WO2021171316A1 - Fixed bed reactor with layered dimethyl ether synthesis catalysts - Google Patents
Fixed bed reactor with layered dimethyl ether synthesis catalysts Download PDFInfo
- Publication number
- WO2021171316A1 WO2021171316A1 PCT/IN2021/050187 IN2021050187W WO2021171316A1 WO 2021171316 A1 WO2021171316 A1 WO 2021171316A1 IN 2021050187 W IN2021050187 W IN 2021050187W WO 2021171316 A1 WO2021171316 A1 WO 2021171316A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- methanol synthesis
- methanol
- fixed bed
- bed reactor
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 292
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 149
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 147
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 108
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 574
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 59
- 230000018044 dehydration Effects 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 20
- 239000011029 spinel Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 69
- 239000010949 copper Substances 0.000 claims description 66
- 229910052802 copper Inorganic materials 0.000 claims description 62
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 53
- 230000000694 effects Effects 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- -1 carbon olefins Chemical class 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000001603 reducing effect Effects 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 241000894007 species Species 0.000 description 8
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910001960 metal nitrate Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 230000006870 function Effects 0.000 description 5
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 238000010297 mechanical methods and process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
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- 229910052566 spinel group Inorganic materials 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 238000005580 one pot reaction Methods 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XRFJZINEJXCFNW-UHFFFAOYSA-N [Zn+2].[O-][Mn]([O-])(=O)=O Chemical compound [Zn+2].[O-][Mn]([O-])(=O)=O XRFJZINEJXCFNW-UHFFFAOYSA-N 0.000 description 1
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- LOEUCBBZEHMJQN-UHFFFAOYSA-N hydrazine;oxalic acid Chemical compound NN.OC(=O)C(O)=O LOEUCBBZEHMJQN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012808 vapor phase 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0476—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds
- B01J8/048—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds the beds being superimposed one above the other
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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
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
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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
- 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
- B01J37/04—Mixing
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
- B01J2208/023—Details
- B01J2208/024—Particulate material
- B01J2208/025—Two or more types of 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
- 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
- B01J23/72—Copper
Definitions
- the present disclosure relates to a fixed bed reactor having layered dimethyl ether synthesis catalysts for production of dimethyl ether. Specifically, the disclosure relates to spinel structured methanol synthesis catalyst used in alternate layers along with methanol dehydration catalyst in a mixed bed reactor.
- the dimethyl ether (DME) is being increasingly viewed as the fuel of the future on account of its many favorable attributes. It is a clean burning fuel with physicochemical properties comparable to Liquid petroleum gas (LPG) and Cetane number higher than high speed Diesel. It, therefore, can serve as an effective substitute for LPG as well as diesel. Lurthermore, it can be made from a wide variety of feedstocks such as coal, natural gas, agricultural wastes etc. and it can be blended with LPG and diesel in any proportions desired.
- Methanol synthesis is optimally carried out at a temperature of 200° C -300° C, and at a pressure of 50 - 80 bar normally using CuZnOAhCh catalyst, with long catalyst life of 2 to 5 years.
- the optimum conditions for methanol to dimethyl ether conversion are temperature of 100° C to 300° C and pressure of 20 bar, using solid acid catalysts such as heteropoly acids (temperature 100-200° C), HZSM-5 (around 200°C) or g-AhCh (above 250°C) with long catalyst life.
- dimethyl ether can be directly manufactured from syngas deficient in hydrogen (H2/CO ⁇ 1).
- the low hydrogen syngas can be readily manufactured from coal and agricultural waste.
- the single step process is desirable due to multiple benefits: High conversion efficiency 60% to 77%, high energy efficiency and freedom to use lean syngas deficient in hydrogen.
- the overall process can be represented by a summation of 2 moles methanol formed by reaction 1 followed by reactions 2 and 3.
- the overall reaction 4 is represented as follows:
- a single pot DME process using a fixed bed reactor is carried out by combining methanol synthesis catalyst with a methanol dehydration catalyst. Both, a methanol synthesis catalyst and a methanol dehydration catalyst are needed for single pot synthesis. Much of the current efforts were directed towards a single pellet containing both functionalities of methanol synthesis and methanol dehydration.
