CN105642306B - A kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas - Google Patents

Abstract

The present invention relates to a kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas, the catalyst includes active component, auxiliary agent and carrier, and described method for preparing catalyst includes：Handle waste residue oil hydrogenation catalysts and catalyst precarsor A is made；Then reduction treatment is carried out to catalyst precarsor A using reducing atmosphere；Catalyst precarsor A after reduction and polyhydric alcohol solutions are added in autoclave and carry out hydrogenation reaction, reaction effluent is placed and then filtered and dried, obtains catalyst precarsor B；Active component presoma is soluble in water, solution C is obtained, catalyst precarsor B is then added, after drying, calcination process, obtains catalyst.The inventive method not only takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, and promotes more multiple active components and disperse in carrier surface, had both improved the utilization rate of active metal, and had improved the conversion ratio of carbon monoxide and the selectivity of product again.

Description

A kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas

Technical field

The present invention relates to a kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas, more particularly, to one kind The support type catalyst with base of molybdenum preparation method of synthesis gas full methanation preparing 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 Among technique.Methanation is a kind of important catalysis technique, particularly in fuel applications field, can be used for improving combustion gas heat Value, it is allowed to the conversion of coke-stove gas, coal or biomass to natural gas.In recent years, with China's coal substitute natural gas industry Fast development, the methanation as one of core technology is of increased attention.

China be one " rich coal, oil-poor, few gas " country, using abundant coal resources, pass through coal based synthetic gas Methanation production natural gas has good economic benefit in Waste Era of Oil, to solving the problem of complex utilization of coal resources, Alleviate the present situation of Chinese postman problem algorithm shortage, safeguard energy security, realize CO₂Emission reduction, environmental protection are respectively provided with important strategy Meaning.

It was found from the basic research result of open report and relevant information, reacted for synthesis gas preparing natural gas by methanation, Ni base catalyst（High Ni contents, 20% ~ 70%）For main fluid catalyst；The easy coking deactivation of Fe base catalyst；Co bases catalyst is resistant to Property is strong, but poor selectivity；Ru bases catalyst activity is higher than Ni base catalyst, but its cost is high；The auxiliary agent or carrier material of use There are aluminum oxide, titanium oxide, silica, cerium oxide, lanthana, zirconium oxide, calcium oxide, magnesia etc..In a word, to natural gas from coal The requirement of industrial catalyst is mainly：Low temperature, efficiently（I.e. reaction temperature is low, and the hydrogen-carbon ratio scope of unstripped gas is wide, CO and CO₂'s Hydrogenation conversion is high, CH₄Selectivity it is high）, stability is good（It is i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning）, service life is long, into This is low.Reach these requirements, the compositing formula of catalyst and the reasonable selection of fabricating technology are crucial.

Methanation catalyst is with Al disclosed in Chinese patent CN1043639A₂O₃For carrier, nickel is active component, with rare earth Metal, or alkaline-earth metal, or alkali metal are auxiliary agent.Methanation catalyst disclosed in United States Patent (USP) US3933883 with high-purity gamma- Al₂O₃For carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in Chinese patent CN1043449A, nickel For active component, rare earth metal and magnesium are co-catalyst, and remaining is aluminum oxide.

Although catalyst made from above-mentioned patented method obtains preferable synthesis gas methanation reaction performance, due to The reaction is a fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）, reactant to Completed up to reaction while catalyst external surface, thus the inner surface of catalyst is contributed goal response less, this just makes Relatively low rate of metal in into carrier duct, add the preparation cost of catalyst.

The content of the invention

In order to overcome weak point of the prior art, the invention provides a kind of synthesis gas full methanation preparing natural gas Method for preparing catalyst.This method not only make use of Mo, Co and alumina support in useless hydrotreating catalyst, Er Qiechong Divide the Ni and V that make use of and deposited on useless hydrotreating catalyst, solve the pollution problem of dead catalyst, and economize on resources, Increase the benefit, technically easily implement, the synthesis gas methanation catalyst of gained has that cost is cheap, metal component utilization rate The characteristics of high, selective good, anti-carbon deposition ability is strong and stability is good.

