CN1207958A - Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide - Google Patents
Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide Download PDFInfo
- Publication number
- CN1207958A CN1207958A CN 98118187 CN98118187A CN1207958A CN 1207958 A CN1207958 A CN 1207958A CN 98118187 CN98118187 CN 98118187 CN 98118187 A CN98118187 A CN 98118187A CN 1207958 A CN1207958 A CN 1207958A
- Authority
- CN
- China
- Prior art keywords
- mos
- catalyzer
- carrier
- methyl mercaptan
- load
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 title claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 150000003624 transition metals Chemical group 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 3
- 235000015320 potassium carbonate Nutrition 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000005303 weighing Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- -1 methine halide Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalyst has one carrier of SiO2, gamma-Al2O3 or TiO2 and its active component Mo-S-K radical is transformed from precursor K2MoS4 or (NH4)2MoS4+K2CO3. Its transition of RE metal oxide promoter are mainly metal oxide of Mn, Fe, Co, Ni, La, etc. Under the conditions of 295 deg.c temperature, 0.2MPa pressure, volume proportion of high-sulphur synthesis gas CO-H2-H2S being 1 to 2 to 0.1-1, and 2000-5000/hr space velocity, the catalyst can result in methyl mercaptan space-time yield of 0.37 g/hr each gram of catalyst and selectivity of 98.6%.
Description
The present invention is a kind of being used for by containing high H
2Synthetic gas (the CO+H of S concentration
2) be raw material, single stage method synthesis of methyl mercaptan (CH
3SH) loading type Mo-S-K is catalyst based and preparation method thereof.
Thiomethyl alcohol is synthetic egg amino acid, the important industrial chemicals of medicine and agricultural chemicals, and its classical production process is formed by potassium bisulfide and methine halide effect.The exploitation of other synthetic route was arranged again afterwards successively, U.S. Pat app1.856 for example, 232, a kind of method of making thiomethyl alcohol with hydrogen sulfide and methyl alcohol or ether reaction is disclosed; French Patent FR app1.93,112,491 to disclose a kind of be catalyzer with the transition metal, the method for dimethyl sulfide hydrogenation system thiomethyl alcohol; European patent EP 167,354 discloses a kind ofly makes carrier with titanium oxide, and nickel oxide or tantalum oxide are active ingredient, is the method that raw material is made thiomethyl alcohol with hydrogen sulfide and carbon monoxide.
The objective of the invention is to develop that a kind of to be used for the synthetic gas that contains high hydrogen sulfide be raw material, the load shape Mo-S-K with transition metal or lanthanide rare metal oxide promoted of single stage method synthesis of methyl mercaptan is catalyst based.
Detailed description of the present invention:
Catalyzer of the present invention is made up of active ingredient, promotor and carrier, and active ingredient is the Mo-S-K based composition and use thereof in packaging, and said Mo-S-K based composition and use thereof in packaging is from its presoma tetrathio potassium molybdate (K
2MoS
4) or tetrathio amine molybdate (NH
4)
2MoS
4Add salt of wormwood (K
2CO
3); Promotor is the oxide compound of a kind of oxide compound that is selected from transition metal or lanthanide series rare-earth elements, particularly iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), lanthanum (La), cerium (Ce), and carrier is selected from silicon-dioxide (SiO
2), activated alumina, especially γ～Al
2O
3, titanium oxide (TiO
2).Catalyst system can be expressed as Mo-S-K/MO
x/ carrier, MO in the formula
xRepresent the oxide compound of transition metal or lanthanide series rare-earth elements, wherein the weight ratio of each composition is: as if the weight with carrier is 1, then MO
xWeight be 0.001～0.1, preferably 0.01～0.05, active ingredient is with MoS
2Meter accounts for 0.01～0.85 (weight), preferably accounts for 0.1～0.6 (weight).
