CN105642289B - A kind of preparation method of synthesis gas full methanation catalyst - Google Patents
A kind of preparation method of synthesis gas full methanation catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of synthesis gas full methanation catalyst, the catalyst includes active component Ni, the first auxiliary agent, the second auxiliary agent and carrier, and 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
It is complete more particularly, to a kind of synthesis gas the present invention relates to a kind of preparation method of synthesis gas full methanation catalyst
The preparation method of full methanation 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 system of synthesis gas full methanation catalyst
Preparation Method, catalyst prepared by this method have that cost is cheap, metal component utilization rate is high, selectivity is good, anti-carbon deposition ability is strong
And stability it is good the characteristics of.
The preparation method of synthesis gas full 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 Co, and the second auxiliary agent is in Ca, Mg, Zr, Ce or La
One or more, carrier be aluminum oxide and silica in any one；Carrier quality is accounted for each element quality in catalyst
Percentage on the basis of, the content of active component is 20wt%~40wt%, preferably 25wt%~35wt%, and the content of the first auxiliary agent is
1wt%~5wt%, preferably 1wt%~3wt%, the content of the second auxiliary agent is 3wt%~5wt%, and surplus is carrier；The catalyst
Preparation method comprises the following steps：
（1）Active component presoma and the first auxiliary agent presoma are dissolved in aqueous solutions of organic acids, add surfactant,
Stirring adds the inorganic salts or silicon source of aluminium to after being completely dissolved, and stirs 24h, and then gel is made in stirring at 50 ~ 90 DEG C, institute
It is aged again to obtain gel, dries, is calcined and catalyst precarsor A is made；
（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.
1. in the preparation method of synthesis gas full methanation catalyst of the present invention, step（1）The active component presoma
For the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or nickel acetate；First auxiliary agent
Presoma is the one or more in cobalt nitrate, cobalt acetate, cobaltous sulfate or cobalt chloride, preferably cobalt nitrate or cobalt acetate；The table
Face activating agent is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, lauryl sodium sulfate, detergent alkylate
One or more in sodium sulfonate or polyethylene glycol, preferably cetyl trimethylammonium bromide or polyethylene glycol；The nothing of the aluminium
Machine salt is the one or more in aluminum nitrate, aluminium chloride or aluminum sulfate, preferably aluminum nitrate；The silicon source be positive quanmethyl silicate,
One or more in tetraethyl orthosilicate, Ludox or silicic acid, preferably tetraethyl orthosilicate or Ludox；The organic acid is
One or more in citric acid, tartaric acid, malic acid, oxalic acid or butanedioic acid, optimization citric acid or tartaric acid；The above method
In, the active component, the first auxiliary agent, surfactant, silicon source（Or silicon source）, organic acid and water mol ratio for 0.01 ~
0.15:0.01~0.15:0.1~1:1:0.15~1:50~200；Wherein, active component, the first auxiliary agent, silicon source（Or silicon source）Respectively
With Elements C o, Ni, Al（Si）Meter.Described Aging Temperature is 30 ~ 50 DEG C, and digestion time is 6 ~ 12h；Drying temperature be 100 ~
120 DEG C, drying time is 6 ~ 15h；Sintering temperature is 400 ~ 700 DEG C, and roasting time is 3 ~ 6h；In the catalyst precarsor A, nickel
Weight content in the carrier is counted as 1wt%~5wt% using element.
In the preparation method of synthesis gas full methanation catalyst of the present invention, step（2）Described in reducing atmosphere be hydrogen
The mixed gas of gas or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.It is specific to go back
Former processing procedure is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen and nitrogen
The mixed gas of 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 full methanation catalyst of the present invention, step（3）Described in polyalcohol can be
One or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%~10%；It is more
First alcoholic solution and step（2）Obtained reduction rear catalyst precursor A volume ratio is 5~10.
In the preparation method of synthesis gas full methanation catalyst of the present invention, step（5）In, the active component presoma
For the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or nickel acetate；Second auxiliary agent
Presoma is calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, one kind in lanthanum nitrate or more
Kind, preferably zirconium nitrate；The concentration of active component nickel is 3.5~8.5mol/L in the solution D, and the concentration of the second promoter metal is
0.2~2.5mol/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 full methanation catalyst of the present invention, step（5）Described in drying temperature be 70~
150 DEG C, preferably 80~120 DEG C, drying time are 2~12h, preferably 4~8h.The sintering temperature is 350~650 DEG C,
Preferably 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 full methanation preparing natural gas.Catalyst exists
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 full methanation preparing natural gas reacts, and preferable process conditions are：The composition H of unstripped gas2/ CO mol ratios be 1.0~
4.0, Ar, N can be contained in unstripped gas2Or the dilution such as He property gas, 2000~20000h of unstripped gas air speed-1, reaction pressure is
0.1~5Mpa, reaction temperature are 250~650 DEG C.
