CN103657635A - Catalyst for preparing methyl mercaptan from carbon disulfide and methanol and preparation method thereof - Google Patents
Catalyst for preparing methyl mercaptan from carbon disulfide and methanol and preparation method thereof Download PDFInfo
- Publication number
- CN103657635A CN103657635A CN201410004410.3A CN201410004410A CN103657635A CN 103657635 A CN103657635 A CN 103657635A CN 201410004410 A CN201410004410 A CN 201410004410A CN 103657635 A CN103657635 A CN 103657635A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methyl mercaptan
- carbon disulfide
- alkali metal
- preparation
- 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 132
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- -1 alkali metal molybdate compound Chemical class 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 25
- 239000011609 ammonium molybdate Substances 0.000 claims description 25
- 229940010552 ammonium molybdate Drugs 0.000 claims description 25
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 18
- YVCPOVMXSJIFAF-UHFFFAOYSA-N methanethiol;methanol Chemical compound OC.SC YVCPOVMXSJIFAF-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007605 air drying Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005518 chemical engineering design Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing methyl mercaptan from carbon disulfide and methanol and a preparation method thereof and relates to a catalyst for synthesizing the methyl mercaptan. The catalyst for preparing the methyl mercaptan from the carbon disulfide and the methanol is a K2O-MoO3/gamma-Al2O3 catalyst, wherein a mass ratio of K2O to MoO3 to gamma-Al2O3 is (10 to 30):(10 to 70):100. The preparation method comprises the following steps of: preparing an alkali metal molybdate compound; adding the prepared alkali metal molybdate compound into metered deionized water, then adding metered organic acid, regulating a pH value into the range of 6 to 10 by ammonia water, and aging to obtain impregnation liquid; adding gamma-Al2O3 into the impregnation liquid, filtering after impregnation, and removing the impregnation liquid to obtain a methyl mercaptan catalyst precursor; air-drying the methyl mercaptan catalyst precursor, and roasting after drying to obtain the catalyst for preparing the methyl mercaptan from the carbon disulfide and the methanol. The preparation method is simple, does not require special equipment and is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of catalyst of synthesis of methyl mercaptan, especially relate to the Catalysts and its preparation method of a kind of carbon disulfide and Methanol methyl mercaptan.
Background technology
Methyl mercaptan (CH
3sH) be a kind of important organic synthesis intermediate, at aspects such as synthetic material, feed, agricultural chemicals and medicine, have a wide range of applications.Particularly, over nearly 20 years, the demand that the methyl mercaptan of take is the synthetic methionine of raw material grows with each passing day, and has greatly stimulated the production development of methyl mercaptan industry.
The method of current industrial production methyl mercaptan is mainly with hydrogen sulfide and methyl alcohol synthesis of methyl mercaptan, the catalyst of the method synthesis of methyl mercaptan mainly comprises the activated alumina system of alkali carbonate or alkali tungstates, reaction synthesis of methyl mercaptan, normally at 300～500 ℃, carries out under the condition of 0.19～1.4MPa.For example, US Patent No.-PS2820062 is disclosed a kind ofly take gama-alumina as carrier, the catalyst that the potassium tungstate of take is auxiliary agent; And the publication number disclosed catalyst of Chinese patent that is CN1178136A.
Another technology path of synthesis of methyl mercaptan is by carbon disulfide and methyl alcohol reaction synthesis of methyl mercaptan, but the report of relevant this technology path is less.
As far back as 1962, the clear 37-15608 of patent that Japan Sanko Co., Ltd. delivers, adopt carbon disulfide to react with the mixture of methyl alcohol or methyl ether or methyl alcohol and methyl ether, take activated alumina or be loaded with cadmium or the aluminium oxide of thorium is produced methyl sulfide and methyl mercaptan as catalyst, and add water to improve yield in reaction system, the product obtaining after reaction is mainly methyl sulfide, and reaction temperature is generally wanted more than 400 ℃.
