CN1440310A - 使用掺杂的、热稳定的催化剂载体的高活性费-托合成 - Google Patents
使用掺杂的、热稳定的催化剂载体的高活性费-托合成 Download PDFInfo
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- CN1440310A CN1440310A CN01809240A CN01809240A CN1440310A CN 1440310 A CN1440310 A CN 1440310A CN 01809240 A CN01809240 A CN 01809240A CN 01809240 A CN01809240 A CN 01809240A CN 1440310 A CN1440310 A CN 1440310A
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- Prior art keywords
- catalyst
- adulterant
- aluminium oxide
- gamma
- oxide carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 156
- 238000000034 method Methods 0.000 claims abstract description 44
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000000694 effects Effects 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000003426 co-catalyst Substances 0.000 claims description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- -1 aluminum alkoxide Chemical class 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- 239000004575 stone Substances 0.000 claims description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical group [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims 3
- 239000007789 gas Substances 0.000 description 29
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 241000640882 Condea Species 0.000 description 11
- 238000001354 calcination Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006853 Ziegler synthesis reaction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- JWXFFWOSZTYVQD-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Ru+3] JWXFFWOSZTYVQD-UHFFFAOYSA-N 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
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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
- B01J23/83—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 rare earths or actinides
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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
- B01J23/89—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
- B01J23/8913—Cobalt and noble metals
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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Abstract
