- y ) 2 ⁇ 4, silica-containing pellets that were described above, and collecting the liquid hydrocarbons formed.
- the carbon monoxide-containing gaseous stream is not necessarily neat CO and may contain, in addition to carbon monoxide, also carbon dioxide up to molar fraction of 0.25, e.g., a feedstock consisting of CO:C02 mixture with a molar ratio of more than 3:1, e.g., more than 4:1, is perfectly acceptable: the experimental results reported below clearly show that the process of the invention runs swiftly in the presence of carbon dioxide in the feedstock material.
- the conversion of carbon monoxide to hydrocarbons is achieved without feeding a stream of hydrogen reactant to the reactor where the reaction takes place.
- the process contemplates the use of substantially hydrogen-free carbon monoxide-containing gaseous stream and steam.
- the inclusion of hydrogen is possible, for example, up to molar 3 ⁇ 4 : CO of 0.25 and even up to 0.5 (as shown by (33) in Figure 7) .
- the extrudates are used to catalyze the conversion of H 2 -lean syngas (H2/CO ⁇ 1) to hydrocarbons.
- the H 2 -lean syngas may be obtained by dry reforming of natural gas.
- GTL gas to liquid
- FTS Fischer-Tropsch synthesis
- Feed of the autothermal reforming process contains oxygen thus combustion also takes place:
- one aspect of the invention is a process for preparing liquid hydrocarbons, comprising converting carbon monoxide and hydrogen-containing gas stream with a molar ratio H2/CO ⁇ 1 to hydrocarbons in the presence of the potassium- promoted Fe 2+ ( Fe 3+ y Al 3+ i-y) 2 ⁇ 4, silica-containing pellets (extrudates) that were described above, and collecting the liquid hydrocarbons formed.
- the molar ratio H2/CO in the feed stream is in the range of 0.51 ⁇ H2/CO ⁇ 0.8 (for example, 0.6 ⁇ H 2 /CO ⁇ 0.8) .
- the molar ratio H2/CO in the feed stream is in the range of 0. OKH2/CCKO .51 (for example 0.05 ⁇ H 2 /CO ⁇ 0.51 or 0.1 ⁇ H 2 /CO ⁇ 0.51 ) , and water is added to the feed .
- the carbon monoxide and hydrogen-containing gas stream used as a feedstock may be 3 ⁇ 4-lean syngas obtained by dry reforming of natural gas.
- the invention relates to a process which comprises:
- the so-formed product hydrocarbons obtained in the second CO hydrogenation step may be upgraded by methods known in the art to produce liquid fuels and chemicals.
- a reactor with suitable configuration such as a packed bed reactor (see, for example, ST. C. TEUNER, P. NEUMANN and F. VON LINDE, The Calcor Standard and Calcor economy Processes, OIL GAS European Magazine 3/2001, 44-46; N.R. Udengaard, J.-H. Bak Hansen, D.C. Hanson, J.A. Stal, Sulfur Passivated Reforming Process Lowers Syngas H 2 /CO Ratio, Oil Gas J. 90 (10), (1992) 62) .
- a feed stream consisting of the natural gas (chiefly methane) and carbon dioxide is supplied to the reactor.
- the ratio carbon dioxide to methane is CO2/CH4 ⁇ 1. It is useful to keep this ratio above unity to achieve high stability of the catalyst by avoiding coke formation. Furthermore, the higher this ratio is, the higher the methane conversion and the lower the H2/CO obtained.
- the dry reforming reaction preferably takes place at a temperature between 700 and 1000°C, more preferably between 800 and 950°C, while the pressure is preferably from 1 to 40 atm.
- the hourly space velocity (WHSV) is not less than 20NL/g catalyst hr 1 , preferably not less than 30NL/g catalyst hr 1 and more preferably not less than 40NL/g catalyst hr 1 .
- Catalysts suitable for promoting dry reforming of methane are known in the art.