Within 1972, this method has further been studied by Tso Tat Co., Ltd., Japan, deliver the clear 47-41327 of patent, add active oxidation aluminium powder carry out mixing and make catalyst the aqueous solution of alkali metal salt that has dissolved the 6th subgroup element (molybdenum, tungsten), the mol ratio of reactant carbon disulfide and methyl alcohol is 1: (2.6～3), 300～350 ℃ of reaction temperatures, load as (0.17～0.30) gCS
2/ (ml
catalysth), after reaction, the conversion ratio of methyl alcohol is the highest also only has 75%.
Nineteen eighty-two, Shenyang China Chemical Engineering Design research institute was studied the method for carbon disulfide and methyl alcohol synthesis of methyl mercaptan, and it is carrier that the people such as Lu Chuande select gama-alumina, and load regulation six subgroup elements, make methyl mercaptan selectively and yield reaches 60%.And over nearly more than 20 years, about the catalyst research of carbon disulfide and methyl alcohol synthesis of methyl mercaptan is very few, do not find the report of pertinent literature.
And the raw material hydrogen sulfide of industrial synthesis of methyl mercaptan is mainly to make by natural gas and sulfur burning reaction, CH
4+ 4S → 2H
2s+CS
2, this byproduct of reaction is CS
2account for 50%, at present CS
2the market demand is few, hoards surplus, and price is low again.Employing for methyl mercaptan, can make up the defect by hydrogen sulfide-methyl alcohol legal system methyl mercaptan by carbon disulfide-methyl alcohol legal system.From considering economically to there are three industrial wastes by carbon disulfide-methyl alcohol legal system for methyl mercaptan few, take up an area the advantages such as little, small investment, and Chinese carbon disulfide aboundresources is easy to get, and accumulating is relatively easy.For the place that lacks natural gas, develop feed addictive, by carbon disulfide-methyl alcohol legal system, for the method for methyl mercaptan, there is promotional value.Thereby, be badly in need of a kind of catalyst by carbon disulfide and methyl alcohol reaction synthesis of methyl mercaptan of exploitation.
Summary of the invention
The object of the present invention is to provide the Catalysts and its preparation method of a kind of carbon disulfide and Methanol methyl mercaptan.
The catalyst of carbon disulfide of the present invention and Methanol methyl mercaptan is K
2o-MoO
3/ γ-Al
2o
3catalyst, wherein K
2o: MoO
3: γ-Al
2o
3mass ratio be (10～30): (10～70): 100; Preferred K
2o: MoO
3: γ-Al
2o
3mass ratio be (20～30): (15～40): 100.
The preparation method of the catalyst of carbon disulfide of the present invention and Methanol methyl mercaptan, comprises the following steps:
1) prepare alkali metal molybdate compound;
2) the alkali metal molybdate compound of being prepared by step 1) is added in the deionized water of metering, then adds the organic acid of metering, then regulates pH value to 6～10 with ammoniacal liquor, aging, obtains maceration extract;
3) in step 2) add gama-alumina in the maceration extract of gained, after dipping, filter, remove maceration extract, obtain methyl mercaptan catalyst precursor;
4) step 3) gained methyl mercaptan catalyst precursor is dried, after oven dry, calcine, obtain the catalyst of carbon disulfide and Methanol methyl mercaptan.
In step 1), described alkali metal can adopt potassium etc., and described alkali metal molybdate compound can be selected from KOH-(NH
4)
6mo
7o
244H
2o etc.; The described concrete grammar of preparing alkali metal molybdate compound can be: by the ammonium molybdate { (NH of metering
4)
6mo
7o
244H
2o} is dissolved in the deionized water of metering, obtains ammonium molybdate aqueous solution A; Take the described alkali metal hydroxide of metering and be dissolved in the deionized water of metering, making alkali metal hydroxide aqueous solution B, described alkali metal hydroxide can adopt potassium hydroxide etc.; The temperature of controlling ammonium molybdate aqueous solution A is preferably 90 ℃, and alkali metal hydroxide aqueous solution B is joined in ammonium molybdate aqueous solution A, stirs, and makes solution evaporation, crystallization, and then suction filtration, dries filter cake, obtains alkali metal molybdate compound; Described oven dry can be dried 5h at 95 ℃.