The method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, the catalyst include living Property component, auxiliary agent and carrier；The active component is Mo, the one or more in auxiliary agent Ni, Co, V；Carrier is aluminum oxide； On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, active component Mo content for 15wt%~ 35wt%, the content of auxiliary agent is 5wt%~10wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：

（1）Useless hydrotreating catalyst is extracted to the oil removed on catalyst surface, roasted after being dried in 80~150 DEG C Burning processing, the sintering temperature are 300 ~ 600 DEG C, and roasting time is 2~6h；

（2）By step（1）Obtained useless hydrotreating catalyst is ground；

（3）To step（2）Strong inorganic acid is added in dead catalyst after being ground, dissolves and obtains after filtering Filtrate；

（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving, then adds and intends Boehmite, heating stirring to solution are evaporated, and obtain solids；

（5）Step（4）Obtained solids obtains catalyst precarsor A by drying, being calcined, shaping；

（6）Using reducing atmosphere to step（5）Obtained catalyst precarsor A carries out reduction treatment；

（7）By step（6）Catalyst precarsor A after obtained reduction is added in autoclave with polyhydric alcohol solutions, Replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；

（8）By step（7）Obtained reaction effluent places 1~3h, then filters, gained solid sample enters at room temperature Row drying, until sample surfaces without liquid phase, obtain catalyst precarsor B；

（9）Active component presoma is soluble in water, solution C is obtained, then adds step（8）Obtained catalyst precarsor B, after drying, calcination process, obtain catalyst.

The present invention is used in the method for preparing catalyst of synthesis gas methanation, step（1）The useless hydrotreating catalyst Refer to that not reached former reaction requires, or because grading reason in the fixed bed or ebullated bed of complete deactivation without making Catalyst for hydrotreatment of residual oil, generally residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.It is described Useless hydrotreating catalyst using aluminum oxide as carrier, active metal component contains Mo and Co, described useless hydrotreating catalyst Due to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, part metals Ni is typically had Deposited with V.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（1）Described in catalysis Mo content is 3wt% ~ 10wt% in agent precursor A, and Co content is 1wt% ~ 3wt%, and V content is 1wt% ~ 3wt%, Ni content For 3wt% ~ 8wt%.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（2）In give up hydrotreating Catalyst is ground to more than 120 mesh, preferably more than 200 mesh.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（3）Described in strong nothing Machine acid is concentrated nitric acid, the one or more in the concentrated sulfuric acid, concentrated hydrochloric acid, and the preferably concentrated sulfuric acid or concentrated nitric acid and concentrated hydrochloric acid forms The mixed acid of mixed acid or concentrated nitric acid and the concentrated sulfuric acid composition.The concentration of the strong inorganic acid is generally 30wt%~100wt%, its The concentration of middle concentrated hydrochloric acid is in more than 30wt%, and the concentration of concentrated nitric acid is in more than 50wt%, and the concentration of the concentrated sulfuric acid is in more than 50wt%.Institute The volume ratio for stating the dead catalyst after grinding and strong inorganic acid is 1:1~1:10；Step（3）Described in dead catalyst dissolving During need to heat, temperature needs strong stirring at 40 ~ 80 DEG C in course of dissolution.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（4）Described in containing Ni's Presoma is Ni soluble-salt, is specifically as follows nickel nitrate, nickel chloride, nickel sulfate, preferably nickel nitrate；The organic acid is Mo mol ratio is 0.5 ~ 1.5 in one or more in citric acid, tartaric acid, malic acid, with useless hydrotreating catalyst.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（4）Described in temperature Stirring is all evaporated to solution at 50 ~ 80 DEG C.The addition of the boehmite is according to dead catalyst and final catalyst Requirement add.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（5）Described in drying Condition is that 4 ~ 12h is dried at 60 ~ 120 DEG C, and roasting condition is that 2 ~ 6h is calcined at 400 ~ 700 DEG C.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（6）Described in reduction Atmosphere is hydrogen or the mixed gas of hydrogen and nitrogen, and hydrogen volume content is 10%~95% in the mixed gas.It is described 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, room temperature is down in a nitrogen atmosphere.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（7）Described in it is polynary Alcohol can be the one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5% ~10%；The polyhydric alcohol solutions and step（6）Obtained reduction rear catalyst precursor A volume ratio is 5~10.

