CN106944061B - A kind of preparation method of synthesis gas methanation catalyst - Google Patents

A kind of preparation method of synthesis gas methanation catalyst Download PDF

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CN106944061B
CN106944061B CN201610003122.5A CN201610003122A CN106944061B CN 106944061 B CN106944061 B CN 106944061B CN 201610003122 A CN201610003122 A CN 201610003122A CN 106944061 B CN106944061 B CN 106944061B
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catalyst
solution
auxiliary agent
added
presoma
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CN106944061A (en
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孙晓丹
张舒冬
刘继华
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides

Abstract

The present invention relates to a kind of preparation methods of synthesis gas methanation catalyst, the catalyst includes active component, first auxiliary agent, second auxiliary agent and carrier, the preparation method of the catalyst includes the following steps: to prepare catalyst precarsor A first, then reduction treatment is carried out to catalyst precarsor A, it is uniformly mixed with furfural aqueous solution by auxiliary agent presoma is soluble in water, then it is added in autoclave together with catalyst precarsor A, it is reacted after solution C is added, filtering obtained solid sample is again through drying after obtained solidliquid mixture processing separation, after calcination process, obtain catalyst.The catalyst reaction activity of this method preparation is high, not only reduces metal consumption, but also improve the selectivity of methane.

Description

A kind of preparation method of synthesis gas methanation catalyst
Technical field
The present invention relates to a kind of preparation methods of synthesis gas methanation catalyst, more particularly, to a kind of synthesis gas methanation The preparation method of loading type nickel-based catalyst.
Background technique
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 Etc. among techniques.Methanation is a kind of important catalysis technique, especially in fuel applications field, can be used to improve combustion gas heat Value allows coke-stove gas, coal or biomass to the conversion of natural gas.In recent years, with China's coal substitute natural gas industry Fast development, the methanation as one of core technology is receive more and more attention.
China is one, and the country of " rich coal, oil-poor, few gas " passes through coal based synthetic gas using coal resources abundant Methanation produce natural gas it is with good economic efficiency in Waste Era of Oil, to solve coal resources problem of complex utilization, Alleviate the status of Chinese postman problem algorithm shortage, safeguard energy security, realizes CO2Emission reduction, protection environment all have important strategy Meaning.
From basic research result and the relevant information of open report it is found that being reacted for synthesis gas preparing natural gas by methanation, Ni base catalyst (high Ni content, 20%~70%) is main fluid catalyst；The easy coking deactivation of Fe base catalyst；The tolerance of Co base catalyst Property is strong, but poor selectivity；Ru base catalyst activity is higher than Ni base catalyst, but its is at high cost；The auxiliary agent or carrier material of use There are aluminium oxide, titanium oxide, silica, cerium oxide, lanthana, zirconium oxide, calcium oxide, magnesia etc..In short, 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 range of unstripped gas is wide, CO and CO2's Hydrogenation conversion is high, CH4Selectivity it is high), stability is good (i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning), long service life, at This is low.Reach these requirements, the compositing formula of catalyst and the reasonable selection of fabricating technology are crucial.
Methanation catalyst disclosed in Chinese patent CN1043639A is with Al2O3For 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 is 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, remaining is aluminium 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 carries out under conditions of being typically at mass transport limitation), and reactant arrives Reaction is completed while up to catalyst external surface, thus the inner surface of catalyst contributes less goal response, this just makes At lower metal utilization in carrier duct, the preparation cost of catalyst is increased.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of preparation sides of synthesis gas methanation catalyst Method, the catalyst of this method preparation have the characteristics that low in cost, metal component utilization rate is high and selectivity is good.
