CN102861612A - Modified catalyst for preparing methyl mercaptan containing sulfur-containing synthesis gas and preparation method thereof - Google Patents
Modified catalyst for preparing methyl mercaptan containing sulfur-containing synthesis gas and preparation method thereof Download PDFInfo
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- CN102861612A CN102861612A CN2012103675550A CN201210367555A CN102861612A CN 102861612 A CN102861612 A CN 102861612A CN 2012103675550 A CN2012103675550 A CN 2012103675550A CN 201210367555 A CN201210367555 A CN 201210367555A CN 102861612 A CN102861612 A CN 102861612A
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Abstract
The invention discloses a modified catalyst for preparing methyl mercaptan containing sulfur-containing synthesis gas and a preparation method thereof. The preparation method is characterized by comprising the steps of: using 5ml of ethanol water solution prepared by water and ethanol in a volume ratio of (0-1):1 by each gram of carrier SiO2; adding an unmodified catalyst Mo-O-K/A/SiO2 into the ethanol water solution; gradually adding 0.2-1ml of a precursor of a modification agent into each gram of the carrier under room-temperature agitation; continually agitating for 2-4 hours, and reflowing and agitating to react for 2-3 hours; and washing and filtering by the ethanol, and drying at 80-120 DEG C for 4-6 hours to obtain the catalyst Mo-O-K/A/SiO2. The modified catalyst Mo-O-K/A/SiO2 catalyst is added and the selectivity of a byproduct CO2 is reduced to be 0.76% from the previous lowest 30.96%; and the ratio of the selectivity of the product methyl mercaptan to the selectivity of the byproduct carbon dioxide is raised to be 19.03 from the previous highest 1.27.
Description
Technical field
The invention belongs to the catalyst technical field of synthesis of methyl mercaptan, be specifically related to by hydrogen sulfide containing synthesis gas (CO+H
2) modified catalyst and preparation method thereof of preparation methyl mercaptan.
Background technology
Methyl mercaptan is a kind of important chemical substance of producing methionine, agricultural chemicals and medicine, mainly reacts to prepare by methyl alcohol and hydrogen sulfide at present.In the published existing synthetic route, the technical process that is directly prepared methyl mercaptan by hydrogen sulfide and one-step method from syngas is a kind of scheme of very attractive.The Mo-S-K/SiO for preparing methyl mercaptan such as the disclosed a kind of synthesis gas be used to containing high-concentration hydrogen sulfide of Chinese patent application CN1207957A
2Catalyst, wherein active component Mo-S-K base is by predecessor K
2MoS
4Perhaps (NH
4) MoS
4Add sylvite and be transformed, but the lower (0.07 ~ 0.15gh of methyl mercaptan space-time yield of this catalyst
-1Ml
-1 Cat), simultaneously to prepare difficulty larger for predecessor, and loaded solvent need to use N, and N-dimethyl formamide (DMF) is so this catalyst manufacture difficulty is larger.Introduced the Mo-O-K/SiO that is used for the synthetic transition metal oxide of methyl mercaptan and rare-earth oxide promotion among Chinese patent application CN1528516A and the CN1528515A
2Catalyst, its active component Mo-O-K base is by precursor K
2MoO
4Or (NH
4)
6Mo
7O
244H
2O adds that sylvite makes, and promoter is selected from Co, and Ni, Fe, the rare earth oxide of the oxide of Mn or La, Ce, this catalyst have the selective of methyl mercaptan preferably, but accessory substance CO simultaneously
2Also have than high selectivity.The disclosed a kind of support type Mo-O-K-Me for preparing methyl mercaptan for the high hydrogen sulfide synthesis gas of Chinese patent application CN101468310A
xO
yCatalyst, wherein Me
xO
yRepresent selected accelerative activator, the oxide of this accelerative activator chosen from Fe, cobalt, nickel, manganese, lanthanum or cerium, wherein x and y depend on the metal compound valency, and the carrier of this catalyst is comprised of porous holder and the coated metal that is deposited on the porous holder, and the porous holder is selected from SiO
2, TiO
2, Al
2O
3-SiO
2, zeolite or CNT and their mixture, coated metal is Fe, Co or Ni, active component is by K
2MoO
4Or (NH
4)
6Mo
7O
244H
2O adds potassium compound or MoO
3Add that potassium compound makes, owing to need carrier is carried out chemical deposit in the preparation process of this catalyst, increased the difficulty of catalyst preparation, make preparation process complicated, simultaneously in the products therefrom, accessory substance carbon dioxide selectively higher reaches 30 ~ 40%.