In the method for preparing catalyst of synthesis gas full methanation preparing natural gas of the present invention, step（9）Described in activity Component presoma is Mo soluble-salt, is specifically as follows ammonium tetramolybdate, preferably ammonium molybdate, ammonium molybdate；It is living in the solution C The concentration of property component molybdenum is 0.5~4mol/L.The specific dipping process of active component is using well known to those skilled in the art Method.The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h.Institute Sintering temperature is stated as 350~650 DEG C, preferably 400~600 DEG C, roasting time is 2~12h, preferably 4~8h.

Catalyst prepared by the inventive method can also need to be made suitable particle shape according to what is used, and bar is such as made Shape, piece shape, cylindricality etc..

Catalyst prepared by the inventive method can apply to the reaction of synthesis gas preparing natural gas by methanation.Catalyst is reacting Before use 2%（Volume fraction）H₂S/H₂Gaseous mixture 3 ~ 6h of presulfurization, preferably 4h；Curing temperature is 400~600 DEG C, and vulcanization is completed After be passed through unstripped gas and reacted.Catalyst prepared by the inventive method reacts applied to synthesis gas preparing natural gas by methanation, tool There is appropriate resistant to sulfur ability, preferable process conditions are：H in unstripped gas₂/ CO mol ratios be 1.0~4.0, sulfur content be 0.5% ~ 1.5%, Ar, N can be contained in unstripped gas₂Or the dilution such as He property gas, 2000~20000h of unstripped gas air speed^-1, reaction pressure is 0.1~6Mpa, reaction temperature are 250~650 DEG C.

Catalyst of the present invention, by the use of the Mo in waste residue oil hydrogenating treatment catalyst as active metal, using useless Co in catalyst, and the Ni and V of deposition on a catalyst, as auxiliary agent, while also take full advantage of the load of dead catalyst Body aluminum oxide, so as to realize the comprehensive utilization of metal and carrier, resource utilization is improved, has saved great amount of cost；Handle The catalyst precarsor arrived is after reduction treatment, and catalytic polyol aqueous phase is hydrogenated with autoclave, the product C of generation₅And C₆ Liquid alkane can be used as atent solvent to the further processing of catalyst precarsor；Catalyst precarsor after treatment loads work again Property component Mo, preferably control in carrier duct load active metal amount, promote more multiple active components in carrier surface It is scattered, both improved the utilization rate of active metal, and reduced catalyst cost, and accelerated reactant and product again in catalyst Adsorption desorption speed in surface and hole, so as to avoid the further conversion of product, improve conversion ratio and the production of carbon monoxide The selectivity of thing.

Embodiment

The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.

Appreciation condition：With 2% at 450 DEG C before catalyst reaction of the present invention（Volume fraction）H₂S/H₂Gaseous mixture presulfurization 4h.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, it is 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 average activity of the catalyst in 300 DEG C of work 20h.

Using the distribution situation of active component on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.This The active component content distribution scanning electron microscope analysis of catalyst obtained by inventive embodiments and comparative example the results are shown in Table 2.

Embodiment 1

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, produce catalyst precarsor A, wherein Mo is accounted in terms of element Catalyst precarsor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；By 20g catalyst precarsors A 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；Catalyst precarsor A after reduction activation and 300mL mass concentrations are added to high pressure for 10% sorbitol solution In reactor, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；By above-mentioned height Reacted mixture in kettle is pressed to place 2h, filtering, gained solid sample is dried at room temperature for obtaining without liquid phase to sample surfaces Catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, steamed in 80 DEG C of stirrings to solution It is dry, it is put into baking oven at 110 DEG C and dries 12h, 4h is calcined at 400 DEG C, i.e., the obtained quality in terms of element accounts for catalyst percentage and contained Measure as 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, be designated as C-1.

Embodiment 2

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds the mixed solution of the 98 wt% concentrated sulfuric acids and 65 wt% concentrated nitric acids 300mL, volume ratio 2:1, constant temperature stirs at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, 41.32g is added into filtrate Nickel nitrate, after stirring and dissolving, add citric acid 40.98g（Citric acid and Mo in useless agent mol ratio are 1.5）, all after dissolving Add boehmite 24.87g, at 70 DEG C stirring be evaporated to solution, by gained solid in 100 DEG C of dry 8 h, at 600 DEG C Lower roasting 4h, produces catalyst precarsor A, and wherein Mo accounts for catalyst precarsor A weight 10wt% in terms of element, and Ni is accounted in terms of element and urged Agent precursor A weight 8wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume in mixed gas Content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By the catalyst precarsor A after reduction activation with The sorbitol solution that 300mL mass concentrations are 10% is added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusted Hydrogen Vapor Pressure reacts 4h to 3MPa at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered, gained is solid Body sample is dried at room temperature for obtaining catalyst precarsor B without liquid phase to sample surfaces；By catalyst precarsor B be added to containing In the aqueous solution of 13.38g ammonium molybdates, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 400 DEG C Lower roasting 4h, that is, it is made and quality is counted using element accounts for catalyst percentage composition as 30%Mo, 1.2%Co, 5.2% Ni, 1.3%V catalysis Agent, it is designated as C-2.

