CN107224980A - Preparation method without the carbon dioxide methanation catalyst of reduction activation - Google Patents

Preparation method without the carbon dioxide methanation catalyst of reduction activation Download PDF

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CN107224980A
CN107224980A CN201610173031.6A CN201610173031A CN107224980A CN 107224980 A CN107224980 A CN 107224980A CN 201610173031 A CN201610173031 A CN 201610173031A CN 107224980 A CN107224980 A CN 107224980A
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China
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preparation method
characterised
catalyst according
deg
catalyst
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CN201610173031.6A
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Chinese (zh)
Inventor
黄先亮
徐本刚
吴学其
张�杰
吴�琳
朱艳芳
王金利
蔡进
魏士新
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中国石油化工股份有限公司
南化集团研究院
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926Copper and noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses the preparation method of the carbon dioxide methanation catalyst without reduction activation, belong to catalysis technical field, the preparation method without the carbon dioxide methanation catalyst of reduction activation, it is characterised in that Al will be contained3+,Cu2+,Ru3+Mixed nitrate solution be added to the water with alkaline precipitating agent cocurrent, and maintain pH value of solution=7 ~ 8;After N-process terminates, by aging, washing, filtering, drying, dried solid is calcined in an inert atmosphere, obtained product and aliphatic hydroxyl acid are dispersed in volatile organic solvent, then dry, be calcined removing organic solvent under anaerobic, finally beat sheetmolding.

Description

Preparation method without the carbon dioxide methanation catalyst of reduction activation

Technical field

The invention belongs to catalysis technical field, and in particular to a kind of carbon dioxide methanation catalyst without reduction activation Preparation method.

Background technology

China is the discharge big country of carbon dioxide, and total emission volumn accounts for a quarter in the whole world, and discharges growth trend 20 ~ 30 years will also be continued.In recent years, the developed country such as America and Europe levied carbon tariff in succession(Or carbon emission tax), this will make China Exporting(Including petrochemicals and high polymer material etc.)Cost is greatly increased.Currently, low-carbon economy and carbon resource Low-carbon using turn into main development trend.

Carbon dioxide is one of reserves the abundantest carbon source on the earth.With the increasingly depleted of petroleum resources, in addition to Serious ecological and environmental problem, industry and academia's active response in air caused by a large amount of discharge carbon dioxide, it is proposed that Many new thoughts, technology path and countermeasure attempt to solve this problem.Therefore, catalytic hydrogenation of carbon dioxide methanation is because of its war Slightly property meaning and practicality turn into the rather noticeable problem during carbon dioxide chemistry is studied.

Carbon monoxide, carbon dioxide methanation reaction belong to strong exothermal reaction, and key reaction formula is as follows:

The key of carbon dioxide methanation reaction is the catalyst for selecting high activity.Since Sabatier etc. is reported in nickel catalysis Since carbon dioxide and the methanation of carbon monoxide under agent effect, the methanation performance of forefathers to the catalyst of different systems Substantial amounts of research is carried out, they have found that the catalyst with methanation activity is broadly divided into three classes:The mistake of oxide carried type Cross metallic catalyst, catalyst and non-supported metallic catalyst derived from cluster compound.Methanation catalyst is generally with Al2O3, oxygen It is carrier to change zirconium, silica, titanium oxide, and methanation catalyst is with high-purity gamma-Al as disclosed in patent US 39338332O3To carry Body, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in patent CN 1043639A is using zirconium oxide as load Body, nickel is active component, and with rare earth metal or alkaline-earth metal, or alkaline-earth metal is co-catalyst.Patent CN 1043449A are disclosed Methanation catalyst, nickel is active component, and rare earth metal and magnesium are co-catalyst, and remaining is aluminum oxide.These methanations are urged Agent is used in trace amounts of CO x methanation reaction, and reaction temperature is not high, and steam partial pressure is relatively low in reacting gas, catalyst With good stability.