In step 2) in, described organic acid can be selected from a kind of in citric acid, oxalic acid, Pidolidone etc.; The described aging time can be 0.5～1h.
In step 3), the time of described dipping can be 8～14h;
In step 2) and 3) in, described alkali metal molybdate compound: organic acid: gama-alumina: the mass ratio of deionized water can be (20～85): (5～12): 100: 160.
In step 4), the condition of described oven dry can be dried 4～6h under 80～120 ℃ of conditions; The condition of described calcining can be placed in Muffle furnace in 200～450 ℃ of calcining 3～5h.
The activity rating of described methyl mercaptan catalyst carries out in fixed bed flowing reactive system, and reaction tube specification is φ 10mm * 56mm, and catalyst is positioned at stove temperature controlling point place, and loadings is 2mL, and particle diameter is 30～60 orders; Controlling reaction temperature is 330 ℃; The mol ratio of reactant feed methyl alcohol and carbon disulfide is 2.2; Reactant feed air speed is 1000h
-1; Reaction pressure is 0.3MPa.
Unstripped gas and product are comprised of gas-chromatography on-line analysis.Chromatogram adopts Shanghai China to like the full-automatic chromatograph of GC9560, chromatographic column: Porapak Q; Column length: 2m; Caliber: Ф 3 * 0.5mm.
The invention provides and there is greater activity and methyl mercaptan catalyst optionally, and the preparation method and application of this methyl mercaptan catalyst, make the methyl mercaptan catalyst making can be used in catalysis carbon disulfide and methyl alcohol reaction synthesis of methyl mercaptan, for industrial synthesis of methyl mercaptan provides a simple and practical novel synthetic.
The invention has the advantages that:
Because the raw material hydrogen sulfide of industrial synthesis of methyl mercaptan is mainly by natural gas (CH
4) and sulphur (S) combustion reaction make, when making hydrogen sulfide, also obtained a large amount of accessory substance carbon disulfide (CS
2), and carbon disulfide intractability is large; The catalyst the present invention relates to not only can be realized carbon disulfide is turned waste into wealth, and reduction is because processing the spent a large amount of manpower and materials of carbon disulfide, and simultaneously also for methyl mercaptan synthetic provides new technique.And in the situation that the yield of methyl mercaptan reaches suitable with it, load of the present invention can reach 1.01g CS
2/ (ml
catalysth), be more than 3 times of the clear 47-41327 load of Japan Patent.
Methyl mercaptan catalyst disclosed by the invention can efficient catalytic carbon disulfide and methyl alcohol reaction synthesis of methyl mercaptan, and its preparation method is simple, does not need special installation, is convenient to suitability for industrialized production, is with a wide range of applications.
The specific embodiment
Embodiment 1: 2.23g ammonium molybdate is dissolved in 20ml deionized water, obtains ammonium molybdate aqueous solution A; Take 1.50g potassium hydroxide and be dissolved in 10ml deionized water, obtaining potassium hydroxide aqueous solution B; The temperature of controlling ammonium molybdate aqueous solution A is 90 ℃, potassium hydroxide aqueous solution B is slowly joined in ammonium molybdate aqueous solution A, and constantly stirring makes solution evaporation, crystallization; Then suction filtration, is placed in baking oven by filter cake and dries 5h at 95 ℃; Then gained solid is joined in 16ml distilled water and make its dissolving under constantly stirring, after dissolving, add wherein 1g citric acid, after stirring 5min, with ammoniacal liquor, regulate pH value to 8～10, standing aged at room temperature 0.5h, then take the spherical gama-alumina of 10g and flood wherein 14h, filter and remove maceration extract, obtain methyl mercaptan catalyst precursor; Gained methyl mercaptan catalyst precursor is dried, under 120 ℃ of conditions, dry after 4h, then be placed in Muffle furnace in 400 ℃ of calcining 3h, obtain methyl mercaptan catalyst.K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 12.6: 20.2: 100, be designated as 1. MoO
3-K
2o/Al
2o
3.