Embodiment 3

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds the mixed solution 450 of 35 wt% concentrated hydrochloric acids and 65 wt% concentrated nitric acids ML, volume ratio 1:1, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, and 54.01g nitre is added into filtrate Sour nickel, after stirring and dissolving, add citric acid 13.66g（Citric acid and Mo in useless agent mol ratio are 0.5）, all add after dissolving Enter boehmite 142.13g, at 70 DEG C stirring be evaporated to solution, by gained solid in 100 DEG C of dry 8 h, at 600 DEG C 4h is calcined, produces catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6wt%, Ni in terms of element and catalyst is accounted in terms of element Precursor A weight 6wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content in mixed gas For 80%, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By the catalyst precarsor A after reduction activation with The sorbitol solution that 300mL mass concentrations are 10% is added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusted Hydrogen Vapor Pressure reacts 4h to 3MPa at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered, gained is solid Body sample is dried at room temperature for obtaining catalyst precarsor B without liquid phase to sample surfaces；By catalyst precarsor B be added to containing In the aqueous solution of 7.36g ammonium molybdates, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, at 400 DEG C 4h is calcined, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 20%Mo, 0.83%Co, 4.6% Ni, 0.9%V catalysis Agent, it is designated as C-3.

Embodiment 4

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4h is calcined at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element and urged Agent precursor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；By 20g catalyst precarsors A in hydrogen Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, reduction Time 4h；It is anti-that the xylitol solution that catalyst precarsor A and 400mL mass concentrations after reduction activation are 10% is added to high pressure Answer in kettle, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；By above-mentioned high pressure Reacted mixture places 2h, filtering in kettle, and gained solid sample is dried at room temperature for being urged without liquid phase to sample surfaces Agent precursor B；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, is evaporated in 80 DEG C of stirring to solution, It is put into baking oven at 110 DEG C and dries 12h, 4h is calcined at 400 DEG C, i.e., the obtained quality in terms of element accounts for catalyst percentage composition and is 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, are designated as C-4.

Embodiment 5

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4h is calcined at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element and urged Agent precursor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；By 20g catalyst precarsors A in hydrogen Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, reduction Time 4h；It is anti-that the mannitol solution that catalyst precarsor A and 200mL mass concentrations after reduction activation are 10% is added to high pressure Answer in kettle, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；By above-mentioned high pressure Reacted mixture places 2h, filtering in kettle, and gained solid sample is dried at room temperature for being urged without liquid phase to sample surfaces Agent precursor B；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, is evaporated in 80 DEG C of stirring to solution, It is put into baking oven at 110 DEG C and dries 12h, 4h is calcined at 400 DEG C, i.e., the obtained quality in terms of element accounts for catalyst percentage composition and is 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, are designated as C-5.

Embodiment 6

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4h is calcined at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element and urged Agent precursor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；By 20g catalyst precarsors A in hydrogen Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, reduction Time 4h；Catalyst precarsor A after reduction activation and 300mL mass concentrations are added to reaction under high pressure for 5% sorbitol solution In kettle, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；By above-mentioned autoclave In reacted mixture place 2h, filtering, gained solid sample is dried at room temperature for being catalyzed without liquid phase to sample surfaces Agent precursor B；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, is evaporated, puts to solution in 80 DEG C of stirrings Enter and dry 12h in baking oven at 110 DEG C, 4h is calcined at 400 DEG C, i.e., the obtained quality in terms of element accounts for catalyst percentage composition and is 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, are designated as C-6.

