CN111867725A - 含钴催化剂的制备 - Google Patents
含钴催化剂的制备 Download PDFInfo
- Publication number
- CN111867725A CN111867725A CN201980018973.9A CN201980018973A CN111867725A CN 111867725 A CN111867725 A CN 111867725A CN 201980018973 A CN201980018973 A CN 201980018973A CN 111867725 A CN111867725 A CN 111867725A
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- Prior art keywords
- catalyst
- precipitate
- fischer
- optionally
- mixture
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000010941 cobalt Substances 0.000 title claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 16
- -1 hydroxide ions Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 229910052702 rhenium Inorganic materials 0.000 claims description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000003870 refractory metal Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 238000004517 catalytic hydrocracking Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 239000003245 coal Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J23/84—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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/84—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
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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
- B01J23/76—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
-
- 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
- B01J23/84—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
- B01J23/8896—Rhenium
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
本发明涉及含钴催化剂、作为中间产物的沉淀物、费‑托催化剂的制备以及由合成气生产通常气态、通常液态和任选地通常固态烃的方法。所述沉淀物和催化剂包含结晶Co(OH)(CO3)0.5,晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。
Description
技术领域
本发明涉及含钴催化剂、作为中间产物的沉淀物、费-托催化剂(Fischer-Tropschcatalyst)的制备以及由合成气生产通常气态、通常液态和任选地通常固态烃的方法。
背景技术
