CN102247833B - Catalyst used in synthesis of methyl mercaptan and preparation method of catalyst - Google Patents
Catalyst used in synthesis of methyl mercaptan and preparation method of catalyst Download PDFInfo
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- CN102247833B CN102247833B CN 201110222337 CN201110222337A CN102247833B CN 102247833 B CN102247833 B CN 102247833B CN 201110222337 CN201110222337 CN 201110222337 CN 201110222337 A CN201110222337 A CN 201110222337A CN 102247833 B CN102247833 B CN 102247833B
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Abstract
The invention discloses a catalyst used in the synthesis of methyl mercaptan and a preparation method of the catalyst, relates to the catalyst, and provides the catalyst with high specific surface area and low-temperature activity used in the synthesis of the methyl mercaptan and the preparation method of the catalyst. The catalyst comprises active gamma-Al2O3 serving as an active ingredient and alkali metal tungstate serving as an auxiliary agent in a mass ratio of 1:(0.05-0.40). The preparation method comprises the following steps of: dissolving the metric aluminum salt in water to prepare aluminum salt solution, heating, adding ammonia water, and controlling the pH value at a finishing point to be between 6 and 8 to obtain mixed solution; ageing the mixed solution, adding tungstate precursor solution to obtain sol, and standing; and drying the stood sol to constant weight, calcining, tabletting, and forming to obtain the catalyst used in the synthesis of the methyl mercaptan. Compared with a catalyst prepared by the conventional impregnation loading method, the obtained finished catalyst product used in the synthesis of the methyl mercaptan has the characteristics of high specific surface area and activity, low reaction temperature and the like.
Description
Technical field
The present invention relates to a kind of catalyst, especially reacted the Catalysts and its preparation method of synthesis of methyl mercaptan by methyl alcohol and hydrogen sulfide.
Background technology
Methyl mercaptan is mainly used in synthetic material, agricultural chemicals, medicine etc. as a kind of important organic synthesis intermediate.Such as methionine, Entex, dimethrin, Kayaphos, prometryn etc. is also for the production of intermediates such as methane sulfonyl chloride, methyl mercapto propyl alcohol.In particular for synthetic methionine, along with development and the emergence of feed additive industry, the methionine demand constantly increased in recent years, had also stimulated the production development of methyl mercaptan.The production method of present industrial methyl mercaptan is to adopt hydrogen sulfide and methyl alcohol at 300～500 ℃, carries out under the pressure of 0.19～1.4MPa.The catalyst of synthesis of methyl mercaptan mainly is the activated alumina system that comprises alkali carbonate or tungstates.(the React.Kinet.Catal.Lett. such as Mashkina, 1987,407-412,) report, the acid site of methyl mercaptan catalyst surface shows higher activity, the major effect catalyst is to the conversion ratio of methyl alcohol, the highly basic center to the activity of catalyst a little less than, but selectively playing an important role to methyl mercaptan.The preparation method of the disclosed alumina support dipping of Chinese patent CN 1141915A sodium carbonate, potash or cesium carbonate thinks that the catalyst of dipping potash has better activity; The disclosed methyl mercaptan catalyst activity with precipitation potassium tungstate aluminium oxide of Chinese patent CN1780814A is higher; Chinese patent CN 1178137 disclosed catalyst with wolframic acid caesium impregnated alumina, the catalyst activity of specific activity dipping potassium tungstate is high.The preparation method of the catalyst that above-mentioned patent is described all adopts infusion process, though with industrial aluminium oxide as the carrier impregnation auxiliary agent, can reduce with the catalyst specific surface of infusion process preparation, tungstates and carrier interaction are not strong, the optimum activity temperature is higher.
Summary of the invention
Purpose of the present invention is intended to provide a kind of Catalysts and its preparation method with synthesis of methyl mercaptan of high-specific surface area and low temperature active.
The catalyst of described synthesis of methyl mercaptan is with active γ-Al
2O
3Be active component, alkali tungstates is auxiliary agent, and the mass ratio of each composition of catalyst is alkali tungstates: aluminium oxide is (0.05～0.40): 1.
Described alkali tungstates can be selected from potassium tungstate etc.
The preparation method of the catalyst of described synthesis of methyl mercaptan may further comprise the steps:
1) the aluminium salt of metering is soluble in water, be mixed with aluminium salt liquid, add ammoniacal liquor after the heating, controlling its endpoint pH is 6～8, gets mixed liquor;
In step 1) in, described aluminium salt can be selected from aluminum nitrate or aluminum acetate etc.; The concentration of described aluminium salt liquid can be 0.25～1.5mol/L, and the temperature of described heating can be 50～80 ℃.
