CN117126086A - Core-shell type K x -MoO 3 @SiO 2 Use of catalyst for synthesizing methyl mercaptan or ethyl mercaptan - Google Patents
Core-shell type K x -MoO 3 @SiO 2 Use of catalyst for synthesizing methyl mercaptan or ethyl mercaptan Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 55
- 239000011258 core-shell material Substances 0.000 title claims abstract description 52
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 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
- ZNZNXSDPNKCWNO-UHFFFAOYSA-N S.CO Chemical compound S.CO ZNZNXSDPNKCWNO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a core-shell type K x ‑MoO 3 @SiO 2 Use of a catalyst in the synthesis of methyl mercaptan or ethyl mercaptan, said core-shell K x ‑MoO 3 @SiO 2 The catalyst is prepared by placing molybdate into ethanol solution of polyvinylpyrrolidone, stirring and mixing uniformly, reacting at 150-240 ℃, separating solid from liquid, washing and drying the solid 2 The method comprises the steps of carrying out a first treatment on the surface of the MoO is carried out 2 Placing in ethanol solution, ultrasonic dispersing, adding diethanolamine and cetyltrimethylammonium bromide into the dispersion under stirring at room temperature, then dripping ethyl orthosilicate, continuously stirring, separating solid from liquid, washing and drying the solid, and bakingFiring to obtain core-shell MoO 3 @SiO 2 A material; core-shell MoO 3 @SiO 2 Adding the material into a potassium precursor solution, uniformly mixing, performing ultrasonic treatment, standing overnight, drying and roasting to obtain the material; the catalyst has the advantages of excellent catalyst activity, high product selectivity and low reaction energy consumption in the preparation of methyl mercaptan and ethyl mercaptan.
Description
Technical Field
The invention relates to a K x -MoO 3 @SiO 2 Preparation method of mesoporous core-shell catalyst and application of mesoporous core-shell catalyst in catalysis of CO/H 2 S/H 2 Mixture gas, C 2 H 4 /H 2 S mixture gas for synthesizing methyl mercaptan (CH) 3 SH) and ethanethiol (C) 2 H 5 SH), belonging to the technical field of methyl mercaptan and ethyl mercaptan preparation.
Background
Methyl mercaptan (CH) 3 SH) is an important chemical intermediate and industrial raw material, and can be used for producing high-value organic sulfur compounds, such as methionine, dimethyl disulfide, methanesulfonic acid and the like. With high sulfur synthesis gas (CO/H) 2 S/H 2 ) Synthesis of CH for raw materials 3 SH can effectively avoid the synthesis of CH by the traditional methanol-hydrogen sulfide method 3 The SH causes resource waste and excessive environmental pollution, and has aroused the interests of vast scholars. With high sulfur synthesis gas (CO/H) 2 S/H 2 ) Synthesis of CH for raw materials 3 The catalyst commonly used for SH is supported on gamma-Al 2 O 3 Or silicon dioxide (SiO) 2 ) MoS on a Carrier 2 A catalyst. Although the catalyst is already in CH 3 The SH synthesis field has received a great deal of attention, however, in CH 3 CO conversion and CH during SH Synthesis 3 The poor SH selectivity has been an unavoidable problem, which leads to CH production by this process 3 SH tends to be less productive and far from productiveThe purpose of industrialized production.
Furthermore, ethanethiol (C) 2 H 5 SH) is also an important chemical intermediate and industrial raw material, and is widely applied to the fields of pesticide and medicine synthesis and the like; can also be used as a molecular weight regulator and a chain transfer agent in the polymerization process of the high molecular polymer; in addition, the ethanethiol has bad smell and can be used as a gas odorizing agent, and can be used as a warning agent to prevent accidents such as fire and explosion caused by leakage. Among the numerous processes for the preparation of ethanethiol, ethylene vulcanization is receiving increasing attention as an atom-economical route. At present, C is prepared by an ethylene vulcanization method 2 H 5 The catalyst commonly used for SH is a cobalt-modified molybdenum oxide-based catalyst. However, the performance of this catalyst is likewise far from being industrially applicable. And CH (CH) 3 SH synthesis is similar, C 2 H 5 The lack of high performance catalyst in SH synthesis process also restricts the efficient synthesis of C by ethylene sulfidation 2 H 5 Important factors for SH.