Catalyst of the present invention, using aluminum oxide or silica support, first load a small amount of active metal component Ni
With the first auxiliary agent Co, obtained catalyst precarsor is after reduction treatment, and catalytic polyol aqueous phase is hydrogenated with autoclave,
The product C of generation5And C6Liquid alkane can be used as atent solvent to the further processing of catalyst precarsor；Urging after treatment
Agent precursor load active component Ni and the second adjuvant component again, preferably control the active metal loaded in carrier duct
Amount, promote more multiple active components in the scattered of carrier surface, both improved the utilization rate of active metal, reduce catalyst into
This, accelerates the adsorption desorption speed of reactant and product in catalyst surface and hole, so as to avoid the further of product again
Conversion, improves 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
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-1.
Embodiment 2
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add tetraethyl orthosilicate（TEOS）, 24h is stirred at room temperature, is then stirred at 60 DEG C
For mixing into gel, gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, 550 DEG C of roasting 4h, catalyst precarsor A is made,
Ni accounts for vehicle weight 3% in terms of element, and Co accounts for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Si：Citric acid：Water=
0.15:0.1:0.5:1:0.6:150。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-2.
Embodiment 3
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 70 DEG C,
Gained gel is aged 12h, 120 DEG C of dry 8h at 30 DEG C, and 450 DEG C of roasting 6h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 5%, Co account for vehicle weight 1% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.05:0.01:0.6:
1:0.8:200。
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 25%Ni, 3%Zr, 1%Co catalyst, be designated as C-3.
Embodiment 4
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 50 DEG C,
Gained gel is aged 6h, 110 DEG C of dry 11h at 50 DEG C, and 600 DEG C of roasting 3h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 5%, Co account for vehicle weight 3% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water:0.05:0.03:0.3:
1:0.5:200。
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 35%Ni, 5%Zr, 3%Co catalyst, be designated as C-4.
Embodiment 5
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add polyethylene glycol 400（PEG-400）,
Stirring adds aluminum nitrate, 24h is stirred at room temperature to after being completely dissolved, and then gel, gained gel is made in stirring at 60 DEG C
10h, 100 DEG C of dry 10h are aged at 40 DEG C, 550 DEG C of roasting 4h, catalyst precarsor A, Ni is made vehicle weight is accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：PEG-400：Al：Citric acid：Water=0.15:0.1:0.3:1:0.6:
150。
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 30%Ni, 4%Ca, 2%Co catalyst, be designated as C-5.
Embodiment 6
Nickel nitrate and cobalt nitrate are dissolved in aqueous tartaric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Tartaric acid：Water=0.15:0.1:0.5:1:
0.6:150。
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 30%Ni, 4%Mg, 2%Co catalyst, be designated as C-6.
Embodiment 7
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Ce, 2%Co catalyst, be designated as C-7.
Embodiment 8
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%La, 2%Co catalyst, be designated as C-8.
Embodiment 9
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-9.
Embodiment 10
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, is designated as C-10.
Embodiment 11
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-
11。
Embodiment 12
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-12.
Embodiment 13
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as C-13.
Comparative example 1
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Its Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
20g catalyst precarsors A is added to 50mLC6In alkane solvent, 20min is impregnated, then filters, does 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 30%Ni, 4%Zr, 2%Co catalyst, is designated as D-1.
Comparative example 2
Nickel nitrate and cobalt nitrate are dissolved in aqueous citric acid solution at room temperature, add cetyl trimethylammonium bromide
（CTAB）, stir to after being completely dissolved, add aluminum nitrate, 24h is stirred at room temperature, then gel is made in stirring at 60 DEG C,
Gained gel is aged 10h, 100 DEG C of dry 10h at 40 DEG C, and 550 DEG C of roasting 4h, obtained catalyst precarsor A, Ni are accounted in terms of element
Vehicle weight 3%, Co account for vehicle weight 2% in terms of element；Wherein Ni：Co：CTAB：Al：Citric acid：Water=0.15:0.1:0.5:1:
0.6:125。
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 30%Ni, 4%Zr, 2%Co catalyst, be designated as
D-2。
Comparative example 3
Weigh appropriate nickel nitrate, zirconium nitrate and cobalt nitrate 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
30%Ni, 4%Zr, 2%Co catalyst, are designated as D-3.