Take by weighing metering, the selected transition metal or the nitrate of lanthanide series rare-earth elements become solution with dissolved in distilled water, selected carrier impregnation with metering, make steeping fluid just flood full carrier, dry 3～4h down at 110 ℃ then, standby at 500-550 ℃ of following calcination 4～5h again; Take by weighing the presoma K of the Mo-S-K base of metering
2MoS
4, and it is dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K
2MoS
4Dissolving fully; The DMF solution of gained presoma again with metering, load the carrier impregnation of transition metal or rare-earth oxide, extract DMF with anhydrous diethyl ether after leaving standstill 1h, in argon gas (Ar) atmosphere, promptly get the catalyzer of Mo-S-K/MOx/ carrier after the vacuum-drying in 300～400 ℃ of following calcination 2～4h.With (NH
4)
2MoS
4And K
2CO
3Be the load of precursor, earlier with load the carrier impregnation of metal oxide at K
2CO
3In the aqueous solution, drying again, K is pressed in 500 ℃ of calcinings then
2MoS
4Carrying method load (NH for precursor
4)
2MoS
4
Activity rating of catalyst carries out in fixed bed flowing reactive system, and the high-sulfur synthetic gas consists of CO/H
2/ H
2S=1/2/ (0.1～1), (V/V), 220～350 ℃ of temperature of reaction, pressure 0.2Mp, air speed (2～5) * 10
3h
-1, unstripped gas and product gc analysis.
The invention provides a kind of being used for to contain high H
2The synthetic gas of S concentration is a raw material, and the loading type Mo-S-K of single stage method synthesis of methyl mercaptan is catalyst based, and said catalyzer space-time yield of thiomethyl alcohol under appreciation condition of the present invention is 0.37g/h.gc.g
Cat, selectivity is up to 98.6%.
Further specify the present invention by embodiment below.Example 1. takes by weighing 0.725g Fe (NO
3)
39H
2O also is dissolved in the 10mL distilled water, is made into iron nitrate aqueous solution, uses 10.0gSiO
2(80～100 order) dipping is dried 3h down at 110 ℃ behind the 20min., moves in the muffle furnace, at 500 ℃ of following calcination 4h again; Take by weighing K
2MoS
41.70g and be dissolved among the 15mL DMF, again with aforementioned load ferric oxide and through the SiO of roasting
2Carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, all is extracted totally until DMF, in vacuum drying oven 100 ℃ down behind the dry 3h again, promptly gets Mo-S-K/Fe in 400 ℃ of following calcination 4h in argon gas (Ar) atmosphere
2O
3/ SiO
2Catalyzer, so the weight of the catalyzer of making forms that (the Mo-S-K base is with MoS
2Meter) be MoS
2/ Fe
2O
3/ SiO
2=0.15/0.03/1, (w/w), activity rating the results are shown in Table 1.2-3. is the carrier S iO in the example 1. for example
2Change γ-Al respectively into
2O
3And TiO
2, all the other practices are with embodiment 1, and the composition and the evaluation result of gained catalyzer see Table 1.Example 4. is measured 50% Mn (NO
3)
2Solution 0.58mL, adding distil water 10mL is made into manganese nitrate solution, and all the other practices are with embodiment 1, and so (the Mo-S-K base is with MoS for the composition of the catalyzer of making
2Meter) be MoS
2/ MnO
2/ SiO
2=0.15/0.025/1, (w/w), activity rating the results are shown in Table 1.5-8. is " 0.725g Fe (the NO in the example 1. for example
3)
39H
2O " change into 1.16g Ni (NO respectively
3)
26H
2O, 1.16gCo (NO
3)
26H
2O, 0.67g La (NO
3)
3, 0.66g Ce (NO
3)
36H
2O, all the other practices are with embodiment 1, and the composition and the activity rating of gained catalyzer the results are shown in Table 1.