Disclosure of Invention
The invention provides a core-shell type K x -MoO 3 @SiO 2 The new application of the catalyst, namely the application of the catalyst in the synthesis of methyl mercaptan or ethyl mercaptan, can simultaneously realize the catalytic synthesis of methyl mercaptan and ethyl mercaptan.
The core-shell type K x -MoO 3 @SiO 2 The catalyst was prepared as follows:
1. placing molybdate into ethanol solution of polyvinylpyrrolidone (PVP), stirring, reacting at 150-240 ℃ for 15-24 h, separating solid from liquid, washing and drying the solid to obtain MoO 2 ；
The mass ratio of the molybdate to the polyvinylpyrrolidone is 1:2-5, and the volume concentration of the ethanol solution in the ethanol solution of the polyvinylpyrrolidone is 15-40%;
2. 10-50 mg MoO 2 Placing the mixture in an ethanol solution with the volume concentration of 15-40%, after ultrasonic dispersion, adding 0.2-1 mL of diethanolamine and 0.5-3 of hexadecyl trimethyl ammonium bromide into the dispersion liquid at room temperature under stirringg, then dripping 0.2-1.6 mL of tetraethoxysilane, continuously stirring for 10-30 h, separating solid from liquid, washing and drying the solid, and roasting to obtain the core-shell MoO 3 @SiO 2 A material; core-shell MoO 3 @SiO 2 Adding the material into a potassium precursor solution, uniformly mixing, performing ultrasonic treatment, standing overnight, drying and roasting to obtain the core-shell Kx-MoO 3 @SiO 2 A catalyst;
the molar ratio of K to Mo in one of potassium carbonate, potassium sulfide and potassium sulfate is 0.5-3:1; the roasting temperature is 450-650 ℃ for 2-8 h.
The core-shell type K prepared by the method x -MoO 3 @SiO 2 The catalyst is prepared by using CO and H in the synthesis of methyl mercaptan 2 And H 2 S gas mixture is used as raw material, wherein the concentration of CO is 100000-200000 ppm, H 2 The concentration of (C) is 200000-500000 ppm H 2 S concentration is 200000 ～ 800000ppm, methyl mercaptan is synthesized under 0-0.2 MPa and at 200-550 ℃, and airspeed of reaction gas is 1000-10000 h -1 。
In the synthesis method of ethanethiol, C is adopted 2 H 4 And H 2 S mixture is used as raw material, wherein C 2 H 4 The concentration of H is 100000-400 000ppm 2 S concentration is 300000 ～ 800000ppm, ethanethiol is synthesized under 0-2 MPa and 100-400 ℃, and airspeed of reaction gas is 1000-10000 h -1 。
The method has the advantages and technical effects that:
(1) The invention uses the mesoporous core-shell K doped with potassium x -MoO 3 @SiO 2 The catalyst not only has excellent performance in the field of methyl mercaptan synthesis, but also has obvious effect in the field of ethyl mercaptan synthesis, has good reaction activity and high target product selectivity, and has excellent catalytic performance and universality in the field of low molecular mercaptan synthesis;
(2) The invention discloses a mesoporous core-shell type K x -MoO 3 @SiO 2 The catalyst has simple synthesis method and excellent catalytic performance, and is beneficial to popularization and large-scale application.
Drawings
FIG. 1 is a core-shell K prepared in example 2 x -MoO 3 @SiO 2 Transmission electron microscopy of the catalyst.
