CN105727969B - A kind of preparation method of synthesis gas methanation catalyst - Google Patents
A kind of preparation method of synthesis gas methanation catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of synthesis gas methanation catalyst, catalyst precarsor A is made in the preparation method of the catalyst first；Then reduction treatment is carried out to catalyst precarsor A using reducing atmosphere；Catalyst precarsor A after reduction and polyhydric alcohol solutions are added in autoclave and carry out hydrogenation reaction, reaction effluent is placed and then filtered and dried, obtains catalyst precarsor B；Active component presoma and the second auxiliary agent presoma is soluble in water, solution C is obtained, catalyst precarsor B is then added, after drying, calcination process, obtains catalyst.The inventive method promotes more multiple active components and disperseed in carrier surface, had both improved the utilization rate of active metal, and had improved the conversion ratio of carbon monoxide and the selectivity of product again.
Description
Technical field
The present invention relates to a kind of preparation method of synthesis gas methanation catalyst, more particularly, to a kind of synthesis gas methanation
The preparation method of loading type nickel-based catalyst.
Background technology
Methanation refers to CO/CO2With H2Under certain temperature, pressure and catalyst action, CH is generated4Process, mesh
Before, this reaction is widely used in synthesizing the removing of trace carbon, gas employing methanation of coke oven, natural gas from coal in ammonia or hydrogen production process
Among technique.Methanation is a kind of important catalysis technique, particularly in fuel applications field, can be used for improving combustion gas heat
Value, it is allowed to the conversion of coke-stove gas, coal or biomass to natural gas.In recent years, with China's coal substitute natural gas industry
Fast development, the methanation as one of core technology is of increased attention.
China be one " rich coal, oil-poor, few gas " country, using abundant coal resources, pass through coal based synthetic gas
Methanation production natural gas has good economic benefit in Waste Era of Oil, to solving the problem of complex utilization of coal resources,
Alleviate the present situation of Chinese postman problem algorithm shortage, safeguard energy security, realize CO2Emission reduction, environmental protection are respectively provided with important strategy
Meaning.
It was found from the basic research result of open report and relevant information, reacted for synthesis gas preparing natural gas by methanation,
Ni base catalyst（High Ni contents, 20%~70%）For main fluid catalyst；The easy coking deactivation of Fe base catalyst；Co bases catalyst is resistant to
Property is strong, but poor selectivity；Ru bases catalyst activity is higher than Ni base catalyst, but its cost is high；The auxiliary agent or carrier material of use
There are aluminum oxide, titanium oxide, silica, cerium oxide, lanthana, zirconium oxide, calcium oxide, magnesia etc..In a word, to natural gas from coal
The requirement of industrial catalyst is mainly：Low temperature, efficiently（I.e. reaction temperature is low, and the hydrogen-carbon ratio scope of unstripped gas is wide, CO and CO2's
Hydrogenation conversion is high, CH4Selectivity it is high）, stability is good（It is i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning）, service life is long, into
This is low.Reach these requirements, the compositing formula of catalyst and the reasonable selection of fabricating technology are crucial.
Methanation catalyst is with Al disclosed in Chinese patent CN1043639A2O3For carrier, nickel is active component, with rare earth
Metal, or alkaline-earth metal, or alkali metal are auxiliary agent.Methanation catalyst disclosed in United States Patent (USP) US3933883 with high-purity gamma-
Al2O3For carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in Chinese patent CN1043449A, nickel
For active component, rare earth metal and magnesium are co-catalyst, and remaining is aluminum oxide.
Although catalyst made from above-mentioned patented method obtains preferable synthesis gas methanation reaction performance, due to
The reaction is a fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）, reactant to
Completed up to reaction while catalyst external surface, thus the inner surface of catalyst is contributed goal response less, this just makes
Relatively low rate of metal in into carrier duct, add the preparation cost of catalyst.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation side of synthesis gas methanation catalyst
Method, catalyst prepared by this method have that cost is cheap, metal component utilization rate is high, the good, anti-carbon deposition ability of selectivity is strong and
The characteristics of stability is good.