The composition of the catalyzer of table 1. embodiment 1-8 and activity rating result
*
| Embodiment | Catalyzer is formed (w/w), and (active ingredient Mo-S-K is with MoS 2Meter) | Generate CH 3SH selectivity (%) | CH 3The space-time yield (g/hgcm) of SH |
| ??1 | ?MoS 2/Fe 2O 3/SiO 2＝0.15/0.03/1 | ????95.2 | ????0.36 |
| ??2 | ?MoS 2/Fe 2O 3/γAl 2O 3＝0.15/0.03/1 | ????75.3 | ????0.21 |
| ??3 | ?MoS 2/Fe 2O 3/TiO 2＝0.15/0.03/1 | ????82.7 | ????0.25 |
| ??4 | ?MoS 2/MnO 2/SiO 2＝0.15/0.025/1 | ????90.2 | ????0.26 |
| ??5 | ?MoS 2/NiO/SiO 2＝0.15/0.03/1 | ????95.2 | ????0.33 |
| ??6 | ?MoS 2/CoO/SiO 2＝0.15/0.03/1 | ????93.8 | ????0.34 |
| ??7 | ?MoS 2/La 2O 3/SiO 2＝0.15/0.025/1 | ????98.6 | ????0.37 |
| ??8 | ?MoS 2/Ce 2O 3/SiO 2＝0.15/0.025/1 | ????96.6 | ????0.35 |
*Appreciation condition: the high-sulfur synthetic gas consists of CO/H
2/ H
2S=1/2/0.3, (V/V),
295 ℃ of temperature of reaction, pressure 0.2Mp, air speed 3 * 10
3h
-1Example 9. takes by weighing 0.725g Fe (NO
3)
39H
2O also is dissolved in the 10mL distilled water, is made into iron nitrate aqueous solution, uses 10.0gSiO
2(80～100 order) dipping is dried 3h down at 110 ℃ behind the 20min., moves to muffle furnace again, and is standby at 550 ℃ of following calcination 4h; Take by weighing K
2CO
32.76g, be dissolved in the distilled water of 10mL the Fe that used above-mentioned load again
2O
3, and through incinerating SiO
2Carrier impregnation, 110 ℃ of oven dry, 500 ℃ of calcinings are standby.Take by weighing (NH
4)
2MoS
45.16g, be dissolved among the DMF of 15mL the K that used load again
2CO
3, Fe
2O
3SiO
2Carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, all is extracted totally until DMF, in vacuum drying oven 100 ℃ down behind the dry 3h again, promptly gets Mo-S-K/Fe in 450 ℃ of following calcination 4h in argon gas (Ar) atmosphere
2O
3/ SiO
2Catalyzer, so the weight of the catalyzer of making forms that (the Mo-S-K base is with MoS
2Meter) be MoS
2/ Fe
2O
3/ SiO
2=0.51/0.03/1, (w/w); Consist of CO/H at the high-sulfur synthetic gas
2/ H
2S=1/2/0.3 (V/V), 400 ℃ of temperature of reaction, normal pressure, air speed 3 * 10
3h
-1Condition under carry out activity rating, the selectivity that the result generates thiomethyl alcohol is 95%, the space-time yield of thiomethyl alcohol is 0.27g/hg
Cat
Claims (5)
1. the synthetic gas with high hydrogen sulfide concentration is a raw material, the catalyzer of single stage method synthesis of methyl mercaptan, said catalyzer is made up of active ingredient, promotor and carrier, it is characterized in that said active ingredient is the Mo-S-K based composition and use thereof in packaging, and the Mo-S-K based composition and use thereof in packaging in the said catalyzer is by presoma K
2MoS
4Or (NH
4)
2MoS
4Add K
2CO
3Through load and calcination and get; Promotor in the said catalyzer is a kind of oxide compound that is selected from transition metal or lanthanide series rare-earth elements, uses MO
xExpression; Said carrier is a kind of SiO of being selected from
2, activated alumina, TiO
2Oxide compound, the amount of the active ingredient Mo-S-K base in the said catalyzer is with MoS
2Meter, the weight ratio of each composition is MoS
2/ MO
x/ carrier=(0.01～0.85)/(0.001～0.1)/1, w/w.
2. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, it is characterized in that the promotor in the said catalyzer is the oxide compound of Fe, Mn, Co, Ni, La, Ce.
3. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, it is characterized in that drawing together property of the carrier aluminum oxide in the said catalyzer is γ-Al
2O
3
4. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, the amount that it is characterized in that the active ingredient Mo-S-K base in the said catalyzer is with MoS
2Meter, the weight ratio of each composition is MoS
2/ MO
x/ carrier=(0.1～0.6)/(0.01～0.05)/1, w/w.