Detailed Description
The present invention will be further described in detail by way of examples, but the scope of the invention is not limited to the above description, where the methods are conventional unless otherwise specified, and the reagents are conventional reagents or reagents formulated according to conventional methods;
example 1: moO without potassium doping 3 @SiO 2 Preparation and application of catalyst
1. 150mg of ammonium molybdate is placed in 32mL of ethanol solution of polyvinylpyrrolidone (31% ethanol solution containing 400mg of PVP), after stirring is carried out for 1h, the mixed solution is transferred into a polytetrafluoroethylene reaction kettle to react for 20h at 200 ℃, the mixture is centrifuged, the solid is washed by the mixed solution of ethanol and acetone (volume ratio is 1:1), and MoO is prepared by drying at 100 DEG C 2 The method comprises the steps of carrying out a first treatment on the surface of the 30mg MoO 2 Placing in 53mL of ethanol solution with volume concentration of 37%, ultrasound for 1h, adding diethanolamine 0.2mL and cetyltrimethylammonium bromide 0.73g into the dispersion at room temperature under stirring, then dropwise adding tetraethoxysilane 0.4mL, continuing stirring for 24h, centrifuging, washing the solid with mixed solution of ethanol and acetone, drying at 100deg.C, and calcining at 550deg.C for 6h to obtain MoO 3 @SiO 2 A catalyst;
2. MoO prepared by the method 3 @SiO 2 Grinding and sieving the catalyst to 40-60 meshes, loading 0.4g into a tubular furnace reactor, and introducing CO/H 2 /H 2 S gas mixture (molar concentration of CO in the gas mixture of 100000ppm, H) 2 The molar concentration in the mixed gas was 400 ppm, H 2 S in the mixed gas with a molar concentration of 500000 ppm) at 0.2MPa and 400 ℃ to synthesize CH 3 SH, total space velocity of gas feed of 3000h -1 CO conversion was 30%, CH 3 SH selectivity 7%;
MoO prepared by the method 3 @SiO 2 Grinding and sieving the catalyst to 40-60 meshes, charging 0.4g into a tubular furnace reactor, and introducing C 2 H 4 /H 2 S gas mixture (C) 2 H 4 The molar concentration in the mixed gas was 250000ppm, H 2 Molar concentration of S in the mixed gas of 750000 ppm) at 1.6MPa and 240 ℃ to synthesize C 2 H 5 SH, total space velocity of gas feed of 3000h -1 ，C 2 H 4 Conversion is 42%, C 2 H 5 SH selectivity was 12%.
Example 2: the invention relates to a core-shell type K 2 -MoO 3 @SiO 2 Preparation and application of catalyst
1. 150mg of ammonium molybdate is placed in 32mL of ethanol solution of polyvinylpyrrolidone (31% ethanol solution containing 400mg of PVP), after stirring for 1h, the mixed solution is transferred into a polytetrafluoroethylene reaction kettle to react for 20h at 200 ℃, the mixture is centrifuged, the solid is washed by the mixed solution of ethanol and acetone, and the MoO is prepared by drying at 100 DEG C 2 The method comprises the steps of carrying out a first treatment on the surface of the 30mg MoO 2 Placing in 53mL of ethanol solution with volume concentration of 37%, performing ultrasound for 1h, adding 0.2mL of diethanolamine and 0.73g of cetyltrimethylammonium bromide into the dispersion liquid at room temperature under stirring, then dropwise adding 0.4mL of tetraethoxysilane, continuously stirring for 24h, centrifuging, washing the solid with a mixed solution (1:1) of ethanol and acetone, drying at 100 ℃, and roasting at 550 ℃ for 6h to obtain MoO 3 @SiO 2 A catalyst; core-shell MoO 3 @SiO 2 Adding the material into a potassium carbonate solution, stirring uniformly, performing ultrasonic treatment for 10min, standing overnight, drying at 100deg.C, and calcining at 550deg.C for 6 hr to obtain core-shell type K 2 -MoO 3 @SiO 2 The transmission electron microscope diagram of the catalyst is shown in figure 1.