一种进行碳氢化合物合成的方法和其所用的一种高稳定性氧化铝载体钴催化剂。本发明方法包含在催化剂存在下在料浆泡罩塔反应器中将合成气反应的步骤。催化剂含有用一定量氧化镧、氧化钡或它们的组合物掺杂的γ-氧化铝载体,所用掺杂剂量在料浆泡罩塔反应器中能够有效增加催化剂的热稳定性同时保持或增加催化剂的活性。
Description
发明背景
1.技术领域
本发明涉及氧化铝载体钴催化剂,其对于在料浆泡罩塔型和其它类型三相反应器中进行的费-托(Fischer-Tropsch(F-T))合成具有改善的稳定性和高活性。
2.背景
在费-托反应中,含有碳氧化物和氢的合成气体在费-托催化剂的存在下反应生成液体碳氢化合物。费-托合成反应最一般的方式是在固定床、气-固或夹杂气体的流化床反应系统中进行,固定床反应系统是最常使用的。但是,本领域中的人们认识到,料浆泡罩塔型反应器系统能够提供比这些通常使用的费-托反应系统高得多的潜在优点。
如上所述,用在费-托反应中的合成气体一般是主要组分是氢和碳氧化物的混合物。合成气体一般是这样生产的,例如,在煤气化反应过程中。从包括天然气的其它碳氢化合物获得合成气体的方法也是公知的。授予Chu等人的美国专利No.4,423,265指出,生产合成气体的主要方法,或者根据碳氢燃料与含氧气体的不完全燃烧或燃料与水蒸气反应,或者根据这两种反应的组合。授予Benham等人的美国专利No.5,324,335解释了用于从甲烷生产合成气的这两种基本方法(即水蒸气转化和部分氧化反应)。由Chu等人认为化学科技百科全书,第二版,第10卷,3553-433(1966),Interscience Publishers,纽约,N.Y.和第三版,第11卷,410-446(1980),John Wiley and Sons,纽约,N.Y.中包括了气体生产的完美总结,包括合成气的生产。
人们很早就认识到通过一氧化碳的催化氢化可以将合成气转化成液态碳氢化合物。费-托合成反应的一般化学方程式如下:
(1)
由费-托合成获得的反应产物的类型和含量,即碳链的长度,根据反应动力学和所选择的催化剂的不同而不同。
先前已经公开了许多提供用于将合成气选择性地转化成液体碳氢化合物的活性催化剂的尝试。授予Soled等人的美国专利No.5,248,701提供了一个相关现有领域的综述。此前用在费-托合成中的两种最常用的催化剂是铁基催化剂和钴基催化剂。授予Benham等人的美国专利No.5,324,335讨论了以下事实,铁基催化剂由于他们的高水气转移活性而有利于在上述反应(2)中的整体反应,而钴基催化剂则有利于反应式(1)。
最近的进展提供了大量在费-托合成中有活性的催化剂。除了铁和钴,其他第VIII族金属,特别是钌,是公知的费-托催化剂。目前的实践是将这些催化剂承载在多孔无机耐火氧化物上,特别优选的载体包括二氧化硅、氧化铝、二氧化硅-氧化铝和二氧化钛。其它选自第III、IV、V、VI和VIII族的耐火氧化物也可以用作催化剂载体。
普遍的实际应用也将助催化剂加入载体催化剂中。助催化剂包括钌(当其未用作主要催化剂组分时)、铼、铪、铈和锆。已知助催化剂能提高催化剂的活性,与未使用助催化剂的催化剂相比,有时使用助催化剂的催化剂能提供三至四倍的催化活性。
现在的钴催化剂一般通过用催化材料浸渍载体来制备。如在授予Chang等人的美国专利No.5,252,613中所描述的,一般催化剂的制备方法包括,通过初期润湿或其它已知的技术,将比如硝酸钴的盐浸渍在二氧化钛、二氧化硅或氧化铝载体上,任选随后或事先用助催化剂材料浸渍。然后除去多余的液体并干燥催化剂前体。在干燥以后,或作为一个连续的过程,灼烧该催化剂使盐或化合物转化成其相应的氧化物。然后用氢或含氢的气体处理将氧化物还原,经足够长的时间基本上将氧化物还原成金属单质或催化形式。授予Long的美国专利No.5,498,638以及美国专利Nos.4,673,993、4,717,702、4,477,595、4,663,305、4,822,824、5,036,032、5140,050和5,292,705公开了公知的催化剂制备技术。
如上所述,费-托合成在此前主要在固定床、气-固反应器和夹杂气体的流化床反应器中进行,最常使用固定床反应器。授予Dyer等人的美国专利No.4,670,472提供了描述这些系统的几个参考文献的目录。美国专利No.4,670,472的全部公开内容在这里引入作为参考。
与本文中这些其它的碳氢化合物合成系统相反,料浆泡罩塔反应器是“三相”(即固、液和气/蒸汽)反应系统,其涉及将流化气体引入反应器中,该反应器装有用烃液体制浆的催化剂颗粒。催化剂颗粒在反应器小室(一般为整个高柱)中的液体碳氢化合物中制成料浆。然后在柱底部通过一个分配器板(其产生小气泡)引入合成气体,气泡向上迁移并通过反应柱,产生有益的搅拌和涡流,同时在催化剂存在下反应生成液态和气态碳氢化合物产物。气态产物在SBCR顶部收集,而液态产物通过一个过滤器回收,该过滤器将液态碳氢产物从催化剂精细颗粒中分离出来。美国专利Nos.4,684,756、4,788,222、5,157,054、5348,982和5,527,473提到了这种类型的系统并提供了对适当的专利和文献书籍的引用。这些专利每一个的全部公开内容在这里引入作为参考。
