WO2004096760A1 - Katalysator zur herstellung von methylmercaptan aus methanol und schwefelwasserstoff - Google Patents
Katalysator zur herstellung von methylmercaptan aus methanol und schwefelwasserstoff Download PDFInfo
- Publication number
- WO2004096760A1 WO2004096760A1 PCT/EP2004/004344 EP2004004344W WO2004096760A1 WO 2004096760 A1 WO2004096760 A1 WO 2004096760A1 EP 2004004344 W EP2004004344 W EP 2004004344W WO 2004096760 A1 WO2004096760 A1 WO 2004096760A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- catalyst according
- tungstate
- hydrogen sulfide
- methanol
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 51
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 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
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 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 class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 150000004763 sulfides Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003568 thioethers Chemical class 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 alkyl mercaptans Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000000151 deposition Methods 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
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 239000000126 substance Substances 0.000 description 1
- 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 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DDXPLCBTGWFAIG-UHFFFAOYSA-N triazanium;phosphate;trihydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.[O-]P([O-])([O-])=O DDXPLCBTGWFAIG-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide.
- Methyl mercaptan is an important intermediate for the synthesis of methionine, for the production of dimethyl sulfoxide and dimethyl sulfone or for the synthesis of alkanesulfonic acids.
- Today methyl mercaptan is mainly produced by the reaction of hydrogen sulfide and methanol on a catalyst made of aluminum oxide in the gas phase.
- the methyl mercaptan is usually synthesized at temperatures between 300 and 500 ° C. and at pressures between 1 and 25 bar.
- the aluminum oxide catalyst is usually doped with alkali tungstate (for example EP-A-832878).
- alkali tungstate for example EP-A-832878.
- Mashkina et al. describes that catalysts that contain acidic centers on the surface are very active, but they each give the same yields of methyl mercaptan and dimethyl sulfide. Catalysts that have strong basic centers are less active, but have a higher selectivity for methyl mercaptan (Mashkina et al., React. Kinet. Catal. Lett. 1987, 407-412). The increase in activity and selectivity is thus explained by the presence of both basic and acidic reaction centers.
- the aluminum oxide is also doped with other substances, for example with alkali carbonate (US 5,847,223).
- An improvement in activity and selectivity can also be obtained by increasing the molar ratio of hydrogen sulfide to alcohol.
- Molar ratios between 1 and 10 are usually used.
- a high molar ratio of 10 to 3 also means a high excess of the hydrogen sulfide in the reaction gas mixture and thus the need to circulate large amounts of gas.
- No. 2,685,605 relates to a process for the preparation of methyl mercaptan by reacting hydrogen sulfide and methanol over a catalyst, preferably over a thorium / pumice catalyst, small amounts of water being introduced into the reactor together with the hydrogen sulfide and the methanol.
- No. 2,647,151 describes the production of alkyl mercaptans by reacting hydrogen sulfide and alcohol over a thorium / pumice catalyst, in which the Formation of the desired alkyl mercaptans is to be increased by suppressing the formation of organic sulfides formed as by-products. This increase in selectivity is achieved by passing small amounts of hydrogen into the reactor.
- DE-A-101 37773 teaches, together with the alcohol and hydrogen sulfide, to introduce oxygen into the reactor in the presence of a catalyst composed of aluminum oxide and potassium tungstate during the course of the reaction.
- the addition of oxygen reduces annoying deposits on the catalyst and regeneration takes place during the process.
- No. 3,935,376 describes a process whose improvement lies in an optimization of the temperature control, whereby catalyst quality losses and by-products are minimized.
- the catalyst consists of aluminum oxide and a promoter. It is disclosed that by creating at least three catalyst zones it is possible to maintain the temperature at the optimal temperature throughout the range.
- the entire amount of hydrogen sulfide is introduced into the first catalyst zone, and the methanol addition can be distributed over the entire catalyst zones.
- the ratio of hydrogen sulfide to methanol is between 1.1 and 2.5.
- EP-A-832 878 describes improved catalysts which can be obtained by depositing the potassium tungstate promoter in two portions on the active aluminum oxide using a special procedure. Furthermore, the catalysts are presulfided under reaction-like conditions.
