CN115228454A - Application of titanium dioxide in synthesis of methyl mercaptan - Google Patents
Application of titanium dioxide in synthesis of methyl mercaptan Download PDFInfo
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- CN115228454A CN115228454A CN202210117081.8A CN202210117081A CN115228454A CN 115228454 A CN115228454 A CN 115228454A CN 202210117081 A CN202210117081 A CN 202210117081A CN 115228454 A CN115228454 A CN 115228454A
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 27
- 238000003786 synthesis reaction Methods 0.000 title abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 45
- 238000000034 method Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000011068 loading method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ZNZNXSDPNKCWNO-UHFFFAOYSA-N S.CO Chemical compound S.CO ZNZNXSDPNKCWNO-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
Abstract
The invention discloses a new application of titanium dioxide, namely a new application of titanium dioxide in synthesizing a sulfur-containing intermediate methyl mercaptan with high added value, wherein high-sulfur synthesis gas is used for synthesizing methyl mercaptan under the catalysis of titanium dioxide at the temperature of 30-400 ℃ and under the pressure of 0.2-0.3MPa, wherein the high-sulfur synthesis gas contains H 2 S、CO、H 2 The mixed gas of (3); compared with the existing supported catalyst, the method can utilize CO/H catalytically without supporting metal 2 S/H 2 CH synthesis from mixed gas 3 SH; the method is simple and convenient to operate, and provides a new idea for synthesizing methyl mercaptan.
Description
Technical Field
The invention belongs to the field of methyl mercaptan synthesis, and particularly relates to a new application of titanium dioxide in synthesis of a sulfur-containing intermediate methyl mercaptan with a high additional value.
Background
Methyl mercaptan (CH) 3 SH) is an important chemical intermediate, and can be used for synthesizing sulfur-containing organic products with high added values, such as: methionine, dimethyl disulfide, methanesulfonic acid, and the like. Currently, the industrial process for preparing methyl mercaptan is mainly a methanol-hydrogen sulfide process, but the methanol raw material needs to pass through synthesis gas (CO + H) 2 ) If the synthesis gas raw material and reduced sulfur-containing species such as hydrogen sulfide generated in the coal gasification process are directly adopted to prepare the methyl mercaptan, the production cost of the methyl mercaptan is greatly reduced. CO/H 2 /H 2 One-step S process for synthesizing CH 3 SH also attracts more attention in recent years from some domestic and foreign scholars, and theoretically, only CH is generated in the reaction process 3 SH and H 2 O, is a green, economic and environment-friendly path.
In the presence of CO/H 2 /H 2 The catalyst for synthesizing methyl mercaptan under the S system mainly comprises: K-W-based catalysts, K-Mo-based catalysts. The prior method for catalytically synthesizing CH under a high-sulfur synthesis gas system 3 Many of SH catalysts are metal-modified supported catalysts, and many researchers have studied the problems of the reaction system such as the reaction path, the reaction mechanism, and the assignment of the active phase. The preparation process of the supported catalyst is complicated and takes long time.
Disclosure of Invention
The invention aims to provide a new application of titanium dioxide, namely the application of titanium dioxide in catalytic synthesis of a sulfur-containing intermediate methyl mercaptan with a high added value.
The method of the invention is to synthesize methyl mercaptan from high-sulfur synthesis gas under the catalysis of titanium dioxide at 30-400 ℃ and 0.2-0.3MPa, wherein the high-sulfur synthesis gas contains H 2 S、CO、H 2 Mixed gas of (2), H in the mixed gas 2 The mass concentration of S is 100000-600000ppm, the mass concentration of CO is 100000-600000ppm, H 2 The mass concentration is 100000-600000ppm; the airspeed of the mixed gas is 1000-5000h -1 。
In order to verify the catalytic effect of titanium dioxide, the invention takes titanium dioxide-based catalyst loaded with single metal potassium or molybdenum and double metals as a contrast, and experimental results show that the titanium dioxide is only used as the catalyst to synthesize methyl mercaptan by using high-sulfur synthesis gas, and the catalytic effect is better compared with the titanium dioxide-based catalyst loaded with metals.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst is simple and easy to obtain, and can be directly obtained by purchasing;
2. the operation is simple. Compared with a supported catalyst which needs impregnation, roasting and other treatments, the catalyst is a commercial catalyst and can be directly used for catalyzing CO/H 2 S/H 2 CH synthesis from mixed gas 3 SH；
3. The performance is better. After loading the metal on commercial titanium dioxide, CH 3 The SH production rate is significantly reduced or does not change significantly.
