CN106944062B - A kind of preparation method of synthesis gas preparing natural gas catalyst - Google Patents

A kind of preparation method of synthesis gas preparing natural gas catalyst Download PDF

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CN106944062B
CN106944062B CN201610003124.4A CN201610003124A CN106944062B CN 106944062 B CN106944062 B CN 106944062B CN 201610003124 A CN201610003124 A CN 201610003124A CN 106944062 B CN106944062 B CN 106944062B
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catalyst
solution
auxiliary agent
active component
nickel
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CN106944062A (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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of preparation methods of synthesis gas preparing natural gas catalyst, the catalyst includes active component, auxiliary agent and carrier, the preparation method of the catalyst includes the following steps: to prepare catalyst precarsor B first, then reduction treatment is carried out to catalyst precarsor B, 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 B, it is reacted after solution D is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.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 preparing natural gas catalyst
Technical field
The present invention relates to a kind of preparation methods of synthesis gas preparing natural gas catalyst, more particularly, to a kind of synthesis gas day The preparation method of right gas 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 preparations of synthesis gas preparing natural gas 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 preparing natural gas catalyst, the catalyst includes active group Point, the first auxiliary agent, the second auxiliary agent and carrier, active component Ni, the first auxiliary agent is Fe, the second auxiliary agent be Ca, Mg, Zr, Ce or One or more of La, carrier are any one of aluminium oxide, silica；Catalyst matter is accounted for each element quality in catalyst On the basis of the percentage of amount, the content of active component is 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, second The content of auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps:
(1) active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is obtained Catalyst precarsor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step Suddenly the catalyst precarsor B that (3) obtain is added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added It into autoclave described in step (4), 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；
(6) solidliquid mixture obtained to step (5) 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 preparing natural gas catalyst of the present invention, active component presoma described in step (1) is One of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride are a variety of, preferably nickel nitrate；The first auxiliary agent presoma is iron Soluble-salt, be specifically as follows one or more of ferric nitrate, iron chloride, ferric sulfate, preferably ferric nitrate；The solution In A, based on the element, mass fraction in solution A A is 1%~7% to active component, the first adjuvant component based on the element, in solution Mass fraction in A is 1%~5%.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, dipping described in step (2) is isometric leaching Stain, dip time are 1~3h；The aging can aging at room temperature, can also the aging under certain steady temperature, aging temperature It is 10~90 DEG C, preferably 20~60 DEG C, ageing time is 1~for 24 hours, preferably 4~12h；Institute in step (2) and step (6) Stating drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；Step (2) with Maturing temperature described in step (6) be 350~650 DEG C, preferably 400~600 DEG C, calcining time be 2~12h, preferably 4~ 8h。
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, carrier described in step (2) is aluminium oxide, oxygen Any one of SiClx, the carrier can use commercially available product, can also prepare by method well known in the art；It is described to urge In agent precursor B, the nickel of load is 1wt%~5wt% of final catalyst, the iron of load is with element wt in terms of element wt Meter is 1wt%~3wt% of final catalyst.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, reducing atmosphere described in step (3) is hydrogen Or the mixed gas of hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specific reduction Treatment 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 preparing natural gas catalyst of the present invention, auxiliary agent presoma described in step (4) is nitre One of sour calcium, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate are a variety of, preferably Zirconium nitrate；In the solution C, based on the element, the mass fraction in solution C 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 (4) and the mass ratio of solution C are 3 ~ 5, described The mass ratio for the reduction rear catalyst precursor B that solution C and the gross mass of furfural aqueous solution and step (3) obtain is 3~6.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, the polymerization of water soluble polymer described in step (5) Object is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；The active group Dividing presoma is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；In the solution D, In active component presoma the nickeliferous mass fraction in solution D based on the element be 0.4%~2%, water soluble polymer polymerization Mass fraction of the object in solution D is 3~6 times of Ni element mass fraction.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, addition dehydrated alcohol or lemon described in step (6) The quality of lemon 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 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 preparing natural gas 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, is on the one hand added using furfural Hydrogen product hinders active metal to the diffusion inside catalyst granules；On the other hand, active metal predecessor and water solubility are utilized Coordination between high molecular polymer reduces concentration difference of the active metallic ion inside and outside catalyst granules in solution, subtracts Delay active metal to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both reduces gold Belong to dosage, and improves 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, reaction pressure 2MPa, 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, including CO conversion ratio and CH4Selectivity.
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
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C； Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute It obtains solid sample and is 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 is 12.4%Ni, and the catalyst of 1.5%Fe, 1.6%Zr are denoted as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 15.1g silica support (Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter 0.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C； Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute It obtains solid sample and is 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 is 12.1%Ni, and the catalyst of 1.7%Fe, 1.4%Zr are denoted as C-2.
Embodiment 3
Weigh 0.99g nickel nitrate, 1.44g ferric nitrate is dissolved in 16mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 16.9g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 1% of final catalyst, and the Fe of load is the 1% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；0.94g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；8.1g polyethylene glycol, 8.92g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D 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 25g 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 8.6%Ni, and the catalyst of 0.8%Fe, 0.7%Zr are denoted as C-3.
Embodiment 4
Weigh 4.96g nickel nitrate, 4.33g ferric nitrate is dissolved in 10mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 13.3g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 5% of final catalyst, and the Fe of load is the 3% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；2.82g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；13.5g polyethylene glycol, 14.87g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C； Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 41g dehydrated alcohol is added, and places 1.5h, then filters, institute It obtains solid sample and is 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 is 16.9%Ni, and the catalyst of 2.2%Fe, 2.4%Zr are denoted as C-4.
Embodiment 5
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；1.25g lanthanum nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C； Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute It obtains solid sample and is 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 is 12.2%Ni, and the catalyst of 1.8%Fe, 1.7%La are denoted as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；2.36g calcium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 3 times of quality are obtained It measures the furfural aqueous solution that score is 30% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；10.8g polyvinylpyrrolidone (k30), 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained； Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, 150 2h is reacted at DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the lemon that 220g mass fraction is 15% is added Lemon aqueous acid is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts at 700 DEG C 6h is burnt, obtaining quality based on the element and accounting for catalyst percentage composition is 12.6%Ni, and the catalyst of 1.2%Fe, 1.4%Ca are denoted as C- 6。
Embodiment 7
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching Stain method is carried on 14.9g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa (absolute pressure), recovery time 4h；4.27g magnesium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 5 times of quality are obtained It measures the furfural aqueous solution that score is 50% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation It answers in kettle；10.8g polyvinyl alcohol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C； Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute It obtains solid sample and is 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 is 12.5%Ni, and the catalyst of 1.7%Fe, 1.8%Mg are denoted as C-7.
Comparative example
It weighs 14.87g nickel nitrate, 2.89g ferric nitrate, 1.88g zirconium nitrate to be dissolved in deionized water, aqueous solution is made；It adopts 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m 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 14.1%Ni, and the catalyst of 1.5%Fe, 1.7%Zr are denoted as D-1.
The reactivity worth of 1 catalyst of table
The distribution results of the active component Ni of 2 catalyst of table, wt%