人们认识到使用SBCR系统进行费-托合成能够提供明显的优点。正如Rice等人在美国专利No.4,788,222中所指明的,由于料浆反应能实行连续的循环、回收和再生过程,该方法与固定床反应相比的潜在优势包括,更好地控制由费-托反应产生的热量以及更好地保持催化剂活性。美国专利Nos.5,157,054、5,348,982和5,527,473也讨论了SBCR方法的优点。
常规的费-托合成操作导致在钴催化剂上积碳的形成,使得随时间的推移催化剂的活性降低,这种活性降低的主要来源的量与所使用的反应条件相关。通常钴催化剂可以通过在相对高温下灼烧(烧掉碳沉积物)然后还原而再生。但是这些催化剂连续处于高温下可能导致载体表面积的稍微降低,随后产生钴颗粒的胶囊化和形成更难于还原或根本不能还原的钴金属化合物。所有这些变化都会伴随着反应试剂可以进入的钴表面积的降低,这种降低在每一个再生循环后引起催化剂活性的稍微降低。
氧化铝是一种通常用作钴基费-托催化剂载体的氧化物,众所周知,它对预处理温度和处于高温下的时间敏感。通常用作催化剂载体的氧化铝晶型是γ-氧化铝。它一般是通过在适当的条件下(一般300-650℃)加热,使氢氧化铝(勃姆石)脱水制得的。或者在预处理步骤中、在催化剂的使用过程中,或者在催化剂的再生过程中进一步加热,可能导致表面积缓慢而连续的降低以及氧化铝从γ-氧化铝相缓慢转变成其他形式(δ-氧化铝,随后转变成θ-氧化铝),这些晶型具有很低的比表面积。最后,特别是在非常高的温度下,可能发生结构坍塌,导致致密的、高稳定的、低比表面积的α-氧化铝形成。
Condea/Vista以及R.Gaugin、M.Graulier和D.Papee在“热稳定的载体(Thermally Stable Carriers)”,
Advances in Chemistry Series,第143卷,147页(1975)中建议,一些γ-氧化铝材料的热稳定性可以通过向该氧化铝中引入少量的二价离子如钙、镁或钡或者稀土氧化物如氧化镧得到增强。人们认为这些增强是因为占据了在尖晶石中的四面体空位并且延迟了Al3+阳离子的扩散。但是,这种载体添加剂对于这样形成的任一催化剂的活性和其他特征的影响还是未知的。例如,人们已经知道费-托催化剂的活性和选择性对于催化剂或载体成分的变化是极度敏感的。
发明概述
本发明出人意料地、令人惊奇地提供了用于费-托合成反应的高稳定性和高活性的氧化铝载体钴催化剂。
另一方面,本发明方法包括以下步骤:在一个料浆泡罩塔反应器系统中在催化剂存在下使合成气反应,所用催化剂包含γ-氧化铝载体,其中该γ-氧化铝载体含有一定数量的氧化镧或氧化钡,其足够有效增加催化剂的热稳定性。
本发明进一步的目的、特征和优点通过研究附图和阅读下面优选实施方案的详细描述将更加明显。
附图简述
图1是掺杂镧和钡的氧化铝与更普通的未掺杂氧化铝的热稳定性的比较图。
图2是在料浆泡罩塔反应器中担载在未掺杂、掺杂镧和掺杂钡的氧化铝上的助催化钴催化剂的费-托合成特性比较图。
优选实施方案详述
催化剂组合物
本发明提供载体钴催化剂,该催化剂非常适用于费-托合成反应。这些催化剂特别适合用于三相反应器的反应中。由本发明提供的一般催化剂组合物的实例包括:(a)钴,没有任何助催化剂,优选担载在掺杂的γ-氧化铝上;(b)钴,带有一种或多种贵金属助催化剂,优选担载在掺杂的γ-氧化铝上;(c)钴,同时用贵金属助催化剂和一种或多种选择性助催化剂(优选碱金属或稀土氧化物)助催化,优选担载在掺杂的γ-氧化铝上;(d)钴,用一种或多种选择性助催化剂助催化并且没有贵金属助催化剂,优选担载在掺杂的γ-氧化铝上。典型助催化剂的实例不受限制地包括,贵金属如钌,金属氧化物如锆、镧或钾的氧化物以及选自IA、IIA、IVB、VB和VIB族元素的氧化物。
优选催化剂组合物包含以下组分(每100份载体重量):约10-70pbw钴;约0.1-8pbw钌(当存在时);约0.1-8pbw钾(当存在时);约0.5-8pbw氧化镧(当存在时)。该催化剂也可以包括其它助催化剂材料。我们已经发现,为了获得所特别期望的选择性和活性的组合,特别是在如料浆泡罩塔反应器的反应系统中,最优选催化剂包含以下组分(每100份载体重量):约15-55pbw(更优选约20-45pbw)钴;约0.2-1.5pbw钌(当存在时);约0.2-1.0pbw钾(当存在时);约0.5-5.0pbw(最优选约0.9-2.5pbw)氧化镧(当存在时)。
催化剂载体
在本发明中使用的催化剂载体优选为镧或钡掺杂的γ-氧化铝,其具有以下性能:低浓度的杂质,特别是硫(优选少于100ppm硫);球形;平均粒径为约10-150μm(最优选约20-80μm);烧结后BET比表面积为约200-260m2/g;孔隙度为约0.4-1.0cm3/g。