- US9295978B2 discloses catalysts and methods for their manufacture and use for the synthesis of dimethyl ether from syngas.
- the catalysts comprise methanol synthesis compositions designated as A, B, C containing ZnO, CuO, ZrCE, alumina and ceria.
- a second acidic component designated as X, Y, Z containing alumina prepared by different methods.
- the catalysts described herein are able to synthesize dimethyl ether directly from synthesis gas, including synthesis gas that is rich in carbon monoxide. The two components are mixed in predetermined proportions in a single pellet.
- US8669295B2 provides a process for preparing methanol, dimethyl ether, and low carbon olefins from syngas, wherein the process comprises the step of contacting syngas with a catalyst under the conditions for converting the syngas into methanol, dimethyl ether, and low carbon olefins, characterized in that, the catalyst contains an amorphous alloy consisting of a first component A1 and a second component, said second component being one or more elements or oxides thereof selected from Group IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB, VIII, and Lanthanide series of the Periodic Table of Elements, and said second component being different from the first component Al.
- the syngas can be converted into methanol, dimethyl ether, and low carbon olefins in a high CO conversion, a high selectivity of the target product, and high carbon availability.
- This patent lists two components to be mixed and converted into single pellet.
- JP4467675B2 relates to a catalyst capable of producing dimethyl ether in a high yield from a gas containing hydrogen and carbon dioxide and having excellent durability, and a method for synthesizing dimethyl ether using the catalyst.
- Composition is Cu, Zn, Al and Ga for methanol synthesis and Al, Zr for methanol dehydration catalyst. The two catalysts are mixed in forming a single pellet.
- KR 100732784B1 discloses a process for the preparation of dimethyl ether from hydrocarbons, including dry-reforming a feedstock mixture comprised of hydrocarbons, carbon dioxide and water vapor in the presence of a dry-reforming catalyst, to prepare a syngas, which then undergoes gas-phase direct synthesis into dimethyl ether in one step in the presence of a hybrid catalyst.
- the methanol synthesis catalyst contains Cu, Zn, Zr, Al, Mn and Ga are in a weight ratio from 22.6 to 67.8: 13.5 to 40.6: 2.3 to 6.7: 10.4 to 31.2: 3.8 to 7.5: 0.9 to 2.7.
- Aluminum is a major ingredient of synthesis catalyst and this is mixed with dehydration catalyst to produce a single pellet with both catalytic functions.
- US8552074B2 provides a process for preparing methanol, dimethyl ether, and low carbon olefins from syngas, wherein the process comprises the step of contacting syngas with a catalyst under the conditions for converting the syngas into methanol, dimethyl ether, and low carbon olefins, characterized in that, the catalyst contains an amorphous alloy consisting of components M and X wherein the component X represents an element B and/or P, the component M represents two or more elements selected from Group IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB, VIII and Lanthanide series of the Periodic Table of Elements.
- the syngas can be converted into methanol, dimethyl ether, and low carbon olefins in a high CO conversion, a high selectivity of the target product, and high carbon availability.
- This patent also discloses methanol synthesis catalyst combined with acidic dehydration catalyst into a single pellet.
- KR100810739B1 relates to a process for the preparation of a catalyst for methanol and dimethyl ether synthesis from syngas, and more particularly, CuO, ZnO and A12 O Cu-Zn-Al- based porous catalyst.
- methanol synthesis function catalyst is precipitated in pores of alumina- dehydration catalyst, resulting in single pellet with both catalysts.
- JPH09173845A discloses preparation of a catalyst for producing dimethyl ether, wherein the catalyst is prepared by precipitating oxide of copper, oxide of zinc, and alumina in the pores of alumina. And dimethyl ether is produced by passing mixed gas of carbon monoxide and hydrogen through slurry in which the catalyst is suspended, and at that moment, gas or mixed gas containing carbon dioxide and/or water vapor is led into pores of alumina to produce dimethyl ether with a high yield.