Comparative example 1

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds the mL of the 98 wt% concentrated sulfuric acids 260, constant temperature stirs at 50 DEG C, makes Solid dissolving, filtrate is collected by filtration, 54.01g nickel nitrates are added into filtrate, after stirring and dissolving, add citric acid 27.31g（Lemon Lemon it is sour with useless agent in Mo mol ratio be 1）, boehmite 142.13g all is added after dissolving, is stirred at 70 DEG C to solution It is evaporated, by gained solid in 100 DEG C of dry 8h, is calcined 4h at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element Catalyst precarsor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；20g catalyst precarsors A is added to 50mLC₆In alkane solvent, 20min is impregnated, then filters, is dried at room temperature for, until catalysis is made without liquid phase in precursor surface Agent precursor B；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, is evaporated, puts to solution in 80 DEG C of stirrings Enter and dry 12h in baking oven at 110 DEG C, 4h is calcined at 400 DEG C, i.e., the obtained quality in terms of element accounts for catalyst percentage composition and is 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, are designated as D-1.

Comparative example 2

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4h is calcined at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element and urged Agent precursor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；20g catalyst precarsors A is added to 300mL Mass concentration is in 10% sorbitol solution, impregnates 20min, then filters, be dried at room temperature for, until precursor surface aneroid Phase, catalyst precarsor B is made；Catalyst precarsor B is added in the aqueous solution containing 11.19g ammonium molybdates, in 80 DEG C of stirrings extremely Solution is evaporated, and is put into baking oven at 110 DEG C and is dried 12h, and 4h is calcined at 400 DEG C, that is, the quality in terms of element is made and accounts for catalyst Percentage composition is 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalyst, is designated as D-2.

Comparative example 3

From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al₂O₃）, removed by extracting Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（Contain Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al₂O₃：71.2 wt%）, catalyst is ground to 200 mesh （Finger passes through 200 mesh sieves）, 100 grams of powder weight is weighed, adds 98 wt% concentrated sulfuric acid 260mL, constant temperature stirs at 50 DEG C, makes solid Body dissolves, and filtrate is collected by filtration, the addition 54.01g nickel nitrates into filtrate, after stirring and dissolving, adds citric acid 27.31g（Lemon Mo mol ratio is 1 in sour and useless agent）, boehmite 142.13g all is added after dissolving, stirring to solution steams at 70 DEG C It is dry, by gained solid in 100 DEG C of dry 8h, 4h is calcined at 600 DEG C, produces catalyst precarsor A, wherein Mo is accounted in terms of element and urged Agent precursor A weight 6wt%, Ni account for catalyst precarsor A weight 6wt% in terms of element；By 20g catalyst precarsors A be added to containing In the aqueous solution of 11.19g ammonium molybdates, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 400 DEG C Lower roasting 4h, that is, it is made and quality is counted using element accounts for catalyst percentage composition as 25%Mo, 0.7%Co, 4.1% Ni, 0.8%V catalysis Agent, it is designated as D-3.

The reactivity worth of the catalyst of table 1

The active component content distribution of the catalyst of table 2（wt%）

Claims (28)

1. a kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas, the catalyst includes active component, helped Agent and carrier, the active component are Mo, auxiliary agent Ni, Co and V, and carrier is aluminum oxide；Accounted for each element quality in catalyst On the basis of the percentage of catalyst quality, active component Mo content is 15wt%~35wt%, the content of auxiliary agent for 5wt%~ 10wt%, surplus are carrier, and the preparation method of the catalyst comprises the following steps：

（1）Useless hydrotreating catalyst is extracted to the oil removed on catalyst surface, carried out after being dried in 80~150 DEG C at roasting Reason, the sintering temperature are 300 ~ 600 DEG C, and roasting time is 2~6h；

（2）By step（1）Obtained useless hydrotreating catalyst is ground；

（3）To step（2）Strong inorganic acid is added in dead catalyst after being ground, dissolves and is filtered after filtering Liquid；

（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving, then adds and intends thin water Aluminium stone, heating stirring to solution are evaporated, and obtain solids；

（5）Step（4）Obtained solids obtains catalyst precarsor A by drying, being calcined, shaping；

（6）Using reducing atmosphere to step（5）Obtained catalyst precarsor A carries out reduction treatment；

（7）By step（6）Catalyst precarsor A after obtained reduction is added in autoclave with polyhydric alcohol solutions, is sealed Replaced 2~5 times with hydrogen afterwards, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；

（8）By step（7）Obtained reaction effluent places 1~3h, then filters, gained solid sample is done at room temperature It is dry, until sample surfaces without liquid phase, obtain catalyst precarsor B, described polyalcohol be xylitol, sorbierite, mannitol, I One or more in primary alconol；

（9）Active component presoma is soluble in water, solution C is obtained, then adds step（8）Obtained catalyst precarsor B, warp Dry, after calcination process, obtain catalyst.

