CN1780814A - 用于由甲醇和硫化氢制备甲硫醇的催化剂 - Google Patents
用于由甲醇和硫化氢制备甲硫醇的催化剂 Download PDFInfo
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- CN1780814A CN1780814A CNA2004800117113A CN200480011711A CN1780814A CN 1780814 A CN1780814 A CN 1780814A CN A2004800117113 A CNA2004800117113 A CN A2004800117113A CN 200480011711 A CN200480011711 A CN 200480011711A CN 1780814 A CN1780814 A CN 1780814A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 title abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical class [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- B01J23/30—Tungsten
-
- 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
- B01J37/28—Phosphorising
-
- 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
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
-
- 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
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本发明涉及一种由硫化氢和甲醇合成甲硫醇的催化剂和一种制备所述甲硫醇的方法。该催化剂包含其上沉积了碱金属钨酸盐和铵盐的活性氧化铝。
Description
本发明涉及一种由甲醇和硫化氢制备甲硫醇的催化剂。
甲硫醇是一种重要的合成甲硫氨酸、制备二甲亚砜和二甲砜或合成链烷磺酸的中间体。甲硫醇目前主要通过硫化氢与甲醇于气相中在包含氧化铝的催化剂上反应制得。甲硫醇的合成通常在300至500℃和1至25巴的压力下进行。
为了提高所述氧化铝催化剂的活性和选择性,习惯上向其中掺杂碱金属钨酸盐(参照,例如EP-A-832 878)。Mashkina等指出,表面含有酸中心的催化剂非常活泼,但是生成相等产率的甲硫醇和甲硫醚。表面具有强碱中心的催化剂活性较弱,但对甲硫醇显示了较高的选择性(Mashkina等,React.Kinet.Catal.Lett.,1987,407-412)。因此活性和选择性的提高被解释为由于碱性和酸性反应中心的存在。然而,所述氧化铝同样掺杂有其他物质,如碱金属碳酸盐(US 5,847,223)。
通过提高硫化氢与醇的摩尔比同样可以提高活性和选择性。通常使用1至10的摩尔比。然而,10至3的高摩尔比还意味着在所述反应气混合物中大量过量的硫化氢,从而使得必须循环大量气体。
US 2,685,605涉及一种通过将硫化氢和甲醇在催化剂、优选钍/浮石催化剂上反应制备甲硫醇的方法,其中将少量水与硫化氢和甲醇一起引入所述反应器中。
US 2,647,151描述了通过将硫化氢和醇在钍/浮石催化剂上反应而制备烷基硫醇的方法,其中据说是通过抑制作为副产物的有机硫化物的生成来增加形成所需的烷基硫醇。这种选择性的提高是通过向反应器中引入少量氢气而实现的。
DE-A-101 37 773教导了将氧气与所述醇和硫化氢一起引入所述反应器中,同时该反应在含有氧化铝和钨酸钾的催化剂存在下进行。氧气的加入减少了所述催化剂上引起麻烦的沉积物,并且可在所述过程中实现再生。
US 3,935,376描述了一种包括以下改进的方法:温度条件的优化、使得催化剂质量下降和副产物达到最小化。所述催化剂包含氧化铝和助催化剂剂。其中公开了当产生至少三个催化剂区时可以将整个区域的温度保持在最适宜的水平。将全部的硫化氢供入第一催化剂区,同时在所有催化剂区上分配添加甲醇。硫化氢与甲醇的比例在1.1至2.5的范围内。
EP-A-832 878描述了改进的催化剂,其可通过借助特定的方法在所述活性氧化铝上分两部分沉积所述钨酸钾助催化剂而获得。此外,所述催化剂在与反应条件类似的条件下经过预硫化处理。
Mashkina等(React.Kinet.Catal.Lett.,1988,159-164)使用七钨酸盐、十二钨酸盐和偏钨酸盐改变了使用所述助催化剂的方式。此外,使用了掺杂碳酸钾的钨酸铵、添加了少量酸和/或添加了氧化硅的钨酸钾。该全面研究的结果是,简单掺杂钨酸钾而不另外加入助催化剂或进行处理可以就甲硫醇的选择性和反应速率而言得到最好的结果。
