CN106944086B - A kind of synthesis gas methanation substitutes the preparation method of natural gas catalyst - Google Patents
A kind of synthesis gas methanation substitutes the preparation method of natural gas catalyst Download PDFInfo
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
Abstract
The present invention relates to the preparation methods that a kind of synthesis gas methanation substitutes natural gas catalyst, and the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst includes the following steps：Catalyst precarsor A is prepared 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 with together with catalyst precarsor A, it is reacted after solution C is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.This method takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, the catalyst reaction activity of preparation is high, not only reduces metal consumption, but also improve the selectivity of methane.
Description
Technical field
The present invention relates to the preparation methods that a kind of synthesis gas methanation substitutes natural gas catalyst, more particularly, to one kind
Synthesis gas methanation substitutes the support type catalyst with base of molybdenum preparation method of natural gas.
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
Etc. among techniques.Methanation is a kind of important catalysis technique, especially in fuel applications field, can be used for improving 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 of increased attention.
China is one, and the country of " rich coal, oil-poor, few gas " passes through coal based synthetic gas using abundant coal resources
Methanation production natural gas is with good economic efficiency in Waste Era of Oil, to solving the problem of complex utilization of coal resources,
The present situation for alleviating Chinese postman problem algorithm shortage safeguards energy security, realizes CO2Emission reduction, environmental protection 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 contents, 20%~70%）For main fluid catalyst；The easy coking deactivation of Fe base catalyst；Co base catalyst is resistant to
Property is strong, but poor selectivity；Ru base catalyst activities are higher than Ni base catalyst, but its is of 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, CH4High selectivity）, stability is good（It is i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning）, service life is long, at
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 is with high-purity gamma-disclosed in United States Patent (USP) US3933883
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, which is typically at, to be carried out under conditions of mass transport limitation）, reactant to
It is completed up to reaction while catalyst external surface, thus the inner surface of catalyst contributes less goal response, this just makes
At lower rate of metal in carrier duct, the manufacturing cost of catalyst is increased.
Invention content
In order to overcome shortcoming in the prior art, the present invention provides a kind of synthesis gas methanations to substitute natural gas
The preparation method of catalyst.Mo, Co and alumina support in useless hydrotreating catalyst, Er Qiechong is not only utilized in this method
Divide and the Ni and V deposited on useless hydrotreating catalyst is utilized, solves the pollution problem of dead catalyst, and economize on resources,
It improves benefit, is technically easy to implement, the synthesis gas methanation catalyst of gained has of low cost, metal component utilization rate
Feature high and that selectivity is good.
The present invention provides the preparation method that a kind of synthesis gas methanation substitutes natural gas catalyst, the catalyst packets
Include active component, auxiliary agent and carrier；The active component is Mo, one or more of auxiliary agent Ni, Co, V, and carrier is oxidation
The composite oxides of aluminium and silica；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, activearm
It is 15wt%~25wt% to divide the content of Mo, and the content of auxiliary agent is 3wt%~8wt%, and surplus is carrier；SiO in catalyst2Content
For 50wt%~80wt%, Al2O3Content be 15wt%~30wt%；The preparation method of the catalyst includes the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C are dry,
High-temperature roasting processing is carried out, calcination temperature is 300~600 DEG C, and roasting time is 2~6h；
（2）By step（1）Obtained waste residue oil hydrogenating treatment catalyst is ground；
（3）To step（2）Middle addition strong inorganic acid is filtered to remove solid insoluble after dead catalyst dissolving；
（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving；
（5）To step（4）Silica silicon source is added in obtained solution, and the pH value of control system is 3~5,60~
Stirring extremely generates gel at 90 DEG C；
（6）Step（5）Obtained gel, aging, drying, roasting, molding, obtain catalyst at 20~30 DEG C
Precursor A；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）High molecular weight water soluble polymer, active component presoma is soluble in water, solution B is obtained, and water-soluble with furfural
Liquid be uniformly mixed, then with step（7）Obtained catalyst precarsor A is added in autoclave together, and hydrogen is used after sealing