In sum, prepare the process of methyl mercaptan for hydrogen sulfide containing synthesis gas, the catalyst of prior art preparation can't effectively reduce the selective of accessory substance carbon dioxide.It is not yet seen about utilizing modifier that thereby catalyst modification is suppressed the report that hydrogen sulfide containing synthesis gas generates at preparation methyl mercaptan byproduct in process thing carbon dioxide.
Summary of the invention
The objective of the invention is to propose a kind ofly to prepare modified catalyst of methyl mercaptan and preparation method thereof for the sulfur-bearing synthesis gas, to obtain to have the support type modified catalyst that higher methyl mercaptan reduces the accessory substance carbon dioxide selectivity selectively, simultaneously.
Of the present inventionly prepare the preparation method of the modified catalyst of methyl mercaptan for the high-sulfur synthesis gas, comprising: be that 0.15 ~ 0.35:1 gets Ammonium Molybdate Tetrahydrate and carrier S iO in mass ratio
2
With Ammonium Molybdate Tetrahydrate ((NH
4)
6Mo
7O
244H
2O): potassium hydroxide (KOH): accelerative activator is 1:0.5 ~ 2:(0.05 ~ 0.3 in molar ratio) mix, obtain maceration extract after being dissolved in water and come impregnated carrier SiO
2, institute's amount of water is to just submergence carrier S iO
2Behind aging 8～12h, in 80～120 ℃ of oven dry, obtain the modification procatalyst, be designated as Mo-O-K/A/SiO
2
It is characterized in that:
Be 0 ~ 1:1 preparation ethanol water by water and ethanol volume ratio, according to every gram carrier S iO
2Use the 5ml ethanol water, with the modification procatalyst Mo-O-K/A/SiO that obtains before
2Join in the ethanol water, the presoma that under stirring at room, dropwise adds 0.2～1ml modifier by every gram carrier, after continuing to stir 2 ~ 4h, return stirring reacts 2 ~ 3h again, be cooled to room temperature, wash suction filtration with ethanol, at 80～120 ℃ of drying 4～6h, namely obtain catalyst Mo-O-K/A/B/SiO at last
2
The presoma of described modifier B is selected from MTES (MTES), trim,ethylchlorosilane (TMCS), 3-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or trifluoromethyl trimethyl silane (TFMTMS).
The addition of the presoma of described modifier B preferably adds the presoma of 0.4 ~ 0.8ml modifier by every gram carrier.
That adopts that said method prepares of the present inventionly prepares the modified catalyst of methyl mercaptan for the sulfur-bearing synthesis gas, it is characterized in that wherein molybdenum source Mo and carrier S iO
2Mass ratio be 0.15 ~ 0.35:1; The mol ratio of potassium source K and molybdenum source Mo is 0.5 ~ 2:1; The mol ratio of accelerative activator A and molybdenum source Mo is 0.05 ~ 0.3:1; This modified catalyst can be designated as Mo-O-K/A/B/SiO
2, wherein Mo-O-K represents active component, accelerative activator A is Co salt, Fe salt or Ni salt; The presoma of described modifier B is selected from MTES (MTES), trim,ethylchlorosilane (TMCS), 3-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or trifluoromethyl trimethyl silane (TFMTMS).
The present invention adopts the catalyst of said method preparation, and its activity rating can carry out at the flowable state fixed-bed micro-reactor, and the loadings of taking each catalyst is 0.5ml, and reaction temperature is 300 ℃, and reaction pressure is 0.2MPa, and air speed is 3000h
-1, the reaction procatalyst is H through volume ratio through 300 ℃ of reduction activations of hydrogen again
2S/H
2The sulfide hydrogen synthesis gas of/CO=2:1:1 is analyzed in 300 ℃ of sulfuration 1h post-samplings, and product is by the gas chromatograph on-line analysis.