The preparation method of synthesis gas methanation catalyst of the present invention, the catalyst include active component, first
Auxiliary agent, the second auxiliary agent and carrier, active component Ni；First auxiliary agent is Mo, and the second auxiliary agent is one in Ca, Mg, Zr, Ce or La
Kind is several, and carrier is any one in aluminum oxide, silica, HZSM-5；Carrier matter is accounted for each element quality in catalyst
On the basis of the percentage of amount, the content of active component is 30wt%~60wt%, preferably 40wt%~50wt%, the content of the first auxiliary agent
For 1wt%~5wt%, preferably 1wt%~3wt%, the content of the second auxiliary agent is 1wt%~5wt%, and surplus is carrier；The catalyst
Preparation method comprise the following steps：
（1）Normal octane, n-hexyl alcohol and surfactant are mixed, the microemulsion stablized, then added into microemulsion
Enter active component presoma and the first auxiliary agent presoma, hydrazine hydrate solution is added after being sufficiently stirred at 20~60 DEG C and is reduced
Agent, carrier is added after continuing 4~6h of stirring, after continuing 1~3h of stirring at 70~90 DEG C, filtering, gained solid precipitation second
Alcohol washs 3~5 times, then catalyst precarsor A is made through drying, roasting；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）By step（2）Catalyst precarsor A after obtained reduction is added in autoclave with polyhydric alcohol solutions,
Replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；
（4）By step（3）Obtained reaction effluent places 1~3h, then filters, gained solid sample enters at room temperature
Row drying, until sample surfaces without liquid phase, obtain catalyst precarsor B；
（5）Active component presoma and the second auxiliary agent presoma is soluble in water, solution C is obtained, then adds step（4）
Obtained catalyst precarsor B, after drying, calcination process, obtains catalyst.
In the preparation method of synthesis gas methanation catalyst of the present invention, step（1）The surfactant can be poly- second
One or more in glycol octyl phenyl ether and Tween 80, the active component presoma are nickel nitrate, nickel acetate, nickel sulfate
Or the one or more in nickel chloride, preferably nickel nitrate or nickel acetate；The first auxiliary agent presoma is ammonium dimolybdate, four molybdic acids
One or more in ammonium or ammonium molybdate, preferably ammonium molybdate；The normal octane, n-hexyl alcohol, surfactant, active component,
The mol ratio of one auxiliary agent is 0.5~1:1:0.2~0.5:1.5~8.5：1, the mass fraction of hydrazine hydrate is in hydrazine hydrate solution
50%~80%, the volume ratio with normal octane is 1:30~1:40；Step（1）The drying condition is 100~120 DEG C of temperature, when
Between 4~6h；Roasting condition is 400 DEG C~500 DEG C of temperature, time 4h~8h；In the catalyst precarsor A, nickel in terms of element
Weight content in carrier is 1wt%~5wt%.
In the preparation method of synthesis gas methanation catalyst of the present invention, step（2）Described in reducing atmosphere for hydrogen or
The mixed gas of person's hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specifically go back original place
Reason process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen and nitrogen
Mixed gas, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, room temperature is down in a nitrogen atmosphere.
In the preparation method of synthesis gas methanation catalyst of the present invention, step（3）Described in polyalcohol can be xylose
One or more in alcohol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%~10%；Polyalcohol
Solution and step（2）Obtained reduction rear catalyst precursor A volume ratio is 5~10.
In the preparation method of synthesis gas methanation catalyst of the present invention, step（5）In, the active component presoma is nitre
One or more in sour nickel, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or nickel acetate；The second auxiliary agent forerunner
Body is the one or more in calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate,
It is preferred that zirconium nitrate；The concentration range of active component nickel is 5~13mol/L in the solution D, the concentration range of the second promoter metal
For 0.05~2.5mol/L.Auxiliary agent and the specific dipping process of active component are to use method well known to those skilled in the art.
In the preparation method of synthesis gas methanation catalyst of the present invention, step（2）Described in drying temperature be 70~150
DEG C, preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h.The sintering temperature is 350~650 DEG C, preferably
For 400~600 DEG C, roasting time is 2~12h, preferably 4~8h.