- the ratio between copper oxide, zinc oxide, and alumina to be precipitated in the pores of alumina is such that the ratio of copper oxide to zinc oxide is 1:(0.1- 5) and alumina is (0-0.5).
- methanol synthesis function catalyst is precipitated in pores of alumina- dehydration catalyst, resulting in single pellet with both catalysts.
- KR970069123A discloses a method of manufacturing a catalyst for dimethyl ether and a method of manufacturing the dimethyl ether.
- methanol synthesis catalyst is deposited on periphery of alumina particle, thus creating a single pellet with MS & MD functionality.
- KR100588948B1 discloses a catalyst for making dimethyl ether, method of preparing the same and method of preparing dimethyl ether using the same.
- This patent describes a uniformly mixed methanol synthesis (MS) and methanol dehydration (MD) catalyst.
- a single pot process using a fixed bed reactor is not yet commercially practiced due to rapid deactivation of methanol synthesis catalyst with about 30% of catalyst loss over 200 hours of operation.
- a major hindrance to commercialization of the single pot process has been short life of the methanol synthesis catalyst.
- the objective of the present invention is to analyze the reasons for the premature catalyst failure and to provide effective measures to prolong the catalyst life at reasonable activity.
- the present invention overcomes the limitation of the prior-art documents and provides a mixed metal oxide heterogeneous catalyst for production of dimethyl ether from syn gas in a single fixed bed reactor.
- a fixed bed reactor for the production of dimethyl ether is disclosed.
- the reactor includes multiple layers of catalysts. In the multiple layers, a layer having a methanol synthesis catalyst alternates with a layer having a methanol dehydration catalyst. Further, at least 60 atomic percent of the methanol synthesis catalyst composition has spinel structure.
- Figure 2 illustrates a ternary composition diagram of a compound comprising group I, group II and group III elements, in accordance with an embodiment of the present disclosure.
- One or more of the embodiments of the present disclosure include a fixed bed reactor for the production of dimethyl ether.
- the mixed bed reactor has both the methanol synthesis catalyst and the methanol dehydration catalyst.
- the role of methanol synthesis catalyst is very important, as the methanol synthesis step is the rate determining step in the overall production of the dimethyl ether.
- methanol synthesis catalysts are a mixture of oxides of three or more elements at the molecular level. The three elements belong to group I, II and III of the periodic table. Copper and silver are the most used active hydrogenation centers, mostly in their oxidation state 0 or +1. Copper in oxidation state +1 is also anchoring point for CO gas.
- Group - II elements the most important elements are Zn and to a lesser extent Mg, Cd, Ca, Ba, and Sr. Oxides of these elements act as spacers for copper atoms, reduce mobility of copper atoms, and prevent sintering of copper. Further, presence of these oxides increases the catalytic activity by substantially enlarging the surface area of the catalyst. At operating temperature of the reactor, and under reducing atmosphere of syngas, the oxygen vacancies increase, and electrons are released to the lattice of ZnO, rendering it a n- type semiconductor. About 30% of copper atoms are embedded in the ZnO matrix. A strong electronic interaction between copper atoms and ZnO is desirable for the effective functioning of the methanol synthesis catalyst.
- the group-III elements form extremely stable oxides. These oxides, support the Cu and Zn active centers, improve dispersion of copper atoms and prevent sintering of copper. They also act as dopants for ZnO, increasing oxygen vacancies and increasing its electronic conductivity. Apart from Al, Cr, Mn, and V, various other elements and actinides have also been utilized to this effect. For example, elements such as Cr, Mn, V, actinides, and lanthanides despite belonging to other groups are also included in group-III, as they are present at valance state 3 in the catalyst. [0030] Methanol dehydration catalyst is the second catalyst required for the single step process in the fixed bed reactor.
