CN108479754A - 一种制备氧化锆负载的耐硫甲烷化催化剂的方法 - Google Patents
一种制备氧化锆负载的耐硫甲烷化催化剂的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
- 239000011593 sulfur Substances 0.000 title claims abstract description 50
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 41
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 20
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 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 description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 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 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 238000000498 ball milling Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical class [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- -1 actinide metals Chemical class 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DDKLZGLANVCKAZ-UHFFFAOYSA-N C.[S] Chemical compound C.[S] DDKLZGLANVCKAZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
本发明公开了一种载体为氧化锆的耐硫甲烷化催化剂,包括5‑40wt%活性组分、20‑90wt%的载体氧化锆和5‑40wt%的催化剂助剂。本发明还公开了所述催化剂的制备方法。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种制备氧化锆负载的耐硫甲烷化催化剂的方法。
背景技术
甲烷化反应时指在一定的的温度、压力及催化剂的作用下,合成气中的有效组分CO和H2进行反应生成CH4的过程。反应式可表示为:
CO+3H2=CH4+H2O(1)
CO+H2O=CO2+H2(2)
2CO+2H2=CH4+CO2(3)
在煤制天然气工艺中,煤气化技术已经成熟,甲烷化催化剂是关键技术。现有的工业甲烷化催化剂中,以NiO为活性组分的负载型催化剂具有较好的转化率和选择性,但是合成气需要先经过水汽变换和精脱硫,调整H2/CO比例至3:1 并脱除硫化氢等酸性气体至1ppm以下含量,而后进行甲烷化反应。与之相比,以MoO3为活性组分的耐硫甲烷化催化剂,具有良好的抗硫性能和低H2/CO比例的耐受性。耐硫甲烷化工艺可省去水汽变换和精脱硫工段,极大地简化了工艺流程并降低了能耗。
专利US4151191公开了一种甲烷化催化剂,包括镧系和/或锕系金属氧化物以及Mo金属氧化物,其中镧系和/或锕系金属与Mo的原子比为9:1。该催化剂在H2/CO为1:1和硫化物含量高达3%的条件下表现出优越的甲烷化催化特性。专利CN103933966A和CN103801287A分别公开了负载型耐硫甲烷化催化剂的制备方法,采用浸渍法或沉积沉淀法制备催化剂,以Co、Ni、La和/或K的氧化物为催化剂助剂,以Mo、W和/或V的氧化物为催化剂活性组分,以Ce、Zr、 Ti、Mg和/或Si的氧化物为载体改性剂,以Al2O3为催化剂载体。专利CN103191720A公开了一种镁铝尖晶石负载的耐硫甲烷化催化剂,以Co、Ni、 La和/或K的氧化物为催化剂助剂,以Mo、W和/或V的氧化物为催化剂活性组分,以Ce、Zr、Ti和/或Si的氧化物为载体改性剂。以上催化剂均在高温条件下表现出优异的催化活性。
甲烷化反应为放热反应,一般采用若干个绝热反应器串联的工艺来保证CO 和H2的充分反应。催化剂的起活温度越低,低温条件下的催化性能越高,工艺所需的串联反应器数量越少。因此,需要开发一种耐硫催化剂,具有较低的起活温度,且在低温条件下仍可保证良好的催化性能。
专利CN103962123A公开了一种ZrO2负载的耐硫甲烷化催化剂的制备方法,由浸渍法、共沉淀法或溶胶凝胶法制备催化剂,以Co、Ni、La和/或K的氧化物为催化剂助剂,以Mo、W和/或V的氧化物为催化剂活性组分,以Ce、Al、 Ti、Mg和/或Si的氧化物为催化剂改性剂,以ZrO2为催化剂载体。该催化剂具有起活温度低,低温催化性能好的特点。专利CN103433026A公开了一种ZrO2负载的高稳定性耐硫甲烷化催化剂,通过沉淀法、沉积沉淀法或溶胶凝胶法制备ZrO2载体或选用商购ZrO2载体,并通过浸渍法或沉积沉淀法将催化剂活性组分 MoO3和催化剂助剂Y2O3负载在ZrO2载体上。该催化剂在高H2S气氛中具有高甲烷化反应催化活性、低逆水汽变换反应活性和高催化活性稳定性的特点。
上述所有文献再次全文引入以作参考。
采用传统的浸渍法或共沉淀法等方法制备耐硫甲烷化催化剂,需要将载体、活性组分和助剂的前驱体溶液进行共沉淀或者分步沉淀,在经过多次混合、洗涤和过滤之后,才能去除多余的沉淀杂质。在操作过程中会产生大量的废水,对环境影响较大;同时,对于大规模的工业生产,传统方法制备工艺复杂且活性组分易流失,存在制备重现性差、生产周期长、单耗和能耗大等问题。
发明内容
本发明的目的在于克服上述现有技术的缺陷,提供一种载体为氧化锆的耐硫甲烷化催化剂,该催化剂在低温高H2S气氛下具有良好的催化活性;并且解决了其他制备方法过程中存在的组分易流失、制备重现性差等问题,重现性好。