Displacement 2~5 times, then Hydrogen Vapor Pressure is adjusted to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（9）Wait for step（8）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl 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.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（1）Described in waste residue
For oil hydrogenating treatment catalyst using aluminium oxide as carrier, active metal component contains Mo and Co, be former reaction has been not achieved to require, or
Residual oil hydrocatalyst of the person due to grading without being used on the fixed bed of complete deactivation or ebullated bed；It is described useless to urge
Agent, so in hydrogenation process, generally has part gold due to being hydrotreating catalyst used in hydrogenation process
Belong to Ni and V depositions；The content of Mo is 3wt%~5wt% in the catalyst precarsor A, and the content of Co is 0.1wt%~1wt%, V
Content be 0.1wt%~1wt%, the content of Ni is 1wt%~5wt%.Step（1）Described in extracting solvent can be petroleum ether,
One or both of toluene.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（2）In give up hydrotreating
Catalyst is ground to more than 120 mesh, more than preferably 200 mesh.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（3）Described in strong nothing
Machine acid is one or more mixed acid in concentrated nitric acid, the concentrated sulfuric acid, concentrated hydrochloric acid, and the preferably concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid is mixed
Close acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.The concentration of strong inorganic acid is generally 30wt%~100wt%, and wherein concentrated hydrochloric acid is dense
Degree is in 30wt% or more, and the concentration of concentrated nitric acid is in 50wt% or more, and the concentration of the concentrated sulfuric acid is in 50wt% or more.The addition of strong inorganic acid
Amount, it is 1 to make the volume ratio of strong inorganic acid and dead catalyst:1~1:10；Step（3）Described in need in dead catalyst course of dissolution
It heats, temperature needs strong stirring at 40~80 DEG C in course of dissolution.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（4）Described in containing Ni's
Presoma is the soluble-salt of Ni, is specifically as follows one or more of nickel nitrate, nickel chloride, nickel sulfate, preferably nitric acid
Nickel；The organic acid is one or more in citric acid, tartaric acid, malic acid, the organic acid and useless hydrorefining catalyst
The molar ratio of Mo is 0.5~1.5 in agent.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（5）Described in oxidation
Silicon silicon source is ethyl orthosilicate and/or Ludox.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（6）Described in gel
4~12h of aging at 20~30 DEG C, then dry 5~10h at 100~120 DEG C, roast 2 at 500~700 DEG C~
6h。
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（7）Described in reduction
Atmosphere is the mixed gas of hydrogen or hydrogen and nitrogen, and hydrogen volume percentage composition is 10%~95% in the mixed gas.
Specific reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then pass to hydrogen or
The mixed gas of hydrogen and nitrogen, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, it is down to room temperature in a nitrogen atmosphere.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（8）Described in it is water-soluble
High molecular polymer is polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）One or more of；
The active component presoma is the soluble-salt of Mo, is specifically as follows ammonium tetramolybdate and/or ammonium molybdate, preferably ammonium molybdate；
In the solution B, the mass fraction in solution B is 0.5%~5% to contained molybdenum based on the element in active component presoma, water-soluble
Property mass fraction of the high molecular polymer in solution B be 2~5 times of Mo element mass fractions；Chaff in the furfural aqueous solution
The mass fraction of aldehyde is 30%~50%；Step（8）Described in furfural aqueous solution and step（7）The matter of obtained catalyst precarsor A
Amount is than being 2~4.
Synthesis gas methanation of the present invention substitutes in the preparation method of natural gas catalyst, step（9）Described in nothing is added
The mass ratio of the quality and high molecular weight water soluble polymer of water-ethanol or citric acid is 2~4；The quality of the aqueous citric acid solution
Score is 10%~20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably
For 4~8h；The calcination temperature be 350~650 DEG C, preferably 400~600 DEG C, roasting time be 2~12h, preferably 4~
8h。
Catalyst prepared by the method for the present invention can be applied to synthesis gas methanation and substitute natural solid/liquid/gas reactions.Catalyst exists
2% is used before reaction（Volume fraction）H2S/H2Gaseous mixture 3~6h of presulfurization, preferably 4h；Curing temperature is 400~600 DEG C, vulcanization
Unstripped gas is passed through after the completion to be reacted.It is anti-that catalyst prepared by the method for the present invention is applied to synthesis gas preparing natural gas by methanation
It answers, the resistant to sulfur ability with appropriateness, preferable process conditions are：H in unstripped gas2/ CO molar ratios are 1.0~4.0, and sulfur content is
0.5%~1.5%, Ar, N can be contained in unstripped gas2Or the dilution property gas such as He, 2000~20000h of unstripped gas air speed-1, reaction
Pressure is 0.1~6Mpa, and reaction temperature is 250~650 DEG C.