- Methanol dehydration is an exothermic reversible reaction that proceeds without change in mole number. For this reason, reaction pressure does not affect conversion equilibrium, while lower reaction temperatures have a thermodynamic advantage towards higher DME production. Methanol dehydration is an acid- catalyzed reaction and an active, selective and stable catalyst at relative low temperature is desired for the afore-mentioned reaction. Furthermore, this technology is readily available from several industrial technology suppliers. Depending on catalyst characteristics, methanol dehydration can be carried out in both vapor and liquid phase, with reaction temperature in the range 100 °C - 300 °C.
- y-AhCE is a solid acid catalyst that can be used as a dehydration catalyst, considering its cost advantage, high surface area, good thermal and mechanical stability. y-AhCE shows high selectivity for DME even at high temperature (up to 400 °C) because of the presence of weak Lewis acid sites, which are unable to promote side reactions. These acid characteristics require reaction temperature higher than 250 °C to favor high methanol conversion.
- the catalyst activity of y-AFCh can be further improved by modifying y-AFCh surface with copper, zinc, silica, aluminum-phosphates, titanium, niobium, boron or other species.
- Zeolites also have a high potential for dehydration of methanol on account of their multiple favorable characteristics, such as tunable acidity, high surface area, micro-porosity or ability to support metal and/or metal-oxide.
- the acidity of zeolite may have to be carefully tuned in order to achieve a balance between catalytic activity and resistance to deactivation by water.
- ZSM-5 with high Si/Al ratio e.g., 127) showed high resistance in presence of water but low capacity to dehydrate methanol, while more acidic samples (e.g., ZSM-5 with Si/Al ratio of 27) offers high methanol conversion but poor water resistance and low DME selectivity.
- a Si/Al ratio of 38 showed the best performance in terms of CO conversion, DME yield and water resistance.
- Zeolites show good activity at temperatures around 200° C.
- the textural properties of zeolite crystals also strongly influence the catalytic behavior of hybrid catalysts.
- the one-pot CO-to-DME reaction carried out in presence of hybrid grains prepared via co-precipitation of Cu-Zn-Zr precursors on zeolite crystals with different channel systems i.e., MOR, FER and MFI
- MOR, FER and MFI channel systems
- the microscopy analysis of hybrid grains revealed that zeolite crystal features strongly affect the metal-oxide(s) distribution, producing a very homogenous distribution over lamellar FER-type crystals and a formation of metal clusters on the other zeolite systems.
- the catalyst system of the present disclosure is highly stable and has long life.
- the methanol synthesis catalyst has a mixed metal oxide of spinel structure decorated with nanoparticles of copper and cuprous oxide. Further, the peak temperature reached within catalyst pellet is lowered, thereby reducing the deactivation of the methanol synthesis catalyst.
- the disclosed fixed bed reactor for the production of dimethyl ether has multiple layers 100 of catalysts as shown in Figure 1.
- “multiple layers” refers to number of layers equal to or greater than 10. The number of layers may be increased further to have an intimate reaction and fast production of dimethyl ether. In some embodiments, the number of catalysts layers are more than 20. In some embodiments, the layers are more than 40 in number.
- the multiple layers 100 of catalysts include layers 110 of the methanol synthesis catalyst and layers 120 of the methanol dehydration catalyst in alternate manner i.e., in the multiple layers 100 of catalysts, a methanol synthesis catalyst layer 110 is separated from another methanol synthesis catalyst layer 110 by a methanol dehydration catalyst layer 120 and vice versa.
- phrases such as “a layer of the methanol synthesis catalyst” and “a layer of the methanol dehydration catalyst” are used for brevity here and does not necessarily mean that the layers contain only the respective catalysts. There may be inclusion of other materials along with the respective catalyst materials in the referred particular layers.
- a layer 110 comprising methanol synthesis catalyst alternates with a layer 120 comprising a methanol dehydration catalyst, there may or may not be any other layers or materials present in between the layer of the methanol synthesis catalyst and the layer of the methanol dehydration catalyst.
- an optional layer 130 is shown between the layer 110 of comprising methanol synthesis catalyst and a layer 120 comprising a methanol dehydration catalyst.
- the layer 110 of the methanol synthesis catalyst and the layer 120 of the methanol dehydration catalyst, along with the optional layer 130 separating them forms a repeat unit 140 of the multiple layers 100.
