CN106732626A - A kind of Co Ce Cu catalyst, preparation method and the application in carbon dioxide methanation reaction - Google Patents

A kind of Co Ce Cu catalyst, preparation method and the application in carbon dioxide methanation reaction Download PDF

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CN106732626A
CN106732626A CN201611171705.5A CN201611171705A CN106732626A CN 106732626 A CN106732626 A CN 106732626A CN 201611171705 A CN201611171705 A CN 201611171705A CN 106732626 A CN106732626 A CN 106732626A
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CN106732626B (en
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段清
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Shishou Jinyuan catalyst Co.,Ltd.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers

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Abstract

The present invention relates to a kind of Co Ce Cu catalyst, preparation method and the application in carbon dioxide methanation reaction, belong to catalyst technical field.It includes Co, Ce and Cu, and its carrier is nano silicon oxide.Problem of the present invention for the more accessory substance CO generations present in of carbon dioxide methanation course of reaction, there is provided a kind of new composite catalyst, mainly use Co, Ce, Cu is used as active component, after wherein Ce is acted on other active components, the amount of the CO of reaction generation can be significantly decreased, the other catalyst is using nano silicon oxide as carrier, standby is hydroxyl silicon oil modified during by being generated to carrier, it can be improved with polar solvent and the active force of particle, make the catalyst carrier of generation that preferable hollow structure is presented, improve the deposition and load capacity of catalyst active component, improve reactivity.