本发明第一方面公开了一种载体为氧化锆的耐硫甲烷化催化剂,包括 5-40wt%活性组分、20-90wt%的载体氧化锆和5-40wt%的催化剂助剂;
优选地,所述活性组分为硫化钼,所述催化剂助剂为氧化钙、氧化钡、氧化镧、氧化镍、氧化钴、氧化铁、氧化镁、氧化锰、氧化铜、氧化铈、氧化钇、氧化钛和氧化铝中的一种或几种。
本发明第二方面公开了所述的载体为氧化锆的耐硫甲烷化催化剂的制备方法,其特征在于,包括以下步骤:
(1)将活性组分前驱体、载体氧化锆前驱体和催化剂助剂前驱体按一定比例进行混合,进行球磨3-6小时;加入量为保持5-40wt%活性组分、20-90wt%的载体氧化锆和5-40wt%的催化剂助剂。
(2)将步骤(1)得到的物料在300-600℃的煅烧3-6小时,然后自然冷却即得到所述的载体为氧化锆的耐硫甲烷化催化剂。
(3)将步骤(2)得到的固溶体粉末在300℃和常压下,在3wt%硫化氢和 97wt%氢气的气氛中硫化4h,粉碎到20-80目后即得到所述的甲烷化催化剂。
优选地,所述活性组分前驱体为钼盐或钼酸盐;所述载体氧化锆前驱体为锆盐或酸盐。
优选地,所述催化剂助剂前驱体为钙、钡、镧、镍、钴、铁、镁、锰、铜、铈、钇、钛和铝的硝酸盐、氯盐、草酸盐、甲酸盐、乙酸盐或铵盐。
有益效果:
①本发明的耐硫甲烷化催化剂,加入的催化剂助剂在活性组分晶粒之间形成隔离以达到减小活性组分晶粒尺寸的目的,阻碍反应过程中活性组分晶粒的迁移和长大,从而提高催化剂结构的稳定性。
②本发明的制备方法无传统工艺的浸渍、干燥、焙烧等繁复的工艺步骤,制备过程操作简单,流程周期短,由3-4天大幅缩减至12小时之内,因此制备过程所需能耗也大幅减少。
③本发明的制备方法无传统工艺中的反复洗涤和过滤,制备过程中无活性组分损失,重现性好,并且制备过程中无废水产生,对环境友好。
具体实施方式
下面结合具体实施例对本发明做进一步的详细描述,但以下包括实施例的描述仅用于使本发明所属技术领域的普通技术人员能够更加清楚地理解本发明的原理和精髓,不构成对本发明做任何限制。
本发明的载体为氧化锆的耐硫甲烷化催化剂可用于将H2、CO和浓度通常在 0.1-3.0v/v%的气态硫化物的合成气转化为甲烷,上述甲烷化反应的H2/CO摩尔比通常为0.5-4.0,优选为1.0-2.0;反应操作温度通常为250-650℃,优选为270-500℃;反应操作压力通常为0.5-8.0MPa,优选为1.0-6.0MPa。
实施例1
称取12.3克仲钼酸铵和139.6克硝酸锆混合均匀,将物料放入球磨机中球磨 4小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为450℃的恒温马弗炉中,在100mL/min空气流量下焙烧5小时,然后自然冷却,得到 20MoO3-80ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在450℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的活性评价结果详见附表1。
实施例2
称取15.3克仲钼酸铵和130.9克硝酸锆混合均匀,将物料放入球磨机中球磨 5小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为550℃的恒温马弗炉中,在100mL/min空气流量下焙烧4小时,然后自然冷却,得到 25MoO3-75ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在400℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例3
称取18.4克仲钼酸铵和122.2克硝酸锆混合均匀,将物料放入球磨机中球磨 5小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为550℃的恒温马弗炉中,在100mL/min空气流量下焙烧4小时,然后自然冷却,得到30MoO3-70ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在450℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例4
称取63.6克硝酸钇、12.3克仲钼酸铵、130.9克硝酸锆混合均匀,将物料放入球磨机中球磨5小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为 450℃的恒温马弗炉中,在100mL/min空气流量下焙烧5小时,然后自然冷却,得到20MoO3-5Y2O3-75ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在450℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例5
称取18.4克硝酸铝、18.4克仲钼酸铵和104.7克硝酸锆混合均匀,将物料放入球磨机中球磨4小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为 450℃的恒温马弗炉中,在100mL/min空气流量下焙烧5小时,然后自然冷却,得到30MoO3-35Al2O3-35ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在400℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例6
称取31.5克硝酸铈、15.3克仲钼酸铵、87.3克硝酸锆混合均匀,将物料放入球磨机中球磨4小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为 450℃的恒温马弗炉中,在100mL/min空气流量下焙烧5小时,然后自然冷却,得到25MoO3-25CeO2-50ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在450℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例7