The activity rating of gained methyl mercaptan catalyst carries out in fixed bed flowing reactive system, and reaction tube specification is φ 10mm * 56mm, and catalyst is positioned at stove temperature controlling point place, and loadings is 2mL, and particle diameter is 30～60 orders; Reaction temperature is 330 ℃; The mol ratio of reactant feed methyl alcohol and carbon disulfide is 2.2; Reactant feed air speed is 1000h
-1; Reaction pressure is 0.3MPa.Unstripped gas and product are comprised of gas-chromatography on-line analysis.Chromatogram adopts Shanghai China to like the full-automatic chromatograph of GC9560, chromatographic column: Porapak Q; Column length: 2m; Caliber: Ф 3 * 0.5mm.Activity rating the results are shown in Table 1.
Embodiment 2: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 2.97g and 2g, and all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 16.8: 26.9: 100, be designated as 2. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Embodiment 3: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 3.71g and 2.50g, and all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 21: 33.6: 100, be designated as 3. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Embodiment 4: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 4.45g and 2.82g, and all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 23.7: 40.3: 100, be designated as 4. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Embodiment 5: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 4.45g and 2.82g, and 1.0g citric acid makes 0.5g oxalic acid into, and all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 23.7: 40.3: 100, be designated as 5. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Embodiment 6: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 4.45g and 2.82g, and 1.0g citric acid makes 1.2gL-glutamic acid into, and all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 23.7: 40.3: 100, be designated as 6. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Comparative example 1: the consumption of the ammonium molybdate in embodiment 1 and potassium hydroxide is made respectively into 4.45g and 3.47g, but do not add organic acid in preparation process, all the other steps are with embodiment 1, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 23.7: 40.3: 100, be designated as 7. MoO
3-K
2o/Al
2o
3, activity rating the results are shown in Table 1.
Comparative example 2: 3.0g potassium molybdate (Chemical Reagent Co., Ltd., Sinopharm Group) is joined in 16ml distilled water and make its dissolving under constantly stirring, after dissolving, add wherein 1.0g citric acid, after stirring 5min, with ammoniacal liquor, regulate pH value to 8～10, standing aged at room temperature 0.5h, then take the spherical gama-alumina of 10.0g and flood wherein 14h, filter and remove maceration extract, obtain methyl mercaptan catalyst precursor; Gained methyl mercaptan catalyst precursor is dried, under 120 ℃ of conditions, dry after 4h, then be placed in Muffle furnace in 400 ℃ of calcining 3h, obtain methyl mercaptan catalyst.Potassium molybdate in gained methyl mercaptan catalyst: the mass ratio of gama-alumina is 30: 100, is designated as K
2moO
4/ Al
2o
3, activity rating condition is with embodiment 1, and activity rating the results are shown in Table 1.
The catalyst activity evaluation result of table 1 embodiment 1～6 and comparative example 1,2
Activity rating condition: T=330 ℃, P=0.3MPa, CH
3oH/CS
2=2.2, GHSV=1000h
-1,
Loaded catalyst: 2ml, 30～60 orders.