Chinese patent CN 1054269 discloses a kind of methanation catalyst preparation method of producing synthesis gas from coal, catalyst Active component is using preceding needing to use 10% H2/N2Program is warming up to 250 DEG C ~ 350 DEG C reductase 12 h ~ 6h.

Reduction activation process before catalyst use needs to consume H2, and usually need to take a long time, to catalysis Agent brings additional energy and inconvenience using process.

The content of the invention

The invention provides a kind of preparation method of the carbon dioxide methanation catalyst without reduction activation.Utilize the party Method can obtained methanation catalyst there is good catalytic activity and stability.

The present invention's is mainly characterized by by introducing aliphatic hydroxyl acid in catalyst preparation process, under an inert atmosphere After burning, aliphatic hydroxyl acid, which decomposes the gas produced, has pore-creating effect, and CuO can be reduced for metal by decomposing obtained CO Cu。

The technical scheme is that:Al will be contained3+,Cu2+,Ru3+Mixed nitrate solution and alkaline precipitating agent cocurrent It is added to the water, and maintains pH value of solution=7 ~ 8;, will be dried by aging, washing, filtering, drying after N-process terminates Solid is calcined in an inert atmosphere, obtained product and aliphatic hydroxyl acid is dispersed in volatile organic solvent, so Dry afterwards, be calcined removing organic solvent under anaerobic, finally beat sheetmolding.

Usually, the amount of material Al, Cu, Ru total in nitrate solution of the present invention is 1, wherein, Al elements contain It is that 20% ~ 50%, Ru constituent contents are 0.5% ~ 2% to measure as 30% ~ 80%, Cu constituent contents.

Also contain Mg in mixed nitrate solution of the present invention2+、La3+、Zr4+、Ce3+And Ga3+In one kind or many Kind, the ratio between the amount of its total material and the amount of Al elemental substances are 0.01 ~ 0.2.

Alkaline precipitating agent used of the invention is Na2CO3、NaHCO3、K2CO3Or KHCO3The aqueous solution.

Hydroxyl polycarboxylic acid of the present invention is citric acid or tartaric acid.

The amount ratio of hydroxyl polycarboxylic acid's usage amount of the present invention and Al elemental substances in product is 0.01 ~ 0.2.

Volatile organic solvent of the present invention is ethanol, acetone, ether.

Sintering temperature is 350 DEG C ~ 700 DEG C under inert atmosphere of the present invention.

The temperature that roasting under anaerobic of the present invention removes organic solvent is 200 DEG C ~ 400 DEG C..

It is good using the methanation catalyst catalytic activity and stability prepared by the present invention.

Embodiment

With reference to embodiment, the present invention is described in detail.

Embodiment 1

Weigh 302.0g Al (NO3)3·9H2O、28.8g Cu(NO3)2·3H2O, 1.5g nitrosyl nitrate ruthenium are dissolved in water-soluble Total salt concentration is made into liquid for 1mol/L solution, by mixed nitrate solution and 1mol/L Na2CO3Solution is preheated to 60 DEG C Afterwards, cocurrent is added in 60 DEG C of deionized waters and maintains pH=7 ~ 8;After aging 30min, sediment is washed with deionized water Wash, filter cake is obtained after filtering, is dried overnight, 350 DEG C of roastings;15.0 citric acids are weighed, and are together dispersed in filter cake 3L second In alcohol, after stirring at normal temperature 30min, temperature rises to 60 DEG C and reclaims ethanol distillation, the 200 DEG C of roastings under anaerobic of obtained solid 2h is burnt, room temperature is down to afterwards, obtained solid is beaten into sheetmolding, catalyst I is obtained.