- the thickness of each layerl 10/120/130 may be changed to suit the overall proportionality.
- a total thickness (considering all the layers 110 present) of the methanol synthesis catalyst is about 2-3 times more than the total thickness (considering all the layers 120 present) of the methanol dehydration catalyst in the fixed bed reactor.
- At least some part of the material of the methanol synthesis catalyst has a spinel structure.
- a spinel has a general formulation of AB2X4, crystallizing in the isometric cubic crystal system, with the X anions such as oxygen and sulfur arranged in a cubic close-packed lattice and the cations A and B occupying some or all of the octahedral and tetrahedral sites in the lattice.
- the spinel structure specifically aids the dispersion and binding of the copper atoms of the methanol synthesis catalyst. Specifically, a major portion of the copper present in the methanol synthesis catalyst is in a bound form in the spinel structure and is not available for sintering. Further, oxidation of copper active centers by water vapor and CO2 content is reduced by binding the copper atoms in the spinel structure.
- the methanol synthesis catalyst of the present disclosure at least 60 molecular percent of the metal components in the total methanol synthesis catalyst composition has spinel structure.
- a quantity of copper present in the methanol synthesis catalyst composition of the present disclosure is less than the normal quantity of the copper present in generally used methanol synthesis catalysts.
- the methanol synthesis catalyst in the fixed bed reactor, has copper in a quantity less than 40 atomic percent of the metal components in the methanol synthesis catalyst composition. In some embodiments, the quantity of copper present in the methanol synthesis catalyst is less than 30 atomic percent. Reduction of copper content in the methanol synthesis catalyst is particularly advantageous in reducing sintering of the copper particles. Reduction in copper content increases copper dispersion in the catalyst in turn reducing the copper particles available for combining with the neighboring copper particles for sintering. Therefore, the activity of the copper particles is maintained in the catalyst composition and the useful life of the catalyst is enhanced.
- the sintering of the copper particles and the loss of activity is further reduced by decreasing the copper content present in a free form in the catalyst composition.
- Copper may be termed to be in a free form, if the copper atoms are not bound in a specific structure in a composition. Binding the copper atoms in a specific structure, such as spinel decreases the copper atoms that are available freely for the reaction with other copper particles or any other atoms, resulting in sintering or forming other compounds respectively, and thereby decreasing the availability of active copper sites for the catalyst functioning.
- a quantity of copper present in a free form in the methanol synthesis catalyst is less than 60 atomic percent of the total copper present in the catalyst.
- total free copper atoms present in the methanol synthesis catalyst is less than 50 atomic percent of the total copper present in the catalyst. In some specific embodiments, the free form of copper present is in a range from about 4 atomic percent to 30 atomic percent of the total copper present in the methanol synthesis catalyst.
- the methanol synthesis catalyst may be primarily made of one or more oxide materials, generally combining three active metal components in different proportions. These components can be classified as mono, di and tri valent species and can be grouped into A, B, C components based on valency. Copper - mostly in monovalent Cu20 form is the most active component- designated as A and surface area of copper specie is strongly correlated with activity of the catalyst.
- Component B the divalent specie
- Zn is also active catalytic component, however often the main function attributed to B component is promoter actively lowering the size of A crystallites and causing a fine dispersion of A.
- Component C trivalent specie, functions by causing even higher dispersion of components A & B.
- the methanol synthesis catalyst includes a mixed metal oxide composition.
- a mixed metal oxide is an oxide having cations of more than one chemical element or cations of a single element in more than one states of oxidation.
- Mixed metal oxides may be salts of weak metallic acids or two different oxides that bond together strongly.
- the mixed metal oxides may also include solid solution of metal oxides.
- the methanol synthesis catalyst includes manganese and zinc. In some embodiments, most part of the mixed metal oxides of the methanol synthesis catalyst is in one or more mixed spinel structure.
- Figure 2 illustrates a ternary phase diagram using normally used group I (A), group II (B) and group III (C) elements, using the relative compositions listed in table 1 below.