Claims (26)

1. a kind of preparation method of synthesis gas preparing natural gas catalyst, the catalyst includes active component, the first auxiliary agent, second Auxiliary agent and carrier, active component Ni, the first auxiliary agent are Fe, and the second auxiliary agent is one or more of Ca, Mg, Zr, Ce or La, Carrier is any one of aluminium oxide, silica；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, The content of active component is 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, and the content of the second auxiliary agent is 1wt% ~3wt%, surplus are carrier；The preparation method of the catalyst includes the following steps:
(1) active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is catalyzed Agent precursor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step (3) the catalyst precarsor B obtained is added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step Suddenly it in autoclave described in (4), 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 (PEG), polyvinylpyrrolidone (PVP), one or more of polyvinyl alcohol (PVA)；
(6) solidliquid mixture obtained to step (5) 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: active component presoma described in step (1) be nickel nitrate, One of nickel acetate, nickel sulfate, nickel chloride are a variety of.
3. method according to claim 1 or 2, it is characterised in that: active component presoma described in step (1) is nitric acid Nickel.
4. according to the method for claim 1, it is characterised in that: the first auxiliary agent presoma described in step (1) can for iron One or more of soluble, specially ferric nitrate, iron chloride, ferric sulfate.
5. according to method described in claim 1 or 4, it is characterised in that: the first auxiliary agent presoma described in step (1) is nitric acid Iron.
6. according to the method for claim 1, it is characterised in that: in solution A described in step (1), active component is with element Meter, mass fraction in solution A are 1%~7%, the first adjuvant component based on the element, the mass fraction in solution A is 1%~ 5%。
7. according to the method for claim 1, it is characterised in that: dipping described in step (2) is incipient impregnation, dipping Time is 1~3h.
8. according to the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10~90 DEG C, aging Time be 1~for 24 hours.
9. according to method described in claim 1 or 8, it is characterised in that: aging temperature described in step (2) is 20~60 DEG C, Ageing time is 4~12h.
10. according to the method for claim 1, it is characterised in that: drying temperature described in step (2) and step (6) is 70 ~150 DEG C, drying time is 2~12h.
11. according to method described in claim 1 or 10, it is characterised in that: drying temperature described in step (2) and step (6) It is 80~120 DEG C, drying time is 4~8h.
12. according to the method for claim 1, it is characterised in that: maturing temperature described in step (2) and step (6) is 350 ~650 DEG C, calcining time is 2~12h.
13. according to method described in claim 1 or 12, it is characterised in that: maturing temperature described in step (2) and step (6) It is 400~600 DEG C, calcining time is 4~8h.
14. according to the method for claim 1, it is characterised in that: in catalyst precarsor B described in step (2), the nickel of load It is 1wt%~5wt% of final catalyst in terms of element wt, the iron 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 (3) 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: auxiliary agent presoma described in step (4) be calcium nitrate, One of 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: auxiliary agent presoma described in step (4) is nitric acid Zirconium.
18. according to the method for claim 1, it is characterised in that: in solution C described in step (4), the second auxiliary agent is with element Meter, the mass fraction in solution C 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 (4) 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 C described in step (4) Amount is than being 3 ~ 5.
21. according to the method for claim 1, it is characterised in that: solution C described in step (4) and furfural aqueous solution it is total The mass ratio for the reduction rear catalyst precursor B that quality and step (3) obtain is 3~6.
22. according to the method for claim 1, it is characterised in that: active component presoma described in step (5) is nitric acid One of nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
23. according to method described in claims 1 or 22, it is characterised in that: active component presoma described in step (5) is nitre Sour nickel.
24. according to the method for claim 1, it is characterised in that: in solution D described in step (5), active component presoma Middle the nickeliferous mass fraction in solution D based on the element is 0.4%~2%, matter of the water soluble polymer in solution D Measure 3~6 times that score is Ni element mass fraction.
25. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (6) The mass ratio of quality and water soluble polymer is 2 ~ 4.
26. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (6) It is 10%~20%.
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