Drawings
FIG. 1 shows SBA-15 and TiO of example 1 2 The results of the CO conversion rate of the catalyst used in the methyl mercaptan synthesis are shown schematically;
FIG. 2 shows SBA-15 and TiO of example 1 2 The catalyst is used for a schematic diagram of the synthetic result of methyl mercaptan in the synthesis of methyl mercaptan;
FIG. 3 shows TiO in example 2 2 With Mo/TiO 2 The catalyst is used for a CO conversion rate result schematic diagram in the methyl mercaptan synthesis;
FIG. 4 shows TiO in example 2 2 With Mo/TiO 2 The catalyst is used for a schematic diagram of the synthetic result of methyl mercaptan in the synthesis of methyl mercaptan;
FIG. 5 shows TiO in example 3 2 With K/TiO 2 The catalyst is used for a CO conversion rate result schematic diagram in the methyl mercaptan synthesis;
FIG. 6 shows TiO in example 3 2 With K/TiO 2 The catalyst is used for a schematic diagram of the synthetic result of methyl mercaptan in the synthesis of methyl mercaptan;
FIG. 7 shows TiO in example 4 2 With K-Mo/TiO 2 The results of the catalyst for CO conversion in methyl mercaptan are shown schematically;
FIG. 8 shows TiO in example 4 2 With K-Mo/TiO 2 The results of the catalyst used for synthesizing methyl mercaptan from methyl mercaptan are shown schematically.
Detailed Description
The present invention is further illustrated in detail by the following examples, but the scope of the present invention is not limited thereto, wherein the methods are all conventional methods unless otherwise specified, and the reagents are all conventional reagents or reagents prepared by conventional methods unless otherwise specified;
example 1: catalytic synthesis of methyl mercaptan from titanium dioxide
0.4g of commercially available titanium dioxide was charged into a tube furnace reactor and CO/H was passed 2 S/H 2 The mass concentration of CO in the mixed gas is 100000ppm 2 The mass concentration of S is 500000ppm, H 2 The mass concentration is 400000ppm, and the total space velocity of mixed gas feeding is 3000h -1 The pressure of a reaction system is 0.2MPa, and the preparation of methyl mercaptan is carried out at the reaction temperature of 200-400 ℃;
simultaneously, synthesizing methyl mercaptan by using an SBA-15 catalyst under the same synthesis condition as titanium dioxide, wherein the SBA-15 catalyst is prepared as follows: dissolving 24g P123 in 650mL deionized water, and stirring until the solution is completely dissolved; adding 140mL of HCl under the condition of water bath at 40 ℃, and stirring for 3h; then, 65mL of tetraethyl orthosilicate is added dropwise and stirred for 24 hours; then crystallizing for 24 hours at the temperature of 90 ℃; and then carrying out vacuum filtration, drying for 24h and calcining at 550 ℃ to obtain SBA-15.