Because the present invention has introduced modifier in catalyst preparation process, thereby has changed the polarity of catalyst surface, has affected character and the performance of catalyst, under above-mentioned appreciation condition, adopt the modified catalyst Mo-O-K/A/B/SiO of the inventive method preparation
2, with modification procatalyst Mo-O-K/A/SiO
2Compare accessory substance CO
2Selectively be decreased significantly, drop to minimumly 0.76% by original minimum 30.96%, the selective ratio of the selective and accessory substance carbon dioxide of product methyl mercaptan rises to 19.03 by original the highest 1.27 simultaneously.
The specific embodiment
Embodiment 1:
Take by weighing 1.50g Ammonium Molybdate Tetrahydrate, 0.95g potassium hydroxide and 0.49g Nickelous nitrate hexahydrate, add the configuration of 10ml deionized water dissolving
BecomeMaceration extract impregnated in and makes just submergence carrier on the 6g silica-gel carrier, and behind the 8h that wore out, dry 6 ~ 8h. obtains the modification procatalyst under 100 ℃ of conditions, is designated as Mo-O-K/Ni/SiO
2
Again at Mo-O-K/Ni/SiO
2In the middle adding 30ml ethanol water, this ethanol water is that 1:1 is formulated by water and ethanol by volume; Then the MTES that under agitation dropwise adds again 2.4ml continues to stir at ambient temperature 3h, again return stirring reaction 2.5h, be cooled to room temperature, wash suction filtration with ethanol, under 100 ℃ of conditions, dry, namely getting molybdenum source and carrier mass ratio is 0.25:1, and the mol ratio of potassium source K and molybdenum source Mo is 2:1; The mol ratio of accelerative activator Ni and molybdenum source Mo is 0.2:1; The addition of modifier MTES is the modified catalyst Mo-O-K/Ni/MTES/SiO of every gram carrier 0.4ml
2
Adopt the catalyst of said method preparation, its activity rating can carry out at the flowable state fixed-bed micro-reactor, and the loadings of taking each catalyst is 0.5ml, and reaction temperature is 300 ℃, and reaction pressure is 0.2MPa, and air speed is 3000h
-1, the reaction procatalyst is H through volume ratio through 300 ℃ of reduction activations of hydrogen again
2S/H
2The sulfide hydrogen synthesis gas of/CO=2:1:1 is analyzed in 300 ℃ of sulfuration 1h post-samplings, and product is by the gas chromatograph on-line analysis.
The activity rating of this catalyst for preparing in the present embodiment the results are shown in the table 1 of back, in order to compare.
Embodiment 2:
Change the volume ratio of water and ethanol in the employed ethanol water among embodiment 1 preparation method into 0.5:1, coupling agent changes the TMCS of 3.6ml into, and other conditions are with among the embodiment 1.Preparing at last molybdenum source and carrier mass ratio is 0.25:1, and the mol ratio of potassium source K and molybdenum source Mo is 2:1; The mol ratio of accelerative activator Ni and molybdenum source Mo is 0.2:1; The addition of modifier TMCS is the modified catalyst Mo-O-K/Ni/TMCS/SiO of every gram carrier 0.6ml
2, this catalyst activity evaluation result is listed in the table 1 of back.
Embodiment 3:
Change the volume ratio of water and ethanol in the employed ethanol water among embodiment 1 preparation method into 0.:1, coupling agent changes the KH550 of 4.8ml into, and other conditions are with among the embodiment 1.Preparing at last molybdenum source and carrier mass ratio is 0.25:1, and the mol ratio of potassium source K and molybdenum source Mo is 2:1; The mol ratio of accelerative activator Ni and molybdenum source Mo is 0.2:1; The addition of modifier KH550 is the modified catalyst Mo-O-K/Ni/KH550/SiO of every gram carrier 0.8ml
2, this catalyst activity evaluation result is listed in the table 1 of back.