The present invention provides a kind of preparation method of synthesis gas methanation catalyst, the catalyst include active component, First auxiliary agent, the second auxiliary agent and carrier, active component Ni, the first auxiliary agent are Cu, and the second auxiliary agent is in Ca, Mg, Zr, Ce or La One or more, carrier be any one of aluminium oxide, silica；Catalyst quality is accounted for each element quality in catalyst On the basis of percentage, the content of active component is 10wt%~30wt%, and the content of preferably 15wt%~25wt%, the first auxiliary agent are The content of 1wt%~3wt%, the second auxiliary agent are 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst includes as follows Step:
(1) normal octane, n-hexyl alcohol and surfactant are mixed, obtains stable microemulsion, then added into microemulsion Enter the aqueous solution containing active component presoma and the first auxiliary agent presoma, hydrazine hydrate is added after being sufficiently stirred at 20~60 DEG C Solution makees reducing agent, and carrier is added after continuing 4~6h of stirring, after continuing 1~3h of stirring at 70~90 DEG C, filters, gained is solid Body precipitating is washed 3~5 times with dehydrated alcohol, then catalyst precarsor A is made through drying, roasting；
(2) reduction treatment is carried out to the catalyst precarsor A that step (1) obtains using reducing atmosphere；
(3) the second auxiliary agent presoma is soluble in water, obtain solution B, and be uniformly mixed with furfural aqueous solution, then with step Suddenly the catalyst precarsor A that (2) obtain is added in autoclave together；
(4) water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added It into autoclave described in step (3), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
(5) solidliquid mixture obtained to step (4) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, 1~2h is placed, is then filtered, obtained solid sample after drying, calcination process, obtains catalyst again.
In the preparation method of synthesis gas methanation catalyst of the present invention, surfactant described in step (1) can be poly- Ethylene glycol octyl phenyl ether and/or Tween 80；The active component presoma is nickel nitrate, in nickel acetate, nickel sulfate, nickel chloride One or more, preferably nickel nitrate；The first auxiliary agent presoma be one of copper nitrate, copper sulphate, copper chloride or It is several, preferably copper nitrate；The normal octane, n-hexyl alcohol, surfactant molar ratio be 0.5~1:1:0.2~0.5；Institute Stating the molar ratio of water and surfactant in the aqueous solution containing active component presoma and the first auxiliary agent presoma is 10~20； The mass fraction of hydrazine hydrate is 50%~80% in the hydrazine hydrate solution, the volume ratio that hydrazine hydrate solution and normal octane is added For 1:5~1:10.
In the preparation method of synthesis gas methanation catalyst of the present invention, the carrier is aluminium oxide, any in silica Kind, commercially available product can be used, can also be prepared by method well known in the art.
In the preparation method of synthesis gas methanation catalyst of the present invention, 100~120 DEG C of drying temperature described in step (1), 4~6h of drying time；The roasting condition is 400 DEG C~500 DEG C of maturing temperature, calcining time 4h~8h；Before the catalyst In body A, the nickel of load is 1wt%~5wt% of final catalyst, the copper of load is in terms of element wt, for most in terms of element wt 1wt%~3wt% of whole catalyst.
In the preparation method of synthesis gas methanation catalyst of the present invention, reducing atmosphere described in step (2) be 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 being 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) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of synthesis gas methanation catalyst of the present invention, the second auxiliary agent presoma described in step (3) is One of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate are a variety of, preferably For zirconium nitrate；In the solution B, based on the element, mass fraction in the solution is 1%~4% to the second auxiliary agent；The furfural is water-soluble The mass fraction of furfural is 30%~50% in liquid；Furfural aqueous solution described in step (3) and the mass ratio of solution B are 3~5, institute The mass ratio for the reduction rear catalyst precursor A that the gross mass and step (2) for stating solution B and furfural aqueous solution obtain is 3~6.
In the preparation method of synthesis gas methanation catalyst of the present invention, water soluble polymer described in step (4) For one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；The active component Presoma is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；It is living in the solution C Property component presoma in the nickeliferous mass fraction in solution C based on the element be 0.4%~2.5%, water soluble polymer polymerization Mass fraction of the object in solution C is 3~6 times of Ni element mass fraction.
In the preparation method of synthesis gas methanation catalyst of the present invention, addition dehydrated alcohol or lemon described in step (5) The quality of acid and the mass ratio of water soluble polymer are 2~4；The mass fraction of the aqueous citric acid solution be 10%~ 20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；It is described Maturing temperature is 350~650 DEG C, and preferably 400~600 DEG C, calcining time is 2~12h, preferably 4~8h.
