CN105377420B - 对于合成甲硫醇的催化剂和用于从合成气和硫化氢制备甲硫醇的方法 - Google Patents
对于合成甲硫醇的催化剂和用于从合成气和硫化氢制备甲硫醇的方法 Download PDFInfo
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- CN105377420B CN105377420B CN201480030626.5A CN201480030626A CN105377420B CN 105377420 B CN105377420 B CN 105377420B CN 201480030626 A CN201480030626 A CN 201480030626A CN 105377420 B CN105377420 B CN 105377420B
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- catalyst
- methyl mercaptan
- carrier
- hydroxyapatite
- hydrogen sulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title description 14
- 230000015572 biosynthetic process Effects 0.000 title description 13
- 239000007789 gas Substances 0.000 title description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 19
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 229910020435 K2MoO4 Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910015667 MoO4 Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- LFZAXBDWELNSEE-UHFFFAOYSA-N [S].[K] Chemical compound [S].[K] LFZAXBDWELNSEE-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 1
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 description 1
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- MXKIASVYJZPUMJ-UHFFFAOYSA-N S.SC Chemical compound S.SC MXKIASVYJZPUMJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010685 alcohol synthesis reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/755—Nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及包含基于钼和钾的活性组分和基于羟磷灰石的载体的催化剂,以及涉及用于制备所述催化剂的方法和在催化方法中通过碳氧化物、硫和/或硫化氢和氢气的反应来制备甲硫醇的工艺,包括使用所述催化剂。
Description
获得本发明的研究工作以项目No.241718 EUROBIOREF作为第7 ProgrammeFramework(FP7/2007-2013)的部分而接受了来自欧盟的资助。
本发明涉及用于从合成气和硫化氢制备甲硫醇的特定基于钼和钾的催化剂,和涉及它的制备方法。
本发明还涉及使用这种催化剂制备甲硫醇的方法。
本发明最后涉及羟磷灰石作为用于催化剂的载体的用途,该催化剂用于制备甲硫醇。
甲硫醇具有大的工业益处,特别地作为用于合成甲硫氨酸的原料,甲硫氨酸是在动物饲料中广泛应用的重要氨基酸。在其它应用中,甲硫醇还是用于许多其它分子,特别地二甲基二硫醚(DMDS)的原料,用于在石油馏分中的加氢处理催化剂的硫化添加剂。
甲硫醇通常在工业上大吨位地从甲醇和硫化氢进行制备。希望根据以下反应流程直接地从一氧化碳、氢气和硫化氢制备甲硫醇可以在经济学上显示是有益的:
CO+2H2+H2S→CH3SH+H2O (1)。
这种合成的主要副产物是二氧化碳。因为,氧硫化碳(COS)被认为是反应中间体,其根据以下反应流程在氢化之后产生甲硫醇:
CO+H2S→COS+H2 (2)
COS+3H2→CH3SH+H2O (3)。
二氧化碳其本身来自两个副反应:
CO+H2O→CO2+H2 (4) 和
COS+H2O→CO2+H2S (5)。
这两种副反应,其消耗了主要原材料:一氧化碳,和反应中间体:氧硫化碳,是由于不可避免的水的存在,水在甲硫醇合成期间共产生。二氧化碳任选地可以被再循环以根据以下流程图同样制备甲硫醇:
CO2+3H2+H2S→CH3SH+2H2O (6)。
但是这种反应已知是比从一氧化碳的反应更慢的。因此,存在动机以使得在甲硫醇合成反应器的出口二氧化碳的生成是尽可能低的。
从文件WO2005/040082已知数种用于从合成气和硫化氢合成甲硫醇的催化剂。
特别地,该文件公开了使用包含基于Mo-O-K的活性组分、活性促进剂和任选的载体的催化剂。举例说明的催化剂具有不同的化学性质,如K2MoO4/Fe2O3/NiO或K2MoO4/CoO/CeO2/SiO2,每种担载在二氧化硅上。后者在333℃产生0.88的CO2/MeSH选择性比率。
还从文件US2010/0286448已知由多孔载体(在其上已经电解地沉积了金属)组成的催化剂种类。然后将K2MoO4和另一种作为促进剂的金属氧化物浸渍在载体上。该文件的实施例15描述了K2MoO4/NiO/CoSiO2的制备。使用这种络合催化剂的CO2/MeSH选择性比率是0.65。
最后,US文件2010/0094059描述了基于负载的K2MoO4的催化剂,其中单独或者混合使用的多孔载体选自SiO2、Al2O3、TiO2、Al2O3/SiO2、ZrO2,沸石或者含碳材料。氧化碲(TeO2)用作为促进剂。在300℃测量的CO2/MeSH选择性比率为0.60至0.77。
从这些文件的教导已经观察到具有特定结构的催化剂、促进剂和载体的组合(它们每种进行选择)允许实现有利的选择性比率。
然而,当前存在对合成简单并且产生非常好的选择性的催化剂的现实需要。这种技术问题已经通过由羟磷灰石负载的基于钼和钾的催化剂得到了解决。
已经观察到根据本发明的催化剂是更容易制备的,这是由于促进剂的存在不是必不可少的。它是比在先前提到的文件中公开的那些更便宜的。最后,它产生非常好的CO2/MeSH选择性。
本发明还涉及这种催化剂的制备方法。
本发明还涉及使用根据本发明的催化剂从合成气和硫化氢制备甲硫醇的方法。
本发明还涉及如上面所定义的催化剂用于从合成气和硫化氢合成甲硫醇的用途。
最后本发明涉及羟磷灰石作为用于制备催化剂的载体的用途,该催化剂用于制备甲硫醇,特别地在通过使碳氧化物、硫和/或硫化氢和氢气反应的催化方法中。
本发明的其它特征、特点、目标和优点在阅读随后的说明书和实施例将更清楚地显现。
另一方面,由措辞“在a和b之间”指示的数值范围表示为从大于a至低于b(即排除端值a和b)的数值的范围,而由措辞“a至b”指示的数值范围表示从a至b(即包含端值a和b)的数值范围。
催化剂
本发明涉及催化剂。
这种催化剂包含基于钼和钾的活性组分和基于羟磷灰石的载体。
活性组分
在根据本发明的催化剂中存在的活性组分在相同组分内包含钼和钾。
优选,该基于钼和钾的活性组分选自基于Mo-S-K的化合物,基于Mo-O-K的化合物,和它们的混合物。
基于Mo-S-K的活性组分可以通过沉积和煅烧添加有分别浸渍在载体上的K2CO3的K2MoS4或者(NH4)2MoS4前体获得。
基于Mo-O-K的活性组分可以通过沉积和煅烧添加有分别浸渍在载体上的K2CO3的K2MoO4或者(NH4)2MoO4前体获得。
在钾盐,如硝酸钾KNO3、碳酸钾K2CO3或者氢氧化钾KOH存在时,还可以使用七钼酸铵(NH4)6Mo7O24.4H2O作为反应剂。
这些化合物分别地是基于Mo-S-K和Mo-O-K的活性相的前体。活性相前体在原位的预处理之后获得,例如使用这样的工艺:其在于在250℃用氮气干燥的第一步,然后是在相同的温度下使用硫化氢的硫化1小时,然后在350℃使用H2/H2S还原/硫化步骤1小时。
载体
根据本发明的催化剂的载体是具有式Ca10(PO4)6(OH)2的羟磷灰石,有利地化学计量的羟磷灰石。
优选地,根据本发明使用的羟磷灰石具有1.5至2.1,更优选等于1.67的Ca/P摩尔比,对应于对于化学计量羟磷灰石的预期值。
优选地,根据本发明的催化剂的重量比是:
K2MoS4/Ca10(PO4)6(OH)2=31.3/100
K2MoO4/Ca10(PO4)6(OH)2=50.7/100。
催化活性可以通过使用具有高于25m2/g的比面积的载体材料而得到改善。
优选地,根据本发明的羟磷灰石载体具有至少40m2/g的比表面积,更特别地从40m2/g至300m2/g的比表面积和为1.67的Ca/P摩尔比。