在SU 1316127、SU 1608923、RU 2056940和WO 99/14172中,已经发现当使用硼酸铝载体或通过向所述钨酸盐助催化剂中添加硼氧化物或者借助包含铝酸钾、无定形氧化钨和氧化钠和/或氧化硼的助催化剂混合物时可以提高选择性。
现有技术已知的制备甲硫醇的催化剂和方法在选择性、活性和经济的工艺条件方面仍然需要改进。
因此,本发明的一个目的是提供一种活性和选择性非常高的甲硫醇催化剂,而不需要多步制备该催化剂、引入昂贵或有毒的活性成分或者所述反应器的任何特殊操作模式。此外,硫化氢与醇的比例应该稍微偏离1以减少所需的能耗。
我们已经发现,该目的可以通过一种催化剂来实现,所述催化剂可通过施用碱金属钨酸盐和至少一种铵盐和/或至少一种选自硫酸、磷酸、亚硫酸、钨酸、亚磷酸、次磷酸、氟化氢、溴化氢和碘化氢的质子酸作为助催化剂至活性氧化铝上而得到。此外,已经发现甲硫醇可以有利地使用本发明的催化剂制备。作为碱金属钨酸盐,优选使用钨酸钾。基于所述催化剂的总量,所述钨酸盐有利地以1~20重量%、优选10~16重量%的量施用。
优选使用铵盐。可用的铵盐尤其是硫酸盐、磷酸盐、硫化物、钨酸盐、钼酸盐、亚硫酸盐、过二硫酸盐、亚磷酸盐、次磷酸盐、卤化物和碳酸盐。优选硫酸盐、磷酸盐、硫化物、钨酸盐、钼酸盐、亚硫酸盐、过二硫酸盐、亚磷酸盐和次磷酸盐。特别优选含硫或磷的盐以及钨酸盐。铵盐的混合物同样可用。基于所述催化剂的总量,有利地以0.01~15重量%、特别是0.01~10重量%的量施用铵盐。
可以想到使用选自硫酸、磷酸、亚硫酸、钨酸、亚磷酸和次磷酸的质子酸代替铵盐或与这些盐混合。特别优选含硫或磷的质子酸。
根据本发明,这种催化剂可通过用所述包含碱金属钨酸盐和铵盐的助催化剂混合物浸渍活性氧化铝或者将该助催化剂混合物喷涂到所述氧化铝催化剂上而制得。可以根据吸水能力来进行浸渍,即溶液的量相应于所述载体的孔体积,或者通过在过量的溶液中浸泡,即溶液的体积大于所述孔体积。所述碱金属钨酸盐同样可以通过在施用前将各自呈水合物形式的钨酸盐(如钨酸铵、偏钨酸铵、仲钨酸铵)或钨酸与例如氢氧化钾或氢氧化钠反应而制备。所述催化剂随后在空气中或在氧气存在下煅烧,例如在400至500℃下。
因此该制备方法是一种简单的一步工艺。如果合适的话,可以在施用所述助催化剂之前于300至600℃、优选400至500℃下煅烧所述氧化铝达1至10小时、优选1至5小时。
有利地,获得的所述催化剂的pH值小于9.8,特别地处于5至9.7的范围内。通过制备浓度为10%的待测催化剂的水悬浮液来测量所述pH值。振荡该试样一分钟,放置五分钟,随后通过pH电极测量所述悬浮液的pH值。
与现有技术中描述的催化剂相比,这种催化剂可导致成品催化剂的更高的活性和选择性,尤其是在硫化氢与甲醇的摩尔比为3至1的低摩尔比例下。
作为所述催化剂使用的氧化铝,有利的是使用活性氧化铝。该物质具有约10至400m2/g的高比表面积,并且主要含有氧化铝的结晶相的所述过渡系列氧化物(参见,例如Ullmann’s Encyclopedia of IndustrialChemistry,1985年,A1卷,561~562页)。这些过渡氧化物包括χ-、κ-、γ-、δ-、η-、θ-氧化铝。活性氧化铝在商业上以供催化应用的多种等级和物理形式销售。非常合适的一种类型例如是颗粒化或挤出形式的γ-氧化铝。有利地使用挤出物直径为1至5mm的氧化铝。比表面积优选为150至400m2/g。总孔体积为0.3至1.0ml/g。体积密度为300至1000g/l。
如果合适的话,所述催化剂可以在用于合成之前在与所述甲硫醇的合成条件类似的条件下进行预硫化。为此,在200至450℃和1至25巴的压力下将硫化氢料流通过所述催化剂颗粒达0.5至100小时。
在所述甲硫醇合成中硫化氢与甲醇的摩尔比通常为1∶1至10∶1,优选1∶1至2∶1。所述摩尔比既包括新加入的硫化氢和甲醇,也包括任何被再循环的硫化氢和甲醇。
所述催化剂有利地以直径为1至5mm(如4mm)的固体颗粒形式装入反应器中。
所述反应器进料除了硫化氢和醇以外可以进一步包含氧气、水或氢气以及惰性气体或惰性气体混合物。通常,所述反应器进料包含相对于每摩尔醇来说0至30mol、优选5至30mol的惰性气体。合适的惰性气体例如为氮气、甲烷、乙烷、丙烷、丁烷和/或二氧化碳。通过加入氧气可以避免在所述催化剂上的引起麻烦的沉积物。这样,可以在反应过程中实现催化剂的再生。所述过程中的氧气浓度基于反应器进料的量一般<2.5重量%,因此远远低于爆炸极限。所述氧气浓度优选为10ppm至0.5重量%,特别优选10ppm至500ppm。氧气可以以多种形式引入反应器。可以使用纯氧气,如果合适的话与惰性气体混合。通常以空气形式加入氧气。所述反应器进料可以进一步包含已经从所得甲硫醇中被分离出来的再循环的含硫成分(例如DE-A-1768826中所述的)。