The catalyst of the method for the present invention preparation can be applied 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.The catalyst of the method for the present invention preparation is applied to synthesis The reaction of gas preparing natural gas by methanation, preferable process conditions are as follows: the composition H of unstripped gas2/ CO molar ratio is 1.0~4.0, raw material Ar, N can be contained in gas2Or the dilution property gas such as He, 2000~20000h of unstripped gas air speed-1, reaction pressure be 0.1~ 5Mpa, reaction temperature are 250~650 DEG C.
Compared with prior art, a kind of available active metal outer layer distribution of the preparation method being related to through the invention Synthesis gas methanation catalyst.In the present invention, pre-soaked a part of active metal is to carry out furfural water phase hydrogenation reaction.? Active metal predecessor and water soluble polymer is added simultaneously in the system of furfural hydrogenation, on the one hand utilizes furfural hydrogenation Product hinders active metal to the diffusion inside catalyst granules；On the other hand, active metal predecessor and high water solubility are utilized Coordination between Molecularly Imprinted Polymer reduces concentration difference of the active metallic ion inside and outside catalyst granules in solution, slows down Active metal is to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both reduces metal Dosage, and improve the selectivity of methane.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, preparation process letter It is single, be conducive to industrial amplification.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Evaluation condition: it is used hydrogen reducing 4 hours at 450 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed It is reacted in quartz reactor, 270 DEG C of reaction temperature, unstripped gas forms H2/CO/N2 =67.5/22.5/10(molar ratio), Air speed 3200h-1, product uses gas-chromatography on-line analysis after condensation water removal, and 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.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example The scanning electron microscope analysis of component nickel the results are shown in Table 2.
Embodiment 1
18.11g normal octane, 21.46g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；It will 2.97g nickel nitrate and 1.52g copper nitrate are dissolved in 20mL water, aqueous solution obtained are added in above-mentioned microemulsion, at 40 DEG C It is sufficiently stirred, the hydrazine hydrate solution that 3.5mL mass fraction is 60% is then added, after stirring 5h, 13.92g aluminium oxide (hole is added Hold is 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating is used at 80 DEG C Ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element wt in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Meter, is the 3% of final catalyst, and the Cu of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor A is in hydrogen Mixed atmosphere in activate, in mixed gas hydrogen volume content be 80%, reducing condition be 450 DEG C, 0.2MPa(absolute pressure), also Former time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and be with the mass fraction of its 4 times of quality 40% furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation； 15.3g polyethylene glycol, 16.85g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added to high pressure It in reaction kettle, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned height Solidliquid mixture after reacting in pressure kettle is down to 25 DEG C, and 46g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample Product are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for catalyst percentage composition For 16.7%Ni, the catalyst of 1.2%Cu, 1.4%Zr are denoted as C-1.
Embodiment 2
16.9g normal octane, 15.33g n-hexyl alcohol and 31.75g Triton X-100 are mixed, are made stable micro- Lotion；2.97g nickel nitrate and 1.52g copper nitrate are dissolved in 20mL water, aqueous solution obtained is added in above-mentioned microemulsion, It is sufficiently stirred at 40 DEG C, the hydrazine hydrate solution that 5mL mass fraction is 50% is then added, after stirring 5h, 13.92g titanium dioxide is added Silicon (Kong Rongwei 1.06ml/g, specific surface area 387m2/ g) carrier, continues after stirring 2h, filtering, obtained solid is heavy at 80 DEG C It forms sediment and uses ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Poidometer, is the 3% of final catalyst, and the Cu of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor A is containing It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 70% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted Pressure), recovery time 6h；1.88g zirconium nitrate is dissolved in 16mL deionized water, solution B, and the quality with its 4 times of quality are obtained The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor A after reduction activation In kettle；15.3g polyethylene glycol, 16.85g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 46g dehydrated alcohol is added, and places 1.5h, then filters, gained Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred Dividing content is 15.8%Ni, and the catalyst of 1.1%Cu, 1.3%Zr are denoted as C-2.