已知许多文献描述了将(气态)含烃原料(尤其是甲烷、天然气和/或伴生气)催化转化为液态产物,特别是甲醇和液态烃(尤其是链烷烃)的方法。在此方面,经常提到偏远地区和/或离岸地区,在这些地区,例如通过管道或以液化天然气的形式直接使用天然气并不总是切实可行的。在气体产量和/或气田相对较少的情况下,这种情况更为明显。气体回注将增加石油生产的成本,并且在伴生气的情况下,可能会对原油生产造成不良影响。考虑到烃源的枯竭和空气污染,伴生气的燃烧已成为不受欢迎的选择。费-托法(Fischer-Tropschprocess)可以用作将含烃原料转化为液态和/或固态烃的一部分。通常,原料(例如天然气、伴生气和/或煤层气、煤)在第一步骤中被转化为氢气和一氧化碳的混合物(此混合物通常被称为合成气(synthesis gas/syngas))。然后将合成气送入反应器中,其中在高温和高压下通过合适的催化剂,在一个或多个步骤中将合成气转化成范围是从甲烷到包含多达200个碳原子,或在特定情况下甚至更多个碳原子的高分子量模块的化合物(和水)。
其它可以用于催化转化的含烃原料的实例为煤、生物质、垃圾、油渣和炼油厂的废气。
费-托合成中使用的催化剂通常包含基于负载材料的载体和元素周期表第VIII族的一种或多种金属,特别是来自钴或铁族的金属,任选地与一种或多种作为促进剂的金属氧化物和/或金属组合,所述金属氧化物和/或金属选自锆、钛、铬、钒和锰,特别是锰。此类催化剂在本领域已知并且已在例如WO 9700231 A和US 4595703的说明书中进行了描述。
通常,已经通过用一种或多种可溶性钴盐和一定量的溶剂浸渍多孔载体,然后干燥、煅烧和任选地活化来制备现有技术中的催化剂。在多孔载体的孔隙浸渍的情况下,通常可以从机械强挤出物开始。然而,通过单一浸渍步骤可获得的最大钴负载量受到载体的孔隙体积和钴盐的溶解度的限制。实际上,需要若干浸渍步骤以获得所需量的钴。对于商业规模的催化剂制备来说,需要此类多个步骤是非所必需的。
在现有技术中已经描述,还可以通过将氧化铝(EP 0 455 307)、二氧化硅(EP 0510 771)或氧化锆(EP 0 510 772)与可溶性或不溶性钴源研磨或捏合来制备合适的费-托催化剂。以这种方式,可能获得经挤出、干燥和煅烧的糊状物,以获得可用于费-托反应的催化剂或催化剂前体。特别是在使用不溶性钴源的情况下,可以通过相对简单的方法获得足够高的钴负载量,所述方法适用于商业规模。
费-托反应的一种催化剂是通过将可溶性或不可溶性钴源与二氧化钛一起研磨或捏合。在一种制备催化剂的方式中,氢氧化钴(Co(OH)2)可以用作起始材料。
氢氧化钴和二氧化钛的复合材料通过挤出成型,随后干燥和煅烧,并且接着放入费-托反应器中。在反应器中,氧化钴被还原成钴。
费-托催化剂领域中持续需要改进的催化剂,其具有良好活性的同时还具有良好C5+选择性。
发明内容
本发明的目的是提供一种具有改进的活性的费-托催化剂。
出人意料地发现,根据本发明的用于制备含钴催化剂或催化剂前体、包含载体材料的沉淀物和包含载体材料的费-托催化剂或其前体的方法满足了此目的。
在本发明的一方面,所述方法包括以下步骤:
(a)混合如下(1)、(2)和(3)以形成混合物:
·(1)水;
·(2)第一水溶液,其包含碳酸根离子;
·(3)第二水溶液,其包含钴离子和任选地至少一种促进剂金属化合物的离子,所述促进剂金属化合物选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬;
(b)从步骤(a)中获得的混合物获得沉淀物;
其中在混合期间将步骤(a)的所述混合物的pH值保持在6.5至8.5的范围内,并且将水、第一和第二水溶液以及在步骤(a)中获得的所述混合物的温度保持在50摄氏度和85摄氏度的范围内。
在本发明的一方面,沉淀物包含结晶Co(OH)(CO3)0.5。
在本发明的一方面,费-托催化剂或费-托催化剂前体包含载体材料和结晶Co(OH)(CO3)0.5。
在本发明的一方面,催化剂用于从合成气生产通常气态、通常液态和任选地通常固态烃的方法中,所述方法包括以下步骤:
(i)将所述合成气提供给包含所述催化剂的反应器;以及
(ii)在高温和高压下催化转化步骤(i)的合成气,以获得所述通常气态、通常液态和任选地通常固态烃。
具体实施方式
在本发明的一方面,所述方法包括以下步骤:
(a)混合如下(1)、(2)和(3)以形成混合物:
·(1)水;
·(2)第一水溶液,其包含碳酸根离子;
·(3)第二水溶液,其包含钴离子和任选地至少一种促进剂金属化合物的离子,所述促进剂金属化合物选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬;
(b)从步骤(a)中获得的混合物获得沉淀物;
其中在混合期间将步骤(a)的所述混合物的pH值保持在6.5至8.5的范围内,并且将水、第一和第二水溶液以及在步骤(a)中获得的所述混合物的温度保持在50摄氏度和85摄氏度的范围内。
任选地,向(1)水、(2)包含碳酸根离子的第一水溶液和/或(3)包含钴离子和任选地至少一种促进剂金属化合物的离子的第二水溶液添加表面活性剂,所述促进剂金属化合物选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬。