Embodiment 7: 7.20g ammonium molybdate is dissolved in 20ml deionized water, obtains ammonium molybdate aqueous solution A; Take 1.20g potassium hydroxide and be dissolved in 10ml deionized water, obtaining potassium hydroxide aqueous solution B; The temperature of controlling solution A is 90 ℃, B liquid is slowly joined in A liquid, and constantly stirring makes solution evaporation, crystallization; Then suction filtration, is placed in baking oven by filter cake and dries 5h at 95 ℃; Then gained solid is joined in 16ml distilled water and make its dissolving under constantly stirring, after dissolving, add wherein 1.0g citric acid, after stirring 5min, with ammoniacal liquor, regulate pH value to 8～10, standing aged at room temperature 0.5h, then take the spherical gama-alumina of 10.0g and flood wherein 14h, filter and remove maceration extract, obtain methyl mercaptan catalyst precursor; Gained methyl mercaptan catalyst precursor is dried, under 120 ℃ of conditions, dry after 4h, then be placed in Muffle furnace in 400 ℃ of calcining 3h, obtain methyl mercaptan catalyst.K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 10.1: 63.0: 100, the mol ratio of K/Mo is 1/2, is designated as KMo
2/ Al
2o
3.
The activity rating of gained methyl mercaptan catalyst carries out in fixed bed flowing reactive system, and reaction tube specification is φ 10mm * 56mm, and catalyst is positioned at stove temperature controlling point place, and loadings is 2mL, and particle diameter is 30～60 orders; Reaction temperature is 330 ℃; The mol ratio of reactant feed methyl alcohol and carbon disulfide is 2.2; Reactant feed air speed is 1000h
-1; Reaction pressure is 0.3MPa.Unstripped gas and product are comprised of gas-chromatography on-line analysis.Chromatogram adopts Shanghai China to like the full-automatic chromatograph of GC9560, chromatographic column: Porapak Q; Column length: 2m; Caliber: Ф 3 * 0.5mm.Activity rating the results are shown in Table 2.
Embodiment 8: the consumption of the ammonium molybdate in embodiment 7 and potassium hydroxide is made respectively into 5.56g and 1.76g, and all the other steps are with embodiment 7, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 14.8: 50.4: 100; The mol ratio of K/Mo is 1/1, is designated as KMo/Al
2o
3, activity rating the results are shown in Table 2.
Embodiment 9: the consumption of the ammonium molybdate in embodiment 7 and potassium hydroxide is made respectively into 3.71g and 2.35g, and all the other steps are with embodiment 5, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 19.8: 33.6: 100; The mol ratio of K/Mo is 2/1, is designated as K
2mo/Al
2o
3, activity rating the results are shown in Table 2.
Embodiment 10: the consumption of the ammonium molybdate in embodiment 7 and potassium hydroxide is made respectively into 2.23g and 2.82g, and all the other steps are with embodiment 5, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 23.7: 20.2: 100; The mol ratio of K/Mo is 4/1, is designated as K
4mo/Al
2o
3, activity rating the results are shown in Table 2.
Embodiment 11: the consumption of the ammonium molybdate in embodiment 7 and potassium hydroxide is made respectively into 1.24g and 3.14g, and all the other steps are with embodiment 5, K in gained methyl mercaptan catalyst
2o: MoO
3: γ-Al
2o
3mass ratio be 26.4: 11.3: 100; The mol ratio of K/Mo is 8/1, is designated as K
8mo/Al
2o
3, activity rating the results are shown in Table 2.
Comparative example 3: take 3.53g potassium hydroxide, join in 16ml distilled water and make its dissolving under constantly stirring, after dissolving, add wherein 1.0g citric acid, after stirring 5min, with ammoniacal liquor, regulate pH value to 8～10, standing aged at room temperature 0.5h, then take the spherical gama-alumina of 10.0g and flood wherein 14h, filter and remove maceration extract, obtain catalyst precursor; Gained catalyst precursor is dried, under 120 ℃ of conditions, dry after 4h, then be placed in Muffle furnace in 400 ℃ of calcining 3h, obtain catalyst, be designated as K/Al
2o
3, activity rating condition is with embodiment 7, and activity rating the results are shown in Table 2.
Comparative example 4: the 3.53g potassium hydroxide in comparative example 3 is made into 11.12g ammonium molybdate, and all the other steps, with comparative example 3, are designated as Mo/Al
2o
3, activity rating the results are shown in Table 2.