Embodiment 4:
Take by weighing 1.5g Ammonium Molybdate Tetrahydrate, 0.24g potassium hydroxide and 0.17g Fe(NO3)39H2O, add the 10ml deionized water dissolving and be configured to maceration extract, impregnated in and make just submergence carrier on the 6g silica-gel carrier, wore out behind the 8h, dry 6 ~ 8h. obtains the modification procatalyst under 100 ℃ of conditions, is designated as Mo-O-K/Fe/SiO
2
Again at Mo-O-K/Fe/SiO
2In the middle adding 30ml ethanol water, this ethanol water is that 1:1 is formulated by water and ethanol by volume, stir the lower KH560 that dropwise adds 3.6ml, then at room temperature stir 3h, return stirring reaction 2.5h is cooled to room temperature again, wash suction filtration with ethanol, dry under 100 ℃ of conditions, namely getting molybdenum source and carrier mass ratio is 0.25:1, and the mol ratio of potassium source K and molybdenum source Mo is 0.5:1; The mol ratio of accelerative activator Fe and molybdenum source Mo is 0.05:1; The addition of modifier KH560 is the modified catalyst Mo-O-K/Fe/KH560/SiO of every gram carrier 0.6ml
2, this catalyst activity evaluation result sees Table 1.
Embodiment 5:
Take by weighing 1.53g Ammonium Molybdate Tetrahydrate, 0.49g potassium hydroxide and 0.74g cabaltous nitrate hexahydrate, add the 10ml deionized water dissolving and be configured to maceration extract, impregnated in and make just submergence carrier on the 6g silica-gel carrier, wore out behind the 8h, dry 6 ~ 8h. obtains the modification procatalyst under 100 ℃ of conditions, is designated as Mo-O-K/Co/SiO
2
Again at Mo-O-K/Co/SiO
2In the middle adding 25ml ethanol water, this ethanol water is that 0.5:1 is formulated by water and ethanol by volume, stir the lower TFMTMS that dropwise adds 2.4ml, then at room temperature stir 3h, return stirring reaction 2.5h is cooled to room temperature again, wash suction filtration with ethanol, dry under 100 ℃ of conditions, namely getting molybdenum source and carrier mass ratio is 0.25:1, and the mol ratio of potassium source K and molybdenum source Mo is 1:1; The mol ratio of accelerative activator Co and molybdenum source Mo is 0.3:1; The addition of modifier TFMTMS is the modified catalyst Mo-O-K/Co/TFMTMS/SiO of every gram carrier 0.4ml
2, this catalyst activity evaluation result sees Table 1.
The catalyst activity evaluation is carried out at the flowable state fixed-bed micro-reactor, and the loadings of taking each catalyst is 0.5ml, and reaction temperature is 300 ℃, and reaction pressure is 0.2MPa, and air speed is 3000h
-1, the reaction procatalyst is H through volume ratio through 300 ℃ of reduction activations of hydrogen again
2S/H
2The sulfide hydrogen synthesis gas of/CO=2:1:1 is analyzed in 300 ℃ of sulfuration 1h post-samplings, and product is by the gas chromatograph on-line analysis.
Comparative Examples 1:
Take by weighing 1.50g Ammonium Molybdate Tetrahydrate, 0.95g potassium hydroxide and 0.49g Nickelous nitrate hexahydrate, add the 10ml deionized water dissolving and be configured to maceration extract, impregnated in and make just submergence carrier on the 6g silica-gel carrier, wore out behind the 8h, to obtain support type potassium molybdenum mol ratio be that 2:1, nickel molybdenum mol ratio are that 0.2:1, molybdenum source and carrier mass ratio are the Mo-O-K/Ni/SiO of 0.25:1 to dry 6 ~ 8h. under 100 ℃ of conditions
2Catalyst, this catalyst activity evaluation result sees Table 1
Comparative Examples 2:
Take by weighing 1.5g Ammonium Molybdate Tetrahydrate, 0.24g potassium hydroxide and 0.17g Fe(NO3)39H2O, add the 10ml deionized water dissolving and be configured to maceration extract, impregnated in and make just submergence carrier on the 6g silica-gel carrier, wore out behind the 8h, to obtain support type potassium molybdenum mol ratio be that 0.5:1, iron molybdenum mol ratio are that 0.05:1, molybdenum source and carrier mass ratio are the Mo-O-K/Fe/SiO of 0.25:1 to dry 6 ~ 8h. under 100 ℃ of conditions
2Catalyst, this catalyst activity evaluation result sees Table 1.