Meanwhile, a control catalyst is prepared by adopting an impregnation method, specifically, potassium carbonate and ammonium molybdate are dissolved in 8mL of deionized water according to the proportion of K to Mo molar ratio of 2 (wherein MoO on the microsphere) 3 Theoretical loading of (2) and MoO 3 @SiO 2 Middle MoO 3 2g of micro-silicon spheres are added, after full stirring and ultrasonic treatment are carried out for 10min, the mixture is stood overnight, is dried at 100 ℃ and is roasted for 6h at 550 ℃, and a control catalyst is prepared;
2. the core-shell type K prepared in the step 1 is prepared 2 -MoO 3 @SiO 2 Grinding and sieving the catalyst and the reference catalyst respectively to 40-60 meshes, respectively taking 0.4g of the catalyst and the reference catalyst, loading the catalyst and the reference catalyst into a tubular furnace reactor, and introducing CO/H 2 /H 2 S gas mixture (molar concentration of CO in the gas mixture of 100000ppm, H) 2 The molar concentration in the mixed gas was 400 ppm, H 2 S in the mixed gas with a molar concentration of 500000 ppm) at 0.2MPa and 400 ℃ to synthesize CH 3 SH, total space velocity of gas feed of 3000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Core-shell type K 2 -MoO 3 @SiO 2 The conversion of CO by the catalyst is 63%, CH 3 SH selectivity is 79%; control catalyst had a CO conversion of 38%, CH 3 SH selectivity was 52%;
the core-shell type K prepared in the step 1 is prepared 2 -MoO 3 @SiO 2 Grinding and sieving the catalyst and the reference catalyst respectively to 40-60 meshes, respectively taking 0.4g of the catalyst and the reference catalyst, loading the catalyst and the reference catalyst into a tubular furnace reactor, and introducing C 2 H 4 /H 2 S gas mixture (C) 2 H 4 The molar concentration in the mixed gas was 250000ppm, H 2 Molar concentration of S in the mixed gas of 750000 ppm) at 1.6MPa and 240 ℃ to synthesize C 2 H 5 SH, total space velocity of gas feed of 3000h -1 Core-shell type K 2 -MoO 3 @SiO 2 Catalyst pair C 2 H 4 Conversion is 85%, C 2 H 5 SH selectivity was 96%; comparative catalyst pair C 2 H 4 Conversion of 62%, C 2 H 5 SH selectivity was 78%.
Example 3: the invention relates to a core-shell type K 0.5 -MoO 3 @SiO 2 Preparation and application of catalyst
1. Core-shell type K 0.5 -MoO 3 @SiO 2 The catalyst was prepared in the same way as in example 2, step 1, except that the molar ratio of K to Mo was 0.5;
meanwhile, a control catalyst is prepared by adopting an impregnation method, wherein the molar ratio of K to Mo is 0.5, and the method is the same as that of the example 2;
2. core-shell K 0.5 -MoO 3 @SiO 2 Catalyst, control catalyst used in catalytic methyl mercaptan Synthesis, synthesis conditions were the same as in example 2, resultsCore-shell type K 0.5 -MoO 3 @SiO 2 The conversion of CO by the catalyst is 41%, CH 3 SH selectivity was 25%; control catalyst had a CO conversion of 27%, CH 3 SH selectivity was 15%;
core-shell K 0.5 -MoO 3 @SiO 2 The catalyst and the control catalyst are applied to the synthesis of the catalytic ethanethiol, and the synthesis conditions are the same as those in example 2, so as to obtain the core-shell type K 0.5 -MoO 3 @SiO 2 Catalyst pair C 2 H 4 Conversion is 52%, C 2 H 5 SH selectivity was 31%; comparative catalyst pair C 2 H 4 Conversion of 33%, C 2 H 5 SH selectivity was 16%.