2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in useless hydrotreating catalyst be slag Oil hydrogenating treatment catalyst.

3. according to the method described in claim 1 or 2, it is characterised in that：Step（1）Described in useless hydrotreating catalyst be Residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.

4. in accordance with the method for claim 3, it is characterised in that：Step（1）Described in useless hydrotreating catalyst with oxygen Change aluminium is carrier, and active metal component contains Mo and Co.

5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in catalyst precarsor A in Mo content For 3wt% ~ 10wt%, Co content is 1wt% ~ 3wt%, and V content is 1wt% ~ 3wt%, and Ni content is 3wt% ~ 8wt%.

6. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in give up hydrotreating catalyst grounds travel It is broken to more than 120 mesh.

7. in accordance with the method for claim 6, it is characterised in that：Step（2）Described in give up hydrotreating catalyst grounds travel It is broken to more than 200 mesh.

8. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid for concentrated nitric acid, dense sulphur One or more in acid, concentrated hydrochloric acid.

9. in accordance with the method for claim 8, it is characterised in that：Step（3）Described in strong inorganic acid for the concentrated sulfuric acid or The mixed acid or concentrated nitric acid of concentrated nitric acid and concentrated hydrochloric acid composition and the mixed acid of concentrated sulfuric acid composition.

10. in accordance with the method for claim 8, it is characterised in that：Step（3）Described in the concentration of strong inorganic acid be 30wt%~100wt%, wherein concentrated hydrochloric acid concentration in more than 30wt%, the concentration of concentrated nitric acid in more than 50wt%, the concentrated sulfuric acid it is dense Degree is in more than 50wt%.

11. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in dead catalyst and strong inorganic acid Volume ratio is 1:1~1:10.

12. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in need in dead catalyst course of dissolution Heating, temperature need strong stirring at 40 ~ 80 DEG C in course of dissolution.

13. in accordance with 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.

14. in accordance with the method for claim 13, it is characterised in that：Step（4）Described in the presoma containing Ni be nickel nitrate, Nickel chloride, nickel sulfate.

15. in accordance with the method for claim 14, it is characterised in that：Step（4）Described in the presoma containing Ni be nickel nitrate.

16. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in organic acid be citric acid, tartaric acid, One or more in malic acid.

17. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in organic acid and useless hydrorefining catalyst Mo mol ratio is 0.5 ~ 1.5 in agent.

18. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in boehmite add after, in temperature Stir at 50 ~ 80 DEG C of degree and be all evaporated to solution.

19. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in drying condition be at 60 ~ 120 DEG C 4 ~ 12h of lower drying, roasting condition are that 2 ~ 6h is calcined at 400 ~ 700 DEG C.

20. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in reducing atmosphere be hydrogen or hydrogen The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the gaseous mixture.

21. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in reduction treatment process it is as follows：Nitrogen Catalyst precarsor is warming up to 300~600 DEG C under gas atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, 0.1 After~0.5MPa handles 4~8h, room temperature is down in a nitrogen atmosphere.

22. in accordance with the method for claim 1, it is characterised in that：Step（7）Described in the mass concentrations of polyhydric alcohol solutions be 5%~10%.

23. in accordance with the method for claim 1, it is characterised in that：Step（7）Described in polyalcohol with reduction rear catalyst Precursor A volume ratio is 5~10.

24. in accordance with the method for claim 1, it is characterised in that：Step（9）Described in active component presoma be Mo Soluble-salt.

25. in accordance with the method for claim 24, it is characterised in that：Step（9）Described in active component presoma be molybdenum Sour ammonium.

26. in accordance with the method for claim 1, it is characterised in that：Step（9）Described in solution C active component molybdenum it is dense Spend for 0.5~4mol/L.

27. in accordance with 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, and the sintering temperature is 350~650 DEG C, and roasting time is 2~12h.

28. in accordance with the method for claim 27, it is characterised in that：Step（9）Described in drying temperature be 80~120 DEG C, Drying time is 4~8h, and the sintering temperature is 400~600 DEG C, and roasting time is 4~8h.