Catalyst prepared by the inventive method can also need to be made suitable particle shape according to what is used, and bar is such as made
Shape, piece shape, cylindricality etc..
Catalyst prepared by the inventive method can apply to the reaction of synthesis gas preparing natural gas by methanation.Catalyst is using
It is preceding in a hydrogen atmosphere, 400~600 DEG C of 2~6h of prereduction, preferably 4h.Catalyst prepared by the inventive method is applied to synthesis
Gas preparing natural gas by methanation reacts, and preferable process conditions are：The composition H of unstripped gas2/ CO mol ratios are 1.0~4.0, raw material
Ar, N can be contained in gas2Or the dilution such as He property gas, 2000~20000h of unstripped gas air speed-1, reaction pressure be 0.1~
5Mpa, reaction temperature are 250~650 DEG C.
Catalyst of the present invention, using aluminum oxide, silica or Hydrogen ZSM-5 carriers, first load a small amount of activity
Metal component Ni and the first auxiliary agent Mo, obtained catalyst precarsor are catalyzed polynary after reduction treatment in autoclave
Alcohol aqueous phase is hydrogenated with, the product C of generation5And C6Liquid alkane can be used as atent solvent to the further processing of catalyst precarsor；By
Catalyst precarsor after processing load active component Ni and the second adjuvant component again, preferably control what is loaded in carrier duct
Active metal amount, promote more multiple active components and disperse in carrier surface, both improved the utilization rate of active metal, and reduced
Catalyst cost, the adsorption desorption speed of reactant and product in catalyst surface and hole is accelerated again, so as to avoid product
Further conversion, improve the conversion ratio of carbon monoxide and the selectivity of product.
Embodiment
The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.
Appreciation condition：With hydrogen reducing 4 hours at 450 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
Reacted in quartz reactor, 270 DEG C of reaction temperature, unstripped gas composition H2/CO/N2 = 67.5/22.5/10（Mol ratio）,
Air speed 3200h-1, gas-chromatography on-line analysis is used after the condensed water removal of product, reaction result is shown in Table 1.Reaction result shown in table 1 is
Average activity of the catalyst in 270 DEG C of work 6h.
Using point of active component in the catalyst prepared by the scanning electron microscope analysis present invention and auxiliary agent on a catalyst
Cloth situation.The active component scanning electron microscope analysis of catalyst the results are shown in Table 2 obtained by the embodiment of the present invention.
Embodiment 1
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 3 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 3MPa, 4h is reacted at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, roasted at 400 DEG C
4h is burnt, shaping, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-1.
Embodiment 2
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate Hydrogen ZSM-5 is added（Silica alumina ratio 50, pore volume 0.23ml/g, specific surface area 426m2/g）Carrier, 80
Continue at DEG C after stirring 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, in 450 DEG C of roastings
6h, catalyst precarsor A, Ni is made vehicle weight 3% is accounted in terms of element, Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：
N-hexyl alcohol：Tween 80：Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume of hydrazine hydrate solution and normal octane
Than for 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, roasted at 450 DEG C
3h is burnt, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-2.
Embodiment 3
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate silica is added（Pore volume is 1.06ml/g, specific surface area 387m2/g）Carrier, continue to stir at 80 DEG C
After mixing 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalysis is made
Agent precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween
80：Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 10% in mixed gas,
Reducing condition is 500 DEG C, 0.2MPa（Absolute pressure）, recovery time 6h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 2 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 3MPa, 4h is reacted at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 3h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 120 DEG C and dries 6h, be calcined at 400 DEG C
4h, shaping, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-3.