Comparative Examples 3:
Take by weighing 1.53g Ammonium Molybdate Tetrahydrate, 0.49g potassium hydroxide and 0.74g cabaltous nitrate hexahydrate, add the 10ml deionized water dissolving and be configured to maceration extract, impregnated in and make just submergence carrier on the 6g silica-gel carrier, wore out behind the 8h, to obtain support type potassium molybdenum mol ratio be that 1:1, cobalt molybdenum mol ratio are that 0.3:1, molybdenum source and carrier mass ratio are the Mo-O-K/Co/SiO of 0.25:1 to dry 6 ~ 8h. under 100 ℃ of conditions
2Catalyst, this catalyst activity evaluation result is seen following table 1.
The catalyst activity evaluation result of table 1 embodiment 1 ~ 5 and Comparative Examples 1 ~ 3
With catalyst activity evaluation result data analysis listed in the top table 1 relatively, can find out, add respectively the Mo-O-K/Ni/SiO of modifier MTES, TMCS or KH550
2Mo-O-K/Ni/SiO before catalyst (embodiment 1, embodiment 2, embodiment 3) and the modification
2Catalyst (Comparative Examples 1) is the activity data result compare, the selective of accessory substance carbon dioxide 40.10% drops to 12.74%, 0.76% and 17.27% respectively from Comparative Examples 1, methyl mercaptan ratio selective and carbon dioxide rises by 1.2 and rises to respectively 2.74,19.03 and 1.73, same, comparative example 4 and Comparative Examples 2 can find out the Mo-O-K/Fe/SiO that has added modifier KH560
2Catalyst is so that the selective of accessory substance carbon dioxide drops to 16.23% by 30.96% in the Comparative Examples 2, and methyl mercaptan ratio selective and carbon dioxide rises to 2.50 by 1.27; Comparative example 5 and Comparative Examples 3 can find out the Mo-O-K/Co/SiO that has added modifier TFMTMS
2Catalyst is so that the selective of accessory substance carbon dioxide drops to 4.79% by 38.26% in the Comparative Examples 3, and methyl mercaptan ratio selective and carbon dioxide rises to 4.02 by 1.11.Therefore can learn, add the polarity that modifier has changed catalyst surface, the catalyst of modification effectively suppresses the selective of accessory substance carbon dioxide.
Preparation-obtained modified catalyst can be summed up and be summarized from top embodiment: of the present inventionly prepare the modified catalyst of methyl mercaptan for the sulfur-bearing synthesis gas, can remember and be Mo-O-K/A/B/SiO
2, wherein Mo-O-K represents active component; Accelerative activator A is selected from Co salt, Fe salt or Ni salt; The presoma of modifier B wherein is selected from MTES (MTES), trim,ethylchlorosilane (TMCS), 3-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or trifluoromethyl trimethyl silane (TFMTMS); This catalyst Mo-O-K/A/B/SiO
2Consist of: molybdenum source Mo and carrier S iO
2Mass ratio be 0.15 ~ 0.35:1; The mol ratio of potassium source K and molybdenum source Mo is 0.5 ~ 2:1; The mol ratio of accelerative activator A and molybdenum source Mo is 0.05 ~ 0.3:1; Wherein the presoma of modifier B is MTES (MTES), trim,ethylchlorosilane (TMCS), 3-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or trifluoromethyl trimethyl silane (TFMTMS), and modifier presoma consumption is for pressing every gram carrier 0.2 ~ 1ml.
Can conclude from above-described embodiment and to draw: that adopts that method of the present invention prepares of the present inventionly prepares the modified catalyst of methyl mercaptan, wherein molybdenum source Mo and carrier S iO for the sulfur-bearing synthesis gas
2Mass ratio be 0.15 ~ 0.35:1; The mol ratio of potassium source K and molybdenum source Mo is 0.5 ~ 2:1; The mol ratio of accelerative activator A and molybdenum source Mo is that this modified catalyst of 0.05 ~ 0.3:1 can be remembered and is Mo-O-K/A/B/SiO
2, wherein Mo-O-K represents active component, accelerative activator A is Co salt, Fe salt or Ni salt; The presoma of described modifier B is selected from MTES (MTES), trim,ethylchlorosilane (TMCS), 3-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or trifluoromethyl trimethyl silane (TFMTMS); The addition of the presoma of modifier B is preferably pressed the presoma of every gram carrier 0.4 ~ 0.8ml modifier by the presoma of every gram carrier adding 0.2 ~ 1ml modifier.