Compared with prior art, the preparation method being related to through the invention can obtain a kind of distribution of active metal outer layer
Synthesis gas methanation substitutes natural gas catalyst.In the present invention, furfural water is carried out using waste residue oil hydrogenating treatment catalyst
Phase hydrogenation reaction.Active metal predecessor and high molecular weight water soluble polymer, a side is added simultaneously in the system of furfural hydrogenation
Face hinders active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, before using active metal
The coordination between object and high molecular weight water soluble polymer is driven, active metallic ion is inside and outside catalyst granules in reduction solution
Concentration difference, slow down active metal to the diffusion velocity inside catalyst granules.This method takes full advantage of waste residue oil and adds at hydrogen
Catalyst is managed, has saved cost, the catalyst reaction activity of preparation is high, not only reduces metal consumption, but also improve the choosing of methane
Selecting property.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, and preparation process is simple, is conducive to industrial amplification.
Specific implementation mode
The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.
Evaluation condition：With 2% at 450 DEG C before catalyst reaction of the present invention（Volume fraction）H2S/H2Gaseous mixture presulfurization
4h.It is reacted in continuous sample introduction fixed-bed quartz reactor, 300 DEG C, reaction pressure 2MPa of reaction temperature, unstripped gas composition
H2/CO/N2/H2S= 67.5/22.5/9/1（Volume ratio）, air speed 5000h-1, online with gas-chromatography after the condensed water removal of product
Analysis, reaction result are shown in Table 1.Reaction result shown in table 1 is that catalyst works the average activity of 20h at 300 DEG C.
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 molybdenum the results are shown in Table 2.
Embodiment 1
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C
It mixes, solid is made to dissolve, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid is added
27.31g（The molar ratio of citric acid and Mo in useless agent are 1）, 750.79g ethyl orthosilicates are then added, control system pH value is
4.0, stirring is to gel is generated at 70 DEG C, by gel aging 8h at room temperature, then dry 8h, obtained solid at 110 DEG C
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 4wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 3wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By 14.7g polyethylene glycol, 7.73g
Ammonium molybdate is dissolved in 200mL deionized waters, obtains solution B, and the furfuryl aldehyde solution for being 40% with 60g mass fractions is uniformly mixed, so
It is added in autoclave with together with the catalyst precarsor A after reduction activation afterwards, is replaced 3 times with hydrogen after sealing, then adjusted
Hydrogen Vapor Pressure is saved to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, adds
Enter 44.1g absolute ethyl alcohols, place 1.5h, then filter, obtained solid sample, which is put into baking oven at 110 DEG C, dries 6h, 700 DEG C
Lower roasting 6h, it is 2.5%Ni, 18.6%Mo, 0.6%Co to obtain quality based on the element and account for catalyst percentage composition, and 0.6%V's urges
Agent, is denoted as C-1, SiO in catalyst2Content be 65.7wt%, Al2O3Content be 22.3wt%.
Embodiment 2
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, the mixing of the 98 wt% concentrated sulfuric acids and 65 wt% concentrated nitric acids is added
Solution 300mL, volume ratio 2:1, constant temperature stirs at 50 DEG C, so that solid is dissolved, filtrate is collected by filtration, be added into filtrate
After stirring and dissolving, citric acid 40.98g is added in 11.73g nickel nitrates（The molar ratio of citric acid and Mo in useless agent are 1.5）, then
1155.93g ethyl orthosilicates are added, control system pH value is 4.0, and stirring is to gel is generated at 70 DEG C, by gel in room temperature
Lower aging 8h, then dry 8h, obtained solid roast 4h to get catalyst precarsor A, wherein Mo at 600 DEG C at 110 DEG C
Catalyst precarsor A weight 3wt%, Ni are accounted for based on the element accounts for catalyst precarsor A weight 1wt% based on the element；By 20g catalyst precarsors
A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa
（Absolute pressure）, recovery time 4h；11.03g polyethylene glycol, 5.8g ammonium molybdates are dissolved in 200mL deionized waters, solution B is obtained, and
The furfuryl aldehyde solution for being 40% with 60g mass fractions is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
It in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；It waits for
It states the solidliquid mixture after being reacted in autoclave and is down to 25 DEG C, 33.1g absolute ethyl alcohols are added, place 1.5h, then filter, 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
Point content is 2.3%Ni, 13.6%Mo, 0.5%Co, the catalyst of 0.6%V, is denoted as C-2, SiO in catalyst2Content be
75.9wt%, Al2O3Content be 16.7wt%.