氧化铝载体优选从相对高纯度的合成波姆石制备,如下面所讨论的,波姆石可从在合成脂肪醇的制备中获得的烷氧基铝形成。另外,合适的高纯波姆石材料可从由醇/铝金属反应过程生产的烷氧基铝制得。
优选将烷氧基铝水解来生产高纯度合成的单水合氧化铝。接着,优选将该材料喷雾干燥以获得高多孔性,相对高比表面积的球状波姆石颗粒,然后,优选将颗粒状波姆石材料过筛以除去小颗粒和大颗粒以获得所期望的粒径范围(最优选约20-80μm)。将过筛后的材料烧结以将波姆石颗粒转化成γ-氧化铝载体材料,其具有所期望的比表面积和孔隙度。优选将波姆石材料在至少350℃的温度(更优选约400-700℃,最优选约500℃)灼烧约3-24小时(更优选约5-16小时,最优选约10小时)的时间。所期望的灼烧温度优选通过以约0.5-2.0℃/分钟的速度缓慢加热系统而达到。
La2O3或BaO掺杂物优选以约1-5%La2O3或BaO的用量存在于γ-氧化铝中,基于载体的总重。更优选掺杂物以约2-3%重量百分比,最优选以约3%重量百分比的用量存在于载体中。掺杂剂基本上可以在任意时间加入,但是最优选在波姆石结晶之前加入。
如本领域中的技术人员所共知的,生产合成波姆石材料的方法之一是使用烷氧基铝,该烷氧基铝是由用于制造合成脂肪醇的某些反应(如Ziegler反应)的副反应制得。Ziegler反应包括下列步骤:(1)将高纯度氧化铝粉末与乙烯和氢反应生成三乙基铝;(2)通过将乙烯与三乙基铝接触使之聚合,这样生成烷基铝;(3)将烷基铝用空气氧化生成烷氧基铝;(4)水解烷氧基铝生成乙醇和氧化铝副产物。
在另一方法中,通过将乙醇与高纯铝粉反应形成烷氧基铝,然后水解烷氧基铝生成乙醇和氧化铝,乙醇循环用于烷氧化物形成步骤。为了本发明的目的,任何所期望的用量的掺杂剂,镧和/或钡可以通过下面的方法包括在氧化铝产物中,例如,加入相应掺杂物的烷氧化物并共水解掺杂物烷氧化物和在本反应第一步中形成的烷氧基铝。
为了比较,适用于形成不掺杂的γ-氧化铝载体的市售波姆石材料(其不同于本发明所用的类型)的实例包括由Cordea/Vista提供的CATAPAL和PURAL氧化铝。这些材料可能包含高达2000ppm重量的钛,这依赖于用于制造它们的反应。这种类型的商用材料,其可能对制造高活性F-T钴基催化剂有效,但并不能总是提供足够的热稳定性,并可能限制在这些催化剂的整个寿命过程中所允许的反应-再生循环次数。
图1是由从Condea/Visa获得的数据重新制作出来的,显示了所报道的镧和钡掺杂对氧化铝热稳定性的影响。掺杂的氧化铝分别含有约3重量%的镧和钡氧化物。这些结果表明,常规(未掺杂)氧化铝PuralSB的比表面积在高于1000℃加热几个小时时显著降低。但是,掺杂的氧化铝在进行相同的加热处理时没有发生这种比表面积的急剧降低。因此,即使在氧化铝被认为将转变为具有仅仅几个m2/g比表面积的α相的温度下,镧和钡氧化物在提高这些裸氧化铝的稳定性方面起了关键作用。虽然使用这些氧化铝的F-T催化剂不会遭受这种高温,但是即使在300-500℃的极低温度下的重复再生也可能最终显著降低常规无掺杂氧化铝载体的比表面积。
催化剂制备
优选将优选催化剂的催化组分使用适当的水溶液组成和体积,通过整体水溶液浸渍加到载体上,使所期望金属负载物将载体材料初期润湿。最优选通过整体水溶液共浸渍制备助催化的催化剂。典型助催化剂的实例包括:贵金属;金属氧化物如Zr、La、K的氧化物;其它IA、IIA、IVB、VB和VIB族元素的氧化物。
根据本发明,钴在载体上的整体水溶液浸渍,带有或没有一种或多种助催化剂,优选通过以下步骤完成:(a)用上述方法灼烧氧化铝载体;(b)用硝酸钴或硝酸钴与一种或多种助催化剂化合物(优选一种或多种助催化剂硝酸盐[例如,亚硝酰合钌(III)硝酸盐]和/或助催化剂-氯化物[例如,氯化钌(III)],最优选助催化剂硝酸盐)的水溶液浸渍载体,使用足量的溶液以使初期润湿达到负载期望量的钴和任何所期望的助催化剂;(c)在约80-130℃将所获得的催化剂前体干燥约5-24小时,同时进行中度搅拌,去除溶剂水并获得干燥催化剂;(d)以每分钟约0.5-2.0℃的速度缓慢升高系统温度至约250-400℃,在空气或氮气中灼烧干燥后的催化剂,然后保持至少2小时,获得催化剂的氧化物形式。但希望更高的钴负载时可以进行多次浸渍/共浸渍步骤(b)。
作为一个实例,我们按照下列步骤制备了一种特别优选的钌助催化的钴催化剂。首先,将载体,优选镧或钡掺杂的γ-氧化铝,在约400-700℃(优选约500℃)灼烧约10小时。然后将灼烧过的载体用适量同时含有硝酸钴[Co(No3)2-6H2O]和亚硝酰合钌(III)硝酸盐[Ru(NO)(NO3)3-xH2O]的水溶液浸渍,完成所期望的钴和钌负载在载体上的初期润湿。然后在115℃在中度搅拌下将所得催化剂前体干燥5小时除去溶剂水。随后以1℃/分钟的速度升温至300℃并维持至少2小时,将干燥后的催化剂进行灼烧。