The results are shown in FIGS. 1 and 2, and show that there is catalytic conversion of CO on both catalysts. TiO 2 2 The highest CO conversion rate of the catalyst can reach 17.5 percent, while the highest CO conversion rate of the SBA-15 catalyst is only 10.9 percent; but in TiO 2 CH on catalyst 3 The highest SH generation rate can reach 5.98 multiplied by 10 -4 mol (methyl mercaptan) mol -1 (catalyst) s -1 And almost no CH on SBA-15 catalyst 3 SH formation, indicating that titanium dioxide is a carrier having redox properties in CO/H 2 S/H 2 Can generate CH under the condition of synthesis gas 3 SH。
Example 2: mo/TiO 2 Catalyst catalyzed synthesis of methyl mercaptan
Taking ammonium molybdate as a precursor, and loading Mo on TiO by adopting equal-volume impregnation 2 The loading amount of Mo is 20%; the impregnation process is as follows: dissolving 0.9182g of ammonium molybdate in 5mL of deionized water, and adding 3g of TiO after the ammonium molybdate is dissolved 2 After fully stirring evenly, standing for 12h at room temperature, drying for 6H at 90 ℃, then roasting for 6H at 550 ℃ in a muffle furnace, crushing and sieving by a 60-mesh sieve, then placing in a fixed bed reactor at the total flow rate of 40mL/min in H 2 /H 2 S mixed atmosphere (H) 2 :H 2 S = 9) was heated to 400 ℃ at a temperature of 2 ℃/min and held for 5h to obtain Mo/TiO 2 A catalyst;
mixing Mo/TiO 2 0.4g of catalyst was charged into a tube furnace reactor and CO/H was introduced 2 S/H 2 Mixed reaction gas, CO mass concentration 100000ppm, H 2 The mass concentration of S is 500000ppm, H 2 The mass concentration is 400000ppm, and the total space velocity of the feeding is 3000h -1 The pressure of a reaction system is 0.2Mpa, and the preparation of methyl mercaptan is carried out at the reaction temperature of 200-400 ℃;
the highest CO conversion rate can reach 15.9 percent, and CH 3 SH generation rate of 3.36X 10 at the highest -4 mol (methyl mercaptan) mol -1 (catalyst) s -1 See FIGS. 3 and 4 for the CH, compared to the results for titanium dioxide in example 1 3 The SH formation rate is significantly lower than that of example 1, indicating that the precursor ammonium molybdate is added to cover the titanium dioxide catalyst to synthesize CH 3 The active site of SH.
Example 3: K/TiO 2 Catalyst catalyzed synthesis of methyl mercaptan
Taking potassium carbonate as a precursor, and loading K on TiO by adopting equal-volume impregnation 2 The loading of K is 13%, and the impregnation process is as follows: 0.8008g of potassium carbonate is dissolved in 5mL of deionized water, and 3g of TiO is added after the potassium carbonate is dissolved 2 Fully stirring the mixture evenly, standing the mixture for 12h at room temperature, drying the mixture for 6H at 90 ℃, then putting the mixture into a muffle furnace for roasting the mixture for 6H at the temperature of 550 ℃, crushing the mixture, sieving the crushed mixture by a sieve of 60 meshes, putting the crushed mixture into a fixed bed reactor, and stirring the crushed mixture at the total flow rate of 40mLl/min in H 2 /H 2 S mixed atmosphere (H) 2 :H 2 S =9, 1), temperature programmed at 2 ℃/min to 400 ℃ for 5hObtaining K/TiO 2 A catalyst;
mixing K/TiO 2 0.4g of the catalyst was charged into a tube furnace reactor and CO/H was introduced 2 S/H 2 Mixed reaction gas, CO mass concentration 100000ppm, H 2 The mass concentration of S is 500000ppm, H 2 The mass concentration is 400000ppm, and the total space velocity of feeding is 3000h -1 The methyl mercaptan is prepared under the condition that the pressure of a reaction system is 0.2Mpa and the reaction temperature is 200-400 ℃.
The highest CO conversion rate can reach 6.8 percent, and CH 3 SH generation rate of 1.97X 10 at most -4 mol (methyl mercaptan) mol -1 (catalyst) s -1 (ii) a Referring to FIGS. 5 and 6, the titania catalyst of example 1 has higher CH than the titania of example 1 3 SH selectivity and better catalyst performance show that the potassium carbonate is added to cover the titanium dioxide to synthesize CH 3 The active site of SH.