The reactivity worth of the catalyst of table 1
The content distribution of the catalyst activity component of table 2（wt%）
Claims (24)
1. a kind of preparation method of synthesis gas full methanation catalyst, the catalyst includes active component, the first auxiliary agent, the
Two auxiliary agents and carrier, active component Ni；First auxiliary agent is Co, and the second auxiliary agent is one kind or several in Ca, Mg, Zr, Ce or La
Kind, carrier is any one in aluminum oxide and silica；Using in catalyst each element quality account for the percentage of carrier quality as
Benchmark, the content of active component is 20wt%~40wt%, and the content of the first auxiliary agent is 1wt%~5wt%, and the content of the second auxiliary agent is
3wt%~5wt%, surplus are carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma and the first auxiliary agent presoma are dissolved in aqueous solutions of organic acids, add surfactant, stirring
To after being completely dissolved, the inorganic salts or silicon source of aluminium are added, stir 24h, then gel is made in stirring at 50 ~ 90 DEG C, and gained coagulates
Glue is aged again, dries, and is calcined and is made in catalyst precarsor A, the catalyst precarsor A, weight of the nickel in terms of element in the carrier
Amount content is 1wt%~5wt%；
（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, polyalcohol is
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. according to the preparation method described in claim 1, it is characterised in that：Step（1）And step（5）Described in before active component
Drive body is the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
3. according to the preparation method described in claim 2, 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.
4. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be nitre
One or more in sour cobalt, cobalt acetate, cobaltous sulfate or cobalt chloride.
5. according to the preparation method described in claim 4, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be nitre
Sour cobalt or cobalt acetate.
6. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in surfactant be hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, lauryl sodium sulfate, neopelex or polyethylene glycol
In one or more.
7. according to the preparation method described in claim 6, it is characterised in that：Step（1）Described in surfactant be hexadecane
Base trimethylammonium bromide or polyethylene glycol.
8. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in aluminium inorganic salts for aluminum nitrate,
One or more in aluminium chloride or aluminum sulfate.
9. according to the preparation method described in claim 8, it is characterised in that：Step（1）Described in the inorganic salts of aluminium be aluminum nitrate.
10. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in silicon source be positive silicic acid tetramethyl
One or more in ester, tetraethyl orthosilicate, Ludox or silicic acid.
11. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in silicon source be tetraethyl orthosilicate
Or Ludox.
12. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in organic acid be citric acid, wine
One or more in stone acid, malic acid, oxalic acid or butanedioic acid.
13. according to the preparation method described in claim 12, it is characterised in that：Step（1）Described in organic acid be citric acid or
Tartaric acid.
14. according to the preparation method described in claim 1, it is characterised in that：Step（1）The active component, the first auxiliary agent, table
Face activating agent, silicon source, the mol ratio of organic acid and water are 0.01 ~ 0.15:0.01~0.15:0.1~1:1:0.15~1:50~200.
15. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in Aging Temperature be 30 ~ 50
DEG C, digestion time is 6 ~ 12h；Drying temperature is 100 ~ 120 DEG C, and drying time is 6 ~ 15h；Sintering temperature is 400 ~ 700 DEG C, roasting
The burning time is 3 ~ 6h.
16. according to the preparation method described in claim 1, it is characterised in that：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.
17. according to the preparation method described in claim 1, it is characterised in that：Step（2）Described in reduction treatment process it is as follows：
Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to the mixed gas of hydrogen or hydrogen and nitrogen,
After 0.1~0.5MPa handles 4~8h, room temperature is down in a nitrogen atmosphere.
18. according to the preparation method described in claim 1, it is characterised in that：Step（3）Described in polyhydric alcohol solutions quality it is dense
Spend for 5%~10%；Polyhydric alcohol solutions and step（2）Obtained reduction rear catalyst precursor A volume ratio is 5~10.
19. according to the preparation method described in claim 1, it is characterised in that：Step（5）Described in the second auxiliary agent presoma be nitre
One or more in sour calcium, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate.
20. according to the preparation method described in claim 19, it is characterised in that：Step（5）Described in the second auxiliary agent presoma be
Zirconium nitrate.
21. according to the preparation method described in claim 1, it is characterised in that：Step（5）Described in active component nickel in solution C
Concentration be 3.5~8.5mol/L, the concentration of the second promoter metal is 0.2~2.5mol/L.
22. according to the preparation method described in claim 1, it is characterised in that：Step（5）Described in drying temperature be 70~150
DEG C, drying time is 2~12h, and the sintering temperature is 350~650 DEG C, and roasting time is 2~12h.
23. according to the preparation method described in claim 22, it is characterised in that：Step（5）Described in drying temperature be 80~120
℃；Drying time is 4~8h；The sintering temperature is 400~600 DEG C；Roasting time is 4~8h.
24. according to the preparation method described in claim 1, it is characterised in that：The content of the active component be 25wt%~
35wt%, the content of the first auxiliary agent is 1wt%~3wt%.
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