Embodiment 2

Weigh 150.0g Al (NO3)3·9H2O、28.8g Cu(NO3)2·3H2O、5.0g Mg(NO3)2·6H2O, 1.0g nitrous Acyl group nitric acid ruthenium, which is dissolved in the aqueous solution, is made into total salt concentration for 1mol/L solution, by mixed nitrate solution and 1mol/L NaHCO3Solution is preheated to after 60 DEG C, and cocurrent is added in 60 DEG C of deionized waters and maintains pH=7 ~ 8;After aging 30min, use Deionized water is washed to sediment, and filter cake is obtained after filtering, is dried overnight, 700 DEG C of roastings;15.0 tartaric acid are weighed, and together Filter cake is together dispersed in 3L acetone, after stirring at normal temperature 30min, and temperature rises to 60 DEG C and is distilled to recover acetone, obtains Solid is calcined 2h for 400 DEG C under anaerobic, and room temperature is down to afterwards, obtained solid is beaten into sheetmolding, catalyst II is obtained.

Embodiment 3

Weigh 302.0g Al (NO3)3·9H2O、28.8g Cu(NO3)2·3H2O、5.0g Ce(NO3)3·6H2O, 1.0g nitrous Acyl group nitric acid ruthenium, which is dissolved in the aqueous solution, is made into total salt concentration for 1mol/L solution, by mixed nitrate solution and 1mol/L K2CO3 Solution is preheated to after 60 DEG C, and cocurrent is added in 60 DEG C of deionized waters and maintains pH=7 ~ 8;After aging 30min, deionization is used Water is washed to sediment, and filter cake is obtained after filtering, is dried overnight, 500 DEG C of roastings;15.0 citric acids are weighed, and with filter cake one With being dispersed in 3L ether, after stirring at normal temperature 30min, temperature rises to 60 DEG C and is distilled to recover ether, and obtained solid exists The lower 300 DEG C of roastings 2h of oxygen free condition, is down to room temperature, obtained solid is beaten into sheetmolding, obtain catalyst III afterwards.

Embodiment 4

Weigh 302.0g Al (NO3)3·9H2O、28.8g Cu(NO3)2·3H2O、5.0g La(NO3)3·6H2O, 1.0g nitrous Acyl group nitric acid ruthenium, which is dissolved in the aqueous solution, is made into total salt concentration for 1mol/L solution, by mixed nitrate solution and 1mol/L KHO3 Solution is preheated to after 60 DEG C, and cocurrent is added in 60 DEG C of deionized waters and maintains pH=7 ~ 8;After aging 30min, deionization is used Water is washed to sediment, and filter cake is obtained after filtering, is dried overnight, 500 DEG C of roastings;15.0 citric acids are weighed, and with filter cake one With being dispersed in 3L ethanol, after stirring at normal temperature 30min, temperature rises to 60 DEG C and reclaims ethanol distillation, and obtained solid exists The lower 300 DEG C of roastings 2h of oxygen free condition, is down to room temperature, obtained solid is beaten into sheetmolding, obtain catalyst IV afterwards.

Embodiment 5

Weigh 302.0g Al (NO3)3·9H2O、28.8g Cu(NO3)2·3H2O、5.0g Zr(NO3)3·5H2O, 1.0g nitrous Acyl group nitric acid ruthenium, which is dissolved in the aqueous solution, is made into total salt concentration for 1mol/L solution, by mixed nitrate solution and 1mol/L Na2CO3Solution is preheated to after 60 DEG C, and cocurrent is added in 60 DEG C of deionized waters and maintains pH=7 ~ 8;After aging 30min, spend Ionized water is washed to sediment, and filter cake is obtained after filtering, is dried overnight, 500 DEG C of roastings;15.0 citric acids are weighed, and with filter Cake is together dispersed in 3L ethanol, after stirring at normal temperature 30min, and temperature rises to 60 DEG C and reclaims ethanol distillation, and what is obtained consolidates Body is calcined 2h for 300 DEG C under anaerobic, and room temperature is down to afterwards, obtained solid is beaten into sheetmolding, catalyst V is obtained.

