CN102327769A - Methanation catalyst and application thereof - Google Patents
Methanation catalyst and application thereof Download PDFInfo
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- CN102327769A CN102327769A CN201110157066A CN201110157066A CN102327769A CN 102327769 A CN102327769 A CN 102327769A CN 201110157066 A CN201110157066 A CN 201110157066A CN 201110157066 A CN201110157066 A CN 201110157066A CN 102327769 A CN102327769 A CN 102327769A
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Abstract
The invention which belongs to the technical field of coal processing utilization and coal conversion relates to a highly efficient and stable metal silicide catalyst of for the preparation of methane through carrying out coal-formed gas methanation. The stable metal silicide catalyst is formed through reducing a uniformly dispersed supported metal which is adopted as a precursor in hydrogen, siliconizing a mixed gas SiH4/H2 at a low temperature and normal pressure. The preparative metal silicide catalyst has a high activity and a methane selectivity to CO methanation; and in addition, compared with traditional metal catalysts, the metal silicide catalyst of the invention has the advantages of high thermostability, high anti-sintering, high carbon deposition resistance, difficult loss of carbonyl compounds formed from active components, strong sulfur resistance and the like.
Description
Technical field
The invention belongs to coal processing and utilization and coal transformation technology field, the producing synthesis gas from coal methanation that relates to a kind of efficient stable obtains the metal silicide catalyst of methane.Concretely, adopting homodisperse load type metal is that precursor reduces in hydrogen, under low temperature and normal pressure, uses SiH subsequently
4/ H
2Gaseous mixture carries out silication to it, promptly forms the catalytic applications of the synthesis gas methanation of stabilization metallic silicide catalyst and prepared material.
Background technology
Along with the shortage of petroleum resources, the cleaning of coal resources transforms the key subjects that preparation substitute gas petroleum resources have become present research.Discover that it is that synthesis gas carries out methanation reaction under catalyst action that the main process of natural gas is produced in the coal gasification.This reaction has the calorific value height, and conversion ratio is high, and product is single, and is good in economic efficiency, advantages such as the simple relatively and environmental protection of process route, but the high CO concentration in the course of reaction causes the catalyst poisoning inactivation easily, and easy coking deactivation under the catalyst high temperature.Therefore, seek a kind of have high activity and selectivity, Heat stability is good, strong anti-sulphur property, the methanation catalyst that anti-CO poisons is to become this technological most important thing.
For the CO methanation reaction, the active component of traditional catalyst is Ru, Ni, and Fe, Co etc., but all have problems to a certain extent.Applied Catalysis B:Environmental 88 (2009) 470-478 have reported that the catalyst based relative transition-metal catalyst cost of Ru is high and have combined to form Ru (CO) easily with CO
xEasy distillation causes loss of active component; Journal of Catalysis 260 (2008) 254-261 have reported that Fe is catalyst based easy in the carbon deposit inactivation; Applied Catalysis A:General 289 (2005) 10-15 have reported that Co is catalyst based and have had preferably stability, but relatively poor to the selectivity of methane.Though and the catalyst based initial activity of Ni is high, there are catalyst surface carbon deposit, active component sintering, the easy formation Ni (CO) that combines with CO
4And run off, easy shortcoming such as sulfur poisoning.Therefore, a kind of methanation catalyst with industrial applications prospect of development becomes the focus of present research.It is reported; Transition metal silicide is to get into a type of forming behind the transition metal lattice through silicon atom to have the special physics and the compound of chemical property as a kind of new catalyst, has high-melting-point, low-resistivity, high temperature resistant, the resistance to oxidation and the performance such as corrosion-resistant of conductivity of heat and excellence preferably.And Theoretical Calculation shows that transition metal silicide has higher stability than nitride, carbide and phosphide in the presence of hydrogen sulfide, thereby possibly have stronger sulfur tolerance, and can be applicable to a large amount of catalytic reaction processes under the sulfur-containing compound existence.Therefore, metal silicide has potential industrial application value as methanation catalyst.