- Table 1- Ternary compositions used as methanol synthesis catalyst
- the normally used element A is Cu.
- Mg and Zn are mostly used as B element and Al, Cr, Mn,
- Selected catalysts of the table were prepared by various synthesis methods as disclosed below and the relative activity of the catalysts were tested.
- One of the methods used for the synthesis of the catalysts is a co-precipitation method.
- the catalysts When the catalysts are prepared using precipitation method, it was observed that for the same catalyst composition, changing ageing time from 1 hour to 3 hours increased the catalyst activity by factor of 1.5 to 2.
- Eleven shortlisted catalyst compositions were prepared by K2CO3 co precipitation method using metal nitrate and metal acetate mixture. They were further characterized by XRD analysis and methanol decomposition test for activity.
- Combustion Synthesis method is another method used for synthesizing the catalyst compositions.
- Combustion synthesis technique involves a self-sustained reaction between an oxidizer, typically precursor metal nitrates and fuels such as glycine, urea and hydrazine oxalic acid, citric acid, metal acetates, and even palmitic acid have been used.
- an oxidizer typically precursor metal nitrates and fuels
- fuels such as glycine, urea and hydrazine oxalic acid, citric acid, metal acetates, and even palmitic acid have been used.
- the reaction mixture turns to be viscous liquid followed by a self-ignition process. Due to the high exothermic nature of the system, the combustion temperature rapidly reaches ⁇ 800° C and converts the precursor material to fine crystallites.
- catalyst compositions were prepared using different fuels and metal nitrates with good results.
- a catalyst made by mixing 60% metal acetate and remaining metal nitrates via solution combustion route showed relative activity of 1.1.
- Another method used for synthesizing the catalyst compositions is redox precipitation method.
- tartaric acid complex of Cu, Mg, Zn nitrate mixture were added to hot alkaline solution of glucose under vigorous stirring at 70° C to get a red precipitate of the reduced methanol synthesis catalyst. After washing the precipitate free of alkali, it was dried and directly used.
- Yet another method used for synthesizing the catalyst compositions is double decomposition method.
- a 150 ml. mixture of metal nitrates (0.5 M) and 50 ml. potassium chromate (2M) solution were mixed at 70° C with constant stirring.
- the potassium chromate was added dropwise into metal nitrate solution.
- the resulting precipitate was washed free of alkali, dried and then calcined at 300° C for 1 hour.
- Composition of serial number 5 in table 1 synthesized by this method showed activity of 0.90.
- Yet one more method used for synthesizing the catalyst compositions is chemo- mechanical method.
- the selected catalysts prepared by different methods of catalyst preparation were tested in methanol decomposition set up, for their methanol decomposition activity at a temperature of 250°C and atmospheric pressure.
- a relative ranking of the catalysts prepared using various methods of preparation are as shown in Table 2.
- the methanol synthesis catalyst is free of intentionally added aluminum and is essentially aluminum-free.
- Aluminum is found to be reducing activity of methanol synthesis catalyst.
- One of the reasons for the reduction of methanol synthesis catalyst activity in the presence of aluminum may be the hydrophilic nature of aluminum.
- a hydrophilic aluminum may attract water and thereby promote oxidation of copper present in the methanol synthesis catalyst thereby reducing the copper available for the catalytic activity. Therefore, an aluminum-free methanol synthesis catalyst is envisaged to reduce degradation of catalytic activities of methanol synthesis catalyst by avoiding usage of hydrophilic alumina in MS catalyst composition.
- Cu2Mn6Zn is a non-limiting example composition of an aluminum-free methanol synthesis catalyst.
- (3 ⁇ 4Mh 6 Zh has a mixed spinel structure having a mixture of spinels CuMmC ⁇ and ZnM CU. These copper and zinc manganate spinels can exist in solid solution form. Copper present in a spinel is highly dispersed thereby preventing agglomeration of the copper present within the spinel structures.