表面活性剂为表面活性物质。适用于本发明的表面活性剂类型为阴离子、阳离子、两性离子和/或非离子表面活性剂。用于本发明的合适的阴离子表面活性剂的实例为:硫酸酯、磺酸酯和磷酸酯;羧酸盐,但不限于此列表。用于本发明的合适的阳离子表面活性剂的实例(但不限于此表面活性剂)为季铵盐。用于本发明的合适的非离子表面活性剂的实例为:乙氧基化物;脂肪酸酯;氧化胺;亚砜;氧化膦,但不限于此列表。合适的两性离子表面活性剂的实例(但不限于这些表面活性剂)为氨基酸。
在本发明的一方面,沉淀物包含表面积为至少80m2/g的结晶Co(OH)(CO3)0.5。
在本发明的一方面,费-托催化剂或费-托催化剂前体包含载体材料和结晶Co(OH)(CO3)0.5。
在本发明的一方面,催化剂用于从合成气生产通常气态、通常液态和任选地通常固态烃的方法中,所述方法包括以下步骤:
(i)将所述合成气提供给包含所述催化剂的反应器;以及
(ii)在高温和高压下催化转化步骤(i)的合成气,以获得通常气态、通常液态和任选地通常固态烃。
本发明人发现,本发明的方法提供了含有小型针状钴的晶体。晶体包含Co(OH)(CO3)0.5,并且至少具有至少80m2/g的表面积。晶体优选至少具有至少100m2/g的表面积。通过BET表面积测量来确定表面积。小晶体与高表面积一起允许晶体在催化剂中良好分布。此外,所述高表面积为反应物和催化活性相的接触提供了高表面积。与现有技术催化剂相比,这会产生更高的催化剂的活性。
在本发明的一方面,包含钴离子的第二水溶液进一步含有至少一种促进剂金属化合物的离子,所述促进剂金属化合物选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬。
在本发明的一方面,第一水溶液包含碳酸根和氢氧根离子。在本发明的一方面,碳酸根和氢氧根离子以1:1的比例存在。
在本发明的一方面,第二水溶液进一步包含以下阴离子中的一种或多种:氯离子、溴离子、碘离子、氯酸根、高氯酸根、硝酸根、亚硝酸根、硫酸根或钴盐可溶于水的任何其它阴离子。
在本发明方法的一方面,在步骤(a)中,将第一和第二水溶液混合到水中。本发明人发现,这允许在混合期间良好控制pH值。
沉淀的Ph范围需要控制在6.5-8.5之间,以使Co盐的溶解性降到最低。在优选的pH范围之外,可溶性Co盐保留在上清液中且不经济地使用。
在本发明的一方面,所述方法进一步包括以下步骤:
(c)将载体材料和沉淀物共研磨以获得共研磨的材料,其中在共研磨之前对沉淀物进行洗涤。共研磨的材料可以在淤浆反应器中用作费-托催化剂。这些反应器的实例公开于WO2007069317、US 8,722,748、US 8,013,025和US 6,265,452。共研磨产物也可在微通道反应器中用作催化剂,如在US 7,084,180中所公开的。
在本发明的一方面,所述方法进一步包括以下步骤:
(d)将步骤(c)中获得的所述共研磨的材料成型和干燥以获得成型材料。
任选地,在不干燥的情况下成型所述共研磨的材料,或在不成型和不干燥的情况下进一步使用所述共研磨的材料。
通常,将混合物的成分研磨持续5至120分钟,优选15至90分钟。在研磨过程期间,通过研磨设备将能量输入混合物中。可以在宽温度范围内,优选在15至90℃下进行研磨。由于在研磨过程期间向混合物中输入了能量,因此在研磨期间混合物的温度将升高。研磨过程宜在环境压力下进行。可以使用任何合适的市售研磨机。
为了改进混合物的流动特性,优选在挤出之前在混合物中包括一种或多种流动改进剂和/或挤出助剂。包括在混合物中的合适的添加剂包括脂肪胺、季铵化合物、聚乙烯吡啶、磺基鎓、锍、鏻和碘鎓化合物、烷基化芳香族化合物、无环一元羧酸、脂肪酸、磺化芳香族化合物、醇硫酸酯、醚醇硫酸酯、硫酸化脂肪和油、膦酸盐、聚氧伸乙基烷基苯酚、聚氧伸乙基醇、聚氧伸乙基烷基胺、聚氧伸乙基烷基酰胺、聚丙烯酰胺、多元醇和炔二醇。优选添加剂以商标Nalco和Superfloc销售。
为了获得强挤出物,优选在挤出之前在混合物中包括至少一种用作二氧化钛的胶溶剂的化合物。包括在可挤出混合物中的合适胶溶剂是本领域众所周知的,并且包括碱性和酸性化合物。碱性化合物的实例为氨、氨释放化合物、铵化合物或有机胺。此类碱性化合物在煅烧时去除,并且不保留在挤出物中从而减损最终产物的催化性能。优选的碱性化合物为有机胺或铵化合物。最合适的有机胺为乙醇胺。合适的酸性胶溶剂包括弱酸,例如甲酸、乙酸、柠檬酸、草酸和丙酸。
任选地,在挤出之前,混合物中可包括烧尽材料,以便在所得的挤出物中产生大孔。合适的烧尽材料在本领域中通常是已知的。
