CN102020525A - Applications of Ni/SiC catalyst to methane production through syngas conversion - Google Patents
Applications of Ni/SiC catalyst to methane production through syngas conversion Download PDFInfo
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- CN102020525A CN102020525A CN2009101873254A CN200910187325A CN102020525A CN 102020525 A CN102020525 A CN 102020525A CN 2009101873254 A CN2009101873254 A CN 2009101873254A CN 200910187325 A CN200910187325 A CN 200910187325A CN 102020525 A CN102020525 A CN 102020525A
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Abstract
The invention discloses the applications of a Ni/SiC catalyst to methane production through syngas conversion. Silicon carbide with favorable thermal conductivity and mechanical strength is used as a carrier of a nickel catalyst, wherein the catalyst contains 1-20 percent of nickel metal, and the preparation method is simple and practical. The catalyst can rapidly export a great number of heat generated in a methane production reaction through syngas conversion, avoid congregation of nickel catalyst particles due to partial overheat and inactivation caused by carbon deposition, have the advantages of strong abrasion resistance, high activity, strong carbon deposition resistance, and the like and can be operated at a higher airspeed under high pressure.
Description
Technical field
The present invention relates to methanation catalyst, specifically a kind of nickel catalyzator that supports on Carboround.
Background technology
Along with the minimizing day by day of whole world prospective oil and produced quantity, because the oil crisis that the petroleum-based energy shortage causes is more and more serious.Therefore, how utilizing coal resources existing on the earth effectively and rationally is important topics of current research.From the angle of energy utilization, coal directly burning is converted into heat to be used for the needs of resident living and industry heating, is the mode that heat energy utilization is the most direct, the efficiency utilization ratio is the highest.Yet the distribution of coal is subjected to regional impact bigger, and transportation and storage all are subjected to bigger restriction.Coal reserves such as China western part is very big, and the east then is in great demand.After coal is transformed into synthetic gas, highly selective transforms into methane again, then can be delivered to the user of east by the natural gas line of transfering natural gas from the west to the east, the alternative artificial coal gas that generally uses now is used for resident living, is the other very effective approach that synthetic gas utilizes.
Methanation reaction is a strong exothermal reaction.According to patent CN101391218A result calculated, every mole of complete hydrocracking of CO is CH
4, liberated heat is 260,000 kilojoules.In this case, a large amount of heats that generate in the reaction process are difficult in time spread out, and will cause the appearance of beds focus, cause the gathering of the carbon distribution and the nickel metallics of catalyzer, thereby cause rapid catalyst deactivation.
The heat conductivility of support of the catalyst is the important factor of the decision beds temperature difference.The Al that common methanation catalyst uses
2O
3Perhaps ZrO
2Deng inorganic matter carrier, its thermal conductivity all is lower than 10W/ (m.K), and heat conductivility is relatively poor, so inactivation is than very fast.In addition, have a large amount of water to generate under reaction conditions, this can make Al
2O
3Perhaps ZrO
2Carrier possesses certain acidity, has accelerated the generation of reaction carbon distribution.
Therefore, use a kind of support of the catalyst, will play an important role for the stability that improves heat transfer efficiency and catalyzer with high thermal conductivity coefficient.
Summary of the invention
The invention provides a kind of Ni/SiC catalyzer and transform the application of making in the methane at synthetic gas.Different is with catalyzer in the past, and catalyzer of the present invention is a carrier with the silicon carbide with good heat conductive performance and high mechanical strength, and its thermal conductivity is up to 490W/ (m.K), far above the Al of routine
2O
3And ZrO
2Carrier.Therefore, carry out even be reflected under very high air speed and the CO transformation efficiency, catalyzer still can be soon with produce in the methanation reaction process heat derive, avoid the appearance of focus, thereby greatly prolonged life of catalyst.
For achieving the above object, the technical solution used in the present invention is:
A kind of Ni/SiC catalyzer transforms the application of making in the methane at synthetic gas, and described catalyzer is that carrier, metallic nickel are active constituent with SiC, and wherein the quality percentage composition of nickel in catalyzer is 1%-10%.
Described Preparation of catalysts process is as follows:
1) in required ratio the presoma of nickel metal is mixed with the aqueous solution; The precursor solution of nickel can use the formation soluble in water of the nickel salt of any solubility; The presoma of described nickel metal is nickelous nitrate, nickelous chloride, single nickel salt, nickelous acetate or other water-soluble nickel salt;
2) Carboround is added in the nickel solution that step (1) obtains according to required ratio, adopt the method for dipping, Ni is loaded on the SiC carrier, through 80-200 ℃ of oven dry; Described SiC is the strip or the bulk of powdery, particulate state or process extrusion molding;
3) catalyzer that then (2) is obtained is at 300-850 ℃ of following H
2Reduction is handled in the atmosphere, promptly obtains being carried on the nickel catalyzator on the silicon carbide.