Description

A kind of Co-Ce-Cu catalyst, preparation method and carbon dioxide methanation reaction In application
Technical field
The present invention relates to a kind of Co-Ce-Cu catalyst, preparation method and answering in carbon dioxide methanation reaction With belonging to catalyst technical field.
Background technology
CO2Methanation reaction is proposed by french chemist Paul Sabatier, therefore, the reaction is called to be done Sabatier reacts, and course of reaction is will by a certain percentage to mix CO2And H2Gas by the reactor equipped with catalyst, one CO under the conditions of fixed temperature and pressure2And H2React generation water and methane.Chemical equation is as follows.
CO2+4H2=CH4+2H2O
Hydrogenation of carbon dioxide methanation with clear and definite application prospect due to receiving much concern.Current research is focused primarily upon urges In the exploitation of agent.For metal active constituent therein, numerous studies show, most of group VIII metal catalyst are to CO2/ CH4Conversion has catalytic action.Noble metal catalyst has activity of conversion higher, and wherein Rh, Ru, Ir catalytic performance is best, Pt, Pd is slightly worse, and transition-metal Fe, Co, Ni activity are also higher, and wherein the catalytic performance of Ni is only second to Rh, and activity order is:Ni>Co》 cu》Fe.In selecting catalyst, in addition to investigating activity, it is also contemplated that carbon deposit.Rostrup-Nielsen et al. have studied Pt Race's noble metal and Ni catalyst, as a result show, Rh and Ru has optimal coking resistivity, the hardly carbon deposit on Rh catalyst, Though Ni catalyst is with the catalytic performance suitable with Rh, Ru, carbon deposit is more serious.Al-ubaid et al. is in Pt/Zro2Catalysis In agent, in 853K, V (CO2):V(CH4)=1:Under conditions of 1, to CO2/CH4Reforming reaction has carried out the stability test of 500h, And thermogravimetric analysis/differential calorimetric scan (TGA/DSC) analysis has been carried out to the catalyst after experiment, show on catalyst without carbon deposit Generation.A.T.Aschroft et al. then have studied load Ni, Ru, Rh and Ir catalyst coking resistivity in the reaction, knot Fruit finds Ni, Pd catalyst because carbon deposit is inactivated quickly, and Ru, Rh catalyst with coking resistivity are still protected after 260h is run Hold activity very high.Some nearest results of study show, load Rh, Pt and Ni catalyst choice TiO2During as carrier, energy Greatly suppress carbon deposit.The main cause for suppressing carbon deposit is probably due to TiO2Species distribution is in metal surface, so as to destroy profit The formation of the big active metal group formed in carbon, also precisely due to TiO2In O easily from TiO2Move to metal surface, So as to the carbon deposit in oxidized metal surface, TiO2In oxygen migration ability be most strong in single metal oxides, be exactly then ZrO2、MgO、A12O3And SiO2。
CN1114955A discloses a kind of catalyst of hydrogenation of carbon dioxide methanation and urges, and used catalyst carrier is special Zirconium glue.Zirconium glue carrier is impregnated uniform with the mixed solution containing active component nickel, ruthenium and rare earth element, then through drying, roasting, Reduction, that is, be made.CN103551153A discloses a kind of copper-based carbon dioxide methanation catalyst, the chief active of the catalyst into It is divided into the oxide of metal, the metal includes one or more in copper, cobalt, aluminium, zinc, and magnesium, iron and manganese.
But above-mentioned catalyst does not solve the side reaction generation CO occurred in the middle of carbon dioxide methanation course of reaction The many problems of amount.
The content of the invention
The purpose of the present invention is：For the more accessory substance CO generations present in of carbon dioxide methanation course of reaction A kind of problem, there is provided new composite catalyst, mainly using Co, Ce, Cu as active component, by precipitation reaction, Prepared after roasting, it is possible to achieve the effect of low CO by-products.
Technical scheme is：
A kind of Co-Ce-Cu catalyst, it includes Co, Ce and Cu, and its carrier is nano silicon oxide.
The preparation method of Co-Ce-Cu catalyst, comprises the following steps：
1st step, by weight, mixes equal by 30~40 parts of sodium metasilicate, 3~5 parts of sodium sulphate, 400~500 parts of water It is even, it is warming up to 70~90 DEG C afterwards, aqueous acetic acid is added dropwise, make pH between 9~10, after letting cool, carry out first time ageing；Again Aqueous acetic acid is added dropwise, makes pH between 4~5, then carry out second ageing, add 30~35 parts of hydroxy silicon oil, stirring is equal After even, third time ageing is carried out, obtain the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 10~12 parts of cobalt nitrate, 4~6 parts of cerium chloride and copper nitrate 5~8 Part, after being well mixed, then it is slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, adjusts the pH value of solution It is 9~10, in the case where being stirred continuously, is slowly added dropwise and heating response, make the complete Precipitation of hydrous oxide, leaches and wash；
3rd step, is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, obtains catalyst.
In the 1st described step, the 5~10wt% of concentration of aqueous acetic acid, the time of ageing is 2~4h for the first time, second The time of ageing is 3~5h；The time of third time ageing is 5~15h.
In the 3rd described step, the time of ageing is 12~15h.
In the 4th described step, 450~500 DEG C of sintering temperature, roasting time is 1~4h.
By the catalyst obtained by above-mentioned preparation method.
Application of the above-mentioned catalyst in carbon dioxide methanation reaction.
Beneficial effect
Problem of the present invention for the more accessory substance CO generations present in of carbon dioxide methanation course of reaction, there is provided one New composite catalyst is planted, mainly using Co, Ce, Cu as active component, wherein Ce is acted on other active components Afterwards, the amount of the CO of reaction generation can be significantly decreased, the catalyst is using nano silicon oxide as carrier, by right in addition Standby is hydroxyl silicon oil modified when carrier is generated, and can improve itself and polar solvent and the active force of particle, makes the catalyst of generation Carrier is presented preferable hollow structure, improves the deposition and load capacity of catalyst active component, improves reactivity.
Specific embodiment
Embodiment 1
The preparation method of Co-Ce-Cu catalyst, comprises the following steps：