Example 4: the invention relates to a core-shell type K 1 -MoO 3 @SiO 2 Preparation and application of catalyst
1. Core-shell type K 1 -MoO 3 @SiO 2 The catalyst was prepared in the same way as in example 2, step 1, except that the molar ratio of K to Mo was 1;
meanwhile, a control catalyst is prepared by adopting an impregnation method, wherein the molar ratio of K to Mo is 1, and the method is the same as that of example 2;
2. core-shell K 1 -MoO 3 @SiO 2 The catalyst and the control catalyst are applied to the synthesis of the catalytic methyl mercaptan, and the synthesis conditions are the same as those of the example 2, so that the core-shell type K is obtained 1 -MoO 3 @SiO 2 The conversion of CO by the catalyst is 54%, CH 3 SH selectivity was 56%; control catalyst had a CO conversion of 33%, CH 3 SH selectivity was 38%;
core-shell K 1 -MoO 3 @SiO 2 The catalyst and the control catalyst are applied to the synthesis of the catalytic ethanethiol, and the synthesis conditions are the same as those in example 2, so as to obtain the core-shell type K 1 -MoO 3 @SiO 2 Catalyst pair C 2 H 4 Conversion was 68%, C 2 H 5 SH selectivity was 59%; comparative catalyst pair C 2 H 4 Conversion of 49%, C 2 H 5 SH selectivity was 53%.
Example 5: the invention relates to a core-shell type K 3 -MoO 3 @SiO 2 Preparation and application of catalyst
1. Core-shell type K 3 -MoO 3 @SiO 2 The catalyst was prepared in the same way as in example 2, step 1, except that the molar ratio of K to Mo was 3;
meanwhile, a control catalyst is prepared by adopting an impregnation method, wherein the molar ratio of K to Mo is 1, and the method is the same as that of example 3;
2. core-shell K 3 -MoO 3 @SiO 2 The catalyst and the control catalyst are applied to the synthesis of the catalytic methyl mercaptan, and the synthesis conditions are the same as those of the example 2, so that the core-shell type K is obtained 3 -MoO 3 @SiO 2 The conversion of CO by the catalyst is 57%, CH 3 SH selectivity was 61%; control catalyst had a CO conversion of 35%, CH 3 SH selectivity was 45%;
core-shell K 3 -MoO 3 @SiO 2 The catalyst and the control catalyst are applied to the synthesis of the catalytic ethanethiol, and the synthesis conditions are the same as those in example 2, so as to obtain the core-shell type K 3 -MoO 3 @SiO 2 Catalyst pair C 2 H 4 Conversion of 72%, C 2 H 5 SH selectivity was 70%; comparative catalyst pair C 2 H 4 Conversion was 58%, C 2 H 5 SH selectivity was 66%.
Example 6: the invention relates to a core-shell type K 2 -MoO 3 @0.5SiO 2 Preparation and application of catalyst
1. 150mg of ammonium molybdate is placed in 32mL of ethanol solution of polyvinylpyrrolidone (31% ethanol solution containing 400mg of PVP), after stirring for 1h, the mixed solution is transferred into a polytetrafluoroethylene reaction kettle to react for 20h at 200 ℃, the mixture is centrifuged, the solid is washed by the mixed solution of ethanol and acetone, and the MoO is prepared by drying at 100 DEG C 2 The method comprises the steps of carrying out a first treatment on the surface of the 30mg MoO 2 Placing in 53mL of ethanol solution with volume concentration of 37%, ultrasound for 1h, adding diethanolamine 0.2mL and cetyltrimethylammonium bromide 0.73g into the dispersion at room temperature under stirring, then dropwise adding tetraethoxysilane 0.2mL, continuing stirring for 24h, centrifuging, washing the solid with mixed solution of ethanol and acetone, drying at 100deg.C, and calcining at 550deg.C for 6h to obtain MoO 3 @0.5SiO 2 Catalytic reactionAn agent; core-shell MoO 3 @0.5SiO 2 Adding the material into a potassium carbonate solution, stirring uniformly, performing ultrasonic treatment for 10min, standing overnight, drying at 100deg.C, and calcining at 550deg.C for 6 hr to obtain core-shell type K 2 -MoO 3 @0.5SiO 2 A catalyst.