- nickel-based catalysts on support, or catalysts based on noble metals can be used, such as those described by Guo et al . , who reported that dry reforming of methane was successfully achieved over nickel catalysts supported on magnesium aluminate spinels [Applied Catalysis A: General 273, p. 75-82 (2004)].
- Ni-substituted hexaaluminate catalyst with the general formula BaNi x Aln- x Oi9-5 was prepared and used.
- the H2/CO ratio in the syngas can be decreased further to much lower values by separating water from the product and running the gaseous mixture through a commercial reverse water gas shift process.
- the composition of the syngas may be modified over the ratio range 0.01 ⁇ H2/CO ⁇ 1 by adding a reverse water gas shift process after dry reforming to reduce that ratio to the desired value, producing H2-lean syngas which can serve as a useful feedstock with the aid of a suitable catalyst, that is, the extrudates of the invention, as will now be described in detail.
- the conversion of the H2-lean syngas to hydrocarbons may take place in fixed-bed reactor, where the extrudates are placed (e.g., in an apparatus which is essentially similar to that shown in Figures 2 and 7) .
- the 3 ⁇ 4-lean syngas stream is continuously fed to the reactor at weight WHSV of not less than 0.4h _1 , preferably not less than 0.5h _1 and more preferably not less than 0.6 hr 1 .
- the reaction is carried out at a temperature in the range from 270 to 310°C at pressure of not less than 20 atmospheres, e.g., from 20 to 50.
- the feed may further contain water, depending on the composition of the H2-lean syngas.
- hydrocarbons obtained on converting 3 ⁇ 4-lean syngas with the aid of the catalysts described above can be upgraded, e.g., through catalytic processes under known conditions [Arno de Klerk "Fischer-Tropsch fuels refinery design", Energy Environ. Sci. , 2011, 4, 1177] .
- the invention provides a process comprising dry reforming of natural gas with carbon dioxide to yield 3 ⁇ 4- lean syngas (H2/CO ⁇ 1), and converting said 3 ⁇ 4-lean syngas in the presence of a catalyst to hydrocarbons.
- Figure 1 is a scheme of an apparatus suitable for conducting the hydrogenation of CO2 to form liquid hydrocarbons.
- Figure 2 shows a scheme of an experimental set-up used for conducting the reaction of CO with steam to form liquid hydrocarbons, according to an embodiment of the invention.
- the same experimental set-up was also used for converting 3 ⁇ 4-lean syngas into liquid hydrocarbons, according to another embodiment of the invention.
- Figure 3 is a bar diagram showing the content of paraffins, olefins, aromatics, naphthenes and oxygenates in the liquid product obtained on reacting CO with steam.
- Figure 4 is a bar diagram showing the content of paraffins, olefins, aromatics, naphthenes and oxygenates in the liquid product obtained on reacting CO with steam.
- Figure 5 is a simulated distillation curve of products produced according to Example 8.
- Figure 6 shows a scheme of an experimental set-up used in the dry reforming of methane with CO2.
- Figure 7 shows a scheme of an apparatus suitable for conducting the reaction of CO with steam to form liquid hydrocarbons, or converting 3 ⁇ 4-lean syngas into liquid hydrocarbons .
- the catalytically active compound was prepared by co- precipitation from an aqueous solution of Fe and Al nitrates, induced by the addition of aqueous ammonium hydroxide solution.
- 27.0 gram of Al (NO3) 3 ⁇ 9H2O and 57.9 gram of Fe (NO3) 3 ⁇ 9H2O were dissolved in 60 cm 3 of distilled water each.
- the solutions were then mixed together and the pH of the combined solution was adjusted to 8 by adding 250 cm 3 of aqueous NH4OH solution with concentration of ammonium hydroxide of 5 wt%.
- the obtained solid was filtered and washed with distilled water and further dried at 110°C for 24 hours.