Example 4: K-Mo/TiO 2 Catalyst catalyzed synthesis of methyl mercaptan
Ammonium molybdate and potassium carbonate are taken as precursors and are loaded on TiO by adopting equal-volume impregnation 2 The loading amount of Mo is 20%, wherein the molar ratio of K to Mo is 2: dissolving 0.9182g of ammonium molybdate in 5mL of deionized water, adding 0.8008g of potassium carbonate, adding 3g of TiO after dissolving 2 Fully stirring the mixture evenly, standing the mixture for 12h at room temperature, drying the mixture for 6H at 90 ℃, then putting the mixture into a muffle furnace for roasting the mixture for 6H at the temperature of 550 ℃, crushing the mixture, sieving the crushed mixture by a sieve of 60 meshes, putting the crushed mixture into a fixed bed reactor, and stirring the crushed mixture at the total flow rate of 40mL/min in H 2 /H 2 S mixed atmosphere (H) 2 :H 2 S = 9), raising the temperature to 400 ℃ by a program of 2 ℃/min and keeping the temperature for 5h to obtain K-Mo/TiO 2 A catalyst;
mixing K-Mo/TiO 2 0.4g of catalyst was charged into a tubular furnace reactor, and CO/H was introduced 2 S/H 2 Mixed reaction gas, CO mass concentration 100000ppm, H 2 The mass concentration of S is 500000ppm, H 2 The mass concentration is 400000ppm, the total feed airspeed is 3000h < -1 >, the pressure of a reaction system is 0.2Mpa, and the preparation of methyl mercaptan is carried out at the reaction temperature of 200-400 ℃;
the highest CO conversion rate can reach 23.2 percent, and CH 3 SH generation rate of up to 5.58X 10 -4 mol (methyl mercaptan) mol -1 (catalyst) s -1 Referring to FIGS. 7 and 8, the results are shown in which CH is supported after the metal, as compared with the results of titanium dioxide in example 1 3 The SH generation rate is not obviously improved, which indicates that the titanium dioxide is not suitable for loading any metal for synthesizing CH 3 SH。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. The application of titanium dioxide in the catalytic synthesis of methyl mercaptan.
2. Use according to claim 1, characterized in that: synthesizing methyl mercaptan from high-sulfur synthetic gas under the catalysis of titanium dioxide at 30-400 ℃ and 0.2-0.3MPa, wherein the high-sulfur synthetic gas contains H 2 S、CO、H 2 Mixed gas of (2), H in the mixed gas 2 The mass concentration of S is 100000-600000ppm, the mass concentration of CO is 100000-600000ppm, H 2 The mass concentration is 100000-600000ppm; the space velocity of the mixed gas is 1000-5000h -1 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668825A (en) * | 1984-06-29 | 1987-05-26 | Exxon Research And Engineering Co. | Production of methanethiol from H2 S and CO |
| CN1207958A (en) * | 1998-09-10 | 1999-02-17 | 厦门大学 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
| CN101743221A (en) * | 2007-05-25 | 2010-06-16 | 赢创德固赛有限责任公司 | Process for continuously preparing methyl mercaptan from carbon- and hydrogen-containing compounds |
| US20100286448A1 (en) * | 2007-12-28 | 2010-11-11 | Evonik Degussa Gmbh | SUPPORTED MO-O-K-MExOy CATALYST FOR THE SYNTHESIS OF METHANETHIOL FROM HIGH H2S-CONTAINING SYNGAS |
| CN112041299A (en) * | 2017-12-22 | 2020-12-04 | 阿科玛法国公司 | Process for the preparation of methyl mercaptan |
-
2022
- 2022-02-07 CN CN202210117081.8A patent/CN115228454A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668825A (en) * | 1984-06-29 | 1987-05-26 | Exxon Research And Engineering Co. | Production of methanethiol from H2 S and CO |
| CN1207958A (en) * | 1998-09-10 | 1999-02-17 | 厦门大学 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
| CN101743221A (en) * | 2007-05-25 | 2010-06-16 | 赢创德固赛有限责任公司 | Process for continuously preparing methyl mercaptan from carbon- and hydrogen-containing compounds |
| US20100286448A1 (en) * | 2007-12-28 | 2010-11-11 | Evonik Degussa Gmbh | SUPPORTED MO-O-K-MExOy CATALYST FOR THE SYNTHESIS OF METHANETHIOL FROM HIGH H2S-CONTAINING SYNGAS |
| CN112041299A (en) * | 2017-12-22 | 2020-12-04 | 阿科玛法国公司 | Process for the preparation of methyl mercaptan |
Non-Patent Citations (1)
| Title |
|---|
| GUIDO MUL, ET AL: "Catalytic synthesis of methanethiol from hydrogen sulfide and carbon monoxide over vanadium-based catalysts", CATALYSIS TODAY, vol. 78, no. 1, pages 331 * |
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