The invention provides a kind of metal silicide catalyst, not only the preparation method is simple, mild condition, synthetic cost is low, environmental friendliness, and prepared material methanation has high activity and methane selectively to CO.In addition, compare, in the CO methanation reaction, have high heat endurance with the traditional metal catalyst, anti-sintering, anti-carbon deposition ability causes active component difficult formation carbonyls and runs off advantages such as strong sulfur tolerance.
Summary of the invention
The invention provides a kind of high heat endurance that has, anti-sintering, anti-carbon deposition ability, anti-current is lost, and the catalyst of the metal silicide methanation of strong sulfur tolerance is formed and is used.Preparation transition metal silicide catalyst shows high activity and methane selectively in the CO methanation reaction under temperate condition.
Transition metal silicide methanation catalyst of the present invention is with M
yM '
1-ySi
xBeing active component, is carrier with S, and wherein the mass ratio of active component and carrier is: 5-60: 100.Wherein y is 0.25,0.5,0.75 or 1, and x is 1 or 2; Wherein M and M ' are respectively the group VIII element, comprise Ni, Fe, Co, Mo, W etc. and inequality; Metal silicide activity of such catalysts component is nickle silicide (Ni
2Si, NiSi, NiSi
2), cobalt silicide (CoSi, CoSi
2), iron suicide (FeSi), molybdenum silicide (MoSi
2), tungsten silicide (WSi
x), double elements nickle silicide cobalt (Ni
0.75Co
0.25Si
2, Ni
0.50Co
0.50Si
2, Ni
0.25Co
0.75Si
2).Carrier S can be SiO
2, Al
2O
3, ZrO
2, TiO
2, molecular sieve, active carbon, CNT and complex carrier thereof etc.
Above-mentioned metal silicide methanation catalyst is to be presoma with the load type metal, through obtaining with silane reaction.Concrete steps are following:
With porous carrier material carrying metal oxide is presoma, is to rise to reduction temperature 350-600 ℃ with 1-10 ℃/min under the 10-100sccm hydrogen atmosphere at flow, and constant temperature reductase 12-5h transfers to 200-650 ℃ of silication at hydrogen atmosphere; With purity mixing greater than 99.99% silane and hydrogen; Mixing ratio is 5-20vol.%; Sample after reducing is carried out silication 15-60min; Silication drops to room temperature after accomplishing under hydrogen atmosphere, purge passivation down at inert atmosphere (argon gas, helium or nitrogen), promptly obtains the metal silicide methanation catalyst of corresponding high activity and methane selectively.
The preparation method of above-mentioned metal silicide methanation catalyst can be infusion process, chemical vapour deposition technique, the precipitation method etc.
The metal M of above-mentioned metal silicide methanation catalyst and the precursor of M ' can be the precursor (ammonium molybdate, molybdenum chloride etc.) of the precursor (ferric nitrate, iron chloride etc.) of the precursor of nickel (nickel nitrate, nickel acetate, nickel acetylacetonate etc.), iron, the precursor (cobalt chloride, cobalt nitrate etc.) of cobalt, molybdenum, the precursor (ammonium tungstate, sodium tungstate etc.) of tungsten etc.
The carrier of above-mentioned metal silicide methanation catalyst can be SiO
2, Al
2O
3, ZrO
2, TiO
2, molecular sieve, active carbon, CNT and compound thereof etc.
Mainly being applied as of above-mentioned metal silicide catalyst: natural gas is produced in the synthesis gas methanation.
The application conditions of above-mentioned metal silicide methanation catalyst is: reaction raw materials H
2/ CO mol ratio is 1-6, and reaction temperature is 150-600 ℃, and pressure is 0.1-10.0MPa, and volume space velocity is 1000-30000h
-1
The invention provides a kind of at normal pressure; The metal silicide catalyst for preparing under the moderate temperature conditions, the selection of the atomic ratio of its specific area, metal and silicon, reduction temperature, silication time, reactive metal and carrier etc. have very important influence to the formation of transition metal silicide, particle diameter, catalytic activity etc.It is of the present invention that preparation is simple, mild condition, and synthetic cost is low, environmental friendliness.Prepared metal silicide catalyst shows high activity and methane selectively in the CO methanation reaction, and embodies high heat endurance, anti-sintering; Anti-carbon deposition ability; Anti-current is lost, and strong sulfur tolerance is with a wide range of applications aspect Clean Fuel Production.