- a composition such as CinlVlneZn has only about 10% copper or zinc which may exist as free oxide not compounded with manganese. This composition with up to 10% free copper has exhibited higher activity compared to Cu2Mn6Zn. Any free ZnO will further disperse the free copper.
- composition of catalyst with 10-20% excess copper over Cu2Mn6Zn composition will have highly dispersed copper thereby reducing its chance of agglomerating with other copper specie to form larger less reactive copper particle.
- the typical composition of this methanol synthesis catalyst is Cu:Mn:Zn in 3:6:1 atomic ratio, having about 11% excess copper over all spinel composition of Cu:Mn:Zn in 2:6: 1 atomic ratio.
- CinlVlneZn composition is prepared by (i) chemo- mechanical method of mixing metal salts with ammonium carbonate and (ii) co-ppt method, and (iii)KMn0 4 redox method and used along with g alumina as a methanol dehydration catalyst in a layered structure in a fixed bed reactor. Further, experiments were conducted combining alumina-free methanol synthesis catalyst with g alumina in different proportions and a range of MS:MD 2-3 was found to be beneficial in obtaining reasonably high efficiency and very good life of methanol synthesis catalyst. The methanol synthesis catalyst : methanol dehydration catalyst ratio of 2: 2.5 was found to increase the life of the methanol synthesis catalyst by 200%.
- the methanol dehydration catalyst may be any commercially available composition such as g Alumina, Y Zeolite, modified H-ZSM 5 etc.
- g Alumina is specifically known as a commercially viable effective methanol dehydration catalyst.
- the layered structure of the methanol synthesis catalyst and methanol dehydration catalyst in the fixed bed reactor further facilitates avoiding mixing of aluminum with the methanol synthesis catalyst.
- the layered structure is advantageous in preventing entry of aluminum ions into the methanol synthesis catalyst and deactivating the methanol synthesis catalyst and further in reducing the water content in the methanol synthesis catalyst.
- the methanol synthesis catalyst is protected from water by scrupulously excluding aluminum from the methanol catalyst composition.
- Aluminum is a hydrophilic substance that adsorbs water. This water layer, if present in methanol synthesis catalyst, damages Cu20, ZnO present in the methanol synthesis catalyst into respective hydroxyl carbonates by reaction with carbonic acid formed by a reaction between water vapor and CO2.
- Water gas shift reaction occurs on methanol synthesis catalyst and results in lowering water content of the gas.
- An aluminum containing dehydration catalyst creates a local higher water content on dehydration layer due to the high adsorption capacity of alumina for water.
- the local higher water content around aluminum facilitates decreasing the water content in the surrounding gas, thus reducing potential for oxidation of copper in the methanol synthesis catalyst.
- the high-water content is isolated from the methanol synthesis catalyst.
- the fixed bed reactor is free of any liquid form that contacts both the methanol synthesis catalyst and the methanol dehydration catalyst.
- the absence of liquid-phase contacting both the methanol synthesis catalyst and methanol dehydration catalyst ensures prevention of mixing the aluminum from the methanol dehydration catalyst with the composition of the methanol synthesis catalyst, thereby preventing degradation of methanol synthesis catalyst.
- Each of the measures such as layering of the methanol synthesis catalyst and methanol dehydration catalyst, having an aluminum-free methanol synthesis catalyst, and having dispersed copper particles increases the life span of the methanol synthesis catalyst.
- the methanol synthesis catalyst is free of aluminum, the methanol synthesis catalyst has a lifespan greater than 200% as compared to a methanol synthesis catalyst having aluminum.
- Isolation of the methanol synthesis catalyst and methanol dehydration catalyst in the layered structure in the fixed bed reactor can further be enhanced by using packing materials for physical separation of the methanol synthesis catalyst from the methanol dehydration catalyst.
- the packing material may be used as one or more layers in between the methanol synthesis catalyst and methanol dehydration catalyst or alternately may be used as a mix along with any one or both of the methanol synthesis catalyst and methanol dehydration catalyst.
- the fixed bed reactor has at least one packing material that physically separates the methanol dehydration catalyst from the methanol synthesis catalyst. The physical separation achieved by the packing material may or may not be complete.