- the atomic ratio of Fe:Al in the precipitating solution was 2:1.
- the obtained mixture was left for gelation overnight at room temperature.
- the obtained gel was formed into pellets by extrusion through a die with openings diameter of 2.5 mm, followed by cutting the extruded wire into extrudates with a length of 15 mm (a single-screw extruder was used) .
- the extrudates were aged in air at room temperature for 24 hours.
- the aged extrudates were dried in air at 110°C for 6 hours followed by calcination in air at 350°C for period of 6 hours. No Fe203 hematite phase was formed after calcination at 350°C.
- the calcined extrudates had diameter of 1.6 mm and length of 6-10 mm.
- An aqueous solution of K2CO3 was added by incipient wetness impregnation.
- the solid was further dried in air at 110°C for 4 hours followed by calcination in air at 450°C for period of 3 h. No change in the shape and size of the extrudates was detected at the impregnation step.
- the catalytically active compound was prepared by co- precipitation from an aqueous solution of Fe and Al nitrates, induced by the addition of aqueous ammonium hydroxide solution.
- 27.0 gram of Al (NO3) 3 ⁇ 9H2O and 57.9 gram of Fe (NO3) 3 ⁇ 9H2O were dissolved in 60 cm 3 of distilled water each.
- the solutions were then mixed together and the pH of the combined solution was adjusted to 8 by adding 250 cm 3 of aqueous NH4OH solution with concentration of ammonium hydroxide of 5 wt%.
- the obtained solid was filtered and washed with distilled water and further dried at 110°C for 24 hours.
- the atomic ratio of Fe:Al in the precipitating solution was 2:1.
- S1O2 precursor Lidox ® HS-30
- the obtained mixture was mixed-kneaded in the hermetically closed kneader at temperature of 40°C for 5 h.
- the obtained gel was discharged from the kneader and formed into pellets by extrusion through a die with openings diameter of 2.5 mm, followed by cutting the extruded wire into extrudates with a length of 15 mm (a single-screw extruder was used) .
- the extrudates were aged in air at room temperature for 24 hours.
- the aged extrudates were dried in air at 110°C for 6 hours followed by calcination in air at 350°C for period of 6 hours. No Fe203 hematite phase was formed after calcination at 350°C.
- the calcined extrudates had diameter of 1.6 mm and length of 6-10 mm.
- An aqueous solution of K2CO3 was added by incipient wetness impregnation.
- the solid was further dried in air at 110°C for 4 hours followed by calcination in air at 450°C for period of 3 h. No change in the shape and size of the extrudates was detected at the impregnation step.
- Example 1 In the set of experiments reported in Examples 3 to 5, the hydrogenation of carbon dioxide is illustrated.
- the extrudate of Example 1 and comparative catalysts were tested for their ability to advance the reaction of carbon dioxide with hydrogen to produce hydrocarbons .
- the catalytically active material was employed in the form of alumina-containing pellets, prepared as described in Example 29 of WO 2014/111919 (consisting of 66.6% Fe 2+ ( Fe 3+ o.47Al 3 + 0 .53) 2 ⁇ 4, 24.2% AI2O3 and 9.2% K; 3% K was inserted before addition of AI2O3 , the rest - after calcination of Al203-containing extrudates) . Then, 3 g of these pellets were equally divided between the three reactors in the experimental set-up.
- reaction products were cooled down to +4°C and separated in cooled (+4°C) container.
- Gas products were analyzed in online Agilent 7890A Series Gas Chromatograph equipped with 7 columns and 5 automatic valves using helium as a carrier gas. Liquid products were separated into aqueous and organic phases. Aqueous phase was analyzed for Total Organic Carbon in Shimadzu TOC-VCPN Analyzer.
- Example 1 In the set of experiments reported in Examples 7 to 9, the extrudates of Example 1 was tested for its ability to advance the reaction of carbon monoxide with steam to produce hydrocarbons according to the following conditions.