Description of drawings
Fig. 1 is the X-ray diffractogram of the silicon dioxide carried nickle silicide catalyst of different loadings.
Fig. 2 a and Fig. 2 b are 20%NiSi/SiO
2The high-resolution-ration transmission electric-lens photo of catalyst under two kinds of different conditions.
The specific embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1:40%NiSi
2/ SiO
2Preparation of catalysts
Get 0.3g 40%NiO/SiO
2Place quartz reactor.At first purge, switch to H then to wherein feeding Ar
2(30sccm), under 450 ℃, it is reduced 4h, the gained reduzate is at identical H
2Be cooled to silication temperature (250-450 ℃) under the atmosphere it is carried out silication, to wherein feeding 10vol.%SiH
4/ H
2Gaseous mixture 15min, total gas speed is 100sccm, question response finishes, and closes SiH
4, at H
2Be cooled to room temperature under the atmosphere, under Ar atmosphere, it carried out passivation, promptly obtain 40%NiSi
2/ SiO
2Catalyst.
Embodiment 2:40%CoSi
2/ SiO
2Preparation of catalysts
Get 0.3g 40%Co
3O
4/ SiO
2Place quartz reactor.At first purge, switch to H then to wherein feeding Ar
2(30sccm), under 450 ℃, it is reduced 4h, the gained reduzate is at identical H
2Be cooled to silication temperature (250-450 ℃) under the atmosphere it is carried out silication, to wherein feeding 10vol.%SiH
4/ H
2Gaseous mixture 15min, total gas speed is 100sccm, question response finishes, and closes SiH
4, at H
2Be cooled to room temperature under the atmosphere, under Ar atmosphere, it carried out passivation, promptly obtain 40%CoSi
2/ SiO
2Catalyst.
Embodiment 3:20%FeSi
2/ SiO
2Preparation of catalysts
Get 0.3g 20%Fe
2O
3/ SiO
2Place quartz reactor.At first purge, switch to H then to wherein feeding Ar
2(30sccm), under 500 ℃, it is reduced 4h, the gained reduzate is at identical H
2Be cooled to silication temperature (350-550 ℃) under the atmosphere it is carried out silication, to wherein feeding 10vol.%SiH
4/ H
2Gaseous mixture 15min, total gas speed is 100sccm, question response finishes, and closes SiH
4, at H
2Be cooled to room temperature under the atmosphere, under Ar atmosphere, it carried out passivation, promptly obtain 20%FeSi
2/ SiO
2Catalyst.
Embodiment 4:40%NiSi
2/ CNTs Preparation of catalysts
Get 0.3g 40%NiO/CNTs and place quartz reactor.At first purge, switch to H then to wherein feeding Ar
2(30sccm), under 500 ℃, it is reduced 4h, the gained reduzate is at identical H
2Be cooled to silication temperature (350-550 ℃) under the atmosphere it is carried out silication, to wherein feeding 10vol.%SiH
4/ H
2Gaseous mixture 15min, total gas speed is 100sccm, question response finishes, and closes SiH
4, at H
2Be cooled to room temperature under the atmosphere, under Ar atmosphere, it carried out passivation, promptly obtain 40%NiSi
2/ CNTs catalyst.
Embodiment 5: the performance test of nickle silicide catalyst in the CO methanation reaction
With H
2/ CO mol ratio is a unstripped gas at 3: 1, investigates the performance test of nickle silicide in the CO methanation reaction.Be reflected in the fixed bed reactors and carry out.