- the packing material includes dead burnt alumina, dead burnt magnesia, silicon carbide, or combinations thereof.
- the packing material is used as one or more layers in between the methanol synthesis catalyst and methanol dehydration catalyst.
- the packing material is mixed with the methanol synthesis catalyst, methanol dehydration catalyst, or both.
- the layer having the methanol synthesis catalyst includes an inert material in an amount greater than 20 atomic percent of the total content of the layer.
- catalysts with serial number 5 and 8 in table 2 contain up to 10% free copper dispersed on a spinel structure and are expected to perform better in terms of stability.
- Catalysts 5, 8 along with a commercially used catalyst 11 were tested for synthesis of methanol and for synthesis of dimethyl ether. Both stability and activity were tested for all the three catalysts. In these tests syngas was simulated by mixing 3 ⁇ 4 and CO at a ratio 2 for methanol synthesis tests while the ratio was set to 1.1 for the direct dimethyl ether synthesis tests. In each case about 30 gm of methanol synthesis catalyst was used g alumina was used as dehydration catalyst and the catalysts were layered as 4 layers each of MS and MD catalysts. Inert Silicon carbide powder of 60-80 mesh was used to separate the MS and MD catalysts. Activity test results at particular pressure and temperature obtained for the catalyst serial numbers 5, 8, and 11 are summarized in table 3. Table 3- Activity Test
- catalyst 11 is a commercial methanol synthesis catalyst containing aluminum. It showed very good activity only at high pressure of 60 bar and it showed 6 times lower activity for direct dimethyl ether synthesis. Catalysts 5 and 8 showed good activity. [0066] To test stability, tests were carried out only on catalysts 5 and 8 that are free of aluminum and have lower copper content and also of predominantly spinel structure. During direct dimethyl ether synthesis trials, 90 gm of MS catalyst and 45 gm of g alumina were used in a layered configuration with 8 layers of MS and 8 layers of MD catalyst. Silicon carbide 60-80 mesh particles were used as inert packing material separating two types of catalysts. The stability test results normalized for 100 hours duration are shown in table 4.
- the catalyst 11 shows poor activity for low pressure operation but very good activity at typical methanol synthesis condition of 60 bar pressure.
- Catalyst 11 may not be suitable for single pot dimethyl ether synthesis process.
- Catalyst 5 and 8 show excellent activity and stability.
- Catalyst 8 showed better activity than catalyst 5 during activity testing, however showed poorer activity during stability test. The poor performance initially was suspected to be due to silica binder used. This was confirmed with fresh catalyst powder, which showed excellent activity.
- Catalysts 5, 6 and 8 can be considered as excellent candidates for single pot dimethyl ether synthesis.
- composition of the catalyst 6 was not specifically tested and compared in the above tables, the composition of 6 is close to the composition of 8.
- catalyst 8 with CmMneZn composition is an excellent catalyst for the methanol synthesis functionality and g Alumina is a preferred catalyst for methanol dehydration functionality in a one pot, direct dimethyl ether synthesis.
- Chemo-mechanical method of mixing metal salts with ammonium carbonate was found to be a simple preparation method for synthesizing the catalysts. Co-ppt method and KMn0 4 redox method are also likely result in a catalyst of superior activity.
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CN1390640A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process |
US8552074B2 (en) * | 2008-12-18 | 2013-10-08 | China Petroleum & Chemical Corporation | Process for preparing methanol, dimethyl ether, and low carbon olefins from syngas |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1390640A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process |
US8552074B2 (en) * | 2008-12-18 | 2013-10-08 | China Petroleum & Chemical Corporation | Process for preparing methanol, dimethyl ether, and low carbon olefins from syngas |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP4194432A1 (en) * | 2021-12-07 | 2023-06-14 | Linde GmbH | Reactor and method for producing secondary products of methanol and especially dimethyl ether |
WO2023104328A1 (en) * | 2021-12-07 | 2023-06-15 | Linde Gmbh | Reactor and method for producing secondary methanol products, in particular dimethyl ether |
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