1st step, by weight, 30 parts of sodium metasilicate, 3 parts of sodium sulphate, 400 parts of water is well mixed, and is warming up to 70 DEG C Afterwards, 5wt% aqueous acetic acids are added dropwise, make pH between 9, after letting cool, carry out ageing 2h for the first time；5wt% acetic acid water is added dropwise again Solution, makes pH 4, then carries out second ageing 3h, adds 30 parts of hydroxy silicon oil, after stirring, carries out third time ageing 5h, obtains the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 5 parts of 10 parts of cobalt nitrate, 4 parts of cerium chloride and copper nitrate, is well mixed Afterwards, then it is slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 9, is constantly being stirred Mix down, be slowly added dropwise and heating response, make the complete Precipitation of hydrous oxide, leach and wash；
3rd step, 12h is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, 450 DEG C of sintering temperature, roasting Time is 1h, obtains catalyst.
Embodiment 2
The preparation method of Co-Ce-Cu catalyst, comprises the following steps：
1st step, by weight, 40 parts of sodium metasilicate, 5 parts of sodium sulphate, 500 parts of water is well mixed, and is warming up to 90 DEG C Afterwards, 10wt% aqueous acetic acids are added dropwise, make pH between 10, after letting cool, carry out ageing 4h for the first time；10wt% acetic acid is added dropwise again The aqueous solution, makes pH 5, then carries out second ageing 5h, adds 35 parts of hydroxy silicon oil, after stirring, carries out third time old Change 15h, obtain the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 8 parts of 12 parts of cobalt nitrate, 6 parts of cerium chloride and copper nitrate, is well mixed Afterwards, then it is slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 10, continuous Under stirring, it is slowly added dropwise and heating response, makes the complete Precipitation of hydrous oxide, leaches and wash；
3rd step, 15h is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, 500 DEG C of sintering temperature, roasting Time is 4h, obtains catalyst.
Embodiment 3
The preparation method of Co-Ce-Cu catalyst, comprises the following steps：
1st step, by weight, 35 parts of sodium metasilicate, 4 parts of sodium sulphate, 450 parts of water is well mixed, and is warming up to 75 DEG C Afterwards, 7wt% aqueous acetic acids are added dropwise, make pH between 9, after letting cool, carry out ageing 3h for the first time；7wt% acetic acid water is added dropwise again Solution, makes pH 4, then carries out second ageing 4h, adds 32 parts of hydroxy silicon oil, after stirring, carries out third time ageing 12h, obtains the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 6 parts of 11 parts of cobalt nitrate, 5 parts of cerium chloride and copper nitrate, is well mixed Afterwards, then it is slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 9, is constantly being stirred Mix down, be slowly added dropwise and heating response, make the complete Precipitation of hydrous oxide, leach and wash；
3rd step, 13h is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, 480 DEG C of sintering temperature, roasting Time is 2h, obtains catalyst.
Reference examples 1
Difference with embodiment 3 is：Hydroxy silicon oil is not added in silica support sol-process is prepared to nanoparticle sublist Face is modified.
The preparation method of Co-Ce-Cu catalyst, comprises the following steps：
1st step, by weight, 35 parts of sodium metasilicate, 4 parts of sodium sulphate, 450 parts of water is well mixed, and is warming up to 75 DEG C Afterwards, 7wt% aqueous acetic acids are added dropwise, make pH between 9, after letting cool, carry out ageing 3h for the first time；7wt% acetic acid water is added dropwise again Solution, makes pH 4, then carries out second ageing 16h, obtains the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 6 parts of 11 parts of cobalt nitrate, 5 parts of cerium chloride and copper nitrate, is well mixed Afterwards, then it is slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 9, is constantly being stirred Mix down, be slowly added dropwise and heating response, make the complete Precipitation of hydrous oxide, leach and wash；
3rd step, 13h is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, 480 DEG C of sintering temperature, roasting Time is 2h, obtains catalyst.
Reference examples 2
Difference with embodiment 3 is：Cerium chloride is not added, its consumption is replaced for cobalt nitrate.
The preparation method of Co-Cu catalyst, comprises the following steps：
1st step, by weight, 35 parts of sodium metasilicate, 4 parts of sodium sulphate, 450 parts of water is well mixed, and is warming up to 75 DEG C Afterwards, 7wt% aqueous acetic acids are added dropwise, make pH between 9, after letting cool, carry out ageing 3h for the first time；7wt% acetic acid water is added dropwise again Solution, makes pH 4, then carries out second ageing 4h, adds 32 parts of hydroxy silicon oil, after stirring, carries out third time ageing 12h, obtains the colloidal sol containing modified nano silicon oxide carrier；
2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds 6 parts of 16 parts of cobalt nitrate and copper nitrate, after being well mixed, then slowly NH is added dropwise4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 9, in the case where being stirred continuously, slow drop Adduction heating response, makes the complete Precipitation of hydrous oxide, leaches and washs；
3rd step, 13h is aged to sediment with ethanol；
4th step, the sediment after ageing is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, 480 DEG C of sintering temperature, roasting Time is 2h, obtains catalyst.
The application of catalyst：Weigh 0.1g catalyst to be placed in fixed bed reactors, 3h is reduced at 350 DEG C using hydrogen, will Reaction system is lowered the temperature, and switches to reactant gas source, is CO in unstripped gas composition2/H2(volume ratio)=1: 5, reaction velocity is 12000h-1, reaction pressure is 0.1MPa, and reaction temperature is to carry out carbon dioxide methanation reaction under conditions of 280 DEG C, gained The result that catalyst is applied to hydrogenation of carbon dioxide synthesizing methane is as follows.
Carbon dioxide conversion Methane selectively % Carbon monoxide selective %
Embodiment 1 65.4 99.5 0.78
Embodiment 2 72.3 99.3 0.92
Embodiment 3 85.1 99.7 0.51
Reference examples 1 56.2 98.6 1.25
Reference examples 2 62.9 98.8 1.32
As can be seen from the table, the catalyst that the present invention is provided is applied to be had preferably when carbon dioxide methanation catalytic reaction Reaction conversion ratio, more than 65% can be reached, while having the advantages that methane selectively is high, more than 99.0%, one can be reached The selectivity of carbonoxide is low, below 1.0%.As can be seen that being generated by using to carrier compared with reference examples 1 in embodiment 3 Shi Houyong is hydroxyl silicon oil modified, can improve itself and polar solvent and the active force of particle, and the catalyst carrier of generation is presented Preferable hollow structure, improves the deposition and load capacity of catalyst active component, improves conversion ratio；The relative comparison example 2 of embodiment 3 For, after wherein Ce is acted on other active components, the amount of the CO of reaction generation can be significantly decreased, make carbon monoxide Selectivity reduction.