The catalyst activity evaluation result of table 2 embodiment 7～11 and comparative example 3,4
Activity rating condition: T=330 ℃, P=0.3MPa, CH
3oH/CS
2=2.2, GHSV=1000h
-1,
Loaded catalyst: 2ml, 30～60 orders.
Claims (10)
1. the catalyst of carbon disulfide and Methanol methyl mercaptan, is characterized in that for K
2o-MoO
3/ γ-Al
2o
3catalyst, wherein K
2o: MoO
3: γ-Al
2o
3mass ratio be (10～30): (10～70): 100.
2. the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 1, is characterized in that K
2o: MoO
3: γ-Al
2o
3mass ratio be (20～30): (15～40): 100.
3. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 1, is characterized in that comprising the following steps:
1) prepare alkali metal molybdate compound;
2) the alkali metal molybdate compound of being prepared by step 1) is added in the deionized water of metering, then adds the organic acid of metering, then regulates pH value to 6～10 with ammoniacal liquor, aging, obtains maceration extract;
3) in step 2) add gama-alumina in the maceration extract of gained, after dipping, filter, remove maceration extract, obtain methyl mercaptan catalyst precursor;
4) step 3) gained methyl mercaptan catalyst precursor is dried, after oven dry, calcine, obtain the catalyst of carbon disulfide and Methanol methyl mercaptan.
4. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, is characterized in that in step 1), and described alkali metal adopts potassium, and described alkali metal molybdate compound can be selected from KOH-(NH
4)
6mo
7o
244H
2o.
5. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, is characterized in that in step 1), and the described concrete grammar of preparing alkali metal molybdate compound is: by the ammonium molybdate { (NH of metering
4)
6mo
7o
244H
2o} is dissolved in the deionized water of metering, obtains ammonium molybdate aqueous solution A; Take the described alkali metal hydroxide of metering and be dissolved in the deionized water of metering, making alkali metal hydroxide aqueous solution B, described alkali metal hydroxide adopts potassium hydroxide; The temperature of controlling ammonium molybdate aqueous solution A is preferably 90 ℃, and alkali metal hydroxide aqueous solution B is joined in ammonium molybdate aqueous solution A, stirs, and makes solution evaporation, crystallization, and then suction filtration, dries filter cake, obtains alkali metal molybdate compound.
6. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 5, is characterized in that described oven dry is to dry 5h at 95 ℃.
7. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, is characterized in that in step 2) in, described organic acid is selected from a kind of in citric acid, oxalic acid, Pidolidone; The described aging time can be 0.5～1h.
8. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, is characterized in that in step 3), and the time of described dipping is 8～14h.
9. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, it is characterized in that in step 2) and 3) in, described alkali metal molybdate compound: organic acid: gama-alumina: the mass ratio of deionized water is (20～85): (5～12): 100: 160.
10. the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan as claimed in claim 3, is characterized in that in step 4), and the condition of described oven dry is dried 4～6h under 80～120 ℃ of conditions; The condition of described calcining can be placed in Muffle furnace in 200～450 ℃ of calcining 3～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410004410.3A CN103657635B (en) | 2014-01-04 | 2014-01-04 | The Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410004410.3A CN103657635B (en) | 2014-01-04 | 2014-01-04 | The Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103657635A true CN103657635A (en) | 2014-03-26 |
| CN103657635B CN103657635B (en) | 2015-11-11 |
Family
ID=50297120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410004410.3A Expired - Fee Related CN103657635B (en) | 2014-01-04 | 2014-01-04 | The Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103657635B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226299A (en) * | 2014-09-05 | 2014-12-24 | 厦门大学 | Catalyst for synthesis of methyl mercaptan by carbon disulphide and hydrogen and preparation method of catalyst |
| CN112657486A (en) * | 2020-12-13 | 2021-04-16 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing methane chloride from methanol by gas phase method |