Described catalyzer application conditions is 0.1-10MPa, 300-800 ℃, and CO: H
2=1: 0.1-1: 50 (V/V), air speed 1000-100000h
-1Analytical test shows that the specific surface area of Ni/SiC catalyzer of the present invention is about 29m
2/ g, its tap density is 1g/ml.
The present invention has following advantage:
1. catalyzer can move under high air speed, pressure and temperature of reaction, and the CO transformation efficiency is high and do not have a generation of carbon distribution.Catalyzer of the present invention under situation about existing without any additive, at reaction pressure 0.1-10MPa, body air speed 1000-100000h
-1, operation surpasses 100 hours under temperature of reaction 300-800 ℃ the condition, and the CO transformation efficiency is higher than 90%, and methane selectively is more than 85%, and do not have the generation of carbon distribution.
2. catalyzer has good heat conductivility and mechanical property, can avoid the appearance of focus in the methanation reaction process, has good antiwear property simultaneously, has greatly prolonged life of catalyst.
3. the loading of nickel can be low to moderate 1%, has greatly saved the cost of nickel catalyzator.
4. method for preparing catalyst is simple, is easy to mass-producing and implements.
Embodiment
Do a detailed explanation below by embodiment for whole process, but claim scope of the present invention is not subjected to the restriction of these embodiment.Simultaneously, embodiment has just provided the partial condition of realizing this purpose, but and does not mean that must satisfy these conditions just can reach this purpose.
Embodiment 1
1. get the nickel nitrate solution 10ml of 1.7mol/L, add silicon carbide 10g, in 80 ℃ of baking ovens, dry then.
With the sample that obtains in 1 at mobile H
2Be heated to 650 ℃ and be incubated 180min, the 10%Ni/SiC after obtaining reducing with the speed of 2K/min in the gas
3. the sample that obtains in the step 2 is at 1.5MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 94.7%, methane selectively is 86.9%, all the other are CO
2
Embodiment 2
1. with the step 1 of embodiment 1.
2. with the step 2 of embodiment 1.
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 95.8%, methane selectively is 88.2%, all the other are CO
2
Embodiment 3
1. with the step 1 of embodiment 1.
2. with the step 2 of embodiment 1.
3. the sample that obtains in the step 2 is at 2.5MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 96.4%, methane selectively is 88.6%, all the other are CO
2
Embodiment 4
1. with the step 1 of embodiment 1.
2. with the step 2 of embodiment 1.
3. the sample that obtains in the step 2 is at 2.5MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 76800h
-1Condition under, the transformation efficiency of CO is 94.1%, methane selectively is 87.1%, all the other are CO
2
Embodiment 5
1. with the step 1 of embodiment 1.
2. with the step 2 of embodiment 1.
3. the sample that obtains in the step 2 is at 2.0MPa, and 550 ℃, CO: H
2=1: 4 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 98.8%, methane selectively is 96.3%, all the other are CO
2
Embodiment 5
1. with the step 1 of embodiment 1.
2. with the step 2 of embodiment 1.
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 4 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 98.1%, methane selectively is 96.0%, all the other are CO
2
Embodiment 6
1. get the nickel nitrate solution 5ml of 1.7mol/L, add silicon carbide 10g, in 80 ℃ of baking ovens, dry then.
With the sample that obtains in 1 at mobile H
2Be heated to 650 ℃ and be incubated 180min, the 5%Ni/SiC after obtaining reducing with the speed of 2K/min in the gas
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 97.0%, methane selectively is 87.1%, all the other are CO
2
Embodiment 7
1. with the step 1 among the embodiment 6.
2. with the step 2 among the embodiment 6.
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 57600h
-1Condition under, the transformation efficiency of CO is 96.2%, methane selectively is 86.6%, all the other are CO
2
Embodiment 8
1. get the nickel nitrate solution 1ml of 1.7mol/L, add silicon carbide 10g, in 80 ℃ of baking ovens, dry then.
With the sample that obtains in 1 at mobile H
2Be heated to 650 ℃ and be incubated 180min, the 1%Ni/SiC after obtaining reducing with the speed of 2K/min in the gas
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 38400h
-1Condition under, the transformation efficiency of CO is 97.3%, methane selectively is 87.6%, all the other are CO
2
Embodiment 9
1. with the step 1 among the embodiment 8.
2. with the step 2 among the embodiment 8.