该载体的结构可以是球状的、圆柱形、环状的、星形的、成粒的或者任何其它三维形状的三维结构,或者呈粉末(其可以是压制,挤出,成粒)的形式或者为三维形状。
优选地,该催化剂粒子具有为从0.1毫米至20.0毫米的直径的均匀粒度分布(通过筛析进行测量)。
促进剂
优选地,根据本发明的催化剂由基于钼和钾的活性组分和基于羟磷灰石的载体组成。
然而,可以设想存在本领域技术人员已知的促进剂,如氧化碲、氧化镍或者氧化铁。
催化剂的制备方法
本发明还涉及用于根据本发明的催化剂的制备方法。这种方法包括以下连续步骤:
- 制备活性相的前体
- 制备载体,和
- 使用活性相前体干浸渍该载体。
制备活性相的前体
1/Mo-O-K
1. K2MoO4盐是市售盐。为了制备基于Mo-O-K的催化剂,将固定量的K2MoO4溶于一定体积的水中以获得具有期望浓度的溶液,如,例如0.5-1.0g/mL的浓度。
2. 还可以从分别的钼和钾盐开始,即它们不是相同化合物的一部分。对于这种合成,基于钼的溶液通过在水中加入七钼酸铵进行制备以获得22至33%重量的MoO3浓度。
平行地,基于钾的溶液通过在水中加入硝酸钾进行制备以获得31至43%重量的K2O浓度。
2/Mo-S-K
K2MoS4合成通常分两步进行。
第一步涉及制备四硫钼酸铵(ATTM);第二步骤是从在第一步骤中制备的盐合成四硫钼酸钾(K2MoS4)。
为了制备ATTM,使硫化氢在25%氨水溶液(在其中已经溶解了七钼酸铵(HMA))中连续地鼓泡。溶液温度提高,表明放热反应。当温度下降时停止硫化氢鼓泡(通常在一个小时之后)。
该溶液这时包含具有绿色反光的红色晶体,其对应于四硫钼酸铵。
第二步骤在于在获得的四硫钼酸铵盐的铵离子和钾离子之间的离子交换,钾离子来自氢氧化钾溶液。获得的盐然后在真空下进行保存。将一定量的四硫钼酸钾溶于水中。
可用于根据本发明的催化剂中的钾盐可以来自以下化合物:乙酸钾(KAc)、草酸钾(K2C2O4)、氢氧化钾(KOH)、碳酸钾(K2CO3)、硝酸钾(KNO3)、和碳酸氢钾(KHCO3)。
载体的制备
构成的催化剂载体的羟磷灰石通过共沉淀法进行制备。在搅拌下,将硝酸钙Ca(NO3)2的水溶液滴加至磷酸氢铵(NH4)H2PO4溶液中。温度保持在100℃和通过加入氨溶液(25%)使pH保持在10。
对该获得的白色沉淀物进行过滤,洗涤,在80℃干燥过夜和在400℃煅烧。获得了具有等于1.67的Ca/P摩尔比的羟磷灰石Ca10(PO4)6(OH)2,该摩尔比对应于化学计量的羟磷灰石的预期值。
使用活性相的前体干浸渍该载体
1/Mo-O-K
干浸渍法用来制备催化剂。K2MoO4溶液在一步中被浸渍在载体上。当包含钾和钼的溶液时是分开的,浸渍在2个步骤中进行。
2/Mo-S-K
然后使四硫钼酸钾溶液浸渍在羟磷灰石上。在催化剂中的钼酸盐含量取决于K2MoS4或者K2MoO4的溶解度和载体的孔体积。
K2MoS4的溶解度在0.25g/mL和0.50g/mL之间(0.35g/mL)和K2MoO4溶解度在0.50g/mL和1.50g/mL之间(0.90g/mL)。载体的孔体积在0.8mL/g和2.2mL/g之间。
因此,该使用的溶液的体积进行计算以获得期望的重量比,优选地如上面所定义的重量比。
在浸渍之后,固体经历2小时的熟化步骤,在80℃烘箱干燥24小时,在气体流(典型地空气)下在490℃煅烧4小时。如果第二个浸渍步骤是必要的,该固体再次经历熟化、干燥和煅烧步骤。
甲硫醇的制备方法
本发明涉及在催化方法中通过碳氧化物、硫和/或硫化氢和氢气的反应来制备甲硫醇的工艺,包括使用如上面所定义的催化剂。
CO或者CO2/H2S/H2摩尔比为1/1/0至1/8/8,或者当硫用来代替硫化氢时,CO或者CO2/H2S/H2/S反应剂的摩尔比为1/1/0/1至1/8/8/8。
优选地,CO或者CO2/H2S/H2摩尔比为1/2/1至1/4/4,当硫用来代替硫化氢时,CO或者CO2/H2S/H2/S反应剂的摩尔比为1/2/2/1至1/4/4/4。
这些摩尔比考虑了CO2。因此,它们同时考虑反应流程(1)和反应流程(6)。
优选地,反应可以在管式、多管式固定床、催化壁微通道或者流化床反应器中发生。
本发明还涉及如上面所定义的催化剂用于从合成气和硫化氢制备甲硫醇的用途。
最后本发明涉及羟磷灰石作为用于制备催化剂的载体的用途,该催化剂用于在催化方法中,特别地通过使碳氧化物、硫和/或硫化氢和氢气反应制备甲硫醇。
本发明将现在描述在以下的实施例中进行描述,给出这些实施例仅仅用于举例说明,当然非限制性的。
实施例
实施例1
根据本发明的催化剂根据干浸渍法如上面所定义地进行制备。
如此获得的催化剂具有以下特征:
表1:催化剂的元素分析。
实施例2:使用的催化剂是在羟磷灰石上的K2MoO4。
实施例3:测试的催化剂是在SiO2上的K2MoO4。