| CN113083334A (en) * | 2021-02-24 | 2021-07-09 | 山西铁峰化工有限公司 | Catalyst for synthesizing methyl mercaptan, preparation method and application thereof |
| CN113398918A (en) * | 2021-07-07 | 2021-09-17 | 武汉纺织大学 | Catalyst for synthesizing methyl mercaptan and preparation and application methods thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658208A (en) * | 2012-04-28 | 2012-09-12 | 重庆紫光天化蛋氨酸有限责任公司 | Methyl mercaptan catalyst, and preparation method and application thereof |
-
2014
- 2014-01-04 CN CN201410004410.3A patent/CN103657635B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658208A (en) * | 2012-04-28 | 2012-09-12 | 重庆紫光天化蛋氨酸有限责任公司 | Methyl mercaptan catalyst, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 卞国柱等: "K-MoO3/γ-Al2O3催化剂表面物种状态、组成和性能", 《物理化学学报》, vol. 9, no. 5, 28 October 1993 (1993-10-28), pages 650 - 656 * |
| 陆传德: "甲硫醇合成的研究", 《沈阳化工》, no. 01, 2 March 1982 (1982-03-02), pages 1 - 9 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226299A (en) * | 2014-09-05 | 2014-12-24 | 厦门大学 | Catalyst for synthesis of methyl mercaptan by carbon disulphide and hydrogen and preparation method of catalyst |
| CN112657486A (en) * | 2020-12-13 | 2021-04-16 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing methane chloride from methanol by gas phase method |
| CN113083334A (en) * | 2021-02-24 | 2021-07-09 | 山西铁峰化工有限公司 | Catalyst for synthesizing methyl mercaptan, preparation method and application thereof |
| CN113398918A (en) * | 2021-07-07 | 2021-09-17 | 武汉纺织大学 | Catalyst for synthesizing methyl mercaptan and preparation and application methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103657635B (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103657635B (en) | The Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan | |
| CN107626291B (en) | Application of supported catalyst in trifluoromethane cracking | |
| CN102066001B (en) | Catalyst for producing acrolein and acrylic acid through glycerin dehydration and production method of same | |
| CN102764645B (en) | SCR (selective catalytic reduction) nitrogen oxide catalyst, and preparation method and application thereof | |
| CN108203365B (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| CN101422735B (en) | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof | |
| CN105013509A (en) | Catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and preparation method and application method thereof | |
| CN101579639B (en) | Catalyst for synthesizing fatty nitrile, preparation method and applications | |
| CN102658208A (en) | Methyl mercaptan catalyst, and preparation method and application thereof | |
| CN105435799A (en) | Catalyst for ethanol preparation by ethyl acetate hydrogenation and preparation method for catalyst | |
| CN104190401A (en) | Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst | |
| CN102658183B (en) | Catalyst for catalyzing dimethyl sulfide and hydrogen sulfide to synthesize methyl mercaptan, and preparation method and application thereof | |
| CN104226299A (en) | Catalyst for synthesis of methyl mercaptan by carbon disulphide and hydrogen and preparation method of catalyst | |
| CN103920501B (en) | By the Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan | |
| CN109806881A (en) | A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol | |
| CN101602004B (en) | Method for preparing styrene catalyst by ethylbenzene dehydrogenation | |
| CN103804224B (en) | Method for preparing nitrile compounds via catalyzing to ammoniate glycerinum | |
| CN103691440A (en) | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof | |
| CN109422638B (en) | Method for preparing ketone compound by ABE fermentation liquor conversion | |
| CN104311404A (en) | Method for producing cinnamyl aldehyde | |
| CN112898142B (en) | Method for preparing 2-pentanone | |
| JP2018034090A (en) | HYDROGENATION CATALYST FOR γ-VALEROLACTONE, AND METHOD FOR PRODUCING 1,4-PENTANEDIOL FROM γ-VALEROLACTONE USING THE CATALYST | |
| CN103877965B (en) | A kind of preparation and application of tin dioxide solid super basic catalyst | |
| CN104998669A (en) | Preparation method of sulfur-tolerant methanation catalyst | |
| CN103880787A (en) | Method for preparing gamma-butyrrolactone and acetone through coupling reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151111 |