催化剂活化
为提供最佳的性能,目前优选在含氢气体中通过缓慢升高催化剂的温度(优选以约0.5-2.0℃/分钟的速度)至约250-400℃(优选350℃)并在所期望温度下保持至少2小时将催化剂活化/还原。还原后,优选催化剂在氮气流中冷却。
还原气体优选含有约1-100体积%的氢气,其它气体成分(如果有)为惰性气体,一般为氮气。优选还原气体以约2-4(优选3)升每小时每g催化剂的速度释放。优选还原过程在流化床反应器中进行。最优选还原过程在一定条件(即温度、流速、氢浓度等)下进行,该条件能够有效地确保在过程中保持很小的水蒸气分压。
费-托反应过程
根据本发明制备并活化的催化剂可用于任何常规的费-托合成反应过程。对于料浆泡罩塔和其它三相反应系统,优选将催化剂在费-托蜡中或在具有类似费-托蜡特性的合成流体(例如可由Chevron提供的商品名为SYNFLUID的C30-C50的异链烷烃聚α烯烃)中料浆化。优选在催化剂料浆中催化剂的浓度为约5-40重量%,基于料浆总重。
在反应过程中所使用合成气进料中的CO:H2的体积比优选为0.5-3.0,惰性气体(即氮气、氩气或其他气体)浓度基于进料的总体积,优选为0-60体积%。惰性气体优选为氮气。
在引发反应过程之前,优选将活化后的催化剂保存在惰性气氛中。在加入催化剂之前,优选将料浆流体用氮气或其它惰性气体清洗以除去任何的溶解氧。也优选在惰性气氛下将料浆组合物转入反应系统中。
一个特别优选的SBCR反应过程包含以下步骤:(a)在惰性气氛下将活化过的催化剂料浆加入到SBCR中;(b)在惰性气氛下加热加压SBCR至所期望的预处理条件(优选温度为约220-250℃,压力为约50-500psig);(c)用氢气取代惰性气体并在这些条件下保持系统约2-20小时;(d)用惰性气体清洗系统并降低反应系统温度,如果需要,降至低于所期望反应温度至少约10℃;(e)小心地用所期望合成气代替惰性气体;(f)加热加压反应系统,如果需要,加热至所期望的操作温度,优选为约190-300℃,加压至所期望的操作压力,优选为约50-900psig。
实施例
下列实施例描述了各种催化剂的制备过程和这些催化剂将合成气转化成碳氢化合物的测试结果。在进行测试之前,通过缓慢升高催化剂的温度,以约1.0℃/分钟的速度,至约350℃并在该温度下保持10小时在纯氢气中将每一种催化剂还原。氢气的释放速度为约3升每小时每g催化剂。在还原以后,催化剂在氮气流中冷却。
对于料浆泡罩塔反应器测试,在流化床反应器中进行还原过程。在冷却至室温以后,在惰性气氛下将催化剂称重,在Synfluid中浆化并转入SBCR中。在SBCR中测试的所有F-T反应都在230℃、450psig、900sl/hr合成气的条件下使用15-25g还原后的催化剂进行,所用合成气含有60%的氮气而且H2/CO比为2。催化剂的比较基于经过连续24小时后所获得的结果。
下列催化剂用相同的方法制备并具有相同的钴和钌负载,但使用不同的氧化铝载体。
催化剂1:(担载在CATAPAL B氧化铝上的钌助催化的钴F-T催化剂,含有20重量%的钴和0.5重量%的钌)
制备过程
Condea/Vista的波姆石形式的Catapal B氧化铝在500℃灼烧10小时将其转化成γ-氧化铝。然后将其预筛成400-170目(或者粒径范围大于38微米小于88微米)。
γ-氧化铝然后用硝酸钴[Co(No3)2-6H2O]和亚硝酰合钌(III)硝酸盐[Ru(NO)(NO3)3-xH2O]的水溶液浸渍,使用适当的数量达到具有所期望钴负载的初期润湿(约1.2ml/g)。然后在空气中在115℃干燥催化剂前体5小时并在空气中在300℃灼烧2小时(以约1℃/分钟的速度加热至300℃)。
在反应前的还原过程
以约1.0℃/分钟的速度加热至约350℃并保持10小时在3000cc/g/hr的纯氢气流中将催化剂还原。
下列催化剂2-5都用与催化剂1相同的方法制备。在催化剂2-5中使用的特定载体如下:
催化剂2:Condea/Vista提供的PURAL SB载体。PURAL SB由Condea/Vista使用与Catapal B相同的方法生产,但是使用混合过程在不同的工厂生产。
催化剂3:载体PURAL SB1也由Condea/Vista提供,并且除了PURAL SB1载体不含有钛以外与PURAL SB相同。
催化剂4:载体PURALOX DP/L3也由Condea/Vista提供,并且除了PURALOX DP/L3载体用2.8重量%的氧化镧(La2O3)掺杂并被制造商在与制造催化剂1-3的相同条件下进行预烧结以获得可比的比表面积(200-250m2/g)以外,其它与PURAL SB相同。
催化剂5:载体PURALOX DP/B3也由Condea/Vista提供,并且除了PURALOX DP/B3载体用2.7重量%的氧化钡(BaO)掺杂并被制造商在与制造催化剂1-3的相同条件下进行预烧结以获得可比的比表面积(200-250m2/g)以外,其它与PURAL SB相同。