2. The core-shell type K prepared in the step 1 is prepared 2 -MoO 3 @SiO 2 Grinding and sieving the catalyst and the reference catalyst respectively to 40-60 meshes, respectively taking 0.4g of the catalyst and the reference catalyst, loading the catalyst and the reference catalyst into a tubular furnace reactor, and introducing CO/H 2 /H 2 S gas mixture (molar concentration of CO in the gas mixture of 100000ppm, H) 2 The molar concentration in the mixed gas was 400 ppm, H 2 S in the mixed gas with a molar concentration of 500000 ppm) at 0.2MPa and 400 ℃ to synthesize CH 3 SH, total space velocity of gas feed of 3000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Core-shell type K 2 -MoO 3 @SiO 2 The conversion of catalyst to CO is 66%, CH 3 SH selectivity was 83%;
the core-shell type K prepared in the step 1 is prepared 2 -MoO 3 @SiO 2 Grinding and sieving the catalyst and the reference catalyst respectively to 40-60 meshes, respectively taking 0.4g of the catalyst and the reference catalyst, loading the catalyst and the reference catalyst into a tubular furnace reactor, and introducing C 2 H 4 /H 2 S gas mixture (C) 2 H 4 The molar concentration in the mixed gas was 250000ppm, H 2 Molar concentration of S in the mixed gas of 750000 ppm) at 1.6MPa and 240 ℃ to synthesize C 2 H 5 SH, total space velocity of gas feed of 3000h -1 Core-shell type K 2 -MoO 3 @SiO 2 Catalyst pair C 2 H 4 Conversion of 87%, C 2 H 5 SH selectivity was 97%.
Claims (5)
1. Core-shell type K x -MoO 3 @SiO 2 The catalyst is applied to the synthesis of methyl mercaptan or ethyl mercaptan;
the core-shell type K x -MoO 3 @SiO 2 The catalyst is prepared by placing molybdate into ethanol solution of polyvinylpyrrolidone, stirring and mixing uniformly, reacting for 15-24 h at 150-240 ℃, separating solid from liquid, washing solidDrying to obtain MoO 2 The method comprises the steps of carrying out a first treatment on the surface of the 10-50 mg MoO 2 Placing the mixture in an ethanol solution with the volume concentration of 15-40%, performing ultrasonic dispersion, adding 0.2-1 mL of diethanolamine and 0.5-3 g of cetyltrimethylammonium bromide into the dispersion liquid at room temperature under stirring, then dropwise adding 0.2-1.6 mL of tetraethoxysilane, continuously stirring for 10-30 h, performing solid-liquid separation, washing and drying the solid, and roasting to obtain the core-shell MoO 3 @SiO 2 A material; core-shell MoO 3 @SiO 2 Adding the material into the potassium precursor solution, uniformly mixing, performing ultrasonic treatment, standing overnight, drying and roasting to obtain the product.
2. The use according to claim 1, characterized in that: the mass ratio of the molybdate to the polyvinylpyrrolidone is 1:2-5, and the volume concentration of the ethanol solution in the ethanol solution of the polyvinylpyrrolidone is 15-40%.
3. The use according to claim 1, characterized in that: the potassium precursor is one of potassium carbonate, potassium sulfide and potassium sulfate.
4. The use according to claim 1, characterized in that: the roasting temperature is 450-650 ℃ for 2-8 h.
5. The use according to claim 1, characterized in that: the molar ratio of K to Mo is 0.5-3:1.
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