本发明的由硫化氢与甲醇在催化剂上反应制备甲硫醇的方法通常在管式反应器中以气相反应进行。顺序连接的多个管式反应器也可以。通常,将甲醇和硫化氢加热到足够高以使得甲醇和甲硫醇均以气相存在、但是低于甲硫醇的分解温度的温度。一般地,本发明的方法在250至500℃、优选300至450℃下进行。准确的反应温度尤其依赖于所使用的催化剂和反应压力。
本发明的方法通常在1至25巴的压力下进行。当然,保持所述压力低于反应器进料或甲硫醇会液化的压力。本发明方法中的压力优选1至10巴。为了减少喷射危险,可以将压力设为1至3巴,优选接近大气压。
本发明的方法通常连续进行。通过本领域技术人员已知的方法处理得到的甲硫醇。
WHSV(重时空速=起始原料重量/以每小时每管计的催化剂重量)通常为0.1至0小时-1,优选0.1至5小时-1,特别优选0.5至2小时-1。
本发明方法的转化率通常为80至100%,优选95至100%,基于以子摩尔量使用的成分的量(即基于所述甲硫醇合成中的甲醇)。通过本发明的方法可获得80至100%的甲硫醇选择性。
实施例
实施例1:对比催化剂的制备(γ-Al2O3上14重量%的K2WO4)
将203克偏钨酸铵水合物溶于0.385升水中,然后加入182克浓度为48%的氢氧化钾水溶液,随后补充该溶液达到相当于所述载体的吸水能力的体积。将1.048升这种浸渍溶液均匀地喷涂到1.588千克γ-Al2O3挤出物上。最后将该催化剂在对流炉中于450℃下煅烧2小时。
由氧化铝、钨酸钾和铵盐制备根据本发明的催化剂。
实施例2:磷酸铵
将72.3克偏钨酸铵水合物溶于0.150升水中,然后加入29.7克氢氧化钾和88.3克三水合磷酸铵。补充该溶液达到相当于所述载体的吸水能力的体积。将该浸渍溶液均匀地施用于500克γ-Al2O3挤出物上,最后将该催化剂在对流炉中于450℃下煅烧2小时。
实施例3:硫酸铵
采用类似实施例2的方法,由偏钨酸铵水合物、氢氧化钾和30.9克硫酸铵制备水溶液,将该水溶液施用于500克γ-Al2O3挤出物上,最后将该催化剂在对流炉中于450℃下煅烧2小时。
实施例4:硫化铵
采用类似实施例2的方法,由偏钨酸铵水合物、氢氧化钾和36.1克硫化铵制备水溶液,将该水溶液施用于500克γ-Al2O3挤出物上,最后将该催化剂在对流炉中于450℃下煅烧2小时。
催化剂的表征
催化剂 | 助催化剂 | ABET[m2/g] | pH | 化学分析[重量%] | |
类型 | 量[重量%] | ||||
对比实施例1 | - | - | 221 | 9.8 | - |
实施例2 | 磷酸铵 | 5%P2O5 | 162 | 7.9 | P:2.2 |
实施例3 | 硫酸铵 | 5%(NH4)2SO4 | 190 | 6.0 | S:1.1 |
实施例4 | 硫化铵 | 3%(NH4)2S | 189 | 8.2 | S:0.4 |
pH测量:由待测催化剂制备10%的水悬浮液。将试样振荡一分钟,放置五分钟,随后用pH电极测量所述悬浮液的pH值。
ABET测量:DIN 66131
性能测试:
向MeSH反应器(长度:600mm,直径:25mm)中加入280克催化剂挤出物。在390℃(反应器中部)和1.1巴压力下,向所述管式反应器中供入48g/h(1.5摩尔)气态甲醇和64g/h(1.9摩尔)硫化氢。通过气相色谱测定气体组成。
实施例 | 热点温度[℃] | 分解产物[GC%面积] | 选择性[%] | 甲醇转化率[%] | 甲醇产率[%] |
对比实施例1 | 432 | 1.10 | 83.8 | 97.7 | 81.9 |
实施例2 | 440 | 1.78 | 89 | 99 | 89 |
实施例3 | 440 | 1.44 | 89 | 97 | 87 |
实施例4 | 443 | 1.38 | 88 | 97 | 86 |
Claims (11)
1.一种用于合成甲硫醇的催化剂,其可由氧化铝、碱金属钨酸盐和至少一种铵盐和/或至少一种选自硫酸、磷酸、亚硫酸、钨酸、亚磷酸、次磷酸、氟化氢、溴化氢和碘化氢的质子酸制得。
2.权利要求1所述的催化剂,其可由氧化铝、碱金属钨酸盐和至少一种铵盐制得。
3.权利要求1或2所述的催化剂,其中所用的碱金属钨酸盐是钨酸钾。
4.权利要求1或2所述的催化剂,其中所用的铵盐为硫酸盐、磷酸盐、硫化物、钨酸盐、钼酸盐、亚硫酸盐、过二硫酸盐、亚磷酸盐和次磷酸盐。
5.权利要求1或2所述的催化剂,其中所用的铵盐为含硫或磷的盐或钨酸盐。
6.权利要求1或2所述的催化剂,其中基于所述催化剂的总量,以10至16重量%的量施用碱金属钨酸盐。
7.权利要求1或2所述的催化剂,其中基于所述催化剂的总量,以0.01至15重量%的量施用铵盐。
8.权利要求1或2所述的催化剂,其pH小于9.8。
9.权利要求1或2所述的催化剂,其pH为5至9.7。
10.一种通过甲醇与硫化氢反应制备甲硫醇的方法,其中使用权利要求1至9中任一项所述的催化剂。
11.权利要求10所述的方法,其中在制备甲硫醇中以1∶1至2∶1的摩尔比使用硫化氢和甲醇。