在催化剂1中使用的特殊CATAPAL B载体材料经测定含有二氧化钛“杂质”的量为约1000ppm重量分(按钛重量表达为ppm),其是作为Ziegler过程的部分,在波姆石结晶之前附带加入的。在500℃烧结10小时的CATAPAL B氧化铝的BET比表面积为221m2/g。相对照,在催化剂2中使用的特殊PURAL SB载体材料通过混合过程形成并且发现仅仅含有约500ppm的钛。在500℃烧结10小时的PURAL SB氧化铝的BET比表面积为204m2/g。在催化剂3中使用的特殊γ-氧化铝,PURAL SB1载体材料是由Condea/Vista为我们特别生产的。除了采用特殊的方法防止钛加入以外,PURAL SB1与PURAL SB是相同的。元素分析测试表明PURAL SB1载体仅仅含有7ppm的钛。在500℃烧结10小时的PURAL SB1氧化铝的BET比表面积为209m2/g。
在催化剂4中使用的特殊γ-氧化铝,PURALOX DP/L3载体材料是由Condea/Vista为我们特别生产的。除了PURALOX DP/L3载体用镧掺杂并被制造商在与制造催化剂1-3的相同条件下进行预烧结以获得可比的比表面积以外,其它与PURAL SB相同。元素分析测试表明PURALOX DP/L3载体仅仅含有2.8重量%的氧化镧(La2O3)和1865ppm重量分的二氧化钛(TiO2)。它的BET比表面积为201m2/g。
在催化剂5中使用的特殊γ-氧化铝,PURALOX DP/B3载体材料也是由Condea/Vista为我们特别生产的。除了PURALOX DP/B3载体用钡掺杂并被制造商在与制造催化剂1-3的相同条件下进行预烧结以获得可比的比表面积以外,其它与PURALOX DP/L3相同。元素分析测试表明PURALOX DP/B3载体仅仅含有2.7重量%的氧化钡(BaO)和40ppm重量分的二氧化钛(TiO2)。它的BET比表面积为226m2/g。
催化剂1-5的测试在一个料浆泡罩塔反应器中进行。表1和图2表明了每一种催化剂在首次使用24小时后所表现出的活性(表达为g-HC/Kg-cat/Hr)。催化剂1-3的比较说明了二氧化钛对钌助催化的氧化铝载体钴催化剂的有害影响。随着在载体中二氧化钛数量的增加,催化剂的活性从催化剂3的约1400,降至催化剂2的约1322,再降至催化剂1的约1195。
然而,使用镧掺杂被认为扭转了二氧化钛的影响。催化剂4含有和催化剂1相同量的二氧化钛,但是它的活性,在实验的误差范围内,和那些含有较低含量二氧化钛的催化剂的活性一样高。
催化剂5的载体几乎不含二氧化钛,但是使用约3%的氧化钡掺杂。这种BaO掺杂的催化剂的活性,在实验误差的范围内,几乎与催化剂4的活性相同。
除了这些所期望的和令人惊讶的结果外,五种催化剂(见表1)的选择性的比较表明氧化铝的掺杂对催化剂的选择性没有影响。在实验误差的范围内,五种催化剂对甲烷和C5 +的选择性被认为是相同的。
这样,氧化铝载体的镧或钡掺杂出人意料地、令人惊讶地不仅给催化剂提供了更高的稳定性,而且给费-托合成提供了更高的活性,对选择性没有任何负作用。
这样,本发明非常适合于进行这些目标并达到上述目的和优点,以及其本身固有的那些优点。虽然本发明已经用一定程度的特殊性进行了描述,显然在不脱离这种公开内容的精神和范围内可以进行多种改变。应当理解本发明并不限于上述为了举例说明所列出的实施方案。
表1
载体掺杂剂-SBCR影响总结数据
(第一个24小时平均值)
催化剂# | 氧化铝 | 掺杂剂 | 重量(g) | 温度(℃) | CO浓度(%) | THC(g-HC/kg-cat/hr) | 选择性(%C) | ||
CH4 | C5+ | CO2 | |||||||
催化剂1 | Catapal B | Ti,1000ppm | 23.5 | 230.4 | 35.8 | 1195.0 | 7.8 | 82.5 | 0.9 |
催化剂2 | Pural SB | Ti,500ppm | 21.5 | 229.9 | 36.3 | 1322.4 | 8.5 | 81.9 | 0.7 |
催化剂3 | Pural SB-1 | Ti,7ppm | 15.1 | 230.9 | 27.1 | 1399.8 | 8.4 | 80.5 | 0.7 |
催化剂4 | Puralox DP/L3 | La2O3,2.8%;TiO2,1865ppm | 15.1 | 230.2 | 25.1 | 1294.7 | 8.2 | 80.7 | 0.7 |
催化剂5 | Puralox DP/B3 | BaO,2.7%;TiO2,40ppm | 15.1 | 230.7 | 26.0 | 1342.4 | 8.3 | 80.7 | 0.6 |
反应条件:压力=150psig;流速(SLPH):H2=240,CO=120,N2=540.
