CN106944068A - A kind of preparation method for methane portion oxidation synthesis gas catalyst - Google Patents
A kind of preparation method for methane portion oxidation synthesis gas catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method for methane portion oxidation synthesis gas catalyst, the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst comprises the following steps：Catalyst precarsor A is prepared first, then reduction treatment is carried out to catalyst precarsor A, solution B and furfural aqueous solution are well mixed and are added to together with catalyst precarsor A in autoclave, add after solution C and react, filtering gained 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, and the catalyst reaction activity of preparation is high, both reduces metal consumption, and the focus generation during methane portion oxidation is inhibited again.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst for methane portion oxidation synthesis gas, more particularly, to a kind of loading type nickel-based catalyst preparation method for methane portion oxidation synthesis gas.
Background technology
The 90% of gas component is one of effective way of gas utilization by methane through synthesis gas synthetic fuel and chemicals again above is methane.With traditional vapour reforming ratio, methane portion oxidation synthesis gas has the advantages that required reaction vessel volume is small, reaction rate is fast, energy consumption is low and the synthesis gas of generation is suitable as the unstripped gas of methanol and Fiscber-Tropscb synthesis.In addition, exploitation methane portion oxidation technology is possible to replace highly endothermic methane steam reformation technique to be used to produce synthesis gas, it is significant especially for remote or offshore natural gas resource utilization.
The main catalyst system of methane portion oxidation synthesis gas is by active component noble metal（Pt, Pd, Rh, Ru, Ir）, nickel or cobalt be supported on the carriers such as aluminum oxide, silica, magnesia, zirconium oxide, titanium oxide, while alkali metal, alkaline-earth metal or rare-earth oxide can be used to be modified to improve the reactivity worth of catalyst.
CN
101049566A discloses a kind of for Ni base catalyst of methane portion oxidation synthesis gas and preparation method thereof.The carrier of catalyst is complex carrier Mg-Al-Ce-Zr-O, and active component is NiO.Complex carrier is made using coprecipitation method in the patent, and obtained carrier is dipped in into Ni (NO3)2In solution, methane conversion reaches that more than 84%, CO selectively reaches more than 99% on obtained catalyst.
CN
101219393A discloses a kind of for cobalt-based loaded catalyst of methane portion oxidation synthesis gas and preparation method thereof.Catalyst takes step impregnation method to prepare, using Co as active component, using a kind of alkaline-earth metal or rare earth metal as auxiliary agent, using HZSM-5 as carrier, and obtained catalyst activity is high, coking resistivity is strong, good stability.
CN
101284241A discloses a kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof.Using transition metal Co and noble metal as active component, using a kind of element selected from alkaline-earth metal as auxiliary agent, with γ-Al2O3For carrier, the catalyst of methane portion oxidation synthesis gas is made using infusion process.Catalyst has the advantages that high activity, excellent coking resistivity, high stability.
Although catalyst made from above-mentioned patented method obtains preferable methane portion oxidation synthesis gas reactivity worth, because the reaction is a fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）, reactant reaction while catalyst external surface is reached has been completed, thus the inner surface of catalyst contributes little to goal response, and this has resulted in rate of metal relatively low in carrier duct, while can also accelerate the deep oxidation of product.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method for methane portion oxidation synthesis gas catalyst, the characteristics of catalyst prepared by this method has with low cost, metal component utilization rate high and is selective good.