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CN102247833A (zh) * | 2011-08-04 | 2011-11-23 | 厦门大学 | 一种合成甲硫醇的催化剂及其制备方法 |
CN104010726A (zh) * | 2011-12-19 | 2014-08-27 | 赢创德固赛有限公司 | 用于合成烷基硫醇的催化剂及其制造方法 |
CN105056937A (zh) * | 2015-08-17 | 2015-11-18 | 山东新和成氨基酸有限公司 | 一种用于硫化氢和甲醇制备甲硫醇的催化剂、制备方法及其应用 |
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DE102004061016A1 (de) * | 2004-12-18 | 2006-06-22 | Degussa Ag | Halogenidhaltige Alkaliwolframate enthaltende Katalysatoren zur Synthese von Alkylmercaptan und Verfahren zu ihrer Herstellung |
DE102006032635A1 (de) | 2006-07-13 | 2008-01-17 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Alkylmercaptanen in einem Mehrzonenfestbettreaktor |
FR3023288B1 (fr) | 2014-07-04 | 2016-07-15 | Arkema France | Procede de preparation de disulfure de dimethyle |
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FR3041636B1 (fr) | 2015-09-30 | 2018-11-16 | Arkema France | Procede de production de mercaptans par hydrogenolyse enzymatique de disulfures a l'aide d'hydrogene |
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CN102247833A (zh) * | 2011-08-04 | 2011-11-23 | 厦门大学 | 一种合成甲硫醇的催化剂及其制备方法 |
CN102247833B (zh) * | 2011-08-04 | 2013-02-13 | 厦门大学 | 一种合成甲硫醇的催化剂及其制备方法 |
CN104010726A (zh) * | 2011-12-19 | 2014-08-27 | 赢创德固赛有限公司 | 用于合成烷基硫醇的催化剂及其制造方法 |
CN104010726B (zh) * | 2011-12-19 | 2017-09-12 | 赢创德固赛有限公司 | 用于合成烷基硫醇的催化剂及其制造方法 |
US9764309B2 (en) | 2011-12-19 | 2017-09-19 | Evonik Degussa Gmbh | Catalyst for the synthesis of alkyl mercaptans and process for producing it |
CN105056937A (zh) * | 2015-08-17 | 2015-11-18 | 山东新和成氨基酸有限公司 | 一种用于硫化氢和甲醇制备甲硫醇的催化剂、制备方法及其应用 |
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EP1625113A1 (de) | 2006-02-15 |
DE10319739A1 (de) | 2004-11-18 |
WO2004096760A1 (de) | 2004-11-11 |
RU2358803C2 (ru) | 2009-06-20 |
EP1625113B1 (de) | 2020-09-09 |
US20070015941A1 (en) | 2007-01-18 |
JP2006524563A (ja) | 2006-11-02 |
CN100334075C (zh) | 2007-08-29 |
RU2005137019A (ru) | 2006-05-27 |
US7687667B2 (en) | 2010-03-30 |
JP4367658B2 (ja) | 2009-11-18 |
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