Claims (33)
1.一种催化剂,包含:
一种含有掺杂剂的γ-氧化铝载体,该掺杂剂选自镧掺杂剂、钡掺杂剂及其组合;和
担载在所述γ-氧化铝载体上的钴,其数量能在料浆泡罩塔型反应系统中有效用于碳氢化合物合成,
其中所述掺杂剂在所述γ-氧化铝载体中存在的量能够有效增加用在所述料浆泡罩塔型反应系统中的所述催化剂的热稳定性,同时不降低用于所述碳氢化合物合成的催化剂的活性。
2.权利要求1的催化剂,其中存在于所述载体中的掺杂剂的用量基于所述γ-氧化铝载体的总重,为约1-5重量%。
3.权利要求1的催化剂,其中存在于载体中的掺杂剂的用量基于所述γ-氧化铝载体的总重,为约2-3重量%。
4.权利要求1的催化剂,其中存在于载体中的掺杂剂的用量基于所述γ-氧化铝载体的总重,为约3重量%。
5.权利要求1的催化剂,其中所述γ-氧化铝载体由烷氧基铝生产,使用有效的喷雾干燥和烧结过程,使得γ-氧化铝载体为球形,BET比表面积为约200-260m2/g,孔隙度为约0.4-1.0cm3/g。
6.权利要求1的催化剂,其中通过加入掺杂剂烷氧基化物并共水解掺杂剂烷氧基化物和烷氧基铝而将所述掺杂剂掺入γ-氧化铝载体中。
7.权利要求1的催化剂,其中掺杂剂是氧化钡。
8.权利要求1的催化剂,其中掺杂剂是氧化镧。
9.权利要求1的催化剂,其中存在于γ-氧化铝载体中的掺杂剂的用量在料浆泡罩塔型反应系统中能有效增加用于碳氢化合物合成的催化剂的活性。
10.权利要求1的催化剂,其中通过整体水溶液浸渍将钴加入载体中。
11.权利要求1的催化剂,其还含有至少一种助催化剂。
12.权利要求11的催化剂,其中通过整体水溶液浸渍将钴和助催化剂加入载体中。
13.权利要求11的催化剂,其中助催化剂是钌助催化剂。
14.一种费-托碳氢化合物合成的方法,其包括在催化剂存在下在费-托反应系统中将合成气反应的步骤,所述催化剂包含:
一种具有包含γ-氧化铝和控制量的掺杂剂的内部结构的γ-氧化铝载体,该掺杂剂选自镧掺杂剂、钡掺杂剂及其组合,和
担载在所述γ-氧化铝载体上的钴,其数量能在所述费-托反应系统中有效作用于所述费-托碳氢化合物合成,
其中所述掺杂剂的控制量能够有效增加用在所述费-托反应系统中的所述催化剂的热稳定性,同时不降低用于所述费-托碳氢化合物合成的催化剂的活性。
15.权利要求14的方法,其中在γ-氧化铝载体的内部结构中存在的掺杂剂的控制量基于γ-氧化铝的总重,为约1-5重量%。
16.权利要求14的方法,其中在γ-氧化铝载体的内部结构中存在的掺杂剂的控制量基于γ-氧化铝的总重,为约2-3重量%。
17.权利要求14的方法,其中在γ-氧化铝载体的内部结构中存在的掺杂剂的控制量基于γ-氧化铝的总重,为约3.0重量%。
18.权利要求14的方法,其中在内部结构中存在控制量的掺杂剂的γ-氧化铝载体由烷氧基铝产生,使用有效的喷雾干燥和烧结方法,使得γ-氧化铝载体为球形,BET比表面积为约200-260m2/g,孔隙度为约0.4-1.0cm3/g。
19.权利要求14的方法,其中γ-氧化铝载体由烷氧基铝生成,而控制量的掺杂剂通过加入掺杂剂烷氧基化物并共水解所述掺杂剂烷氧基化物和烷氧基铝而掺入γ-氧化铝载体的内部结构中。
20.权利要求14的方法,其中掺杂剂是氧化钡。
21.权利要求14的方法,其中掺杂剂是氧化镧。
22.权利要求14的方法,其中存在于γ-氧化铝载体中的掺杂剂的用量在料浆泡罩塔型反应系统中能有效增加用于碳氢化合物合成的催化剂的活性。
23.权利要求14的方法,其中通过整体水溶液浸渍将钴加入载体中。
24.权利要求14的方法,其中所述催化剂还含有至少一种助催化剂。
25.权利要求24的方法,其中通过整体水溶液共浸渍将钴和助催化剂加入载体中。
26.权利要求24的方法,其中助催化剂是钌助催化剂。
27.权利要求14的方法,其中:
γ-氧化铝载体由合成波姆石生产;并且
控制量的掺杂剂在合成波姆石结晶之前加入γ-氧化铝载体中。
28.一种费-托碳氢化合物合成的方法,其包括在催化剂存在下在费-托反应系统中将合成气反应的步骤,所述催化剂包含:
一种γ-氧化铝载体;
担载在所述γ-氧化铝载体上的钴,其数量能在费-托反应系统中有效用于该费-托碳氢化合物合成;和
至少一种在带有所述钴的γ-氧化铝载体上的助催化剂,
所述γ-氧化铝载体的内部结构包含γ-氧化铝;至少500ppm的二氧化钛,表达为元素钛的含量并且基于该γ-氧化铝的总重;和控制量的掺杂剂,该掺杂剂选自镧掺杂剂、钡掺杂剂及其组合,并且
其中所述控制量的掺杂剂的用量能够有效增加在所述费-托反应系统中用于所述费-托碳氢化合物合成的所述催化剂的活性和热稳定性。
29.权利要求28的方法,其中助催化剂是钌。