The invention provides a kind of preparation method for methane portion oxidation synthesis gas catalyst, the catalyst includes active component, auxiliary agent and carrier, and active component is Ni, and auxiliary agent is the one or more in Ca, Mg, Zr, Ce or La, and carrier is aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 8wt%~15wt%, and the content of auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted to the oil removed on catalyst surface, after 80~150 DEG C are dried, high-temperature roasting processing is carried out, sintering 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）In add strong inorganic acid in obtained dead catalyst, after after dead catalyst dissolving, be filtered to remove solid insoluble；
（4）To step（3）Active component presoma is added in obtained filtrate, organic acid is added after dissolving；
（5）Boehmite is added to step（4）In obtained solution, heating stirring to solution is evaporated, and obtains solids；
（6）Step（5）Obtained solids is by drying, being calcined, shaping, obtains catalyst precarsor A；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）Auxiliary agent presoma is soluble in water, solution B is obtained, and be well mixed with furfural aqueous solution, then with step（7）Obtained catalyst precarsor A is added in autoclave together；
（9）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added to step（8）In described autoclave, replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（10）Treat step（9）Obtained solidliquid mixture is down to 20~30 DEG C, adds absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（1）Described in waste residue oil hydrogenating treatment catalyst be that, using aluminum oxide as carrier, active metal component contains Mo and Co, be not reached former reaction to require, or due to level with reason without the residual oil hydrocatalyst that is used in the fixed bed or ebullated bed of complete deactivation；Described dead catalyst is due to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, typically having part metals Ni and V deposition.Step（1）Described in extracting solvent can be the one or two in petroleum ether or toluene.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（2）Described in give up hydrotreating catalyst grind to more than 120 mesh, it is more than preferably 200 mesh.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（3）Described in strong inorganic acid be one or more mixed acid in concentrated nitric acid, the concentrated sulfuric acid, concentrated hydrochloric acid, the preferably concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid mixed acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.The concentration of strong inorganic acid is generally 30wt%~100wt%, and wherein the concentration of 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%.The volume ratio of dead catalyst and strong inorganic acid is 1:1~1:10；Step（3）Described in heating is needed in dead catalyst course of dissolution, temperature needs strong stirring at 40~80 DEG C in course of dissolution.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（4）Described in presoma containing active component be Ni soluble-salt, be specifically as follows nickel nitrate, nickel chloride, nickel sulfate, preferably nickel nitrate；The organic acid is the one or more in citric acid, tartaric acid, malic acid, and the mol ratio with Mo in useless hydrotreating catalyst is 0.5~1.5.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（5）Described in boehmite be added to step（4）In obtained solution, stir to solution and be all evaporated at 50~80 DEG C of temperature.The addition of the boehmite is added according to the requirement of dead catalyst and final catalyst.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（6）Described in drying condition be at 60~120 DEG C dry 4~12h, roasting condition be at 400~700 DEG C be calcined 2~6h.Mo content is 1wt%~3wt% in described catalyst precarsor A, and Ni content is 1wt%~5wt%.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（7）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the gaseous mixture.Specific reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, in 0.1~0.5MPa（Absolute pressure）Handle after 4~8h, room temperature is down in a nitrogen atmosphere.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（8）Described in auxiliary agent presoma be one or more in calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate, preferably lanthanum nitrate；In the solution B, auxiliary agent is in terms of element, and mass fraction in the solution is 1%~5%；The mass fraction of furfural is 30%~50% in the furfural aqueous solution；Step（8）Described in furfural aqueous solution and the mass ratio of solution B be 3~5, the gross mass and step of the solution B and furfuryl aldehyde solution（7）Obtained reduction rear catalyst precursor A mass ratio is 3~6.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（9）Described in high molecular weight water soluble polymer be polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）In one or more；The active component presoma is the one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate；In the solution C, in active component presoma it is nickeliferous mass fraction in solution C is counted as 0.1%~2% using element, mass fraction of the high molecular weight water soluble polymer in solution C is 3~6 times of Ni element mass fractions.
The present invention is used in the preparation method of methane portion oxidation synthesis gas catalyst, step（10）Described in add the quality of absolute ethyl alcohol or citric acid and the mass ratio of high molecular weight water soluble polymer be 2~4；The mass fraction of the aqueous citric acid solution is 10%~20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；The sintering temperature is 500~900 DEG C, and preferably 600~800 DEG C, roasting time is 2~12h, preferably 4~8h.