Embodiment 3
18.11g normal octane, 21.46g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；It will 0.99g nickel nitrate and 0.76g copper nitrate are dissolved in 20mL water, aqueous solution obtained are added in above-mentioned microemulsion, at 40 DEG C It is sufficiently stirred, the hydrazine hydrate solution that 3.5mL mass fraction is 60% is then added, after stirring 5h, 14.41g aluminium oxide (hole is added Hold is 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating is used at 80 DEG C Ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element wt in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Meter, is the 1% of final catalyst, and the Cu of load is the 1% of final catalyst in terms of element wt；Catalyst precarsor A is in hydrogen Mixed atmosphere in activate, in mixed gas hydrogen volume content be 80%, reducing condition be 450 DEG C, 0.2MPa(absolute pressure), also Former time 4h；0.94g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and be with the mass fraction of its 4 times of quality 40% furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation； 12.6g polyethylene glycol, 13.87g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added to high pressure It in reaction kettle, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned height Solidliquid mixture after reacting in pressure kettle is down to 25 DEG C, and 38g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample Product are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for catalyst percentage composition For 12.3%Ni, the catalyst of 0.4%Cu, 0.5%Zr are denoted as C-3.
Embodiment 4
18.11g normal octane, 21.46g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；It will 4.96g nickel nitrate and 2.28g copper nitrate are dissolved in 20mL water, aqueous solution obtained are added in above-mentioned microemulsion, at 40 DEG C It is sufficiently stirred, the hydrazine hydrate solution that 3.5mL mass fraction is 60% is then added, after stirring 5h, 13.42g aluminium oxide (hole is added Hold is 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating is used at 80 DEG C Ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element wt in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Meter, is the 5% of final catalyst, and the Cu of load is the 3% of final catalyst in terms of element wt；Catalyst precarsor A is in hydrogen Mixed atmosphere in activate, in mixed gas hydrogen volume content be 80%, reducing condition be 450 DEG C, 0.2MPa(absolute pressure), also Former time 4h；2.82g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and be with the mass fraction of its 4 times of quality 40% furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation； 18g polyethylene glycol, 19.82g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；It is anti-that solution C is also added to high pressure It answers in kettle, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned high pressure Solidliquid mixture after reacting in kettle is down to 25 DEG C, and 54g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample It is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, quality based on the element is obtained and accounts for catalyst percentage composition and be The catalyst of 22.1%Ni, 1.6%Cu, 1.5%Zr, are denoted as C-4.
Embodiment 5
21.13g normal octane, 37.8g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；By 2.97g Nickel nitrate and 1.52g copper nitrate are dissolved in 20mL water, and aqueous solution obtained is added in above-mentioned microemulsion, is sufficiently stirred at 30 DEG C It mixes, the hydrazine hydrate solution that 6mL mass fraction is 60% is then added, after stirring 5h, 13.86g aluminium oxide (Kong Rongwei is added 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating uses ethyl alcohol at 80 DEG C Catalyst precarsor A is made in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h in washing 4 times, and the Ni of load is in terms of element wt The 3% of final catalyst, the Cu of load are the 2% of final catalyst in terms of element wt；Catalyst precarsor A is in the mixed of hydrogen Close and activated in atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), when reduction Between 4h；1.25g lanthanum nitrate is dissolved in 16mL deionized water, solution B is obtained, and is 40% with the mass fraction of its 4 times of quality Furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation；It will 15.3g polyethylene glycol, 16.85g nickel nitrate are dissolved in 200mL deionized water, obtain solution C；It is anti-that solution C is also added to high pressure It answers in kettle, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned high pressure Solidliquid mixture after reacting in kettle is down to 25 DEG C, and 46g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample It is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, quality based on the element is obtained and accounts for catalyst percentage composition and be The catalyst of 16.1%Ni, 1.1%Cu, 1.2%La, are denoted as C-5.