Embodiment 4
Appropriate normal octane, n-hexyl alcohol and Triton X-100 are mixed, stable microemulsion is made, to micro emulsion
The aqueous solution containing appropriate nickel nitrate and ammonium molybdate is added in liquid, is sufficiently stirred at 60 DEG C, then adds appropriate 50% hydration
Hydrazine solution, after stirring 6h, add appropriate aluminum oxide（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, at 90 DEG C
Under continue after stirring 1h, filtering, gained solid precipitation wash 3 times with ethanol, then at 100 DEG C of dry 5h, in 500 DEG C of roasting 4h,
Catalyst precarsor A, Ni is made vehicle weight 5% is accounted in terms of element, Mo accounts for vehicle weight 3% in terms of element；Wherein normal octane：Just oneself
Alcohol：Triton X-100：Active component nickel：First auxiliary agent molybdenum=0.5:1:0.5:2.7:1, hydrazine hydrate solution with it is just pungent
The volume ratio of alkane is 1:40.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to carrier surface without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400 DEG C
Lower roasting 4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 40%Ni, 1%Zr, 3%Mo catalyst, be designated as C-4.
Embodiment 5
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 20 DEG C, then adds appropriate 80% hydrazine hydrate solution, stir
After 4h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 70 DEG C
After 3h, filtering, gained solid precipitation is washed 5 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 1% in terms of element, and Mo accounts for vehicle weight 1% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=1:1:0.5:1.6:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:30.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to carrier surface without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400 DEG C
Lower roasting 4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 50%Ni, 5%Zr, 1%Mo catalyst, be designated as C-5.
Embodiment 6
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of calcium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400 DEG C
Lower roasting 4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Ca, 2%Mo catalyst, be designated as C-6.
Embodiment 7
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of magnesium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400 DEG C
Lower roasting 4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Mg, 2%Mo catalyst, be designated as C-7.
Embodiment 8
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added containing appropriate nickel nitrate and
In the mixed aqueous solution of cerous nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, at 400 DEG C
4h is calcined, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Ce, 2%Mo catalyst, be designated as C-8.
Embodiment 9
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The sorbitol solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 2MPa, 2h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to sample surfaces without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of lanthanum nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400 DEG C
Lower roasting 4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%La, 2%Mo catalyst, be designated as C-9.
Embodiment 10
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 50% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 6h；By the catalyst precarsor A after reduction activation and 400mL mass
The xylitol solution that concentration is 10% is added in autoclave, is replaced 3 times with hydrogen after sealing, is then adjusted Hydrogen Vapor Pressure
To 3MPa, 4h is reacted at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample exists
Dry at room temperature to carrier surface without liquid phase, obtain catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate
In the mixed aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 120 DEG C and dries 8h, at 400 DEG C
4h is calcined, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-10.
Embodiment 11
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in hydrogen atmosphere, reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, during reduction
Between 3h；Catalyst precarsor A after reduction activation and 200mL mass concentrations are added to reaction under high pressure for 10% mannitol solution
In kettle, replaced 2 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 4MPa, react 3h at 280 DEG C；By above-mentioned autoclave
In reacted mixture place 2h, filtering, gained solid sample is dried at room temperature for being catalyzed without liquid phase to sample surfaces
Agent precursor B；Catalyst precarsor B is added in the mixed aqueous solution containing appropriate nickel nitrate and zirconium nitrate, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 80 DEG C and is dried 12h, and 4h is calcined at 400 DEG C, that is, the quality in terms of element is made and accounts for carrier percentage
Content is 45%Ni, 3%Zr, 2%Mo catalyst, is designated as C-11.
Embodiment 12
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
The arabite solution that concentration is 10% is added in autoclave, is replaced 4 times with hydrogen after sealing, is then adjusted hydrogen pressure
Power reacts 2h to 2MPa at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample
It is dried at room temperature for obtaining catalyst precarsor B without liquid phase to sample surfaces；Catalyst precarsor B is added to containing appropriate nitric acid
In the mixed aqueous solution of nickel and zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, 400
4h is calcined at DEG C, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-
12。
Embodiment 13
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
Concentration be 5% sorbitol solution be added in autoclave, after sealing with hydrogen replace 4 times, then adjust Hydrogen Vapor Pressure to
2MPa, react 2h at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample is in room
Temperature is lower to be dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate and
In the aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, be calcined at 400 DEG C
4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-13.
