CN104190425A - Catalyst for preparing synthesis gas by reforming methane and carbon dioxide - Google Patents
Catalyst for preparing synthesis gas by reforming methane and carbon dioxide Download PDFInfo
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- CN104190425A CN104190425A CN201410438192.4A CN201410438192A CN104190425A CN 104190425 A CN104190425 A CN 104190425A CN 201410438192 A CN201410438192 A CN 201410438192A CN 104190425 A CN104190425 A CN 104190425A
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- catalyst
- reforming methane
- cobalt
- nickel
- montmorillonite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the technical field of catalysts for preparing synthesis gas by reforming methane and carbon dioxide and in particular relates to a catalyst for preparing synthesis gas by reforming methane and carbon dioxide. According to the catalyst, montmorillonite is used as a carrier; and nickel and cobalt are used as active components. The catalyst for preparing the synthesis gas by reforming methane and carbon dioxide has the advantages that the montmorillonite is used as the carrier of the catalyst; alkyl quaternary ammonium salts are intercalated in the montmorillonite, so that nickel oxide and cobalt oxide can be relatively well dispersed on the surface of the montmorillonite; the resistance to carbon deposition of the catalyst is improved; the service life of the catalyst is prolonged; nickel and cobalt complexes are adopted, so that the active components which comprise the nickel and the cobalt can be dispersed and loaded relatively fully; the catalytic performance of the catalyst is improved.
Description
Technical field
The invention belongs to the catalyst technical field for synthesizing gas by reforming methane with co 2, be specifically related to a kind of catalyst for synthesizing gas by reforming methane with co 2.
Background technology
Synthesizing gas by reforming methane with co 2 (DRM) provides a comprehensive utilization carbon source, hydrogen source, transforms two kinds of difficult activated micromoleculars simultaneously, and eliminates the technology path of two kinds of main greenhouse gas, has the multiple researching value of economy, environmental protection, science.
The synthesis gas (hydrogen and carbon monoxide) that methane reforming with carbon dioxide produces is the synthetic desirable feedstock of preparing the liquid fuels such as diesel oil, paraffin of Fischer-Tropsch, is also the important source material of preparing methyl alcohol and dimethyl ether.Methane carbon dioxide reformation process is specially adapted to rich carbonated gas field simultaneously, has reduced the expense that separating carbon dioxide brings.
Take noble metal that Pt, Pd be representative and the VII metalloid that Ni, Co be representative of take has activity to methane reforming with carbon dioxide, but because of the noble metals such as Pt, Pd expensive.
Summary of the invention
The present invention is directed in the prior art of synthesizing gas by reforming methane with co 2 and have the expensive problem of noble metal and a kind of catalyst for synthesizing gas by reforming methane with co 2 is provided.
The technical scheme that realizes the object of the invention is: a kind of catalyst for synthesizing gas by reforming methane with co 2, take imvite as carrier, and take nickel cobalt as active component, make nickel cobalt/montmorillonite catalyst.
Described nickel cobalt/montmorillonite catalyst, is made by following concrete steps:
1) take analytically pure nickel nitrate, cobalt nitrate, and be dissolved in and in alcohol solvent, form nickel cobalt clear solution;
2) add citric acid or oxalic acid, stirring, standing;
3) organo montmorillonite is joined to step 2) in the solution of gained, stir;
4) under water bath condition, dry, be transferred in baking oven dry;
5) put into Muffle furnace and carry out high-temperature roasting, make nickel cobalt/montmorillonite catalyst.
Further, the nickel nitrate described in step 1) and the mass ratio 1:5 of ethanol, the mass ratio of cobalt nitrate and nickel nitrate is 1:(1～3).
Wherein, the mol ratio of the citric acid described in step 3) or oxalic acid and nickel nitrate is 1:1.
Wherein, the roasting condition of step 5) is: 350 ℃～500 ℃ of sintering temperatures, roasting time 2～4 hours.
Further, imvite of the present invention is made by following treatment step: imvite is scattered in DMF solvent, under high-speed stirred condition, add hexadecyltrimethylammonium chloride, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
Wherein, the mass ratio of imvite and DMF solvent is 1:(5～15), the mass ratio of imvite and hexadecyltrimethylammonium chloride is 1:(0.2～0.6).
The invention has the advantages that: 1) catalyst of the present invention selects imvite as carrier, imvite is through the intercalation of alkyl quaternary ammonium salts, nickel oxide, cobalt oxide can be disperseed better on imvite surface, improve the anti-carbon deposition ability of catalyst, extending catalyst service life.2) the present invention adopts nickel cobalt complex, can make active component nickel cobalt spread loads obtain more abundant, improves the catalytic performance of catalyst.
The specific embodiment
Below in conjunction with embodiment, the present invention is done further and described.
A kind of catalyst for synthesizing gas by reforming methane with co 2 of the present invention, this catalyst be take imvite as carrier, take nickel cobalt as active component, specifically by following concrete steps, is made:
1) take analytically pure nickel nitrate, cobalt nitrate, and be dissolved in and in alcohol solvent, form nickel cobalt clear solution;
2) add citric acid or oxalic acid, stirring, standing;
3) organo montmorillonite is joined to step 2) in the solution of gained, stir;
4) under water bath condition, dry, be transferred in baking oven dry;
5) put into Muffle furnace and carry out high-temperature roasting, make nickel cobalt/montmorillonite catalyst.