2) with step 1) the aging rear tungstates precursor solution that adds of resulting mixed liquor, get colloidal sol and leave standstill again;
In step 2) in, the described aging time can be 1～3h, and the concentration of described tungstates precursor solution can be 0.5～1.5mol/L; Described leaving standstill can at room temperature be left standstill at least 24h.
3) colloidal sol after will leaving standstill is dried to constant weight, and again after the calcining, compression molding gets the catalyst of synthesis of methyl mercaptan.
In step 3) in, the temperature of described oven dry can be 80～120 ℃; The temperature of described calcining can be 450～650 ℃, and the time of calcining can be 3～12h.
The activity rating of the catalyst of described synthesis of methyl mercaptan carries out in fixed bed flow system, the reaction tube specification is Φ 10mm * 900mm, catalyst is positioned at stove temperature controlling point place, bed volume is 2ml, the control reaction temperature is 320～360 ℃, methyl alcohol and hydrogen sulfide mol ratio are 1: 1.5, and pressure is 0.6MPa, and air speed GHSV is 1900h
-1Catalyst first at 400 ℃ of lower activation 2h of low pressure hydrogen sulfide, is forced into required pressure before use again, passes into methyl alcohol.Product adopts online gas chromatographic analysis.
Active component aluminium oxide in the catalyst of the synthesis of methyl mercaptan that the present invention is prepared adopts the sol-gal process preparation, the additive alkali metal tungstates adds in preparation alumina sol gel method process, the catalyst finished product of gained synthesis of methyl mercaptan with compare with the prepared catalyst of traditional dip loading method, have large, active high, the characteristics such as reaction temperature is low of specific surface.
The specific embodiment
Embodiment 1
200ml 1mol/L aluminum nitrate solution is heated to 75 ℃, under the condition that stirs, drips ammoniacal liquor, the pH value of control terminal point is 7.0, keeps temperature stabilization at 75 ℃ in the titration process.Then aging 2h under agitation after titration is finished adds the 1.5g potassium tungstate, stirs, the colloidal sol that obtains is at room temperature left standstill 36h, then dry to constant weight under 110 ℃, at 580 ℃ of lower calcining 8h, the catalyst tablet forming after the calcining is the catalyst finished product of synthesis of methyl mercaptan again.
The activity rating of the catalyst of synthesis of methyl mercaptan carries out in fixed bed flow system, the reaction tube specification is Ф 10mm * 900mm, catalyst is positioned at stove temperature controlling point place, bed volume is 2ml, the control reaction temperature is 320～360 ℃, methyl alcohol and hydrogen sulfide mol ratio are 1: 1.5, and pressure is 0.6MPa, and air speed GHSV is 1900h
-1The catalyst of synthesis of methyl mercaptan first at 400 ℃ of lower activation 2h of low pressure hydrogen sulfide, is forced into required pressure before use again, passes into methyl alcohol.Product adopts online gas chromatographic analysis.Methanol conversion and methyl mercaptan yield the results are shown in Table 1.
Embodiment 2
" 200ml 1mol/L aluminum nitrate solution " among the embodiment 1 changed into " 200ml 1mol/L Burow's Solution ", and all the other steps are with embodiment 1.The evaluation result of catalyst sees Table 1.
Embodiment 3
" 1.5g potassium tungstate " among the embodiment 1 changed into " the 2.5g potassium tungstate, all the other steps are with embodiment 1.The evaluation method of catalyst the results are shown in Table 1 with embodiment 1.
Comparative Examples 1
200ml 1mol/L aluminum nitrate solution is heated to 75 ℃, under the condition that stirs, drips ammoniacal liquor, the pH value of control terminal point is 7.0, keeps temperature stabilization at 75 ℃ in the titration process.2h under agitation wears out after titration is finished, the colloidal sol that obtains is at room temperature left standstill 36h, then under 110 ℃, dry to constant weight, again at 580 ℃ of lower calcining 8h, catalyst tablet forming after the calcining, then contain the 1.5g potassium tungstate by the water absorption rate incipient impregnation, be the catalyst finished product at 580 ℃ of lower calcining 8h again after 110 ℃ of lower oven dry.Press the evaluating catalyst method evaluation catalyst of embodiment 1, the results are shown in Table 1.