Catalyst prepared by the inventive method can apply to methane portion oxidation synthesis gas reaction.Catalyst using before in a hydrogen atmosphere, 700~800 DEG C of 1~3h of prereduction.Catalyst prepared by the inventive method reacts applied to methane portion oxidation synthesis gas, and preferable process conditions are：The composition CH of unstripped gas4/O2Mol ratio is 1.75~2.2, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 20000~200000h of unstripped gas air speed-1, reaction pressure is 0.1~1Mpa, and reaction temperature is 600~900 DEG C.
Compared with prior art, the catalyst for methane portion oxidation synthesis gas that a kind of active metal outer layer is distributed can be obtained by preparation method of the present invention.In the present invention, furfural aqueous phase hydrogenation reaction is carried out using waste residue oil hydrogenating treatment catalyst.Add active metal predecessor and high molecular weight water soluble polymer simultaneously in the system of furfural hydrogenation, on the one hand hinder active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, using the coordination between active metal predecessor and high molecular weight water soluble polymer, concentration difference of the active metallic ion inside and outside catalyst granules in reduction solution slows down active metal to the diffusion velocity inside catalyst granules.This method takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, and the catalyst reaction activity of preparation is high, both reduces metal consumption, and the focus generation during methane portion oxidation is inhibited again.Catalyst precarsor processing simultaneously is completed with the step of catalyst preparation one, and preparation technology is simple, is conducive to industrial amplification.
Embodiment
The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.
Appreciation condition：With hydrogen reducing 2 hours at 700 DEG C before catalyst reaction of the present invention.Reacted in continuous sample introduction fixed-bed quartz reactor, 750 DEG C of reaction temperature, unstripped gas composition CH4/O2/Ar
= 2/1/4（Mol ratio）, air speed 1 × 105h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Sampling analysis after reacting 1 hour, evaluation result is shown in Table 1.
The metal element content in catalyst is determined using XRF analysis technology.Using the distribution situation of active component on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.The scanning electron microscope analysis of catalyst activity component nickel the results are shown in Table 2 obtained by the embodiment of the present invention and comparative example.
Embodiment 1
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, is added into filtrate after 85.72g nickel nitrates, stirring and dissolving, citric acid 27.31g is added（Citric acid is 1 with the mol ratio of Mo in useless agent）, boehmite 740g all is added after dissolving, stirs to solution and is evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 2wt%, Ni in terms of element and catalyst precarsor A weight 3wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.56g lanthanum nitrates are dissolved in 15mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；11g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add 33g absolute ethyl alcohols, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 10.6%Ni, 1.4%La catalyst, is designated as C-1.
Embodiment 2
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, the mixed solution 300mL of the 98 wt% concentrated sulfuric acids and 65 wt% concentrated nitric acids is added, volume ratio is 2:1, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, and is added into filtrate after 54.01g nickel nitrates, stirring and dissolving, adds citric acid 40.98g（Citric acid is 0.5 with the mol ratio of Mo in useless agent）All boehmite 1665.94g is added after dissolving, stir to solution and be evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8 h, 4h is calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 1wt%, Ni in terms of element and catalyst precarsor A weight 1wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；5.34g magnesium nitrates are dissolved in 15mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；8.1g polyethylene glycol, 8.92g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add 25g absolute ethyl alcohols, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 6.8%Ni, 0.6%Mg catalyst, is designated as C-2.
Embodiment 3
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, the mixed solution 450mL of 35 wt% concentrated hydrochloric acids and 65 wt% concentrated nitric acids is added, volume ratio is 1:1, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, and is added into filtrate after 96.29g nickel nitrates, stirring and dissolving, adds citric acid 13.66g（Citric acid is 0.5 with the mol ratio of Mo in useless agent）All boehmite 431.41g is added after dissolving, stir to solution and be evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8 h, 4h is calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 3wt%, Ni in terms of element and catalyst precarsor A weight 5wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.95g calcium nitrate is dissolved in 15mL deionized waters, solution B is obtained, and is well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, is then added to together with the catalyst precarsor A after reduction activation in autoclave；13g polyethylene glycol, 13.63g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add 39g absolute ethyl alcohols, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 13.8%Ni, 2.2%Ca catalyst, is designated as C-3.