Reaction condition is: catalyst nickle silicide: 0.5g, and temperature, 150-600 ℃, pressure: 1.0MPa, volume space velocity is: 10000h
-1Product (H
2, CO, CH
4, CO
2, H
2O) and other hydrocarbons adopt gas chromatographic analysis, gas adopts thermal conductivity detector (TCD), other hydrocarbons adopt hydrogen flame detectors.The nickle silicide catalyst is at the 100sccm hydrogen flow rate, and 400 ℃ of following activation 2h react under different temperatures respectively then.Reaction result shows: under 350 ℃, the CO conversion ratio is 94%, and the selectivity of methane is 90%.Discover that through XRD spectrum and TEM electromicroscopic photograph reaction back nickle silicide catalyst particle still is evenly distributed on the carrier, ICP result shows the loss of not finding active component.
Embodiment 6: at H
2S exists down, the performance test of nickle silicide catalyst in the CO methanation reaction
With H
2/ CO mol ratio 3: 1 contains H
2S 10ppm is a unstripped gas, investigates the performance test of nickle silicide in the CO methanation reaction.Be reflected in the fixed bed reactors and carry out.
Reaction condition is: catalyst nickle silicide: 0.5g, and temperature, 150-600 ℃, pressure: 1.0MPa, volume space velocity is: 10000h
-1Product (H
2, CO, CH
4, CO
2, H
2O, H
2S) and other hydrocarbons adopt gas chromatographic analysis, gas adopts thermal conductivity detector (TCD), other hydrocarbons adopt hydrogen flame detectors.The nickle silicide catalyst is at the 100sccm hydrogen flow rate, and 400 ℃ of following activation 2h react under different temperatures respectively then.Reaction result shows: under 350 ℃, the CO conversion ratio is 94%, and the selectivity of methane is 90%.Discover that through XRD spectrum and TEM electromicroscopic photograph reaction back nickle silicide catalyst particle still is evenly distributed on the carrier, ICP result shows the loss of not finding active component.The XPS data analysis does not find that catalyst poisons phenomenon.
Embodiment 7: the performance test of iron suicide catalyst in the CO methanation reaction
With H
2/ CO mol ratio is a unstripped gas at 3: 1, investigates the performance test of iron suicide in the CO methanation reaction.Be reflected in the fixed bed reactors and carry out.
Reaction condition is: catalyst iron suicide: 0.5g, and temperature, 150-600 ℃, pressure: 1.0MPa, volume space velocity is: 10000h
-1Product (H
2, CO, CH
4, CO
2, H
2O) and other hydrocarbons adopt gas chromatographic analysis, gas adopts thermal conductivity detector (TCD), other hydrocarbons adopt hydrogen flame detectors.The iron suicide catalyst is at the 100sccm hydrogen flow rate, and 500 ℃ of following activation 2h react under different temperatures respectively then.Reaction result shows: under 550 ℃, the CO conversion ratio is 90%, and the selectivity of methane is 85%.Discover that through XRD spectrum and TEM electromicroscopic photograph reaction back iron suicide catalyst activity component stable existence is not found agglomeration on carrier.
Embodiment 8: the performance test of cobalt silicide catalyst in the CO methanation reaction
With H
2/ CO mol ratio is a unstripped gas at 3: 1, investigates the performance test of cobalt silicide in the CO methanation reaction.Be reflected in the fixed bed reactors and carry out.
Reaction condition is: catalyst cobalt silicide: 0.5g, and temperature, 150-600 ℃, pressure: 1.0MPa, volume space velocity is: 10000h
-1Product (H
2, CO, CH
4, CO
2, H
2O) and other hydrocarbons adopt gas chromatographic analysis, gas adopts thermal conductivity detector (TCD), other hydrocarbons adopt hydrogen flame detectors.The cobalt silicide catalyst is at the 100sccm hydrogen flow rate, and 400 ℃ of following activation 2h react under different temperatures respectively then.Reaction result shows: under 450 ℃, the CO conversion ratio is 85%, and the selectivity of methane is 90%.Find that through XRD and TEM data analysis carbon deposit does not take place reacted cobalt silicide catalyst surface.ICP result shows that the catalyst activity component runs off.