在本发明的一方面,通过挤出共研磨的材料来实现成型。可以使用任何常规的市售挤出机进行挤出。确切地说,可以使用螺杆式挤出机来迫使混合物穿过合适的模板中的孔,以产生所需形式的挤出物。挤出时形成的股线可以切割成所需的长度。
在本发明的一方面,所述方法进一步包含对在步骤(d)中获得的成型材料进行煅烧或干燥的步骤。煅烧在高温下进行,优选在400与750℃之间,更优选在500与650℃之间的温度下进行。煅烧处理的持续时间通常从5分钟至若干小时,优选从15分钟至4小时。适当地,煅烧处理在含氧气氛中进行,优选在空气中进行。应了解,任选地,可以将干燥步骤和煅烧步骤组合。
可以将有关所述方法的本发明的一个或多个方面组合。
本发明的方法提供沉淀物作为中间产物。所述沉淀物包含结晶Co(OH)(CO3)0.5H2O且为本发明的一方面。
在本发明的一方面,沉淀物进一步包含X(OH)(CO3)0.5,其中X选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬,其中晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。
在本发明的一方面,沉淀物由Co(OH)(CO3)0.5和X(OH)(CO3)0.5组成,其中X选自由以下组成的组:锰、钒、铼、钌、锆、钛、铂或铬,其中晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。优选地,Co(OH)(CO3)0.5与X(OH)(CO3)0.5的摩尔比为至少10:1。
在本发明的一方面,沉淀物可以通过根据本发明的方法获得。优选地,沉淀物通过根据本发明的方法获得。
可以将有关沉淀物的本发明的一个或多个方面组合。
在本发明的一方面,费-托催化剂或费-托催化剂前体包含载体材料和结晶Co(OH)(CO3)0.5。结晶Co(OH)(CO3)0.5在本发明中被称为活性相。
如本文所使用的术语“费-托催化剂或费-托催化剂前体”通常是指活性相材料或其前体,其具有惰性载体,例如难熔氧化物,通常以纳米大小的颗粒的形式存在。活性相材料或其前体可以是催化活性金属或其前体。
费-托催化剂或费-托催化剂前体可以例如是在负载物上包含催化剂材料的挤出物、粒料或一种或多种颗粒。用于负载费-托催化剂或费-托催化剂前体的基材可以是本领域已知的多种材料中的一种或多种。这些包括如钢,优选不锈钢的金属。其它包括陶瓷以及其组合。
在本发明的一方面,费-托催化剂包含作为载体材料的难熔金属氧化物或其前体。
在本发明的一方面,催化剂进一步包含结晶X(OH)(CO3)0.5,其中X选自由以下组成的组:锰、钒、铼、钌、锆、钛、铂或铬,其中晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。
在本发明的一方面,催化剂为挤出颗粒,其包含如上所定义的结晶Co(OH)(CO3)0.5,并且优选结晶X(OH)(CO3)0.5。挤出颗粒可用于固定床反应器中。
可以将有关费-托催化剂的本发明的一个或多个方面组合。
在本发明的一方面,催化剂用于从合成气生产通常气态、通常液态和任选地通常固态烃的方法中。所述方法包括以下步骤:
(i)将所述合成气提供给包含所述催化剂的反应器;以及
(ii)在高温和高压下催化转化步骤(i)的合成气,以获得通常气态、通常液态和任选地通常固态烃。
在本说明书中,通常气态、通常液态和通常固态烃是指相应烃在环境条件(20℃和1巴)下的状态。
费-托合成优选在125-150至350℃,更优选175至275℃,最优选180至270℃范围内的温度下进行。压力优选在1-5至150-200巴绝对压力,更优选10至70巴绝对压力范围内。优选地,使用费-托催化剂,其产生大量的链烷烃,更优选地大量无支链的链烷烃。一部分可能会在所谓的中间馏分的沸点范围以上沸腾至通常固态烃。为此目的最合适的催化剂为含钴的费-托催化剂。如本文所使用的术语“中间馏分”是指烃混合物,其沸点范围基本上对应于在粗矿物油的常规常压蒸馏中获得的煤油和粗柴油馏分的沸点范围。中间馏分的沸点范围通常处于约150至约360℃的范围内。如果存在,那么可以将较高沸点范围的链烷烃分离并进行本领域本身已知的催化加氢裂化步骤,以产生所需的中间馏分。催化加氢裂化是通过在高温和高压下并在氢气的存在下使链烷烃与含有一种或多种具有加氢活性并且负载在载体上的金属的催化剂接触而进行的。合适的加氢裂化催化剂包括催化剂,其包含选自(相同)元素周期表第VIB和第VIII族的金属。优选地,加氢裂化催化剂含有一种或多种来自第VIII族的贵金属。优选的贵金属为铂、钯、铑、钌、铱和锇。用于加氢裂化阶段的最优选催化剂为包含铂的那些催化剂。