Embodiment 6
18.11g normal octane, 21.46g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；It will 2.97g nickel nitrate and 1.52g copper nitrate are dissolved in 20mL water, aqueous solution obtained are added in above-mentioned microemulsion, at 40 DEG C It is sufficiently stirred, the hydrazine hydrate solution that 3.5mL mass fraction is 60% is then added, after stirring 5h, 13.92g aluminium oxide (hole is added Hold is 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating is used at 80 DEG C Ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element wt in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Meter, is the 3% of final catalyst, and the Cu of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor A is in hydrogen Mixed atmosphere in activate, in mixed gas hydrogen volume content be 80%, reducing condition be 450 DEG C, 0.2MPa(absolute pressure), also Former time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and be with the mass fraction of its 3 times of quality 30% furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation； 15.3g polyvinylpyrrolidone (k30), 16.85g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C It is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C 2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and it is water-soluble that the citric acid that 307g mass fraction is 15% is added Liquid is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes Obtaining quality based on the element and accounting for catalyst percentage composition is 17.2 %Ni, and the catalyst of 1.4%Cu, 1.6%Zr are denoted as C-6.
Embodiment 7
18.11g normal octane, 21.46g n-hexyl alcohol and 31.75g Tween 80 are mixed, stable microemulsion is made；It will 2.97g nickel nitrate and 1.52g copper nitrate are dissolved in 20mL water, aqueous solution obtained are added in above-mentioned microemulsion, at 40 DEG C It is sufficiently stirred, the hydrazine hydrate solution that 3.5mL mass fraction is 60% is then added, after stirring 5h, 13.74g aluminium oxide (hole is added Hold is 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid precipitating is used at 80 DEG C Ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element wt in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Meter, is the 3% of final catalyst, and the Cu of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor A is in hydrogen Mixed atmosphere in activate, in mixed gas hydrogen volume content be 80%, reducing condition be 450 DEG C, 0.2MPa(absolute pressure), also Former time 4h；4.27g magnesium nitrate is dissolved in 16mL deionized water, obtains solution B, and be with the mass fraction of its 5 times of quality 50% furfural aqueous solution is uniformly mixed, and is then added in autoclave together with the catalyst precarsor A after reduction activation； 15.3g polyvinyl alcohol, 16.85g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added to high pressure It in reaction kettle, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned height Solidliquid mixture after reacting in pressure kettle is down to 25 DEG C, and 46g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample Product are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for catalyst percentage composition For 16.2%Ni, the catalyst of 1.3%Cu, 1.6%Mg are denoted as C-7.
Embodiment 8
10.28g normal octane, 12.26g n-hexyl alcohol and 27.17g Triton X-100 are mixed, are made stable Microemulsion；2.97g nickel nitrate and 1.52g copper nitrate are dissolved in 15mL water, aqueous solution obtained is added in above-mentioned microemulsion, It is sufficiently stirred at 20 DEG C, the hydrazine hydrate solution that 2mL mass fraction is 80% is then added, after stirring 5h, 13.85g oxidation is added Aluminium (Kong Rongwei 0.71ml/g, specific surface area 236m2/ g) carrier, continues after stirring 2h, filtering, obtained solid is heavy at 80 DEG C It forms sediment and uses ethanol washing 4 times, catalyst precarsor A is made, the Ni of load is with element in 450 DEG C of roasting 6h then at 110 DEG C of dry 5h Poidometer, is the 3% of final catalyst, and the Cu of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor A is containing It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted Pressure), recovery time 4h；2.36g calcium nitrate is dissolved in 16mL deionized water, solution B, and the quality with its 4 times of quality are obtained The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor A after reduction activation In kettle；15.3g polyethylene glycol, 16.85g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 46g dehydrated alcohol is added, and places 1.5h, then filters, gained Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred Dividing content is 15.8%Ni, and the catalyst of 1.4%Cu, 1.6%Ca are denoted as C-8.