- the object of the present invention was therefore to provide a methylm ⁇ captan catalyst which is as active and selective as possible without the need for multistage catalyst preparation, the introduction of expensive or toxic active compositions or a special reactor procedure. Furthermore, the ratio of hydrogen sulfide to alcohol should differ only slightly from 1 in order to reduce the amount of energy required.
- a catalyst which can be obtained by using alkali tungstate and at least one ammonium salt and / or at least one protonic acid selected from the group consisting of sulfuric acid, phosphoric acid, sulfurous acid, tungstic acid, phosphorous acid, on promoted aluminum oxide as promoters. Hypophosphorous acid, hydrogen fluoride, hydrogen bromide and hydrogen iodide can be applied. Furthermore, it was found that methyl mercaptan can advantageously be prepared using the catalyst according to the invention. Potassium tungstate is preferably used as the alkali tungstate. The tungstate is advantageously applied with 1 to 20% by weight, based on the total mass of the catalyst, preferably with 10 to 16% by weight.
- Ammonium salts are preferably used. Particularly suitable ammonium salts are sulfates, phosphates, sulfides, tungstates, molybdates, sulfites, peroxodisulfates, phosphites, hypophosphites, halides and carbonates. Sulfates, phosphates, sulfides, tungstates, molybdates, sulfites, peroxodisulfates, phosphites and hypophosphites are preferred. Sulfur- or phosphorus-containing salts and tungstate salts are particularly preferred. Mixtures of the ammonium salts are also suitable. 0.01 to 15% by weight of ammonium salts, based on the total mass of the catalyst, are advantageously applied, in particular 0.01 to 10% by weight.
- the use of protonic acids selected from the group consisting of sulfuric acid, phosphoric acid, sulfurous acid, tungstic acid, phosphoric acid and hypophosphorous acid is also particularly conceivable.
- Protonic acids containing sulfur or phosphorus are particularly preferred.
- this catalyst can be obtained by soaking the activated alumina with the promoter mixture containing alkali tungstate and ammonium salts or in this promoter mixture on the alumina catalyst. is sprayed on. The impregnation can take place on water absorption, ie the amount of the solution corresponds to the pore volume of the carrier, or by excess soaking, ie the solution volume is larger than the pore volume.
- the alkali tungstate can also be prepared before application by reacting tungstate salts, such as ammonium tungstate, ammonium meta-tungstate, or ammonium paratungstal, in each case in the form of the hydrates, or tungstic acid with, for example, potassium hydroxide solution or sodium hydroxide solution. Finally, the catalyst is calcined in air or in the presence of oxygen, e.g. B. at 400 to 500 ° C.
- the aluminum oxide can be calcined for a period of 1 to 10 hours, preferably 1 to 5 hours, at a temperature of 300 to 600 ° C., preferably 400 to 500 ° C., before the promoters are applied.
- the catalyst obtained advantageously has a pH of less than 9.8, in particular the catalyst has a pH of 5 to 9.7.
- the pH value is measured by producing a 10% aqueous suspension from the catalyst to be examined. This sample is shaken for one minute, left to stand for 5 minutes and then the pH of the suspension is measured by electrode.
- this catalyst leads to a higher activity and selectivity of the finished catalyst, in particular at a low molar ratio of 3 to 1, of hydrogen sulfide to methanol.
- So-called active aluminum oxide is advantageously used as the aluminum oxide for this catalyst.
- This material has high specific surface areas between about 10 and 400 m 2 / g and consists mainly of oxides of the transition series of the crystallographic phases of the aluminum oxide (see for example Ullmann ⁇ s Encyclopedia of Industrial Chemistry from 1985, Vol. A1, pages 561 - 562). These transition oxides include ⁇ -, -, ⁇ -, ⁇ -, ⁇ -, ⁇ -aluminum oxide.
- Active aluminum oxide is commercially available in various qualities and delivery forms for catalytic applications.
- ⁇ -Alumina is particularly suitable, for example, in granulated or extruded form.
- Aluminum oxide with strand diameters of 1 to 5 mm is advantageously used.