存在于加氢裂化催化剂中的催化活性金属量可以在宽界限值内变化,并且按载体材料的重量计,通常在每100重量份约0.05至约5重量份的范围内。催化加氢裂化的合适条件为本领域中已知。通常,加氢裂化在约175至400℃范围内的温度下实现。在加氢裂化过程中施加的典型氢分压在10至250巴范围内。
所述过程可以以单程模式(“一次通过”)或循环模式进行操作。可以使用淤浆床反应器、沸腾床反应器和固定床反应器,固定床反应器为优选的选择方案。
除了水和通常气态烃之外,烃合成和随后的加氢裂化的产物适当地主要包含通常液态烃。通过以此方式选择催化剂和工艺条件使得特别获得通常液态烃,所获得的产物(“合成原油”)可以以液态形式运输或与任何原油流混合而不会对混合物的固化和/或结晶产生任何问题。在此方面观察到,包含大量固体蜡的重烃的生产不太适合与原油混合,而呈液态形式的运输必须在高温下进行,这是不太理想的。
烃合成的废气可包含在合成过程中产生的通常气态烃、氮气、未转化的甲烷和其它原料烃、未转化的一氧化碳、二氧化碳、氢气和水。通常气态烃适当地为C1-5烃,优选地C1-4烃,更优选地C1-3烃。这些烃或其混合物在5-30℃(1巴)的温度下,特别是在20℃(1巴)下为气态。此外,废气中可能存在含氧化合物,例如甲醇、二甲醚。废气可用于在如本文所述的燃气轮机中的膨胀/燃烧过程中产生电力或再循环到所述过程中。所述过程中产生的能量可用于自身使用或输出至当地客户。一部分能量可以用于含氧气体的压缩。如刚刚所描述的过程可以与本说明书中所描述的所有可能的实施例组合。
任何启动燃气涡轮机产生的蒸汽和/或由步骤(i)中产生的蒸汽还可以用于预加热打算用于步骤(ii)中的反应器和/或可以用于在步骤(ii)中使用流化床反应器或淤浆鼓泡塔的情况下产生流化。
除非另有说明,否则本说明书中所提及的任何百分比都是按组合物的总重量或体积计算。当未提及时,百分比视为重量百分比。除非另有说明,否则压力以绝对巴表示。
可以将本发明的一个或多个方面组合。所附权利要求书通过此参考形成本说明书的组成部分。本公开不限于如上所述的实施例和所附权利要求书。可以设想许多修改,并且可以组合相应实施例的特征。
Claims (9)
1.一种制备含钴催化剂或催化剂前体的方法,其包括:
(a)混合如下(1)、(2)和(3)以形成混合物:
·(1)水;
·(2)第一水溶液,其包含碳酸根和氢氧根离子;
·(3)第二水溶液,其包含钴离子和任选地至少一种促进剂金属化合物的离子,所述促进剂金属化合物选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬;
(b)从步骤(a)中获得的混合物获得包含Co(OH)(CO3)0.5的表面积为至少80m2/g的沉淀物;
其中在混合期间将步骤(a)的所述混合物的pH值保持在6.5至8.5的范围内,并且将水、第一和第二水溶液以及在步骤(a)中获得的所述混合物的温度保持在50摄氏度和85摄氏度的范围内。
2.根据权利要求1所述的方法,其中在步骤(a)中将所述第一和第二水溶液与水混合。
3.根据权利要求1或2所述的方法,其进一步包括以下步骤:
(c)将载体材料和沉淀物共研磨以获得共研磨的材料,其中在共研磨之前将沉淀物洗涤。
4.根据前述权利要求中任一项所述的方法,其进一步包括以下步骤:
(d)将步骤(c)中获得的所述共研磨的材料成型和干燥以获得成型材料。
5.根据权利要求4所述的方法,其进一步包括对步骤(d)中获得的所述成型材料进行煅烧或干燥的步骤。
6.一种沉淀物,其包含结晶Co(OH)(CO3)0.5和任选地X(OH)(CO3)0.5H2O,其中X选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬,其中晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。
7.一种费-托催化剂或费-托催化剂前体,其包含载体材料和结晶Co(OH)(CO3)0.5H2O和任选地X(OH)(CO3)0.5H2O,其中X选自由以下组成的组:锰、钒、铼、钌、锆、钛或铬,其中晶体为针状并且具有至少80m2/g的干燥沉淀物的表面积。
8.根据权利要求7所述的费-托催化剂,其中所述载体材料为难熔金属氧化物或其前体。
9.一种根据权利要求7或8所述的费-托催化剂的用途,其用于从合成气生产通常气态、通常液态和任选地通常固态烃的方法中,所述方法进一步包含以下步骤:
(i)将所述合成气提供给包含所述催化剂的反应器;以及
(ii)在高温和高压下催化转化步骤(i)的所述合成气,以获得所述通常气态、通常液态和任选地通常固态烃。
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