Claims (3)
1. one kind is used for the preparation method that the high-sulfur synthesis gas prepares the modified catalyst of methyl mercaptan, comprising: be that 0.15 ~ 0.35:1 gets Ammonium Molybdate Tetrahydrate and carrier S iO in mass ratio
2
With Ammonium Molybdate Tetrahydrate: potassium hydroxide: accelerative activator is 1:0.5 ~ 2:(0.05 ~ 0.3 in molar ratio) mix, obtain maceration extract after being dissolved in water and come impregnated carrier SiO
2, institute's amount of water is to just submergence carrier S iO
2Behind aging 8～12h, in 80～120 ℃ of oven dry, obtain the modification procatalyst, be designated as Mo-O-K/A/SiO
2
It is characterized in that:
Be 0 ~ 1:1 preparation ethanol water by water and ethanol volume ratio, according to every gram carrier S iO
2Use the 5ml ethanol water, with the modification procatalyst Mo-O-KA/SiO that obtains before
2Join in the ethanol water, the presoma that under stirring at room, dropwise adds 0.2～1ml modifier by every gram carrier, after continuing to stir 2 ~ 4h, return stirring reacts 2 ~ 3h again, be cooled to room temperature, wash suction filtration with ethanol, at 80～120 ℃ of drying 4 ~ 6h, namely obtain catalyst Mo-O-K/A/B/SiO at last
2
The presoma of described modifier B is selected from MTES, trim,ethylchlorosilane, 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or trifluoromethyl trimethyl silane.
2. be used for as claimed in claim 1 the preparation method that the high-sulfur synthesis gas prepares the modified catalyst of methyl mercaptan, be characterised in that the addition of the presoma of described modifier B is the presoma by every gram carrier 0.4 ~ 0.8ml modifier.
3. adopt the modified catalyst that the high-sulfur synthesis gas prepares methyl mercaptan that is used for of the described method preparation of claim 1, it is characterized in that: wherein molybdenum source Mo and carrier S iO
2Mass ratio be 0.15 ~ 0.35:1; The mol ratio of potassium source K and molybdenum source Mo is 0.5 ~ 2:1; The mol ratio of accelerative activator A and molybdenum source Mo is 0.05 ~ 0.3:1; This modified catalyst is designated as Mo-O-K/A/B/SiO
2, wherein Mo-O-K represents active component, accelerative activator A is Co salt, Fe salt or Ni salt; The presoma of described modifier B is selected from MTES, trim,ethylchlorosilane, 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or trifluoromethyl trimethyl silane.
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| CN1554484A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Method for surface hydrophobic modification of metal loaded catalyst |
| CN1559676A (en) * | 2004-03-12 | 2005-01-05 | 厦门大学 | Catalyst of synthesizing methyl mercaptan by carbon mono xide and hydrogen sulfide reaction |
| US20100094059A1 (en) * | 2006-09-11 | 2010-04-15 | Yiquan Yang | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| JP2011139991A (en) * | 2010-01-07 | 2011-07-21 | Japan Atomic Energy Agency | Hydrogen combustion catalyst, method for producing the same and hydrogen combustion method |
-
2012
- 2012-09-27 CN CN2012103675550A patent/CN102861612A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554484A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Method for surface hydrophobic modification of metal loaded catalyst |
| CN1559676A (en) * | 2004-03-12 | 2005-01-05 | 厦门大学 | Catalyst of synthesizing methyl mercaptan by carbon mono xide and hydrogen sulfide reaction |
| US20100094059A1 (en) * | 2006-09-11 | 2010-04-15 | Yiquan Yang | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| JP2011139991A (en) * | 2010-01-07 | 2011-07-21 | Japan Atomic Energy Agency | Hydrogen combustion catalyst, method for producing the same and hydrogen combustion method |
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Application publication date: 20130109 |