5. method of making the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, promotor in the said catalyzer is with metering, the selected transition metal or the nitrate of lanthanide series rare-earth elements, become solution with dissolved in distilled water, selected carrier impregnation with metering, dry 3-4h down at 110 ℃ then, again at 500-550 ℃ of following calcination 4-5h; The presoma K that it is characterized in that said catalyst activity component Mo-S-K base
2MoS
4Load be will the metering K
2MoS
4Be dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K
2MoS
4Dissolving fully, the DMF solution of gained presoma is used metering again, said load the carrier impregnation of transition metal oxide, extract DMF with anhydrous diethyl ether after leaving standstill 1h, in argon gas (Ar) atmosphere, promptly get the loaded catalyst that is expressed as the Mo-S-K/MOx/ carrier after the vacuum-drying in 300～400 ℃ of following calcination 2-4h; With (NH
4)
2MoS
4And K
2CO
3Be the load of precursor, be earlier with load the carrier impregnation of metal oxide at K
2CO
3In the aqueous solution, drying again, K is pressed in 500 ℃ of calcinings then
2MoS
4Carrying method load (NH
4)
2MoS
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98118187A CN1072523C (en) | 1998-09-10 | 1998-09-10 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98118187A CN1072523C (en) | 1998-09-10 | 1998-09-10 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1207958A true CN1207958A (en) | 1999-02-17 |
| CN1072523C CN1072523C (en) | 2001-10-10 |
Family
ID=5225952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98118187A Expired - Fee Related CN1072523C (en) | 1998-09-10 | 1998-09-10 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1072523C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334075C (en) * | 2003-04-30 | 2007-08-29 | 巴斯福股份公司 | Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide |
| CN100345629C (en) * | 2003-10-10 | 2007-10-31 | 德古萨股份公司 | Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide |
| CN100443165C (en) * | 2004-03-12 | 2008-12-17 | 德古萨股份公司 | A catalyst for the synthesis of methyl mercaptan by the reaction of carbon monoxide and hydrogen sulfide |
| US7569731B2 (en) | 2003-10-10 | 2009-08-04 | Degussa Ag | Process for the manufacture of methylmercaptan |
| US7723261B2 (en) | 2007-04-17 | 2010-05-25 | Evonik Degussa Gmbh | Catalyst for the preparation of methyl mercaptan |
| US8883670B2 (en) | 2006-09-11 | 2014-11-11 | Evonik Degussa Gmbh | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| JP2016515935A (en) * | 2013-03-29 | 2016-06-02 | アルケマ フランス | Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulfide |
| US9409153B2 (en) | 2007-12-28 | 2016-08-09 | Evonik Degussa Gmbh | Supported Mo—O—K—MexOy catalyst for the synthesis of methanethiol from high H2S-containing syngas |
| CN112316959A (en) * | 2020-11-18 | 2021-02-05 | 昆明理工大学 | K insertion type 1T-MoS2Catalyst, preparation method and application thereof |
| CN115228454A (en) * | 2022-02-07 | 2022-10-25 | 昆明理工大学 | Application of titanium dioxide in synthesis of methyl mercaptan |
| RU2805660C2 (en) * | 2019-01-18 | 2023-10-23 | Адиссео Франс С.А.С. | Method for obtaining the compound of rsh formula by hydrosulphurisation |
| US12162823B2 (en) | 2019-01-18 | 2024-12-10 | Adisseo France S.A.S. | Process for preparing a compound of formula RSH by hydrosulfurization |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0167354A1 (en) * | 1984-06-29 | 1986-01-08 | Exxon Research And Engineering Company | Catalysts comprising niobia and/or tantala supported on titania |
| US5283369A (en) * | 1992-03-24 | 1994-02-01 | Elf Atochem North America, Inc. | Selective synthesis of mercaptans and catalyst therefor |
| CN1178136A (en) * | 1996-09-26 | 1998-04-08 | 底古萨股份公司 | Catalyst, its preparation and use in synthesis of methyl mercaptan |
| DE19639584A1 (en) * | 1996-09-26 | 1998-04-23 | Degussa | Catalyst, process for its preparation and use for the synthesis of methyl mercaptan |
-
1998
- 1998-09-10 CN CN98118187A patent/CN1072523C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334075C (en) * | 2003-04-30 | 2007-08-29 | 巴斯福股份公司 | Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide |
| CN100345629C (en) * | 2003-10-10 | 2007-10-31 | 德古萨股份公司 | Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide |
| US7569731B2 (en) | 2003-10-10 | 2009-08-04 | Degussa Ag | Process for the manufacture of methylmercaptan |
| RU2394023C2 (en) * | 2003-10-10 | 2010-07-10 | Эвоник Дегусса Гмбх | Method of producing methylmercaptan |
| US7833929B2 (en) | 2003-10-10 | 2010-11-16 | Evonik Degussa Gmbh | Process for the manufacture of methylmercaptan |
| CN100443165C (en) * | 2004-03-12 | 2008-12-17 | 德古萨股份公司 | A catalyst for the synthesis of methyl mercaptan by the reaction of carbon monoxide and hydrogen sulfide |
| US8883670B2 (en) | 2006-09-11 | 2014-11-11 | Evonik Degussa Gmbh | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| US7723261B2 (en) | 2007-04-17 | 2010-05-25 | Evonik Degussa Gmbh | Catalyst for the preparation of methyl mercaptan |