- a schematic description of the experimental set-up is shown in Figure 2. Catalysts activation was done by in-situ reduction in hydrogen at 20cm 3 /min*gram C at at temperature of 450°C and atmospheric pressure in reactor (3), for 4 h. 3 ⁇ 4 stream supplied for the activation step is also shown (11) .
- CO reaction with steam was then conducted by passing a mixture of steam and CO streams ( (1) and (2) , respectively) at a molar ratio 0.35:1 through a tubular reactor (3) (16 mm ID, 250 mm long) packed with 12 gram of the extrudates of Example 1 and heated up to 280°C at a total pressure of 30 atm. Steam is produced by vaporizing water stream in a vaporizer (10) . All gaseous reactants are fed via feed line (13) to the reactor (3) .
- reaction products were cooled down to a temperature Ti (Ti>100°C) to form a first mixture consisting of non-condensable and liquid products.
- the first mixture is separated in a first gas-liquid separator (5A) into a first liquid component and a first gaseous component .
- the first liquid component obtained under the experimental conditions consists of organic and aqueous phases.
- the first liquid is therefore separated in a liquid-liquid separator (6) into organic and aqueous phases, which are collected in vessels (7A) and (8), respectively.
- the first gaseous component is cooled down with the aid of a second cooler (4B) to a temperature T2 (T2 ⁇ 10°C), undergoing condensation to form a second mixture consisting of non- condensable materials and liquid products.
- the second mixture is then separated in a second gas-liquid separator (5B) into a second liquid component and a second gaseous component.
- the second liquid component consisting of light organic products, is collected in a vessel ( 7B) .
- the non-condensable components ( 9 ) consist of CO2 , CO, light hydrocarbons and residual 3 ⁇ 4 generated by the water gas shift reaction.
- W ca t is weight of catalyst (gram) loaded into reactor, t -time for collecting WL (hours) .
- X and S stand for conversion and selectivity, respectively.
- composition of the liquid product is shown in Figure 3 in the form of a bar diagram.
- Example 10 shows the generation of 3 ⁇ 4-lean syngas by dry reforming of natural gas with carbon dioxide with the aid of Ni-containing catalyst (the synthesis of the Ni-containing catalyst is shown in Preparation 1 below) .
- Example 11 to 13 the extrudates of Example 1 and 2 according to the invention and comparative extrudates are tested for their ability to advance the conversion of 3 ⁇ 4-lean syngas into hydrocarbons.
- FC Brooks Co .
- Feed and effluent streams were analyzed with an Agilent 7890A GC (GC) equipped with FID and TCD detectors and IR analyzer. Water was condensed (23) from the products gas stream using a cold trap (24) at the outlet of the reactor.
- GC Agilent 7890A GC
- the BaNiAlnOi9-5 catalyst of Preparation 1 was used to promote the reaction of methane with carbon dioxide, to produce 3 ⁇ 4-lean syngas.
- 0.2g of the catalyst of Preparation 1 in powdered form (106-150 ⁇ ) diluted with 0.2g S1O2 was loaded into the reactor.
- a gas mixture containing CH4 and CO2 was fed to the reactor.
- the catalyst was reduced at 900°C for lh in a 60%H 2 -40%N 2 mixture flow.
- the dry reforming of methane was conducted with the catalyst described in Preparation 1 at atmospheric pressure and 870°C.
- the feed was composed of 66 mol% CO2 and 34 mol% CH4.
- CO was contacted with 3 ⁇ 4 and optionally with steam by passing a mixture of CO, 3 ⁇ 4 and optionally H2O streams (indicated by numerals (2) , (11) and (1) , respectively) through a tubular reactor (3) (16 mm ID, 250 mm long) packed with 12 gram of the extrudates of the invention and heated up to 280°C at a total pressure of 30 atm. Steam is produced by vaporizing water stream in a vaporizer (10) . All gaseous reactants are fed via line (13) to the reactor (3) .