Claims (7)

1. a kind of Co-Ce-Cu catalyst, it is characterised in that it includes Co, Ce and Cu, and its carrier is nano silicon oxide.
2. the preparation method of the Co-Ce-Cu catalyst described in claim 1, it is characterised in that comprise the following steps：1st step, By weight, 30~40 parts of sodium metasilicate, 3~5 parts of sodium sulphate, 400~500 parts of water are well mixed, are warming up to 70 ~90 DEG C afterwards, and aqueous acetic acid is added dropwise, and makes pH between 9~10, after letting cool, carries out first time ageing；Acetic acid water is added dropwise again Solution, makes pH between 4~5, then carries out second ageing, adds 30~35 parts of hydroxy silicon oil, after stirring, carries out Three ageings, obtain the colloidal sol containing modified nano silicon oxide carrier；2nd step, in the middle of the colloidal sol that the 1st step is obtained, adds nitre 5~8 parts of 10~12 parts of sour cobalt, 4~6 parts of cerium chloride and copper nitrate, after being well mixed, then are slowly added dropwise NH4The OH aqueous solution and (NH4)2CO3The mixed liquor of the aqueous solution, the pH value for adjusting solution is 9~10, in the case where being stirred continuously, is slowly added dropwise and heating response, Make the complete Precipitation of hydrous oxide, leach and wash；3rd step, is aged to sediment with ethanol；4th step, after ageing Sediment is leached, and after drying under reduced pressure, is placed in electric furnace lower roasting, obtains catalyst.
3. the preparation method of Co-Ce-Cu catalyst according to claim 2, it is characterised in that in the 1st described step, vinegar 5~the 10wt% of concentration of aqueous acid, the time of ageing is 2~4h for the first time, and the time of second ageing is 3~5h；For the third time The time of ageing is 5~15h.
4. the preparation method of Co-Ce-Cu catalyst according to claim 2, it is characterised in that old in the 3rd described step The time of change is 12~15h.
5. the preparation method of Co-Ce-Cu catalyst according to claim 2, it is characterised in that in the 4th described step, roasting 450~500 DEG C of temperature is burnt, roasting time is 1~4h.
6. the catalyst obtained by the preparation method of the Co-Ce-Cu catalyst described in claim 2.
7. application of the catalyst described in claim 6 in carbon dioxide methanation reaction.
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