Embodiment 14
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 90% in mixed gas,
Reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst precarsor A after reduction activation and 300mL mass
Concentration be 8% sorbitol solution be added in autoclave, after sealing with hydrogen replace 4 times, then adjust Hydrogen Vapor Pressure to
2MPa, react 2h at 300 DEG C；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample is in room
Temperature is lower to be dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is added to containing appropriate nickel nitrate and
In the aqueous solution of zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, be calcined at 400 DEG C
4h, that is, it is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as C-14.
Comparative example 1
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is added in 50mLC6 alkane solvents, 20min is impregnated, then filters, do at room temperature
It is dry, until catalyst precarsor B is made without liquid phase in precursor surface；Catalyst precarsor B is added to containing appropriate nickel nitrate and nitric acid
In the aqueous solution of zirconium, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h, be calcined 4h at 400 DEG C, i.e.,
It is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, is designated as D-1.
Comparative example 2
Appropriate normal octane, n-hexyl alcohol and Tween 80 are mixed, stable microemulsion is made, adds and contains into microemulsion
The aqueous solution of appropriate nickel nitrate and ammonium molybdate, is sufficiently stirred at 40 DEG C, then adds appropriate 60% hydrazine hydrate solution, stir
After 5h, appropriate aluminum oxide is added（Pore volume is 0.71ml/g, specific surface area 236m2/g）Carrier, continue to stir at 80 DEG C
After 2h, filtering, gained solid precipitation is washed 4 times with ethanol, then at 110 DEG C of dry 5h, is calcined 6h in 450 DEG C, catalyst is made
Precursor A, Ni account for vehicle weight 3% in terms of element, and Mo accounts for vehicle weight 2% in terms of element；Wherein normal octane：N-hexyl alcohol：Tween 80：
Active component nickel：First auxiliary agent molybdenum=0.8:1:0.3:2.4:1, the volume ratio of hydrazine hydrate solution and normal octane is 1:35.
20g catalyst precarsors A is added in the sorbitol solution that 300mL mass concentrations are 10%, impregnates 20min, then
Filtering, is dried at room temperature for, until catalyst precarsor B is made without liquid phase in precursor surface；By catalyst precarsor B be added to containing
In the aqueous solution of appropriate nickel nitrate and zirconium nitrate, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 100 DEG C and dries 12h,
4h is calcined at 400 DEG C, that is, is made and quality is counted using element accounts for carrier percentage composition as 45%Ni, 3%Zr, 2%Mo catalyst, be designated as
D-2。
Comparative example 3
Weigh appropriate nickel nitrate, zirconium nitrate and ammonium molybdate to be dissolved in appropriate ionized water, the aqueous solution is made；Using isometric
Infusion process is carried on 20g aluminum oxide（Pore volume is 0.71ml/g, specific surface area 236m2/ g, bar shaped, equivalent diameter 1.5mm）Carry
Body, aging 6h, 100 DEG C of dry 12h, 400 DEG C of roasting 4h, i.e., the obtained quality in terms of element account for carrier percentage composition and are at room temperature
45%Ni, 3%Zr, 2%Mo catalyst, are designated as D-3.