- the reaction products were cooled down to a temperature Ti (Ti>100°C) to form a first mixture consisting of non-condensable and liquid products.
- the first mixture is separated in a first gas-liquid separator (5A) into a first liquid component and a first gaseous component .
- the first liquid component obtained under the experimental conditions consists of organic and aqueous phases.
- the first liquid is therefore separated in a liquid-liquid separator (6) into organic and aqueous phases, which are collected in vessels (7A) and (8) , respectively.
- the first gaseous component is cooled down with the aid of a second cooler (4B) to a temperature T2 (T2 ⁇ 10°C), undergoing condensation to form a second mixture consisting of non- condensable materials and liquid products.
- the second mixture is then separated in a second gas-liquid separator (5B) into a second liquid component and a second gaseous component.
- the second liquid component consisting of light organic products, is collected in a vessel (7B) .
- the non-condensable components (9) consist of CO2, CO, light hydrocarbons and residual 3 ⁇ 4 generated by the water gas shift reaction.
- Example 11 the reaction of carbon monoxide with hydrogen to produce hydrocarbons was run in the experimental set-up described above, using the extrudate of Example 1, under the following specific conditions:
- Example 12 the reaction of carbon monoxide with hydrogen to produce hydrocarbons was run in the experimental set-up described above, using the extrudates of Example 2, under the following specific conditions:
- Example 13 a comparative catalyst prepared as described in Preparation 2 was tested for its ability to advance the reaction of carbon monoxide with hydrogen to produce hydrocarbons.
- the catalyst was synthesized according to the procedure of D.B.Bukur et.al [Ind. & Eng . Chem. Res . 1989, 28, 1130], formed into silica-containing extrudates by the method of the invention and then tested under to the following conditions :
- the resulting solution was then poured at 60°C with vigorous stirring into an aqueous solution containing a large excess of (NH4)2C03 to form the hexaaluminate precursor precipitate. During the precipitation, a large amount of CO2 was released while the pH value of the solution was maintained between 7.5 and 8.0.
- the resulting slurry was aged with continuous stirring at 60°C for 3h followed by filtration and washing with deionized water. The obtained cake was then dried at 110°C in air overnight. The powder was further calcined at 500°C for 2 h, followed by calcination at 1300°C and 1400°C for 3-5 h.
- the resulting powder was crushed and sieved to collect the fraction smaller than 160 ⁇ .
- XRD analysis yielded the following phases: Bao.69Ni 0 .48Al 6 .360ii - 95%, - ⁇ 1 2 0 3 -5%.
- the BET surface area is 12 cm 2 /g.
- the obtained gel was formed into pellets by extrusion through a die with openings diameter of 1.8 mm, followed by cutting the extruded wire in pellets with the length of 15 mm. The extrudates were aged in air at room temperature for 24 hours.
- the aged extrudates were dried in air at 110°C for 6 hours followed by calcination in air at 300°C for period of 3 hours.
- the calcined extrudates had diameter of 1.6 mm and length of 6-10 mm.
- An aqueous solution of KHCO3 was added by incipient wetness impregnation at amount yielding 4 wt . % K in extrudates.
- the solid was further dried in air at 110°C for 8 hours followed by calcination in air at 300°C for period of 6 h. No change in the shape and size of the pellets was detected at the impregnation step.