| US9409153B2 (en) | 2007-12-28 | 2016-08-09 | Evonik Degussa Gmbh | Supported Mo—O—K—MexOy catalyst for the synthesis of methanethiol from high H2S-containing syngas |
| JP2016515935A (en) * | 2013-03-29 | 2016-06-02 | アルケマ フランス | Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulfide |
| US9944594B2 (en) * | 2013-03-29 | 2018-04-17 | Arkema France | Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulphide |
| US10377704B2 (en) | 2013-03-29 | 2019-08-13 | Arkema France | Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulphide |
| RU2805660C2 (en) * | 2019-01-18 | 2023-10-23 | Адиссео Франс С.А.С. | Method for obtaining the compound of rsh formula by hydrosulphurisation |
| US12162823B2 (en) | 2019-01-18 | 2024-12-10 | Adisseo France S.A.S. | Process for preparing a compound of formula RSH by hydrosulfurization |
| CN112316959A (en) * | 2020-11-18 | 2021-02-05 | 昆明理工大学 | K insertion type 1T-MoS2Catalyst, preparation method and application thereof |
| CN115228454A (en) * | 2022-02-07 | 2022-10-25 | 昆明理工大学 | Application of titanium dioxide in synthesis of methyl mercaptan |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1072523C (en) | 2001-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110801861B (en) | Environment-friendly catalyst for preparing propylene by direct dehydrogenation of propane and preparation method thereof | |
| CN107285334B (en) | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve | |
| CN1207958A (en) | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide | |
| JPH11217343A (en) | Synthesis of chemical industrial feedstock and high-octane fuel | |
| US5516741A (en) | Reduced chlorine containing platinum catalysts | |
| CN110102338A (en) | A kind of ammoxidation catalyst and preparation method thereof of high nitrogen selective | |
| JPH0336571B2 (en) | ||
| US5116801A (en) | Catalysts for the selective reduction of nitrogen oxides and process for preparing the catalyst | |
| CN101204657A (en) | Catalyzing N2O directly decomposing cobalt and cerium compound oxide catalyst containing alkali metals and preparation method thereof | |
| CN109999922A (en) | A kind of difunction catalyst of methyl propionate and formaldehyde synthesizing methylmethacrylate | |
| CN110479346A (en) | A kind of N doping non-precious metal catalyst and preparation method thereof for purifying formaldehyde | |
| CN110170333B (en) | Catalyst for preparing ethylene from ethane in carbon dioxide atmosphere and preparation method thereof | |
| CN113751062A (en) | Porous copper-based catalyst for hydrogenation of carbon dioxide to ethanol and preparation method thereof | |
| CN1207957A (en) | Catalyst for synthesizing methyl mercaptan from synthesized gas contg. hydrogen sulfide | |
| CN114160144B (en) | Chromium-free catalyst, preparation method and application thereof | |
| US4551444A (en) | Catalyst for alcohol synthesis | |
| CN101121130B (en) | Ammoxidation method to manufacturing unsaturated nitrile catalyst | |
| JPS5929633B2 (en) | Low-temperature steam reforming method for hydrocarbons | |
| CN111672536A (en) | Noble metal catalyst for formaldehyde purification and preparation method thereof | |
| CN1363544A (en) | Impregnation method for preparing 3-hydroxypropanal as hydrocatalyst | |
| US4537909A (en) | Alcohol synthesis | |
| CN113019370B (en) | A kind of catalyst, its preparation method and application | |
| CN104437526B (en) | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method of catalyst | |
| CN100443165C (en) | A catalyst for the synthesis of methyl mercaptan by the reaction of carbon monoxide and hydrogen sulfide | |
| CN1302686A (en) | Deoxidizing agent of molybdenum oxide and its preparing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: XIAMEN UNIVERSITY ASSET MANAGEMENT LTD. Free format text: FORMER OWNER: XIAMEN UNIVERSITY Effective date: 20050415 Owner name: DEGAOSA CO., LTD. Free format text: FORMER OWNER: XIAMEN UNIVERSITY ASSET MANAGEMENT LTD. Effective date: 20050415 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20050415 Address after: Hanau Patentee after: JCDecaux Shakespeare Co. Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: Xiamen University Asset Management Co.,Ltd. Effective date of registration: 20050415 Address after: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee after: Xiamen University Asset Management Co.,Ltd. Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: Xiamen University |
|
| C56 | Change in the name or address of the patentee |
Owner name: EVONIK DEGUSSA CO., LTD. Free format text: FORMER NAME: DEGUSSA CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: essen Patentee after: EVONIK DEGUSSA GmbH Address before: Hanau Patentee before: JCDecaux Shakespeare Co. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20011010 Termination date: 20170910 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |