CN1207958A - Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide - Google Patents

Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide Download PDF

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Publication number
CN1207958A
CN1207958A CN 98118187 CN98118187A CN1207958A CN 1207958 A CN1207958 A CN 1207958A CN 98118187 CN98118187 CN 98118187 CN 98118187 A CN98118187 A CN 98118187A CN 1207958 A CN1207958 A CN 1207958A
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mos
catalyzer
carrier
methyl mercaptan
load
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CN 98118187
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CN1072523C (en
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杨意泉
戴深峻
林仁存
张鸿斌
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Evonik Operations GmbH
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Xiamen University
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Abstract

The catalyst has one carrier of SiO2, gamma-Al2O3 or TiO2 and its active component Mo-S-K radical is transformed from precursor K2MoS4 or (NH4)2MoS4+K2CO3. Its transition of RE metal oxide promoter are mainly metal oxide of Mn, Fe, Co, Ni, La, etc. Under the conditions of 295 deg.c temperature, 0.2MPa pressure, volume proportion of high-sulphur synthesis gas CO-H2-H2S being 1 to 2 to 0.1-1, and 2000-5000/hr space velocity, the catalyst can result in methyl mercaptan space-time yield of 0.37 g/hr each gram of catalyst and selectivity of 98.6%.

Description

A kind of catalyzer that contains the synthetic gas system thiomethyl alcohol of high hydrogen sulfide concentration
The present invention is a kind of being used for by containing high H 2Synthetic gas (the CO+H of S concentration 2) be raw material, single stage method synthesis of methyl mercaptan (CH 3SH) loading type Mo-S-K is catalyst based and preparation method thereof.
Thiomethyl alcohol is synthetic egg amino acid, the important industrial chemicals of medicine and agricultural chemicals, and its classical production process is formed by potassium bisulfide and methine halide effect.The exploitation of other synthetic route was arranged again afterwards successively, U.S. Pat app1.856 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 app1.93,112,491 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 tantalum oxide are active ingredient, is the method that raw material is made thiomethyl alcohol with hydrogen sulfide and carbon monoxide.
The objective of the invention is to develop that a kind of to be used for the synthetic gas that contains high hydrogen sulfide be raw material, the load shape Mo-S-K with transition metal or lanthanide rare metal oxide promoted of single stage method synthesis of methyl mercaptan is catalyst based.
Detailed description of the present invention:
Catalyzer of the present invention is made up of active ingredient, promotor and carrier, and active ingredient is the Mo-S-K based composition and use thereof in packaging, and said Mo-S-K based composition and use thereof in packaging is from its presoma tetrathio potassium molybdate (K 2MoS 4) or tetrathio amine molybdate (NH 4) 2MoS 4Add salt of wormwood (K 2CO 3); Promotor is the oxide compound of a kind of oxide compound that is selected from transition metal or lanthanide series rare-earth elements, particularly iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), lanthanum (La), cerium (Ce), and carrier is selected from silicon-dioxide (SiO 2), activated alumina, especially γ～Al 2O 3, titanium oxide (TiO 2).Catalyst system can be expressed as Mo-S-K/MO x/ carrier, MO in the formula xRepresent the oxide compound of transition metal or lanthanide series rare-earth elements, wherein the weight ratio of each composition is: as if the weight with carrier is 1, then MO xWeight be 0.001～0.1, preferably 0.01～0.05, active ingredient is with MoS 2Meter accounts for 0.01～0.85 (weight), preferably accounts for 0.1～0.6 (weight).
Take by weighing metering, the selected transition metal or the nitrate of lanthanide series rare-earth elements become solution with dissolved in distilled water, selected carrier impregnation with metering, make steeping fluid just flood full carrier, dry 3～4h down at 110 ℃ then, standby at 500-550 ℃ of following calcination 4～5h again; Take by weighing the presoma K of the Mo-S-K base of metering 2MoS 4, and it is dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K 2MoS 4Dissolving fully; The DMF solution of gained presoma again with metering, load the carrier impregnation of transition metal or rare-earth oxide, extract DMF with anhydrous diethyl ether after leaving standstill 1h, in argon gas (Ar) atmosphere, promptly get the catalyzer of Mo-S-K/MOx/ carrier after the vacuum-drying in 300～400 ℃ of following calcination 2～4h.With (NH 4) 2MoS 4And K 2CO 3Be the load of precursor, earlier with load the carrier impregnation of metal oxide at K 2CO 3In the aqueous solution, drying again, K is pressed in 500 ℃ of calcinings then 2MoS 4Carrying method load (NH for precursor 4) 2MoS 4
Activity rating of catalyst carries out in fixed bed flowing reactive system, and the high-sulfur synthetic gas consists of CO/H 2/ H 2S=1/2/ (0.1～1), (V/V), 220～350 ℃ of temperature of reaction, pressure 0.2Mp, air speed (2～5) * 10 3h -1, unstripped gas and product gc analysis.
The invention provides a kind of being used for to contain high H 2The synthetic gas of S concentration is a raw material, and the loading type Mo-S-K of single stage method synthesis of methyl mercaptan is catalyst based, and said catalyzer space-time yield of thiomethyl alcohol under appreciation condition of the present invention is 0.37g/h.gc.g Cat, selectivity is up to 98.6%.
Further specify the present invention by embodiment below.Example 1. takes by weighing 0.725g Fe (NO 3) 39H 2O also is dissolved in the 10mL distilled water, is made into iron nitrate aqueous solution, uses 10.0gSiO 2(80～100 order) dipping is dried 3h down at 110 ℃ behind the 20min., moves in the muffle furnace, at 500 ℃ of following calcination 4h again; Take by weighing K 2MoS 41.70g and be dissolved among the 15mL DMF, again with aforementioned load ferric oxide and through the SiO of roasting 2Carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, all is extracted totally until DMF, in vacuum drying oven 100 ℃ down behind the dry 3h again, promptly gets Mo-S-K/Fe in 400 ℃ of following calcination 4h in argon gas (Ar) atmosphere 2O 3/ SiO 2Catalyzer, so the weight of the catalyzer of making forms that (the Mo-S-K base is with MoS 2Meter) be MoS 2/ Fe 2O 3/ SiO 2=0.15/0.03/1, (w/w), activity rating the results are shown in Table 1.2-3. is the carrier S iO in the example 1. for example 2Change γ-Al respectively into 2O 3And TiO 2, all the other practices are with embodiment 1, and the composition and the evaluation result of gained catalyzer see Table 1.Example 4. is measured 50% Mn (NO 3) 2Solution 0.58mL, adding distil water 10mL is made into manganese nitrate solution, and all the other practices are with embodiment 1, and so (the Mo-S-K base is with MoS for the composition of the catalyzer of making 2Meter) be MoS 2/ MnO 2/ SiO 2=0.15/0.025/1, (w/w), activity rating the results are shown in Table 1.5-8. is " 0.725g Fe (the NO in the example 1. for example 3) 39H 2O " change into 1.16g Ni (NO respectively 3) 26H 2O, 1.16gCo (NO 3) 26H 2O, 0.67g La (NO 3) 3, 0.66g Ce (NO 3) 36H 2O, all the other practices are with embodiment 1, and the composition and the activity rating of gained catalyzer the results are shown in Table 1.
The composition of the catalyzer of table 1. embodiment 1-8 and activity rating result *
Embodiment Catalyzer is formed (w/w), and (active ingredient Mo-S-K is with MoS 2Meter) Generate CH 3SH selectivity (%) CH 3The space-time yield (g/hgcm) of SH
??1 ?MoS 2/Fe 2O 3/SiO 2＝0.15/0.03/1 ????95.2 ????0.36
??2 ?MoS 2/Fe 2O 3/γAl 2O 3＝0.15/0.03/1 ????75.3 ????0.21
??3 ?MoS 2/Fe 2O 3/TiO 2＝0.15/0.03/1 ????82.7 ????0.25
??4 ?MoS 2/MnO 2/SiO 2＝0.15/0.025/1 ????90.2 ????0.26
??5 ?MoS 2/NiO/SiO 2＝0.15/0.03/1 ????95.2 ????0.33
??6 ?MoS 2/CoO/SiO 2＝0.15/0.03/1 ????93.8 ????0.34
??7 ?MoS 2/La 2O 3/SiO 2＝0.15/0.025/1 ????98.6 ????0.37
??8 ?MoS 2/Ce 2O 3/SiO 2＝0.15/0.025/1 ????96.6 ????0.35
*Appreciation condition: the high-sulfur synthetic gas consists of CO/H 2/ H 2S=1/2/0.3, (V/V),
295 ℃ of temperature of reaction, pressure 0.2Mp, air speed 3 * 10 3h -1Example 9. takes by weighing 0.725g Fe (NO 3) 39H 2O also is dissolved in the 10mL distilled water, is made into iron nitrate aqueous solution, uses 10.0gSiO 2(80～100 order) dipping is dried 3h down at 110 ℃ behind the 20min., moves to muffle furnace again, and is standby at 550 ℃ of following calcination 4h; Take by weighing K 2CO 32.76g, be dissolved in the distilled water of 10mL the Fe that used above-mentioned load again 2O 3, and through incinerating SiO 2Carrier impregnation, 110 ℃ of oven dry, 500 ℃ of calcinings are standby.Take by weighing (NH 4) 2MoS 45.16g, be dissolved among the DMF of 15mL the K that used load again 2CO 3, Fe 2O 3SiO 2Carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, all is extracted totally until DMF, in vacuum drying oven 100 ℃ down behind the dry 3h again, promptly gets Mo-S-K/Fe in 450 ℃ of following calcination 4h in argon gas (Ar) atmosphere 2O 3/ SiO 2Catalyzer, so the weight of the catalyzer of making forms that (the Mo-S-K base is with MoS 2Meter) be MoS 2/ Fe 2O 3/ SiO 2=0.51/0.03/1, (w/w); Consist of CO/H at the high-sulfur synthetic gas 2/ H 2S=1/2/0.3 (V/V), 400 ℃ of temperature of reaction, normal pressure, air speed 3 * 10 3h -1Condition under carry out activity rating, the selectivity that the result generates thiomethyl alcohol is 95%, the space-time yield of thiomethyl alcohol is 0.27g/hg Cat

Claims (5)

1. the synthetic gas with high hydrogen sulfide concentration is a raw material, the catalyzer of single stage method synthesis of methyl mercaptan, said catalyzer is made up of active ingredient, promotor and carrier, it is characterized in that said active ingredient is the Mo-S-K based composition and use thereof in packaging, and the Mo-S-K based composition and use thereof in packaging in the said catalyzer is by presoma K 2MoS 4Or (NH 4) 2MoS 4Add K 2CO 3Through load and calcination and get; Promotor in the said catalyzer is a kind of oxide compound that is selected from transition metal or lanthanide series rare-earth elements, uses MO xExpression; Said carrier is a kind of SiO of being selected from 2, activated alumina, TiO 2Oxide compound, the amount of the active ingredient Mo-S-K base in the said catalyzer is with MoS 2Meter, the weight ratio of each composition is MoS 2/ MO x/ carrier=(0.01～0.85)/(0.001～0.1)/1, w/w.
2. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, it is characterized in that the promotor in the said catalyzer is the oxide compound of Fe, Mn, Co, Ni, La, Ce.
3. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, it is characterized in that drawing together property of the carrier aluminum oxide in the said catalyzer is γ-Al 2O 3
4. according to the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, the amount that it is characterized in that the active ingredient Mo-S-K base in the said catalyzer is with MoS 2Meter, the weight ratio of each composition is MoS 2/ MO x/ carrier=(0.1～0.6)/(0.01～0.05)/1, w/w.
5. method of making the catalyzer of the said single stage method synthesis of methyl mercaptan of claim 1, promotor in the said catalyzer is with metering, the selected transition metal or the nitrate of lanthanide series rare-earth elements, become solution with dissolved in distilled water, selected carrier impregnation with metering, dry 3-4h down at 110 ℃ then, again at 500-550 ℃ of following calcination 4-5h; The presoma K that it is characterized in that said catalyst activity component Mo-S-K base 2MoS 4Load be will the metering K 2MoS 4Be dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K 2MoS 4Dissolving fully, the DMF solution of gained presoma is used metering again, said load the carrier impregnation of transition metal oxide, extract DMF with anhydrous diethyl ether after leaving standstill 1h, in argon gas (Ar) atmosphere, promptly get the loaded catalyst that is expressed as the Mo-S-K/MOx/ carrier after the vacuum-drying in 300～400 ℃ of following calcination 2-4h; With (NH 4) 2MoS 4And K 2CO 3Be the load of precursor, be earlier with load the carrier impregnation of metal oxide at K 2CO 3In the aqueous solution, drying again, K is pressed in 500 ℃ of calcinings then 2MoS 4Carrying method load (NH 4) 2MoS 4
CN98118187A 1998-09-10 1998-09-10 Catalyst for preparing methyl mercaptan from synthesized gas containing high concentration of hydrogen sulfide Expired - Fee Related CN1072523C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100334075C (en) * 2003-04-30 2007-08-29 巴斯福股份公司 Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide
CN100345629C (en) * 2003-10-10 2007-10-31 德古萨股份公司 Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide
CN100443165C (en) * 2004-03-12 2008-12-17 德古萨股份公司 Catalyst of synthesizing methyl mercaptan by carbon mono xide and hydrogen sulfide reaction
US7569731B2 (en) 2003-10-10 2009-08-04 Degussa Ag Process for the manufacture of methylmercaptan
US7723261B2 (en) 2007-04-17 2010-05-25 Evonik Degussa Gmbh Catalyst for the preparation of methyl mercaptan
US8883670B2 (en) 2006-09-11 2014-11-11 Evonik Degussa Gmbh Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan
JP2016515935A (en) * 2013-03-29 2016-06-02 アルケマ フランス Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulfide
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
CN112316959A (en) * 2020-11-18 2021-02-05 昆明理工大学 K insertion type 1T-MoS2Catalyst, preparation method and application thereof
CN115228454A (en) * 2022-02-07 2022-10-25 昆明理工大学 Application of titanium dioxide in synthesis of methyl mercaptan
RU2805660C2 (en) * 2019-01-18 2023-10-23 Адиссео Франс С.А.С. Method for obtaining the compound of rsh formula by hydrosulphurisation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1253133A (en) * 1984-06-29 1989-04-25 Claudio C. Chersich Catalysts comprising niobia and/or tantala supported on titania
US5283369A (en) * 1992-03-24 1994-02-01 Elf Atochem North America, Inc. Selective synthesis of mercaptans and catalyst therefor
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

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100334075C (en) * 2003-04-30 2007-08-29 巴斯福股份公司 Catalyst for the production of methyl mercaptan from methanol and hydrogen sulfide
US7833929B2 (en) 2003-10-10 2010-11-16 Evonik Degussa Gmbh Process for the manufacture of methylmercaptan
CN100345629C (en) * 2003-10-10 2007-10-31 德古萨股份公司 Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide
US7569731B2 (en) 2003-10-10 2009-08-04 Degussa Ag Process for the manufacture of methylmercaptan
CN100443165C (en) * 2004-03-12 2008-12-17 德古萨股份公司 Catalyst of synthesizing methyl mercaptan by carbon mono xide and hydrogen sulfide reaction
US8883670B2 (en) 2006-09-11 2014-11-11 Evonik Degussa Gmbh Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan
US7723261B2 (en) 2007-04-17 2010-05-25 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
JP2016515935A (en) * 2013-03-29 2016-06-02 アルケマ フランス Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulfide
US9944594B2 (en) * 2013-03-29 2018-04-17 Arkema France Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulphide
US10377704B2 (en) 2013-03-29 2019-08-13 Arkema France Catalyst for the synthesis of methyl mercaptan and process for producing methyl mercaptan from synthesis gas and hydrogen sulphide
RU2805660C2 (en) * 2019-01-18 2023-10-23 Адиссео Франс С.А.С. Method for obtaining the compound of rsh formula by hydrosulphurisation
CN112316959A (en) * 2020-11-18 2021-02-05 昆明理工大学 K insertion type 1T-MoS2Catalyst, preparation method and application thereof
CN115228454A (en) * 2022-02-07 2022-10-25 昆明理工大学 Application of titanium dioxide in synthesis of methyl mercaptan

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