CN1528516A - Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide - Google Patents
Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide Download PDFInfo
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- CN1528516A CN1528516A CNA2003101004961A CN200310100496A CN1528516A CN 1528516 A CN1528516 A CN 1528516A CN A2003101004961 A CNA2003101004961 A CN A2003101004961A CN 200310100496 A CN200310100496 A CN 200310100496A CN 1528516 A CN1528516 A CN 1528516A
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- moo
- catalyzer
- active ingredient
- carrier
- metering
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Abstract
The invention relates to a catalyst to use synthetical gas containing high concentration H2S as raw material to synthesize methane thiol by one-step method, composed of carrier, active component and active accelerant, where the carrier selects SiO2, TiO2 or heavy rare earth oxide; the active component is Mo-O-K based compound, converted by the fore body K2MoO4 or (NH4)6Mo7O24 plus sylvine or MoO3 plus sylvine; the active accelerant is mainly transition metal like Mn, Fe, Co, Ni, Ce, La, etc, or rare earth oxide; it makes catalysis reaction at 295 deg.C and 0.2 Mpa in the volume ratio of the raw material gases CL/H2/H2S=1/2/(0.1-1) at an airspeed of (1-5) x ten to the power 3 h-1, showing high activity and selectivity, the methane thiol's time-space catching rate is up to 0.18-0.25g.h-1. ml-1cat, and the methane thiol's selectivity is 93.5%-98.8%.
Description
(1) technical field
The present invention relates to a kind of being used for by containing high density H
2Synthetic gas (the CO+H of S
2) be raw material, single stage method synthesis of methyl mercaptan (CH
3SH) loaded catalyst and preparation method thereof.
(2) background technology
Thiomethyl alcohol is the important industrial chemicals of synthetic methionine, medicine and agricultural chemicals, and its classical production process is formed by potassium bisulfide and methyl halide effect.Develop other synthetic route subsequently successively, U.S. Pat appl.856 for example, 232, a kind of method of making thiomethyl alcohol with hydrogen sulfide and methyl alcohol or ether reaction is disclosed; French Patent FR appl.93,112,491 to disclose a kind of be catalyzer with the transition metal, the method for dimethyl sulfide hydrogenation system thiomethyl alcohol; European patent EP 167,354 discloses a kind ofly makes carrier with titanium oxide, and nickel oxide or molybdenum oxide are active ingredient, is the method that raw material is made thiomethyl alcohol with hydrogen sulfide and carbon monoxide.Chinese patent ZL 98118186.4 and ZL 98118187.2 disclose a kind of by containing high density H
2The synthetic gas of S is made the catalyzer of thiomethyl alcohol, and active ingredient Mo-S-K base is by precursor K
2MoS
4Or (NH
4)
2MoS
4Add sylvite and be transformed, the lower (0.08～0.19gh of space-time yield of this catalyzer thiomethyl alcohol
-1Ml
-1 Cat), simultaneously, the manufacture difficulty of precursor is big, and loaded solvent can not select the aqueous solution for use, must use DMF, catalyzer cost of manufacture height.
(3) summary of the invention
The object of the present invention is to provide a kind of raw material cheapness, simple for production, and the space-time yield height of thiomethyl alcohol, having greater activity and optionally being used for the synthetic gas that contains high-concentration hydrogen sulfide is the catalyzer of raw material, single stage method synthesis of methyl mercaptan.
The said catalyzer of the present invention comprises carrier and active ingredient, and carrier is selected from silicon-dioxide (SiO
2), titanium oxide (TiO
2) or heavy rare-earth oxide; Active ingredient is the Mo-O-K base complex, and its presoma is that (active ingredient is with K for potassium molybdate
2MoO
4Measure) or ammonium molybdate [(NH
4)
6Mo
7O
24] add sylvite or molybdenum oxide (MoO
3) (active ingredient is with MoO to add sylvite
3And K
2The O metering); Active ingredient is with K
2MoO
4Metering, it is K that catalyzer is formed weight ratio
2MoO
4/ carrier equals (0.01～0.80)/1, is preferably (0.10～0.60)/1; If active ingredient is with MoO
3And K
2The O metering, then the weight ratio of catalyzer composition is MoO
3/ K
2The O/ carrier equals (0.01～0.80)/(0.01～0.50)/1, preferably (0.10～0.50)/(0.10～0.30)/1.
The Preparation of catalysts method is: with the presoma dissolved in distilled water of active ingredient Mo-O-K base complex of metering, impregnated in the selected carrier 7～9h of metering, in 100～130 ℃ of oven dry, calcine 2～4h for 400～500 ℃.
Activity rating of catalyst carries out in fixed bed flowing reactive system, contains high density H
2The synthetic gas of S consists of (volume ratio) CO/H
2/ H
2S=1/2/ (0.1～1), 220～350 ℃ of temperature of reaction, pressure 0.2～2.0MPa, air speed (2～5) * 10
3h
-1Unstripped gas and the gas chromatographic analysis of product composition.Catalyzer is used H in advance under 300～350 ℃
2Reduction 8h carries out composition measuring to product after feeding unstripped gas 8h then.
As everyone knows, the character of catalyzer and performance are determined by its making raw material and making method (comprising the manufacture craft condition).When catalyzer contains a certain element, for example during Mo, can select for use all simple substance that contain the Mo element or compound to make this catalyzer in principle as one of raw material.But different raw materials certainly will be introduced different other groups or atom, as selects MoO for use
3, then introduce the O atom; Select for use ammonium molybdate then to introduce O atom and NH
4 +Group.Other groups of these introducings will influence physical change and the chemical transformation that is taken place in the catalyzer making processes, thereby finally cause the difference of catalyst property and performance.The present invention suitable contain Mo and contains the K raw material by selecting, and prepares to have high activity and catalyzer optionally, and under appreciation condition of the present invention, the space-time yield of thiomethyl alcohol is up to 0.25gh
-1Ml
-1 Cat, selectivity is up to 98.8%.And selected former cheap and easy to get, manufacture craft is easy.
(4) embodiment
Further specify the present invention by embodiment below:
Embodiment 1. takes by weighing 1.0g K
2MoO
4, use the 5ml dissolved in distilled water, impregnated in 2g SiO
2(40～60 order) 8h, 110 ℃ of oven dry 2h, 500 ℃ of calcining 2h, so the catalyst component weight ratio of making is K
2MoO
4/ SiO
2=0.50/1, activity rating the results are shown in Table 1.
Embodiment 2,3, the carrier S iO among the embodiment 1
2Change TiO into
2Or heavy rare-earth oxide, other making method is with embodiment 1, and activity rating the results are shown in Table 1.
Embodiment 4. takes by weighing 0.72g (NH
4)
6Mo
7O
24With 0.88g K
2CO
3, use the 5ml dissolved in distilled water, impregnated in 2g SiO
2Carrier 8h, 110 ℃ of oven dry, 450 ℃ of calcinings, the catalyst component weight ratio of made is MoO thus
3/ K
2O/SiO
2=0.30/0.30/1.0, its activity rating the results are shown in Table 1.
Embodiment 5. takes by weighing 0.44g K
2CO
3, use the 5ml dissolved in distilled water, impregnated in 2g SiO
24h, 110 ℃ of oven dry; Take by weighing 0.72g (NH
4)
6Mo
7O
24, use the 5ml dissolved in distilled water, impregnated in through K again
2CO
3The SiO that modifies
2Carrier 8h, 110 ℃ of oven dry; 450 ℃ of calcining 2h.The catalyst component weight ratio of made is MoO
3/ K
2O/SiO
2=0.30/0.15/1, activity rating the results are shown in Table 1.
Embodiment 6. is the 0.44g K of embodiment 5
2CO
3Use 0.36g KOH instead, other making method is with embodiment 5, and the catalyst component weight ratio of made is MoO
3/ K
2O/SiO
2=0.30/0.15/1.Activity rating the results are shown in Table 1.
Embodiment 7. takes by weighing 0.6g MoO
3Be dissolved in the hot distilled water of 5ml with 0.36g KOH, impregnated in 2gTiO
2(40～60 order) carrier 8h, 110 ℃ of oven dry, 450 ℃ of calcining 2h.Made catalyst component weight ratio is MoO
3K
2O/TiO
2=0.30/0.15/1.The catalyst activity evaluation result sees Table 1.
Table 1 embodiment 1-7 catalyzer is formed and the activity rating result
*
| Embodiment | Catalyst component (weight ratio) (%) | CH 3SH selectivity (%) | ???CH 3Space-time yield (the g.h of SH -1.ml -1 cat) |
| ????1 | ?K 2MoO 4/SiO 2＝0.5/1 | ????98.5 | ????????0.25 |
| ????2 | ?K 2MoO 4/TiO 2＝0.5/1 | ????98.8 | ????????0.24 |
| ????3 | ?K 2MoO 4/ heavy rare earths=0.5/1 | ????98.8 | ????????0.24 |
| ????4 | ?MoO 3/K 2O/SiO 2＝0.30/0.30/1 | ????96.8 | ????????0.23 |
| ????5 | ?MoO 3/K 2O/SiO 2＝0.30/0.15/1 | ????97.2 | ????????0.24 |
| ????6 | ?MoO 3/K 2O/SiO 2＝0.30/0.15/1 | ????94.2 | ????????0.21 |
| ????7 | ?MoO 3/K 2O/TiO 2＝0.30/0.15/1 | ????93.5 | ????????0.18 |
*Appreciation condition: CO/H
2/ H
2S=1/2/1, (V), 0.2MPa, 295 ℃, 3 * 10
3h
-1
Claims (4)
1. catalyzer by the synthetic gas synthesis of methyl mercaptan that contains high-concentration hydrogen sulfide, said catalyzer comprises carrier and active ingredient, it is characterized in that carrier is selected from silicon-dioxide, titanium oxide or heavy rare-earth oxide; Active ingredient is the Mo-O-K base complex, and its presoma is that (active ingredient is with K for potassium molybdate
2MoO
4Metering) or ammonium molybdate add sylvite or molybdenum oxide and add sylvite (active ingredient is with MoO
3And K
2The O metering); Active ingredient is with K
2MoO
4Metering, it is K that catalyzer is formed weight ratio
2MoO
4/ carrier equals (0.01～0.80)/1; Active ingredient is with MoO
3And K
2The O metering, it is MoO that catalyzer is formed weight ratio
3/ K
2The O/ carrier equals (0.01～0.80)/(0.01～0.50)/1.
2. a kind of catalyzer by the synthetic gas synthesis of methyl mercaptan that contains high-concentration hydrogen sulfide as claimed in claim 1 is characterized in that active ingredient is with K
2MoO
4Metering, it is K that catalyzer is formed weight ratio
2MoO
4/ carrier equals (0.10～0.60)/1.
3. a kind of catalyzer by the synthetic gas synthesis of methyl mercaptan that contains high-concentration hydrogen sulfide as claimed in claim 1 is characterized in that active ingredient is with MoO
3And K
2The O metering, it is MoO that catalyzer is formed weight ratio
3/ K
2The O/ carrier equals (0.10～0.50)/(0.10～0.30)/1.
4. Preparation of catalysts method by the synthetic gas synthesis of methyl mercaptan that contains high-concentration hydrogen sulfide, it is characterized in that its step is the presoma dissolved in distilled water of active ingredient Mo-O-K base complex that will metering, impregnated in the selected carrier 7～9h of metering, in 100～130 ℃ of oven dry, 400～500 ℃ of calcining 2～4h.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101004961A CN100345629C (en) | 2003-10-10 | 2003-10-10 | Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide |
| PCT/EP2004/010872 WO2005040082A2 (en) | 2003-10-10 | 2004-09-29 | Process for the manufacture of methylmercaptan |
| CNA2004800296378A CN1867545A (en) | 2003-10-10 | 2004-09-29 | Process for the manufacture of methylmercaptan |
| EP04765676A EP1670754A2 (en) | 2003-10-10 | 2004-09-29 | Process for the manufacture of methylmercaptan |
| US10/595,333 US7569731B2 (en) | 2003-10-10 | 2004-09-29 | Process for the manufacture of methylmercaptan |
| JP2006530037A JP2007508256A (en) | 2003-10-10 | 2004-09-29 | Method for producing methyl mercaptan |
| KR1020067006926A KR20060132818A (en) | 2003-10-10 | 2004-09-29 | Process for the manufacture of methylmercaptan |
| RU2006115793/04A RU2394023C2 (en) | 2003-10-10 | 2004-09-29 | Method of producing methylmercaptan |
| BRPI0415200-0A BRPI0415200A (en) | 2003-10-10 | 2004-09-29 | process for the manufacture of methylmercaptan |
| US12/509,120 US7833929B2 (en) | 2003-10-10 | 2009-07-24 | Process for the manufacture of methylmercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101004961A CN100345629C (en) | 2003-10-10 | 2003-10-10 | Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528516A true CN1528516A (en) | 2004-09-15 |
| CN100345629C CN100345629C (en) | 2007-10-31 |
Family
ID=34304066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101004961A Expired - Fee Related CN100345629C (en) | 2003-10-10 | 2003-10-10 | Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100345629C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040082A3 (en) * | 2003-10-10 | 2005-07-14 | Degussa | Process for the manufacture of methylmercaptan |
| EP1982764A1 (en) * | 2007-04-17 | 2008-10-22 | Evonik Degussa GmbH | Catalyst for the preparation of methyl mercaptan |
| US9409153B2 (en) | 2007-12-28 | 2016-08-09 | Evonik Degussa Gmbh | Supported Mo—O—K—MexOy catalyst for the synthesis of methanethiol from high H2S-containing syngas |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6084277A (en) * | 1983-10-13 | 1985-05-13 | Sumitomo Metal Ind Ltd | Vapor-phase oxidation of naphthalene |
| DE19639584A1 (en) * | 1996-09-26 | 1998-04-23 | Degussa | Catalyst, process for its preparation and use for the synthesis of methyl mercaptan |
| 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 |
| CN1080584C (en) * | 1997-12-26 | 2002-03-13 | 太原理工大学 | Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. |
| CN1072522C (en) * | 1998-09-10 | 2001-10-10 | 厦门大学 | Catalyst for synthesizing methyl mercaptan from synthesized gas contg. hydrogen sulfide |
| CN1072523C (en) * | 1998-09-10 | 2001-10-10 | 厦门大学 | Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide |
| RU2157366C1 (en) * | 1999-03-10 | 2000-10-10 | Наумейко Анатолий Васильевич | Methylmercaptan production process, method of preparing catalyst for production of methylmercaptan, and method of producing hydrogen sulfide for methylmercaptan production |
-
2003
- 2003-10-10 CN CNB2003101004961A patent/CN100345629C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040082A3 (en) * | 2003-10-10 | 2005-07-14 | Degussa | Process for the manufacture of methylmercaptan |
| US7569731B2 (en) | 2003-10-10 | 2009-08-04 | Degussa Ag | Process for the manufacture of methylmercaptan |
| US7833929B2 (en) | 2003-10-10 | 2010-11-16 | Evonik Degussa Gmbh | Process for the manufacture of methylmercaptan |
| EP1982764A1 (en) * | 2007-04-17 | 2008-10-22 | Evonik Degussa GmbH | Catalyst for the preparation of methyl mercaptan |
| WO2008125452A1 (en) * | 2007-04-17 | 2008-10-23 | Evonik Degussa Gmbh | Catalyst for the preparation of methyl mercaptan |
| US7723261B2 (en) | 2007-04-17 | 2010-05-25 | Evonik Degussa Gmbh | Catalyst for the preparation of methyl mercaptan |
| RU2497588C2 (en) * | 2007-04-17 | 2013-11-10 | Эвоник Дегусса Гмбх | Catalyst for obtaining methyl mercaptan |
| US9409153B2 (en) | 2007-12-28 | 2016-08-09 | Evonik Degussa Gmbh | Supported Mo—O—K—MexOy catalyst for the synthesis of methanethiol from high H2S-containing syngas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100345629C (en) | 2007-10-31 |
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