Embodiment 4
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, is added into filtrate after 85.72g nickel nitrates, stirring and dissolving, citric acid 27.31g is added（Citric acid is 1 with the mol ratio of Mo in useless agent）, boehmite 740g all is added after dissolving, stirs to solution and is evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 2wt%, Ni in terms of element and catalyst precarsor A weight 3wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.35g zirconium nitrates are dissolved in 15mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 3 times of quality for 30% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；11g polyvinyl alcohol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add 22g absolute ethyl alcohols, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 10.1%Ni, 1.3%Zr catalyst, is designated as C-4.
Embodiment 5
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, is added into filtrate after 85.72g nickel nitrates, stirring and dissolving, citric acid 27.31g is added（Citric acid is 1 with the mol ratio of Mo in useless agent）, boehmite 740g all is added after dissolving, stirs to solution and is evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 2wt%, Ni in terms of element and catalyst precarsor A weight 3wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.55g cerous nitrates are dissolved in 15mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 5 times of quality for 50% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；11g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 220g mass fractions are 15%, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 10.4%Ni, 1.2%Ce catalyst, is designated as C-5.
Embodiment 6
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, is added into filtrate after 85.72g nickel nitrates, stirring and dissolving, citric acid 27.31g is added（Citric acid is 1 with the mol ratio of Mo in useless agent）, boehmite 740g all is added after dissolving, stirs to solution and is evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 2wt%, Ni in terms of element and catalyst precarsor A weight 3wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.56g lanthanum nitrates are dissolved in 15mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；By 11g polyvinylpyrrolidones（k30）, 11.89g nickel nitrates be dissolved in 200mL deionized waters, obtain solution C；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 220g mass fractions are 15%, place 1.5h, then filter, gained solid sample is put into baking oven in drying 6h at 110 DEG C, is calcined 6h at 700 DEG C, that is, is made and is counted quality using element and account for catalyst percentage composition as 10.8%Ni, 1.6%La catalyst, is designated as C-6.
Comparative example
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, the oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8h, gained catalyst is calcined 4h, dead catalyst after being handled at 450 DEG C（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 pass through 200 mesh sieves）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature is stirred at 50 DEG C, makes solid dissolving, filtrate is collected by filtration, is added into filtrate after 85.72g nickel nitrates, stirring and dissolving, citric acid 27.31g is added（Citric acid is 1 with the mol ratio of Mo in useless agent）, boehmite 740g all is added after dissolving, stirs to solution and is evaporated at 70 DEG C, by gained solid in 100 DEG C of dry 8h, 4 h are calcined at 600 DEG C, catalyst precarsor A is produced, wherein Mo is accounted for catalyst precarsor A weight 2wt%, Ni in terms of element and catalyst precarsor A weight 3wt% is accounted in terms of element；20g catalyst precarsors A is added to containing in 1.56g lanthanum nitrates, the aqueous solution of 11.89g nickel nitrates, be calcined 6h at 6h, 700 DEG C in being dried at 110 DEG C, that is, is made and quality is counted using element accounts for catalyst percentage composition as 11.3%Ni, 1.6%La catalyst is designated as D-1.