Comparative example
It weighs 19.82g nickel nitrate, 1.52g copper nitrate, 1.88g zirconium nitrate to be dissolved in deionized water, aqueous solution is made；It adopts 13.92g alumina support (Kong Rongwei 0.71mL/g, specific surface area 236m are carried on equi-volume impregnating2/ g, bar shaped, when Measure diameter 1.5mm), 2h is impregnated at room temperature, and aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h obtain quality based on the element and account for Catalyst percentage composition is 18.3%Ni, and the catalyst of 1.4%Cu, 1.6%Zr are denoted as D-1.
The reactivity worth of 1 catalyst of table
The content distribution (wt%) of the active component Ni of 2 catalyst of table

Claims (29)

1. a kind of preparation method of synthesis gas methanation catalyst, the catalyst includes active component, the first auxiliary agent, second helps Agent and carrier, active component Ni, the first auxiliary agent are Cu, and the second auxiliary agent is one or more of Ca, Mg, Zr, Ce or La, are carried Body is any one of aluminium oxide, silica；It is living on the basis of each element quality accounts for the percentage of catalyst quality in catalyst Property component content be 10wt%~30wt%, the content of the first auxiliary agent is 1wt%~3wt%, the content of the second auxiliary agent be 1wt%~ 3wt%, surplus are carrier；The preparation method of the catalyst includes the following steps:
(1) normal octane, n-hexyl alcohol and surfactant are mixed, obtains stable microemulsion, is then added and contains into microemulsion The aqueous solution of active component presoma and the first auxiliary agent presoma, is added hydrazine hydrate solution after being sufficiently stirred at 20~60 DEG C Make reducing agent, carrier is added after continuing 4~6h of stirring, after continuing 1~3h of stirring at 70~90 DEG C, filtering, obtained solid is sunk Shallow lake is washed 3~5 times with dehydrated alcohol, then catalyst precarsor A is made through drying, roasting；
(2) reduction treatment is carried out to the catalyst precarsor A that step (1) obtains using reducing atmosphere；
(3) the second auxiliary agent presoma is soluble in water, obtain solution B, and be uniformly mixed with furfural aqueous solution, then with step (2) the catalyst precarsor A obtained is added in autoclave together；
(4) water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added to step Suddenly it in autoclave described in (3), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C, the water soluble polymer is polyethylene glycol, polyvinylpyrrolidone, polyethylene One or more of alcohol；
(5) solidliquid mixture obtained to step (4) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, and places 1 ~2h, is then filtered, and obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that: the content of active component is 15wt%~25wt%.
3. according to the method for claim 1, it is characterised in that: surfactant described in step (1) is that polyethylene glycol is pungent Base phenyl ether and/or Tween 80.
4. according to the method for claim 1, it is characterised in that: active component presoma described in step (1) be nickel nitrate, One of nickel acetate, nickel sulfate, nickel chloride are a variety of.
5. according to method described in claim 1 or 4, it is characterised in that: active component presoma described in step (1) is nitric acid Nickel.
6. according to the method for claim 1, it is characterised in that: the first auxiliary agent presoma described in step (1) be copper nitrate, One or more of copper sulphate, copper chloride.
7. according to method described in claim 1 or 6, it is characterised in that: the first auxiliary agent presoma described in step (1) is nitric acid Copper.
8. according to the method for claim 1, it is characterised in that: normal octane, n-hexyl alcohol, surface-active described in step (1) The molar ratio of agent is 0.5~1:1:0.2~0.5.
9. according to the method for claim 1, it is characterised in that: contain active component presoma and the described in step (1) The molar ratio of water and surfactant is 10~20 in the aqueous solution of one auxiliary agent presoma.
10. according to the method for claim 1, it is characterised in that: the matter of hydrazine hydrate in hydrazine hydrate solution described in step (1) Measuring score is 50%~80%.
11. according to the method for claim 1, it is characterised in that: addition hydrazine hydrate solution and normal octane described in step (1) Volume ratio be 1:5~1:10.
12. according to the method for claim 1, it is characterised in that: 100~120 DEG C of drying temperature described in step (1) is done Dry 4~6h of time.
13. according to the method for claim 1, it is characterised in that: roasting condition described in step (1) is maturing temperature 400 DEG C~500 DEG C, calcining time 4h~8h.