30.权利要求28的方法,其中在γ-氧化铝载体的内部结构中存在的掺杂剂的控制量基于γ-氧化铝的总重,为约1-5重量%。
31.权利要求28的方法,其中在γ-氧化铝载体的内部结构中存在的掺杂剂的控制量基于γ-氧化铝的总重,为约2-3重量%。
32.权利要求28的方法,其中γ-氧化铝载体由水解生成氧化铝产物的烷氧基铝产生,其中通过加入掺杂剂烷氧基化物并共水解该掺杂剂烷氧基化物和烷氧基铝,将掺杂剂掺入γ-氧化铝载体中,所述烷氧基铝的用量能够在该γ-氧化铝载体的内部结构中有效生成所述控制量的掺杂剂。
33.权利要求28的方法,其中:
γ-氧化铝载体由合成波姆石产生,和
控制量的掺杂剂在所述合成波姆石结晶之前加入γ-氧化铝载体中。
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US09/528,163 US6255358B1 (en) | 2000-03-17 | 2000-03-17 | Highly active Fischer-Tropsch synthesis using doped, thermally stable catalyst support |
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EP (1) | EP1263531B1 (zh) |
JP (1) | JP4933014B2 (zh) |
KR (1) | KR20030041105A (zh) |
CN (1) | CN1440310A (zh) |
AR (1) | AR027675A1 (zh) |
AU (2) | AU2001245713B2 (zh) |
BR (1) | BR0109337B1 (zh) |
CA (1) | CA2403087A1 (zh) |
EA (1) | EA005830B1 (zh) |
EG (1) | EG22430A (zh) |
GC (1) | GC0000273A (zh) |
MX (1) | MXPA02009122A (zh) |
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CN100509152C (zh) * | 2004-08-25 | 2009-07-08 | 约翰森·马瑟公开有限公司 | 高钴含量、高钴表面积的催化剂及其制备和用途 |
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OA12233A (en) | 2006-05-10 |
BR0109337B1 (pt) | 2013-10-29 |
WO2001070394A3 (en) | 2002-03-14 |
KR20030041105A (ko) | 2003-05-23 |
US6255358B1 (en) | 2001-07-03 |
MXPA02009122A (es) | 2003-03-12 |
AU2001245713B2 (en) | 2005-10-13 |
EG22430A (en) | 2003-01-29 |
WO2001070394A2 (en) | 2001-09-27 |
AR027675A1 (es) | 2003-04-09 |
NO20024441L (no) | 2002-10-28 |
JP4933014B2 (ja) | 2012-05-16 |
NO327790B1 (no) | 2009-09-28 |
MY137286A (en) | 2009-01-30 |
GC0000273A (en) | 2006-11-01 |
MY123600A (en) | 2006-05-31 |
US6537945B2 (en) | 2003-03-25 |
US20010031793A1 (en) | 2001-10-18 |
EA200200989A1 (ru) | 2003-10-30 |
EA005830B1 (ru) | 2005-06-30 |
CA2403087A1 (en) | 2001-09-27 |
JP2003531716A (ja) | 2003-10-28 |
BR0109337A (pt) | 2004-12-07 |
AU4571301A (en) | 2001-10-03 |
EP1263531B1 (en) | 2013-05-01 |
EP1263531A2 (en) | 2002-12-11 |
NO20024441D0 (no) | 2002-09-17 |
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