Comparative Examples 2
Select 10g γ-Al
2O
3Ball, sieving is 20～40 orders, then contains the 1.5g potassium tungstate by the water absorption rate incipient impregnation, is the catalyst finished product at 580 ℃ of lower calcining 8h again after 110 ℃ of lower oven dry.Press the evaluating catalyst method evaluation catalyst of embodiment 1, the results are shown in Table 1.
Table 1, embodiment 1～3 and Comparative Examples 1,2 evaluating catalyst result
*Air speed GHSV is 1900h
-1, H
2S/CH
3OH=1.5, P=0.6MPa.
Claims (3)
1. the preparation method of the catalyst of a synthesis of methyl mercaptan is characterized in that described catalyst is with active γ-Al
2O
3Be active component, alkali tungstates is auxiliary agent, and the mass ratio of each composition of catalyst is alkali tungstates: aluminium oxide is (0.05～0.40): 1; Described alkali tungstates is selected from potassium tungstate;
The preparation of catalyst may further comprise the steps:
1) the aluminium salt of metering is soluble in water, be mixed with aluminium salt liquid, add ammoniacal liquor after the heating, controlling its endpoint pH is 6～8, gets mixed liquor;
2) with step 1) the aging rear tungstates precursor solution that adds of resulting mixed liquor, get colloidal sol and leave standstill again;
3) colloidal sol after will leaving standstill is dried to constant weight, and again after the calcining, compression molding gets the catalyst of synthesis of methyl mercaptan;
Step 1) in, the temperature of described heating is 50～80 ℃;
Step 2) in, the described aging time is 1～3h;
Step 2) in, the concentration of described tungstates precursor solution is 0.5～1.5mol/L; Described leaving standstill is at room temperature to leave standstill at least 24h;
Step 3) in, the temperature of described oven dry is 80～120 ℃;
Step 3) in, the temperature of described calcining is 450～650 ℃, and the time of calcining is 3～12h.
2. the preparation method of the catalyst of a kind of synthesis of methyl mercaptan as claimed in claim 1 is characterized in that in step 1) in, described aluminium salt is selected from aluminum nitrate or aluminum acetate.
3. the preparation method of the catalyst of a kind of synthesis of methyl mercaptan as claimed in claim 1 is characterized in that in step 1) in, the concentration of described aluminium salt liquid is 0.25～1.5mol/L.
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| CN102658183B (en) * | 2012-04-28 | 2013-01-30 | 重庆紫光天化蛋氨酸有限责任公司 | Catalyst for catalyzing dimethyl sulfide and hydrogen sulfide to synthesize methyl mercaptan, and preparation method and application thereof |
| CN110918086A (en) * | 2019-12-23 | 2020-03-27 | 浙江新和成股份有限公司 | Supported rare earth modified metal catalyst and preparation method and application thereof |
| CN113578312B (en) * | 2021-06-30 | 2023-08-04 | 浙江大学 | Synergistic site catalyst, preparation method thereof and application thereof in preparation of mercaptan and thioether |
| CN114849693A (en) * | 2022-06-17 | 2022-08-05 | 黄河三角洲京博化工研究院有限公司 | Catalyst for synthesizing methyl mercaptan, preparation method and application |
| CN115608353B (en) * | 2022-10-12 | 2024-03-01 | 山东新和成氨基酸有限公司 | Catalyst for synthesizing alkyl mercaptan, preparation method of catalyst and preparation method of alkyl mercaptan |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178136A (en) * | 1996-09-26 | 1998-04-08 | 底古萨股份公司 | Catalyst, its preparation and use in synthesis of methyl mercaptan |
| EP0832878B1 (en) * | 1996-09-26 | 2002-09-11 | Degussa AG | Catalyst, process for its production and use in the synthesis of methylmercaptan |
| CN1780814A (en) * | 2003-04-30 | 2006-05-31 | 巴斯福股份公司 | Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide |
-
2011
- 2011-08-04 CN CN 201110222337 patent/CN102247833B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178136A (en) * | 1996-09-26 | 1998-04-08 | 底古萨股份公司 | Catalyst, its preparation and use in synthesis of methyl mercaptan |
| EP0832878B1 (en) * | 1996-09-26 | 2002-09-11 | Degussa AG | Catalyst, process for its production and use in the synthesis of methylmercaptan |
| CN1780814A (en) * | 2003-04-30 | 2006-05-31 | 巴斯福股份公司 | Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide |
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