实施例4:测试的催化剂是在Al2O3上的K2MoS4。
实施例5:测试的催化剂是在Al2O3上的K2MoO4。
催化剂的评估
所述催化剂在固定床层反应器中在下面条件中在制备甲硫醇反应中进行评估:
温度:280℃,
压力:10巴,
原料气组成CO/H2/H2S=1/2/1(v/v),
GHSV(气体时空速度)=1333h-1。
反应剂和产物通过气相色谱法在线进行分析。
在该测试之前,催化剂在原位使用第一工艺进行活化,该第一工艺第一步在于在250℃用氮气干燥,然后是使用硫化氢在相同的温度下硫化1小时,然后在350℃使用H2/H2S还原/硫化步骤1小时。
结果概括在下面的表2中。
表2:催化测试的结果。
在表2中介绍的结果显示出根据本发明的催化剂(实施例1和2)得到比在现有技术的载体(二氧化硅:实施例3或者氧化铝:实施例4和5)上的催化剂明显更低的CO2(不希望的产物)选择性。
选择性在一氧化碳等转化率时进行比较,其中这些转化率用每m2的催化剂比面积进行表达。
通过比较使用催化剂1和4得到的结果,观察到在比率方面的30%的改善,并且这种改善与选择羟磷灰石作为载体相关。
当使根据本发明的实施例2与实施例3和5比较时,看见相同的观察结果。
与根据副反应产生的二氧化碳相比,因此观察到提高的甲硫醇选择性。
注意的是,这种选择性不借助于如在现有技术中描述的促进剂如氧化碲、氧化镍或者氧化铁而获得。
Claims (8)
1.催化剂,其包含基于钼和钾的活性组分和基于羟磷灰石的载体,该基于钼和钾的活性组分选自基于Mo-S-K的化合物,基于Mo-O-K的化合物,和它们的混合物,其中羟磷灰石具有1.5至2.1的Ca/P摩尔比。
2.根据权利要求1的催化剂,特征在于催化剂的载体是具有化学计量式Ca10(PO4)6(OH)2的羟磷灰石。
3.根据权利要求1或2的催化剂,特征在于基于Mo-S-K的活性组分的前体具有K2MoS4结构。
4.根据权利要求3的催化剂,特征在于催化剂的重量比是:K2MoS4/Ca10(PO4)6(OH)2=31.3/100。
5.根据权利要求1或2的催化剂,特征在于基于Mo-O-K的活性组分的前体具有K2MoO4结构。
6.根据权利要求5的催化剂,特征在于催化剂的重量比是:
K2MoO4/Ca10(PO4)6(OH)2=50.7/100。
7.制备如在权利要求1-6任一项所定义的催化剂的方法,特征在于它包括以下步骤:
-制备活性相的前体
-制备载体,和
-使用活性相的前体干浸渍该载体。
8.在催化方法中通过碳氧化物、硫和/或硫化氢和氢气的反应来制备甲硫醇的工艺,包括使用如在权利要求1-6任一项所定义的催化剂。
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CN105377420A (zh) | 2016-03-02 |
KR20150135527A (ko) | 2015-12-02 |
US9944594B2 (en) | 2018-04-17 |
TR201809580T4 (tr) | 2018-07-23 |
CA2908374C (fr) | 2018-01-02 |
EP2978525A1 (fr) | 2016-02-03 |
KR101855567B1 (ko) | 2018-05-04 |
BR112015025013A2 (pt) | 2017-07-18 |
PL2978525T3 (pl) | 2018-10-31 |
US20180230093A1 (en) | 2018-08-16 |
SG11201508093RA (en) | 2015-10-29 |
FR3003773B1 (fr) | 2016-12-30 |
JP2016515935A (ja) | 2016-06-02 |
BR112015025013B1 (pt) | 2020-12-15 |
JP6401240B2 (ja) | 2018-10-10 |
US20160326105A1 (en) | 2016-11-10 |
EP2978525B1 (fr) | 2018-06-13 |
FR3003773A1 (fr) | 2014-10-03 |
MY174872A (en) | 2020-05-19 |
US10377704B2 (en) | 2019-08-13 |
CA2908374A1 (fr) | 2014-10-02 |
HUE040272T2 (hu) | 2019-02-28 |
WO2014154885A1 (fr) | 2014-10-02 |
MX2015013834A (es) | 2016-03-01 |
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