Claims (10)
1. a methanation catalyst is characterized in that with M
yM '
1-ySi
xBeing active component, is carrier with S, and the mass ratio of active component and carrier is: 5-60: 100; Wherein y is 0.25,0.5,0.75 or 1, and x is 1 or 2; M, M ' are group VIII element and inequality; Active component is nickle silicide, cobalt silicide, iron suicide, molybdenum silicide, tungsten silicide, double elements nickle silicide cobalt.
2. a kind of methanation catalyst according to claim 1 is characterized in that the group VIII element comprises Ni, Fe, Co, Mo, W.
3. a kind of methanation catalyst according to claim 1 and 2 is characterized in that carrier S is SiO
2, Al
2O
3, ZrO
2, TiO
2, molecular sieve, active carbon, CNT and complex carrier thereof.
4. the preparation method of claim 1 or 2 said methanation catalysts is characterized in that following steps:
With porous carrier material carrying metal oxide is presoma, is to rise to reduction temperature 350-600 ℃ with 1-10 ℃/min under the 10-100sccm hydrogen atmosphere at flow, and constant temperature reductase 12-5h transfers to 200-650 ℃ of silication at hydrogen atmosphere; With purity mixing greater than 99.99% silane and hydrogen; Mixing ratio is 5-20vol.%; Sample after reducing is carried out silication 15-60min; Silication drops to room temperature after accomplishing under hydrogen atmosphere, under inert atmosphere, purge passivation, promptly obtains the metal silicide methanation catalyst of corresponding high activity and methane selectively.
5. the preparation method of the said methanation catalyst of claim 3 is characterized in that following steps:
With porous carrier material carrying metal oxide is presoma, is to rise to reduction temperature 350-600 ℃ with 1-10 ℃/min under the 10-100sccm hydrogen atmosphere at flow, and constant temperature reductase 12-5h transfers to 200-650 ℃ of silication at hydrogen atmosphere; With purity mixing greater than 99.99% silane and hydrogen; Mixing ratio is 5-20vol.%; Sample after reducing is carried out silication 15-60min; Silication drops to room temperature after accomplishing under hydrogen atmosphere, under inert atmosphere, purge passivation, promptly obtains the metal silicide methanation catalyst of corresponding high activity and methane selectively.
6. according to the preparation method of the said methanation catalyst of claim 4, its characteristic is that also described preparation method is infusion process, chemical vapour deposition technique, the precipitation method.
7. according to the preparation method of the said methanation catalyst of claim 5, its characteristic is that also described preparation method is infusion process, chemical vapour deposition technique, the precipitation method.
8. the preparation method of methanation catalyst according to claim 4, its characteristic is that also precursor is: nickel nitrate, nickel acetate or nickel acetylacetonate as precursor, ferric nitrate or the iron chloride of nickel as precursor, cobalt chloride or the cobalt nitrate of iron as precursor, ammonium molybdate or the molybdenum chloride of cobalt as precursor, ammonium tungstate or the sodium tungstate of molybdenum precursor as tungsten.
9. the preparation method of methanation catalyst according to claim 5, its characteristic is that also precursor is: nickel nitrate, nickel acetate or nickel acetylacetonate as precursor, ferric nitrate or the iron chloride of nickel as precursor, cobalt chloride or the cobalt nitrate of iron as precursor, ammonium molybdate or the molybdenum chloride of cobalt as precursor, ammonium tungstate or the sodium tungstate of molybdenum precursor as tungsten.