- the specific surface area is preferably 150 to 400 m 2 / g.
- the total pore volume is between 0.3 and 1.0 ml / g.
- the bulk density is in the range from 300 to 1000 g / l.
- the catalyst can optionally be pre-sulfided under reaction-like conditions before use in methyl mercaptan synthesis.
- a welding hydrogen chloride stream passed at a temperature of 200 to 450 ° C and a pressure of 1 to 25 bar for a period of 0.5 to 100 hours over the catalyst particles.
- the molar ratio of hydrogen sulfide to methanol in the methyl mercaptan synthesis is in general 1 to 1 to 10 to 1, preferably 1 to 1 to 2 to 1.
- the proportions of freshly added hydrogen sulfide and methanol are also in the molar ratios indicated contain the proportions of recycled hydrogen sulfide and methanol.
- the catalyst is advantageously used in the reactor in the form of solid particles with a diameter of 1 to 5 mm, for example 4 mm.
- the reactor feed can contain oxygen, water or hydrogen and also an inert gas or a mixture of inert gases.
- the reactor feed contains 0 to 30 mol, preferably 5 to 30 mol, of inert gas per mol of alcohol.
- Suitable inert gases are e.g. Nitrogen, methane, ethane, propane, butane and / or carbon dioxide.
- the oxygen concentration can preferably be 10 ppm to 0.5% by weight, particularly preferably from 10 ppm to 500 ppm.
- the oxygen can be fed to the reactor in various forms. It is possible to use pure oxygen, if necessary in a mixture with inert gas. The oxygen is usually added in the form of air.
- the reactor feed can also contain recycled sulfur-containing components which have been separated from the methyl mercaptan produced (as described, for example, in DE-A-1768826).
- the process according to the invention for the production of methyl mercaptans by reacting hydrogen sulfide and methanol over a catalyst is generally carried out as a gas phase reaction in a tubular reactor.
- tubular reactors can also be used in series.
- methanol and hydrogen sulfide are heated to a temperature which is high enough for both methanol and methyl mercaptan to be in the vapor phase, but which is below the decomposition temperature of the methyl mercaptan.
- the process according to the invention is carried out at temperatures between 250 and 500 ° C., preferably between 300 and 450 ° C. The exact reaction temperature depends, among other things, on the reaction pressure and the catalyst used.
- the process according to the invention is generally carried out at a pressure of 1 to 25 bar.
- the pressure is not chosen so high that the reactor feed or the methyl mercaptan condenses.
- the pressure in the process according to the invention is preferably 1 to 10 bar. For reasons of reduced emission risk, it can be set to 1 to 3 bar, preferably almost pressureless.
- the process according to the invention is generally carried out continuously.
- the methyl mercaptan obtained is worked up by methods known to those skilled in the art.
- the WHSV is generally 0.1 to 10 h “1 , preferably 0.1 to 5 h “ 1 , particularly preferably 0.5 to 2 h "1 .
- the conversion in the process according to the invention is generally 80 to 100%, preferably 95 to 100%, based on the amount of the component used in the molar deficit (ie based on methanol in the methyl mercaptan synthesis). With the method according to the invention, a methyl mercaptan selectivity of 80 to 100% can be achieved.
- Example 1 Preparation of the comparative catalyst (14% by weight of K 2 WO 4 on ⁇ -Al 2 O 3 ) 203 g of ammonium meta-tungstate hydrate were dissolved in 0.385 l of water, then 182 g of a 48% strength potassium hydroxide solution were added and then topped up to a volume corresponding to the water absorption of the carrier. This 1,0481 impregnation solution was sprayed uniformly onto 1,588 kg ⁇ -Al 2 O 3 strands. Finally, the catalyst was calcined in a circulating air oven at 450 ° C. for 2 hours.