The reactivity worth of the catalyst of table 1
The catalyst activity component Ni content distributions of table 2（wt%）
Claims (25)
1. a kind of preparation method for methane portion oxidation synthesis gas catalyst, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is the one or more in Ca, Mg, Zr, Ce or La, and carrier is aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 8wt%~15wt%, and the content of auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted to the oil removed on catalyst surface, after 80~150 DEG C are dried, high-temperature roasting processing is carried out, sintering 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）In add strong inorganic acid in obtained dead catalyst, after after dead catalyst dissolving, be filtered to remove solid insoluble；
（4）To step（3）Active component presoma is added in obtained filtrate, organic acid is added after dissolving；
（5）Boehmite is added to step（4）In obtained solution, heating stirring to solution is evaporated, and obtains solids；
（6）Step（5）Obtained solids is by drying, being calcined, shaping, obtains catalyst precarsor A；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）Auxiliary agent presoma is soluble in water, solution B is obtained, and be well mixed with furfural aqueous solution, then with step（7）Obtained catalyst precarsor A is added in autoclave together；
（9）High molecular weight water soluble polymer, active component presoma is soluble in water, solution C is obtained, solution C is added to step（8）In described autoclave, replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（10）Treat step（9）Obtained solidliquid mixture is down to 20~30 DEG C, adds absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in waste residue oil hydrogenating treatment catalyst be using aluminum oxide as carrier, active metal component contain Mo and Co.
3. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in give up hydrotreating catalyst grind to more than 120 mesh, it is more than preferably 200 mesh.
4. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid be one or more mixed acid in concentrated nitric acid, the concentrated sulfuric acid, concentrated hydrochloric acid, the preferably concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid mixed acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.
5. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid concentration be 30wt%~100wt%.
6. in accordance with the method for claim 4, it is characterised in that：The concentration of the 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%.
7. 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 be 1:1~1:10.
8. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in active component presoma be Ni soluble-salt, specially nickel nitrate, nickel chloride, nickel sulfate, preferably nickel nitrate.
9. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in organic acid be citric acid, tartaric acid, malic acid in one or more.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in organic acid and useless hydrotreating catalyst Mo mol ratio be 0.5~1.5.
11. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in drying condition be at 60~120 DEG C dry 4~12h, roasting condition be at 400~700 DEG C be calcined 2~6h.
12. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in catalyst precarsor A in Mo content be 1wt%~3wt%, Ni content is 1wt%~5wt%.
13. in accordance with the method for claim 1, it is characterised in that：Step（7）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the gaseous mixture.
14. in accordance with the method for claim 1, it is characterised in that：Step（8）Described in auxiliary agent presoma be one or more in calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate, preferably lanthanum nitrate.
15. in accordance with the method for claim 1, it is characterised in that：Step（8）Described in solution B, auxiliary agent is in terms of element, and mass fraction in the solution is 1%~5%.
16. in accordance with the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution the mass fraction of furfural be 30%~50%.
17. in accordance with the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution and the mass ratio of solution B be 3~5.
18. in accordance with the method for claim 1, it is characterised in that：Step（8）Described in solution B and the gross mass and step of furfuryl aldehyde solution（7）Obtained reduction rear catalyst precursor A mass ratio is 3~6.
19. in accordance with the method for claim 1, it is characterised in that：Step（9）Described in high molecular weight water soluble polymer be polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol in one or more.
20. in accordance with the method for claim 1, it is characterised in that：Step（9）Described in active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate.
21. in accordance with the method for claim 1, it is characterised in that：Step（9）Described in solution C, in active component presoma it is nickeliferous mass fraction in solution C is counted as 0.1%~2% using element, mass fraction of the high molecular weight water soluble polymer in solution C is 3~6 times of Ni element mass fractions.
22. in accordance with the method for claim 1, it is characterised in that：Step（10）Described in add the quality of absolute ethyl alcohol or citric acid and the mass ratio of high molecular weight water soluble polymer be 2~4.
23. in accordance with the method for claim 1, it is characterised in that：Step（10）Described in aqueous citric acid solution mass fraction be 10%~20%.
24. in accordance with the method for claim 1, it is characterised in that：Step（10）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h.
25. in accordance with the method for claim 1, it is characterised in that：Step（10）Described in sintering temperature be 500~900 DEG C, preferably 600~800 DEG C, roasting time be 2~12h, preferably 4~8h.
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| CN111450833A (en) * | 2020-01-15 | 2020-07-28 | 成都理工大学 | Strontium-promoted cobalt-based composite oxide catalyst for autothermal reforming of acetic acid to produce hydrogen |
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