Embodiment 3
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, the mixing of 35 wt% concentrated hydrochloric acids and 65 wt% concentrated nitric acids is added
Solution 450mL, volume ratio 1:1, constant temperature stirs at 50 DEG C, so that solid is dissolved, filtrate is collected by filtration, be added into filtrate
After stirring and dissolving, citric acid 13.66g is added in 54.01g nickel nitrates（The molar ratio of citric acid and Mo in useless agent are 0.5）, then
507.7g ethyl orthosilicates are added, control system pH value is 4.0, and stirring is to gel is generated at 70 DEG C, at room temperature by gel
Aging 8h, the then dry 8h at 110 DEG C, obtained solid roast 4h to get catalyst precarsor A at 600 DEG C, wherein Mo with
Element meter accounts for catalyst precarsor A weight 5wt%, Ni and accounts for catalyst precarsor A weight 5wt% based on the element；By 20g catalyst precarsors A
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；18.4g polyethylene glycol, 9.66g ammonium molybdates are dissolved in 200mL deionized waters, solution B is obtained, and
The furfuryl aldehyde solution for being 40% with 60g mass fractions is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
It in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；It waits for
It states the solidliquid mixture after being reacted in autoclave and is down to 25 DEG C, 55g absolute ethyl alcohols are added, place 1.5h, then filter, gained is solid
Body 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 percentage
Content is 4.2%Ni, 23.8%Mo, 0.5%Co, the catalyst of 0.5%V, is denoted as C-3, SiO in catalyst2Content be
55.5wt%, Al2O3Content be 27.8wt%.
Embodiment 4
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C
It mixes, solid is made to dissolve, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid is added
27.31g（The molar ratio of citric acid and Mo in useless agent are 1）, 750.79g ethyl orthosilicates are then added, control system pH value is
4.0, stirring is to gel is generated at 70 DEG C, by gel aging 8h at room temperature, then dry 8h, obtained solid at 110 DEG C
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 4wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 3wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By 14.7g polyethylene glycol, 7.73g
Ammonium molybdate is dissolved in 200mL deionized waters, obtains solution B, and the furfuryl aldehyde solution for being 30% with 40g mass fractions is uniformly mixed, so
It is added in autoclave with together with the catalyst precarsor A after reduction activation afterwards, is replaced 3 times with hydrogen after sealing, then adjusted
Hydrogen Vapor Pressure is saved to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 20 DEG C, adds
Enter 30g absolute ethyl alcohols, place 1.5h, then filter, obtained solid sample, which is put into baking oven at 110 DEG C, dries 6h, at 700 DEG C
6h is roasted, it is 2.3%Ni, 18.1%Mo, 0.6%Co, the catalysis of 0.6%V to obtain quality based on the element and account for catalyst percentage composition
Agent, is denoted as C-4, SiO in catalyst2Content be 65.7wt%, Al2O3Content be 22.3wt%.
Embodiment 5
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C
It mixes, solid is made to dissolve, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid is added
27.31g（The molar ratio of citric acid and Mo in useless agent are 1）, 750.79g ethyl orthosilicates are then added, control system pH value is
4.0, stirring is to gel is generated at 70 DEG C, by gel aging 8h at room temperature, then dry 8h, obtained solid at 110 DEG C
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 4wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 3wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By 14.7g polyvinyl alcohol, 7.73g
Ammonium molybdate is dissolved in 200mL deionized waters, obtains solution B, and the furfuryl aldehyde solution for being 50% with 80g mass fractions is uniformly mixed, so
It is added in autoclave with together with the catalyst precarsor A after reduction activation afterwards, is replaced 3 times with hydrogen after sealing, then adjusted
Hydrogen Vapor Pressure is saved to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 30 DEG C, adds
Enter 44.1g absolute ethyl alcohols, place 1.5h, then filter, obtained solid sample, which is put into baking oven at 110 DEG C, dries 6h, 700 DEG C
Lower roasting 6h, it is 2.5%Ni, 18.3%Mo, 0.6%Co to obtain quality based on the element and account for catalyst percentage composition, and 0.6%V's urges
Agent, is denoted as C-5, SiO in catalyst2Content be 65.7wt%, Al2O3Content be 22.3wt%.