The reactivity worth of the catalyst of table 1
The content distribution of the active component of the catalyst of table 2（wt%）
Claims (18)
1. a kind of preparation method of synthesis gas methanation catalyst, the catalyst helps including active component, the first auxiliary agent, second
Agent and carrier, active component Ni；First auxiliary agent is Mo, and the second auxiliary agent is the one or more in Ca, Mg, Zr, Ce or La, is carried
Body is any one in aluminum oxide, silica, HZSM-5；Using in catalyst each element quality account for the percentage of carrier quality as
Benchmark, the content of active component is 30wt%~60wt%, and the content of the first auxiliary agent is 1wt%~5wt%, and the content of the second auxiliary agent is
1wt%~5wt%, surplus are carrier；The preparation method of the catalyst comprises the following steps：
（1）Normal octane, n-hexyl alcohol and surfactant are mixed, the microemulsion stablized, then add and live into microemulsion
Property component presoma and the first auxiliary agent presoma, add hydrazine hydrate solution after being sufficiently stirred at 20~60 DEG C, continue stirring 4~
Carrier is added after 6h, after continuing 1~3h of stirring at 70~90 DEG C, filtering, gained solid precipitation is washed 3~5 times with ethanol, then
Catalyst precarsor A is made through drying, roasting；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）By step（2）Catalyst precarsor A after obtained reduction is added in autoclave with polyhydric alcohol solutions, is sealed
Replaced 2~5 times with hydrogen afterwards, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C, described is more
First alcohol is the one or more in xylitol, sorbierite, mannitol, arabite；
（4）By step（3）Obtained reaction effluent places 1~3h, then filters, gained solid sample is done at room temperature
It is dry, until sample surfaces without liquid phase, obtain catalyst precarsor B；
（5）Active component presoma and the second auxiliary agent presoma is soluble in water, solution C is obtained, then adds step（4）Obtain
Catalyst precarsor B, after drying, calcination process, obtain catalyst.
2. in accordance with the method for claim 1, it is characterised in that：The percentage of carrier quality is accounted for each element quality in catalyst
Than on the basis of, the content of active component is 40wt%~50wt%, and the content of the first auxiliary agent is 1wt%~3wt%.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）The surfactant is polyethylene glycol octyl group
One or more in phenyl ether and Tween 80.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）And step（5）Described in active component presoma
For the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
5. according to the method described in claim 1 or 4, it is characterised in that：Step（1）And step（5）Described in before active component
It is nickel nitrate or nickel acetate to drive body.
6. in accordance with the method for claim 1, it is characterised in that：Step（1）The first auxiliary agent presoma is ammonium dimolybdate,
One or more in ammonium tetramolybdate or ammonium molybdate.
7. according to the method described in claim 1 or 6, it is characterised in that：Step（1）The first auxiliary agent presoma is molybdic acid
Ammonium.
8. in accordance with the method for claim 1, it is characterised in that：Step（1）The normal octane, n-hexyl alcohol, surfactant,
Active component, the mol ratio of the first auxiliary agent are 0.5~1:1:0.2~0.5:1.5~8.5：1.
9. in accordance with the method for claim 1, it is characterised in that：Step（1）The quality of hydrazine hydrate in the hydrazine hydrate solution
Fraction is 50%~80%, and the volume ratio of the hydrazine hydrate solution and normal octane is 1:30~1:40.
10. in accordance with the method for claim 1, it is characterised in that：Step（1）The drying condition is temperature 100~120
DEG C, 4~6h of time；Roasting condition is 400 DEG C~500 DEG C of temperature, time 4h~8h.
11. in accordance with the method for claim 1, it is characterised in that：Step（1）In the catalyst precarsor A, nickel is in terms of element
Weight content in the carrier is 1wt%~5wt%.
12. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
13. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in reduction treatment process it is as follows：Nitrogen
Catalyst precarsor A is warming up to 300~600 DEG C under atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, 0.1
After handling 4~8h under~0.5MPa, room temperature is down in a nitrogen atmosphere.
14. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in the mass concentrations of polyhydric alcohol solutions be
5%~10%.
15. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in polyhydric alcohol solutions and step（2）
The reduction rear catalyst precursor A arrived volume ratio is 5~10.
16. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in the second auxiliary agent presoma be nitric acid
One or more in calcium, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate.
17. according to the method described in claim 1 or 16, it is characterised in that：Step（5）Described in the second auxiliary agent presoma be nitre
Sour zirconium.
18. in accordance with the method for claim 1, it is characterised in that：Step（5）The concentration of active component nickel in the solution C
For 5~13mol/L, the concentration of the second promoter metal is 0.05~2.5mol/L.
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| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| CN103480375A (en) * | 2013-09-29 | 2014-01-01 | 福州大学 | Carbon monoxide methanating catalyst and preparation method thereof |
| 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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| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
| CN103480375A (en) * | 2013-09-29 | 2014-01-01 | 福州大学 | Carbon monoxide methanating catalyst and preparation method thereof |
| 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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