称取9.7克硝酸钴、15.3克仲钼酸铵,122.2克硝酸锆混合均匀,将物料放入球磨机中进行球磨4小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为550℃的恒温马弗炉中,在100mL/min空气流量下焙烧4小时,然后自然冷却,得到25MoO3-5CoO-70ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在450℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
实施例8
称取9.7克硝酸镍、31.5克硝酸铈、12.3克仲钼酸铵,87.3克硝酸锆混合均匀,将物料放入球磨机中进行球磨5小时后,将物料转移到坩埚或石英舟内,直接放入预先设定为500℃的恒温马弗炉中,在100mL/min空气流量下焙烧4小时,然后自然冷却,得到20MoO3-5NiO-25CeO2-50ZrO2耐硫甲烷化催化剂。
在固定床反应器中进行。取20-80目的催化剂颗粒装入反应器中,然后通入 3v/v%硫化氢和97v/v%氢气气氛,在400℃温度和常压下硫化4h,即为硫化的催化剂。硫化结束后,将催化剂床层的温度稳定在预先设定的反应温度下,切换为H2/CO比值为1,硫化氢浓度为0.2v/v%的合成气作为原料气,在400℃温度条件、3.0MPa压力条件下进行耐硫甲烷化反应。原料气和反应器出口的气体组成均通过气相色谱在线检测分析,通过计算得到耐硫甲烷化反应的CO转化率和甲烷选择性。催化剂的评价结果详见附表1。
表1为实施例1-8制得的催化剂的催化活性的评价结果
表1实施例1-8的催化剂的催化活性评价结果
从表1可以看出,本发明的载体为氧化锆的耐硫甲烷化催化剂的活性较高, CO转化率在50%以上;CH4的选择性在70%以上。
通过实施例说明,按照本发明的方法,可以通过球磨法一步合成出耐硫甲烷化催化剂。相比于传统的浸渍法、共沉淀法、沉积沉淀法等催化剂制备方法,球磨法制备耐硫甲烷化催化剂具有制备工艺简单、重现性好、周期短、活性组分不易流失、不产生废水污染、成本低等优点,是一种有良好的实际应用前景的合成气低温耐硫甲烷化催化剂。
Claims (5)
1.一种载体为氧化锆的耐硫甲烷化催化剂,其特征在于,包括5-40wt%活性组分、20-90wt%的载体氧化锆和5-40wt%的催化剂助剂。
2.根据权利要求1所述的耐硫甲烷化催化剂,其特征在于,所述活性组分为硫化钼,所述催化剂助剂为氧化钙、氧化钡、氧化镧、氧化镍、氧化钴、氧化铁、氧化镁、氧化锰、氧化铜、氧化铈、氧化钇、氧化钛和氧化铝中的一种或几种。
3.根据权利要求1所述的载体为氧化锆的耐硫甲烷化催化剂的制备方法,其特征在于,包括以下步骤:
(1)将活性组分前驱体、载体氧化锆前驱体和催化剂助剂前驱体按一定比例混合后球磨3-6小时;
(2)将步骤(1)得到的物料在300-600℃的煅烧3-6小时,然后自然冷却得到固体粉末;
(3)将步骤(2)得到的固溶体粉末在300℃和常压下,在3wt%硫化氢和97wt%氢气的气氛中硫化4h,粉碎到20-80目后即得到所述的甲烷化催化剂。
4.根据权利要求3所述的制备方法,其特征在于,所述活性组分前驱体为钼盐或钼酸盐;所述载体氧化锆前驱体为锆盐或锆酸盐。
5.根据权利要求3所述的制备方法,其特征在于,所述催化剂助剂前驱体为钙、钡、镧、镍、钴、铁、镁、锰、铜、铈、钇、钛和铝的盐。
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CN109569645A (zh) * | 2018-12-23 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于丙烷治理的钴锰复合氧化物/碳催化剂的制备及产品和应用 |
CN114100622A (zh) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | 耐硫预变换催化剂及其制备和硫化方法 |
CN114797885A (zh) * | 2022-05-30 | 2022-07-29 | 中国华能集团清洁能源技术研究院有限公司 | 一种耐硫甲烷化催化剂及其制备方法和应用 |
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CN109569645A (zh) * | 2018-12-23 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于丙烷治理的钴锰复合氧化物/碳催化剂的制备及产品和应用 |
CN109569645B (zh) * | 2018-12-23 | 2022-02-08 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于丙烷治理的钴锰复合氧化物/碳催化剂的制备及产品和应用 |
CN114100622A (zh) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | 耐硫预变换催化剂及其制备和硫化方法 |
CN114100622B (zh) * | 2020-08-31 | 2023-08-11 | 中国石油化工股份有限公司 | 耐硫预变换催化剂及其制备和硫化方法 |
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CN114797885B (zh) * | 2022-05-30 | 2023-06-20 | 中国华能集团清洁能源技术研究院有限公司 | 一种耐硫甲烷化催化剂及其制备方法和应用 |
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