Embodiment 6
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C
It mixes, solid is made to dissolve, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid is added
27.31g（The molar ratio of citric acid and Mo in useless agent are 1）, 750.79g ethyl orthosilicates are then added, control system pH value is
4.0, stirring is to gel is generated at 70 DEG C, by gel aging 8h at room temperature, then dry 8h, obtained solid at 110 DEG C
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 4wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 3wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By 14.7g polyvinylpyrrolidones
（k30）, 7.73g ammonium molybdates be dissolved in 200mL deionized waters, obtain solution B, and the furfuryl aldehyde solution for being 40% with 60g mass fractions
It is uniformly mixed, is then added in autoclave with together with the catalyst precarsor A after reduction activation, is replaced with hydrogen after sealing
3 times, Hydrogen Vapor Pressure is then adjusted to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture drop after being reacted in above-mentioned autoclave
To 25 DEG C, the aqueous citric acid solution that 294g mass fractions are 15% is added, places 1.5h, then filters, obtained solid sample is put into
6h is dried in baking oven at 110 DEG C, 6h is roasted at 700 DEG C, it is 2.7% to obtain quality based on the element and account for catalyst percentage composition
The catalyst of Ni, 18.8%Mo, 0.7%Co, 0.6%V, are denoted as C-6, SiO in catalyst2Content be 65.7wt%, Al2O3Contain
Amount is 22.3wt%.
Comparative example
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, gives up and urges after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground
To 200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C
It mixes, solid is made to dissolve, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid is added
27.31g（The molar ratio of citric acid and Mo in useless agent are 1）, 750.79g ethyl orthosilicates are then added, control system pH value is
4.0, stirring is to gel is generated at 70 DEG C, by gel aging 8h at room temperature, then dry 8h, obtained solid at 110 DEG C
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 4wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 3wt%；20g catalyst precarsors A is added in the aqueous solution containing 7.73g ammonium molybdates, in 80
DEG C stirring is evaporated to solution, is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element
It is 2.6%Ni, 19.1%Mo, 0.6%Co to account for catalyst percentage composition, and the catalyst of 0.6%V is denoted as D-1, SiO in catalyst2's
Content is 65.7wt%, Al2O3Content be 22.3wt%.
The reactivity worth of 1 catalyst of table
The active component Mo content distributions of 2 catalyst of table（wt%）
Claims (29)
1. a kind of synthesis gas methanation substitutes the preparation method of natural gas catalyst, the catalyst includes active component, helps
Agent and carrier；The active component is Mo, auxiliary agent Ni, Co and V, and carrier is the composite oxides of aluminium oxide and silica；With
Each element quality accounts on the basis of the percentage of catalyst quality in catalyst, and the content of active component Mo is 15wt%~25wt%,
The content of auxiliary agent is 3wt%~8wt%, and surplus is carrier；SiO in catalyst2Content be 50wt%~80wt%, Al2O3Content
For 15wt%~30wt%；The preparation method of the catalyst includes the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C dry, is carried out
High-temperature roasting is handled, and calcination temperature is 300~600 DEG C, and roasting time is 2~6h；
（2）By step（1）Obtained waste residue oil hydrogenating treatment catalyst is ground；
（3）To step（2）Middle addition strong inorganic acid is filtered to remove solid insoluble after dead catalyst dissolving；
（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving；
（5）To step（4）Silica silicon source is added in obtained solution, and the pH value of control system is 3~5, at 60~90 DEG C
Lower stirring extremely generates gel；
（6）Step（5）Obtained gel, aging, drying, roasting, molding, obtain catalyst precarsor at 20~30 DEG C
A；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）High molecular weight water soluble polymer, active component presoma is soluble in water, solution B is obtained, and mixed with furfural aqueous solution
Close it is uniform, then with step（7）Obtained catalyst precarsor A is added in autoclave together, and 2 are replaced with hydrogen after sealing
~5 times, then Hydrogen Vapor Pressure is adjusted to 2~4MPa, 1~3h, the high molecular weight water soluble polymer are reacted at 100~200 DEG C
For one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol；
（9）Wait for step（8）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl 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：Step（1）Described in waste residue oil hydrogenating treatment catalyst
Using aluminium oxide as carrier, active metal component contains Mo and Co.
3. according to the method for claim 1, it is characterised in that：Step（6）Described in catalyst precarsor A in Mo content
For 3wt%~5wt%, the content of Co is 0.1wt%~1wt%, and the content of V is 0.1wt%~1wt%, the content of Ni be 1wt%~
5wt%。
4. according to the method for claim 1, it is characterised in that：Step（2）In give up hydrotreating catalyst grind to
It is more than 120 mesh.
5. according to the method described in claim 1 or 4, it is characterised in that：Step（2）In give up hydrotreating catalyst grind
To more than 200 mesh.
6. according to the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid be concentrated nitric acid, dense sulphur
One or more mixed acid in acid, concentrated hydrochloric acid.
7. according to the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid be the concentrated sulfuric acid, dense nitre
Acid and concentrated hydrochloric acid mixed acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.
8. according to the method for claim 6, it is characterised in that：Step（3）Described in strong inorganic acid a concentration of 30wt%
~100wt%, the wherein concentration of concentrated hydrochloric acid are in 30wt% or more, and in 50wt% or more, the concentration of the concentrated sulfuric acid exists the concentration of concentrated nitric acid
50wt% or more.
9. according to the method for claim 1, it is characterised in that：Step（3）The volume ratio of middle strong inorganic acid and dead catalyst
It is 1:1~1:10.
10. according to the method for claim 1, it is characterised in that：Step（4）Described in the presoma containing Ni be Ni it is solvable
Property salt.
11. according to the method described in claim 1 or 10, it is characterised in that：Step（4）Described in the presoma containing Ni be nitric acid
One or more of nickel, nickel chloride, nickel sulfate.
12. according to the method for claim 11, it is characterised in that：Step（4）Described in the presoma containing Ni be nickel nitrate.
13. according to the method for claim 1, it is characterised in that：Step（4）Described in organic acid be citric acid, tartaric acid,
It is one or more in malic acid.
14. according to the method for claim 1, it is characterised in that：Step（4）Described in organic acid and useless hydrorefining catalyst
The molar ratio of Mo is 0.5~1.5 in agent.
15. according to the method for claim 1, it is characterised in that：Step（5）Described in silica silicon source be positive silicic acid second
Ester and/or Ludox.
16. according to the method for claim 1, it is characterised in that：Step（6）Described in gel aging at 20~30 DEG C
4~12h, then dry 5~10h at 100~120 DEG C, roasts 2~6h at 500~700 DEG C.
17. according to the method for claim 1, it is characterised in that：Step（7）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
18. according to the method for claim 1, it is characterised in that：Step（8）Described in active component presoma be Mo can
Soluble.
19. according to the method described in claim 1 or 18, it is characterised in that：Step（8）Described in active component presoma be four
Ammonium molybdate.
20. according to the method described in claim 1 or 18, it is characterised in that：Step（8）Described in active component presoma be molybdenum
Sour ammonium.
21. according to the method for claim 1, it is characterised in that：Step（8）Described in solution B, active component presoma
In contained molybdenum based on the element the mass fraction in solution B be 0.5%~5%, matter of the high molecular weight water soluble polymer in solution B
Measure 2~5 times that score is Mo element mass fractions.
22. according to the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution furfural quality
Score is 30%~50%.
23. according to the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution and step（7）?
The mass ratio of the catalyst precarsor A arrived is 2~4.
24. according to the method for claim 1, it is characterised in that：Step（9）Described in absolute ethyl alcohol or citric acid is added
The mass ratio of quality and high molecular weight water soluble polymer is 2~4.
25. according to the method for claim 1, it is characterised in that：Step（9）Described in aqueous citric acid solution mass fraction
It is 10%~20%.
26. according to the method for claim 1, it is characterised in that：Step（9）Described in drying temperature be 70~150 DEG C, do
The dry time is 2~12h.
27. according to the method described in claims 1 or 26, it is characterised in that：Step（9）Described in drying temperature be 80~120
DEG C, drying time is 4~8h.
28. according to the method for claim 1, it is characterised in that：Step（9）Described in calcination temperature be 350~650 DEG C,
Roasting time is 2~12h.
29. according to the method described in claims 1 or 28, it is characterised in that：Step（9）Described in calcination temperature be 400~600
DEG C, roasting time is 4~8h.
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