3. the sample that obtains in the step 2 is at 2.0MPa, and 600 ℃, CO: H
2=1: 3 (V/V), air speed 57600h
-1Condition under, the transformation efficiency of CO is 96.6%, methane selectively is 87.1%, all the other are CO
2
The present invention uses has the carborundum of thermal conductive resin and mechanical strength as the carrier of Raney nickel, and wherein the content of nickel metal in catalyst is 1%-10%, and preparation process is simple. This catalyst can be derived fast synthesis gas and be transformed the amount of heat that generates in the methane reaction processed, avoid hot-spot to cause the gathering of Raney nickel particle and the inactivation that carbon distribution causes, it is strong to have antiwear property, active high, the characteristics such as carbon accumulation resisting ability is strong can reach under the higher pressure in very high air speed and move.
Claims (4)
1. a Ni/SiC catalyzer transforms the application of making in the methane at synthetic gas, and it is characterized in that: described catalyzer is that carrier, metallic nickel are active constituent with SiC, and wherein the quality percentage composition of nickel in catalyzer is 1%-20%.
2. according to the application of claim 1, it is characterized in that: described Preparation of catalysts process is as follows: in required ratio the presoma of nickel metal is mixed with the aqueous solution, adopts the method for dipping, Ni is loaded on the SiC carrier, through 80-200 ℃ of oven dry, then at 300-850 ℃ of following H
2Reduction is handled in the atmosphere, promptly obtains being carried on the nickel catalyzator on the silicon carbide.
3. according to the application of claim 1, it is characterized in that: described SiC is the strip or the bulk of powdery, particulate state or process extrusion molding; The presoma of described nickel metal is nickelous nitrate, nickelous chloride, single nickel salt, nickelous acetate or other water-soluble nickel salt.
4. according to the application of claim 1, it is characterized in that: described catalyzer application conditions is 0.1-10MPa, 300-800 ℃, and CO: H
2=1: 0.1～1: 50 (V/V), air speed 1000-100000h
-1
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|---|---|---|---|
| CN200910187325A CN102020525B (en) | 2009-09-11 | 2009-09-11 | Applications of Ni/SiC catalyst to methane production through syngas conversion |
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|---|---|---|---|
| CN200910187325A CN102020525B (en) | 2009-09-11 | 2009-09-11 | Applications of Ni/SiC catalyst to methane production through syngas conversion |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102495161A (en) * | 2011-11-11 | 2012-06-13 | 河南中分仪器股份有限公司 | Special flame ionization detector for analyzing dissolved gas in insulating oil |
| CN103240090A (en) * | 2012-02-07 | 2013-08-14 | 福特全球技术公司 | Exhaust treatment system including a nickel-based catalyst |
| CN104148101A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Method and catalyst for direct oxygen-free preparation of olefins from methane |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
| US9932280B2 (en) | 2013-05-13 | 2018-04-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Synthesis of olefins from oxygen-free direct conversion of methane and catalysts thereof |
| US10702854B2 (en) | 2013-05-13 | 2020-07-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Oxygen-free direct conversion of methane and catalysts therefor |
| CN115301261A (en) * | 2022-06-24 | 2022-11-08 | 常州大学 | Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method |
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| CN110508301B (en) * | 2019-08-29 | 2022-02-22 | 华南农业大学 | Biological methanol conversion catalyst SrNiO for full components of methane3/SiC-SiO2-Foam and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| NL8200544A (en) * | 1982-02-12 | 1983-09-01 | Veg Gasinstituut Nv | METHOD FOR PREPARING METHANE FROM CARBON MONOXIDE-CONTAINING GAS MIXTURES USING CATALYSTS USING NICKEL |
| CN101185892A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing CO selectivity methanation catalyst in hydrogen-rich gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102495161A (en) * | 2011-11-11 | 2012-06-13 | 河南中分仪器股份有限公司 | Special flame ionization detector for analyzing dissolved gas in insulating oil |
| CN103240090A (en) * | 2012-02-07 | 2013-08-14 | 福特全球技术公司 | Exhaust treatment system including a nickel-based catalyst |
| CN104148101A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Method and catalyst for direct oxygen-free preparation of olefins from methane |
| CN104148101B (en) * | 2013-05-13 | 2016-12-28 | 中国科学院大连化学物理研究所 | The method of a kind of methane anaerobic alkene the most processed and catalyst thereof |
| US9932280B2 (en) | 2013-05-13 | 2018-04-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Synthesis of olefins from oxygen-free direct conversion of methane and catalysts thereof |
| US10702854B2 (en) | 2013-05-13 | 2020-07-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Oxygen-free direct conversion of methane and catalysts therefor |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
| CN104174420B (en) * | 2013-05-28 | 2017-05-24 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
| CN115301261A (en) * | 2022-06-24 | 2022-11-08 | 常州大学 | Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method |
| CN115301261B (en) * | 2022-06-24 | 2024-03-29 | 常州大学 | Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method |
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| CN102020525B (en) | 2012-08-29 |
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