10. a kind of methanation catalyst according to claim 4 is mainly used in the producing synthesis gas from coal methanation and obtains methane.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302929A (en) * | 2011-07-12 | 2012-01-04 | 神华集团有限责任公司 | Sulfur-resisting high-temperature methanation catalyst and preparation method thereof |
| CN103418409A (en) * | 2013-07-20 | 2013-12-04 | 大连理工大学 | Metal silicide catalyst of selective hydrogenation 1,4-butynediol and application of metal silicide catalyst |
| CN104470851A (en) * | 2013-04-19 | 2015-03-25 | 瑞科硅公司 | Corrosion and fouling reduction in hydrochlorosilane production |
| CN104588066A (en) * | 2014-12-19 | 2015-05-06 | 北京宝塔三聚能源科技有限公司 | Methanation catalyst and preparation method thereof |
| CN105080616A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier through methanation of coke oven gas |
| CN107138164A (en) * | 2017-06-13 | 2017-09-08 | 天津大学 | Metalorganic Chemical Vapor Deposition synthesizes metallic catalyst and method |
| CN107413373A (en) * | 2017-08-08 | 2017-12-01 | 太原理工大学 | A kind of high fast preparation method than table bimetallic silicide methanation catalyst |
| CN109529840A (en) * | 2018-11-29 | 2019-03-29 | 西南化工研究设计院有限公司 | A kind of CO2Catalyst for Low-Temperature Methanation, preparation and application |
| CN111229270A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Method for efficiently methanation of carbon dioxide and carbon monoxide simultaneously |
| CN111266130A (en) * | 2020-03-13 | 2020-06-12 | 中国华能集团清洁能源技术研究院有限公司 | Low-temperature sulfur-tolerant methanation catalyst with composite structure carrier and preparation method thereof |
| CN112691685A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Sulfur-tolerant shift methanation bifunctional catalyst, and preparation method and application thereof |
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| CN102302929A (en) * | 2011-07-12 | 2012-01-04 | 神华集团有限责任公司 | Sulfur-resisting high-temperature methanation catalyst and preparation method thereof |
| CN104470851B (en) * | 2013-04-19 | 2017-06-06 | 陕西有色天宏瑞科硅材料有限责任公司 | Reduce the corrosion and fouling in silicane hydroxide production |
| CN104470851A (en) * | 2013-04-19 | 2015-03-25 | 瑞科硅公司 | Corrosion and fouling reduction in hydrochlorosilane production |
| CN103418409A (en) * | 2013-07-20 | 2013-12-04 | 大连理工大学 | Metal silicide catalyst of selective hydrogenation 1,4-butynediol and application of metal silicide catalyst |
| CN103418409B (en) * | 2013-07-20 | 2015-07-29 | 大连理工大学 | A kind of metal silicide catalyst of selec-tive hydrogenation Isosorbide-5-Nitrae-butynediols and application |
| CN105080616B (en) * | 2014-05-08 | 2017-07-11 | 中国石油化工股份有限公司 | A kind of preparation method of coke-oven gas methanation catalyst carrier |
| CN105080616A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier through methanation of coke oven gas |
| CN104588066B (en) * | 2014-12-19 | 2017-03-15 | 北京宝塔三聚能源科技有限公司 | A kind of methanation catalyst and preparation method thereof |
| CN104588066A (en) * | 2014-12-19 | 2015-05-06 | 北京宝塔三聚能源科技有限公司 | Methanation catalyst and preparation method thereof |
| CN107138164A (en) * | 2017-06-13 | 2017-09-08 | 天津大学 | Metalorganic Chemical Vapor Deposition synthesizes metallic catalyst and method |
| CN107413373A (en) * | 2017-08-08 | 2017-12-01 | 太原理工大学 | A kind of high fast preparation method than table bimetallic silicide methanation catalyst |
| CN107413373B (en) * | 2017-08-08 | 2019-10-22 | 太原理工大学 | A kind of fast preparation method of high-specific surface area bimetallic silicide methanation catalyst |
| CN111229270A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Method for efficiently methanation of carbon dioxide and carbon monoxide simultaneously |
| CN111229270B (en) * | 2018-11-28 | 2023-04-11 | 中国科学院大连化学物理研究所 | Method for efficiently methanation of carbon dioxide and carbon monoxide simultaneously |
| CN109529840A (en) * | 2018-11-29 | 2019-03-29 | 西南化工研究设计院有限公司 | A kind of CO2Catalyst for Low-Temperature Methanation, preparation and application |
| CN112691685A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Sulfur-tolerant shift methanation bifunctional catalyst, and preparation method and application thereof |
| CN111266130A (en) * | 2020-03-13 | 2020-06-12 | 中国华能集团清洁能源技术研究院有限公司 | Low-temperature sulfur-tolerant methanation catalyst with composite structure carrier and preparation method thereof |
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Application publication date: 20120125 |