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CA2978832A CA2978832C (en) | 2015-04-07 | 2016-04-06 | Catalyst composition and catalytic processes for producing liquid hydrocarbons |
AU2016245430A AU2016245430B2 (en) | 2015-04-07 | 2016-04-06 | Catalyst composition and catalytic processes for producing liquid hydrocarbons |
EP16776222.8A EP3280529B1 (en) | 2015-04-07 | 2016-04-06 | Catalyst composition, its use and catalytic processes for producing liquid hydrocarbons |
US15/563,700 US10589257B2 (en) | 2015-04-07 | 2016-04-06 | Catalyst composition and catalytic processes for producing liquid hydrocarbons |
IL254524A IL254524B (en) | 2015-04-07 | 2017-09-17 | Catalyst composition and catalytic processes for producing liquid hydrocarbons |
US16/596,398 US20200038844A1 (en) | 2015-04-07 | 2019-10-08 | Catalyst composition and catalytic processes for producing liquid hydrocarbons |
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WO2018051334A1 (en) | 2016-09-19 | 2018-03-22 | B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University | Novel, highly efficient eco-friendly processes for converting co2 or co-rich streams to liquid fuels and chemicals |
US20190144274A1 (en) * | 2017-11-15 | 2019-05-16 | Gas Technology Institute | Noble metal catalysts and processes for reforming of methane and other hydrocarbons |
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SG11202012245WA (en) | 2018-06-29 | 2021-01-28 | Shell Int Research | Electrically heated reactor and a process for gas conversions using said reactor |
ZA202006924B (en) * | 2019-11-11 | 2021-09-29 | Indian Oil Corp Ltd | A process for producing hydrogen and light olefins from resid fluid catalytic cracking |
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US4565831A (en) | 1981-12-16 | 1986-01-21 | Exxon Research And Engineering Co. | Process for producing aromatic hydrocarbons from carbon monoxide and water |
US4582815A (en) | 1984-07-06 | 1986-04-15 | Mobil Oil Corporation | Extrusion of silica-rich solids |
US4559363A (en) | 1984-08-17 | 1985-12-17 | Standard Oil Company (Indiana) | Process for reacting carbon monoxide and water |
US5053374A (en) | 1987-05-01 | 1991-10-01 | Mobil Oil Corporation | Method for preparing a zeolite catalyst bound with a refractory oxide of low acidity |
FR2694013B1 (en) * | 1992-07-27 | 1994-09-30 | Inst Francais Du Petrole | Cobalt-based catalyst and process for converting synthesis gas to hydrocarbons. |
EP1657290B1 (en) * | 2004-11-10 | 2010-05-26 | Research Institute of Petroleum Industry | Process for the production of gasoline from syngas using a catalyst including a step for regeneration of the catalyst |
US7915193B2 (en) * | 2007-08-30 | 2011-03-29 | Rentech, Inc. | Method for activating strengthened iron catalyst for slurry reactors |
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Non-Patent Citations (3)
Title |
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DAS, SATYEN KUMAR ET AL.: "CO-hydrogenation over silica supported iron based catalysts: Influence of potassium loading.", APPLIED ENERGY, vol. 111, 1 November 2013 (2013-11-01), pages 267 - 276, XP028703052 * |
IRANI, M.; ET AL.: "The Effects of Si02 and A1203 Binders on the Activity and Selectivity of Bifunctional Fe/HZSM-5 Catalyst in Fischer-Tropsch Synthesis.", IRANIAN JOURNAL OF CHEMICAL ENGINEERING, vol. 5, no. 2, 1 March 2008 (2008-03-01), pages 64 - 70, XP055320422 * |
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WO2018051334A1 (en) | 2016-09-19 | 2018-03-22 | B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University | Novel, highly efficient eco-friendly processes for converting co2 or co-rich streams to liquid fuels and chemicals |
US10865107B2 (en) | 2016-09-19 | 2020-12-15 | B.G. Negev Technologies & Applications Ltd., At Ben-Gurion University | Novel, highly efficient, eco-friendly processes for converting CO2 or co-rich streams to liquid fuels and chemicals |
US20190144274A1 (en) * | 2017-11-15 | 2019-05-16 | Gas Technology Institute | Noble metal catalysts and processes for reforming of methane and other hydrocarbons |
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CA2978832A1 (en) | 2016-10-13 |
US10589257B2 (en) | 2020-03-17 |
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