Methanation catalyst I, II, III, IV, V is seated in fixed-bed tube reactor respectively, and reaction condition is:Pressure 3.0MPa, gas composition H239.12, CO 1.18, CO26.30, N2For Balance Air, gas space velocity is 5000 ~ 30000h-1, After 600 DEG C of reaction 500h, the activity of catalyst keeps good, wherein CO2Conversion ratio close to 80%, methane selectively close to 90%, The catalytic mechanical intensity removed is still very high, and the surface of catalyst does not have carbon distribution.

Catalyst Air speed CO2Total conversion(%) Methane selectively (%) 10000 79.3 89.5 10000 79.5 89.0 10000 79.8 88.9 10000 79.1 89.1 10000 79.7 89.3

Claims (10)

1. the preparation method of a kind of carbon dioxide methanation catalyst without reduction activation, it is characterised in that Al will be contained3+, Cu2+,Ru3+Mixed nitrate solution be added to the water with alkaline precipitating agent cocurrent, and maintain pH value of solution=7 ~ 8;N-process After end, by aging, washing, filtering, dry, dried solid is calcined in an inert atmosphere, by obtained product with Aliphatic hydroxyl acid is dispersed in volatile organic solvent, is then dried, is calcined removing organic solvent under anaerobic, Finally beat sheetmolding.
2. the preparation method of catalyst according to claim 1, it is characterised in that Al, Cu, Ru in described nitrate solution The amount of total material is 1, wherein, Al constituent contents are that 30% ~ 80%, Cu constituent contents are that 20% ~ 50%, Ru constituent contents are 0.5% ~2%。
3. the preparation method of catalyst according to claim 1, it is characterised in that also contain in described mixed nitrate solution There is Mg2+、La3+、Zr4+、Ce3+And Ga3+In one or more, the ratio between the amount of its total material and the amount of Al elemental substances are 0.01~0.2。
4. the preparation method of catalyst according to claim 1, its feature is Na in alkaline precipitating agent used2CO3、NaHCO3、 K2CO3Or KHCO3The aqueous solution.
5. the preparation method of catalyst according to claim 1, it is characterised in that described is hydroxyl for aliphatic hydroxyl acid Polybasic carboxylic acid.
6. the preparation method of catalyst according to claim 5, it is characterised in that described hydroxyl polycarboxylic acid is citric acid Or tartaric acid.
7. the preparation method of catalyst according to claim 1,5 or 6, it is characterised in that hydroxyl polycarboxylic acid's usage amount and production The amount ratio of Al elemental substances is 0.01 ~ 0.2 in thing.
8. the preparation method of catalyst according to claim 1, it is characterised in that volatile organic solvent be ethanol, acetone, Ether.
9. the preparation method of catalyst according to claim 1, it is characterised in that under inert atmosphere sintering temperature be 350 DEG C ~ 700℃。
10. the preparation method of catalyst according to claim 1, it is characterised in that roasting removes organic molten under anaerobic The temperature of agent is 200 DEG C ~ 400 DEG C.
CN201610173031.6A 2016-03-24 2016-03-24 Preparation method without the carbon dioxide methanation catalyst of reduction activation CN107224980A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103551153A (en) * 2013-10-29 2014-02-05 西南化工研究设计院有限公司 Copper-based catalyst for methanation of carbon dioxide and preparation method of copper-based catalyst
CN104148065A (en) * 2013-05-14 2014-11-19 中国科学院大连化学物理研究所 Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof
CN104275185A (en) * 2013-07-12 2015-01-14 中国石油化工股份有限公司 Preparation method of copper-based hydrogenation catalyst without reduction activation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104148065A (en) * 2013-05-14 2014-11-19 中国科学院大连化学物理研究所 Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof
CN104275185A (en) * 2013-07-12 2015-01-14 中国石油化工股份有限公司 Preparation method of copper-based hydrogenation catalyst without reduction activation
CN103551153A (en) * 2013-10-29 2014-02-05 西南化工研究设计院有限公司 Copper-based catalyst for methanation of carbon dioxide and preparation method of copper-based catalyst

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