- Example 2 Analogously to Example 2, an aqueous solution of ammonium meta-tungstate hydrate, potassium hydroxide and 30.9 g of ammonium sulfate was prepared, added to 500 g of ⁇ -Al 2 O 3 strands and the catalyst was then calcined at 450 ° C. in a forced-air oven for 2 hours ,
- Example 2 Analogously to Example 2, an aqueous solution of ammonium meta-tungstate hydrate, potassium hydroxide and 36.1 g of ammonium sulfide was prepared, applied to 500 g of ⁇ -Al 2 O 3 strands and the catalyst was then calcined at 450 ° C. in a forced-air oven for 2 hours ,
- pH measurement A 10% aqueous suspension was prepared from the catalyst to be investigated. The sample was shaken for one minute, left to stand for 5 minutes and then the pH of the suspension was measured by electrode.
- the MeSH reactor (600 mm long, 25 mm diameter) was filled with 280 g catalyst strands. At a temperature of 390 ° C. (middle of the reactor) and a pressure of 1.1 bar, 48 g / h (1.5 mol) of gaseous methanol and 64 g / h (1.9 mol) of hydrogen sulfide were fed into the tubular reactor. The gas composition was determined by gas chromatography.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP04739104.0A EP1625113B1 (de) | 2003-04-30 | 2004-04-23 | Katalysator zur herstellung von methylmercaptan aus methanol und schwefelwasserstoff |
US10/554,701 US7687667B2 (en) | 2003-04-30 | 2004-04-23 | Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide |
JP2006505249A JP4367658B2 (ja) | 2003-04-30 | 2004-04-23 | メタノールおよび硫化水素からメチルメルカプタンを製造するための触媒 |
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DE10319739.7 | 2003-04-30 | ||
DE10319739A DE10319739A1 (de) | 2003-04-30 | 2003-04-30 | Katalysator zur Herstellung von Methylmercaptan aus Methanol und Schwefelwasserstoff |
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WO2004096760A1 true WO2004096760A1 (de) | 2004-11-11 |
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PCT/EP2004/004344 WO2004096760A1 (de) | 2003-04-30 | 2004-04-23 | Katalysator zur herstellung von methylmercaptan aus methanol und schwefelwasserstoff |
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US (1) | US7687667B2 (de) |
EP (1) | EP1625113B1 (de) |
JP (1) | JP4367658B2 (de) |
CN (1) | CN100334075C (de) |
DE (1) | DE10319739A1 (de) |
RU (1) | RU2358803C2 (de) |
WO (1) | WO2004096760A1 (de) |
Cited By (7)
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WO2006063669A1 (de) * | 2004-12-18 | 2006-06-22 | Degussa Gmbh | Halogenidhaltige alkaliwolframate enthaltende katalysatoren zur synthese von alkylmercaptan und verfahren zu ihrer herstellung |
US7582800B2 (en) | 2006-07-13 | 2009-09-01 | Degussa Gmbh | Process for preparing alkyl mercaptans in a multizone fixed bed reactor |
EP2606967A1 (de) * | 2011-12-19 | 2013-06-26 | Evonik Degussa GmbH | Katalysator zur Synthese von Alkylmercaptanen und Verfahren zu seiner Herstellung |
WO2016001554A1 (fr) | 2014-07-04 | 2016-01-07 | Arkema France | Procédé de préparation de disulfure de diméthyle |
WO2016001553A1 (fr) | 2014-07-04 | 2016-01-07 | Arkema France | Procédé de préparation de méthylmercaptan |
US10648007B2 (en) | 2015-09-30 | 2020-05-12 | Arkema France | Method for producing mercaptans by hydrogen-assisted disulfide enzyme hydrogenolysis |
US11434513B2 (en) | 2015-09-30 | 2022-09-06 | Arkema France | Method for producing mercaptans by disulfide enzyme hydrogenolysis |
Families Citing this family (5)
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DE10338887A1 (de) * | 2003-08-23 | 2005-03-17 | Degussa Ag | Katalysator zur Synthese von Alkylmercaptan und Verfahren zu seiner Herstellung |
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 |