Imvite of the present invention makes through following treatment step: imvite is scattered in DMF solvent, under high-speed stirred condition, add hexadecyltrimethylammonium chloride, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
embodiment 1
1) modification of imvite
10 grams of imvites are scattered in 50 grams of DMF solvents, under high-speed stirred condition, add 2 grams of hexadecyltrimethylammonium chlorides, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
2) preparation of nickel cobalt/imvite
Take analytically pure 10 grams of nickel nitrates, 10 grams of cobalt nitrates, and be dissolved in and in 50 grams of alcohol solvents, form nickel cobalt clear solution; Add 4.4 grams of citric acids, stirring, standing; The imvite that adds step 1) to make, stirs; Under water bath condition, dry, be transferred in baking oven dry; Then put into Muffle furnace and carry out high-temperature roasting, 350 ℃ of sintering temperatures, roasting time 4 hours, makes nickel cobalt/montmorillonite catalyst.
embodiment 2
1) modification of imvite
10 grams of imvites are scattered in 100 grams of DMF solvents, under high-speed stirred condition, add 4 grams of hexadecyltrimethylammonium chlorides, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
2) preparation of nickel cobalt/imvite
Take analytically pure 20 grams of nickel nitrates, 4 grams of cobalt nitrates, and be dissolved in and in 100 grams of alcohol solvents, form nickel cobalt clear solution; Add 8.8 grams of citric acids, stirring, standing; The imvite that adds step 1) to make, stirs; Under water bath condition, dry, be transferred in baking oven dry; Then put into Muffle furnace and carry out high-temperature roasting, 400 ℃ of sintering temperatures, roasting time 3 hours, makes nickel cobalt/montmorillonite catalyst.
embodiment 3
1) modification of imvite
10 grams of imvites are scattered in 150 grams of DMF solvents, under high-speed stirred condition, add 6 grams of hexadecyltrimethylammonium chlorides, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
2) preparation of nickel cobalt/imvite
Take analytically pure 30 grams of nickel nitrates, 10 grams of cobalt nitrates, and be dissolved in and in 150 grams of alcohol solvents, form nickel cobalt clear solution; Add 9.3 grams of oxalic acid, stirring, standing; The imvite that adds step 1) to make, stirs; Under water bath condition, dry, be transferred in baking oven dry; Then put into Muffle furnace and carry out high-temperature roasting, 500 ℃ of sintering temperatures, roasting time 2 hours, makes nickel cobalt/montmorillonite catalyst.
Claims (7)
1. for a catalyst for synthesizing gas by reforming methane with co 2, it is characterized in that: take imvite as carrier, take nickel cobalt as active component, make nickel cobalt/montmorillonite catalyst.
2. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 1, is characterized in that: described nickel cobalt/montmorillonite catalyst, is made by following concrete steps:
Take analytically pure nickel nitrate, cobalt nitrate, and be dissolved in and in alcohol solvent, form nickel cobalt clear solution;
Add citric acid or oxalic acid, stirring, standing;
Organo montmorillonite is joined to step 2) in the solution of gained, stir;
Under water bath condition, dry, be transferred in baking oven dry;
Put into Muffle furnace and carry out high-temperature roasting, make nickel cobalt/montmorillonite catalyst.
3. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 2, is characterized in that: the mass ratio 1:5 of the nickel nitrate described in step 1) and ethanol, wherein the mass ratio of cobalt nitrate and nickel nitrate is 1:(1～3).
4. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 2, is characterized in that: the mol ratio of the citric acid described in step 3) or oxalic acid and nickel nitrate is 1:1.
5. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 2, is characterized in that: the roasting condition of step 5) is: 350 ℃～500 ℃ of sintering temperatures, roasting time 2～4 hours.
6. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 1 or 2, it is characterized in that: described organo montmorillonite is made by following steps: imvite is scattered in DMF solvent, under high-speed stirred condition, add hexadecyltrimethylammonium chloride, under 80 ℃ of constant temperatures, stir, by deionized water washing and suction filtration for product, at 120 ℃, be dried last grind into powder.
7. the catalyst for synthesizing gas by reforming methane with co 2 as claimed in claim 6, it is characterized in that: the mass ratio of imvite and DMF solvent is 1:(5～15), the mass ratio of imvite and hexadecyltrimethylammonium chloride is 1:(0.2～0.6).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410438192.4A CN104190425B (en) | 2014-09-01 | 2014-09-01 | A kind of catalyzer for synthesizing gas by reforming methane with co 2 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410438192.4A CN104190425B (en) | 2014-09-01 | 2014-09-01 | A kind of catalyzer for synthesizing gas by reforming methane with co 2 |
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| CN104190425A true CN104190425A (en) | 2014-12-10 |
| CN104190425B CN104190425B (en) | 2016-06-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371952A (en) * | 2018-02-28 | 2018-08-07 | 西京学院 | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst |
| CN110665543A (en) * | 2019-11-07 | 2020-01-10 | 西安石油大学 | Metal-clay composite catalyst for high-temperature viscosity reduction of thick oil and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176090A (en) * | 1975-11-18 | 1979-11-27 | W. R. Grace & Co. | Pillared interlayered clay materials useful as catalysts and sorbents |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
-
2014
- 2014-09-01 CN CN201410438192.4A patent/CN104190425B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176090A (en) * | 1975-11-18 | 1979-11-27 | W. R. Grace & Co. | Pillared interlayered clay materials useful as catalysts and sorbents |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王莉等: "甲烷与二氧化碳催化重整制取合成气催化剂", 《化学进展》, vol. 24, no. 9, 30 September 2012 (2012-09-30) * |
| 黄传敬等: "甲烷二氧化碳重整制合成气镍-钴双金属催化剂", 《应用化学》, vol. 18, no. 9, 30 September 2001 (2001-09-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371952A (en) * | 2018-02-28 | 2018-08-07 | 西京学院 | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst |
| CN110665543A (en) * | 2019-11-07 | 2020-01-10 | 西安石油大学 | Metal-clay composite catalyst for high-temperature viscosity reduction of thick oil and preparation method thereof |
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| CN104190425B (en) | 2016-06-08 |
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