14. according to the method for claim 1, it is characterised in that: in catalyst precarsor A described in step (1), the nickel of load It is 1wt%~5wt% of final catalyst in terms of element wt, the copper of load is the 1wt% of final catalyst in terms of element wt ~3wt%.
15. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (2) is hydrogen or hydrogen The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
16. according to the method for claim 1, it is characterised in that: the second auxiliary agent presoma described in step (3) is nitric acid One of calcium, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate are a variety of.
17. according to method described in claim 1 or 16, it is characterised in that: the second auxiliary agent presoma described in step (3) is Zirconium nitrate.
18. according to the method for claim 1, it is characterised in that: in solution B described in step (3), the second auxiliary agent is with element Meter, mass fraction in the solution are 1%~4%.
19. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (3) Score is 30%~50%.
20. according to the method for claim 1, it is characterised in that: the matter of furfural aqueous solution and solution B described in step (3) Amount is than being 3~5, the matter for the reduction rear catalyst precursor A that the gross mass and step (2) of the solution B and furfural aqueous solution obtain Amount is than being 3~6.
21. according to the method for claim 1, it is characterised in that: active component presoma described in step (4) is nitric acid One of nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
22. according to method described in claims 1 or 21, it is characterised in that: active component presoma described in step (4) is nitre Sour nickel.
23. according to the method for claim 1, it is characterised in that: in solution C described in step (4), active component presoma Middle the nickeliferous mass fraction in solution C based on the element is 0.4%~2.5%, and water soluble polymer is in solution C Mass fraction is 3~6 times of Ni element mass fraction.
24. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (5) The mass ratio of quality and water soluble polymer is 2~4.
25. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (5) It is 10%~20%.
26. according to the method for claim 1, it is characterised in that: drying temperature described in step (5) is 70~150 DEG C, is done The dry time is 2~12h.
27. according to method described in claims 1 or 26, it is characterised in that: drying temperature described in step (5) is 80~120 DEG C, drying time is 4~8h.
28. according to the method for claim 1, it is characterised in that: maturing temperature described in step (5) is 350~650 DEG C, Calcining time is 2~12h.
29. according to method described in claims 1 or 28, it is characterised in that: maturing temperature described in step (5) is 400~600 DEG C, calcining time is 4~8h.
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Publication number Priority date Publication date Assignee Title
CN1043639A (en) * 1988-12-23 1990-07-11 四川大学 Low-nickel methenyl catalyst and preparation method thereof
CN102319574A (en) * 2011-05-17 2012-01-18 太原理工大学 Synthesis gas methanation catalyst and preparation thereof
CN102500379A (en) * 2011-11-17 2012-06-20 中国石油化工股份有限公司 Catalyst for methanation and preparation method thereof
CN102527405A (en) * 2012-02-15 2012-07-04 华东理工大学 Catalyst used in complete methanation of synthesis gas at high temperature and preparation method thereof
CN103265394A (en) * 2013-05-27 2013-08-28 神华集团有限责任公司 Methanation reaction system and regeneration technology of methanation catalyst
CN104209127A (en) * 2013-06-05 2014-12-17 中国石油天然气股份有限公司 Nickel iron bimetallic methanation catalyst and preparation and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1043639A (en) * 1988-12-23 1990-07-11 四川大学 Low-nickel methenyl catalyst and preparation method thereof
CN102319574A (en) * 2011-05-17 2012-01-18 太原理工大学 Synthesis gas methanation catalyst and preparation thereof
CN102500379A (en) * 2011-11-17 2012-06-20 中国石油化工股份有限公司 Catalyst for methanation and preparation method thereof
CN102527405A (en) * 2012-02-15 2012-07-04 华东理工大学 Catalyst used in complete methanation of synthesis gas at high temperature and preparation method thereof
CN103265394A (en) * 2013-05-27 2013-08-28 神华集团有限责任公司 Methanation reaction system and regeneration technology of methanation catalyst
CN104209127A (en) * 2013-06-05 2014-12-17 中国石油天然气股份有限公司 Nickel iron bimetallic methanation catalyst and preparation and application thereof

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