CN105056937B (zh) * | 2015-08-17 | 2017-08-18 | 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 |
ES2873380T3 (es) | 2016-05-31 | 2021-11-03 | Novus Int Inc | Procedimiento para producir metil mercaptano a partir de sulfuro de dimetilo |
EP3689451A1 (de) | 2019-01-29 | 2020-08-05 | Evonik Operations GmbH | Katalysator zur synthese von alkylmercaptan und verfahren zu dessen herstellung |
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2004
- 2004-04-23 RU RU2005137019/04A patent/RU2358803C2/ru not_active IP Right Cessation
- 2004-04-23 EP EP04739104.0A patent/EP1625113B1/de not_active Expired - Lifetime
- 2004-04-23 WO PCT/EP2004/004344 patent/WO2004096760A1/de active Search and Examination
- 2004-04-23 JP JP2006505249A patent/JP4367658B2/ja not_active Expired - Fee Related
- 2004-04-23 US US10/554,701 patent/US7687667B2/en not_active Expired - Fee Related
- 2004-04-23 CN CNB2004800117113A patent/CN100334075C/zh not_active Expired - Fee Related
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Cited By (15)
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WO2006063669A1 (de) * | 2004-12-18 | 2006-06-22 | Degussa Gmbh | Halogenidhaltige alkaliwolframate enthaltende katalysatoren zur synthese von alkylmercaptan und verfahren zu ihrer herstellung |
JP2008523967A (ja) * | 2004-12-18 | 2008-07-10 | エボニック デグサ ゲーエムベーハー | アルキルメルカプタンを合成するためのハロゲン化物含有のアルカリ金属タングステン酸塩を含む触媒及びその製造方法 |
US8022254B2 (en) | 2004-12-18 | 2011-09-20 | Evonik Degussa Gmbh | Catalysts comprising halide-containing alkali tungstates for the synthesis of alkylmercaptan, and process for their preparation |
US7582800B2 (en) | 2006-07-13 | 2009-09-01 | Degussa Gmbh | Process for preparing alkyl mercaptans in a multizone fixed bed reactor |
RU2635922C2 (ru) * | 2011-12-19 | 2017-11-17 | Эвоник Дегусса Гмбх | Катализатор для синтеза алкилмеркаптанов и способ его получения |
WO2013092129A1 (en) * | 2011-12-19 | 2013-06-27 | Evonik Degussa Gmbh | Catalyst for the synthesis of alkyl mercaptans and process for producing it |
US9764309B2 (en) | 2011-12-19 | 2017-09-19 | Evonik Degussa Gmbh | Catalyst for the synthesis of alkyl mercaptans and process for producing it |
EP2606967A1 (de) * | 2011-12-19 | 2013-06-26 | Evonik Degussa GmbH | Katalysator zur Synthese von Alkylmercaptanen und Verfahren zu seiner Herstellung |
WO2016001554A1 (fr) | 2014-07-04 | 2016-01-07 | Arkema France | Procédé de préparation de disulfure de diméthyle |
WO2016001553A1 (fr) | 2014-07-04 | 2016-01-07 | Arkema France | Procédé de préparation de méthylmercaptan |
US10550077B2 (en) | 2014-07-04 | 2020-02-04 | Arkema France | Method for preparing dimethyl disulphide |
US10689334B2 (en) | 2014-07-04 | 2020-06-23 | Arkema France | Method for preparing methyl mercaptan |
US11104642B2 (en) | 2014-07-04 | 2021-08-31 | Arkema France | Method for preparing methyl mercaptan |
US10648007B2 (en) | 2015-09-30 | 2020-05-12 | Arkema France | Method for producing mercaptans by hydrogen-assisted disulfide enzyme hydrogenolysis |
US11434513B2 (en) | 2015-09-30 | 2022-09-06 | Arkema France | Method for producing mercaptans by disulfide enzyme hydrogenolysis |
Also Published As
Publication number | Publication date |
---|---|
RU2005137019A (ru) | 2006-05-27 |
RU2358803C2 (ru) | 2009-06-20 |
US20070015941A1 (en) | 2007-01-18 |
JP4367658B2 (ja) | 2009-11-18 |
CN100334075C (zh) | 2007-08-29 |
US7687667B2 (en) | 2010-03-30 |
EP1625113B1 (de) | 2020-09-09 |
CN1780814A (zh) | 2006-05-31 |
JP2006524563A (ja) | 2006-11-02 |
DE10319739A1 (de) | 2004-11-18 |
EP1625113A1 (de) | 2006-02-15 |
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