CN106944159A - A kind of preparation method of catalyst for hydrogen production from methane vapor reforming - Google Patents
A kind of preparation method of catalyst for hydrogen production from methane vapor reforming Download PDFInfo
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- CN106944159A CN106944159A CN201610003115.5A CN201610003115A CN106944159A CN 106944159 A CN106944159 A CN 106944159A CN 201610003115 A CN201610003115 A CN 201610003115A CN 106944159 A CN106944159 A CN 106944159A
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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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention relates to a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst comprises the following steps：Catalyst precarsor B is prepared first, then reduction treatment is carried out to catalyst precarsor B, it is well mixed auxiliary agent presoma is soluble in water with furfural aqueous solution, then it is added to together with catalyst precarsor B in autoclave, reacted after adding solution D, filtering gained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.Catalyst reaction activity prepared by this method is high, both reduces metal consumption, the selectivity of product is improved again.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, more particularly, to a kind of preparation method of hydrogen production from methane vapor reforming loading type nickel-based catalyst.
Background technology
Methane is hydrogen-carbon ratio highest hydrocarbon molecules in nature, and its abundance can be used as excellent hydrogen feedstock.At present, the hydrogen producing technology using methane as raw material mainly has hydrogen production from methane vapor reforming, partial oxidation of methane hydrogen, self-heating reforming hydrogen manufacturing etc..This several technology typically all obtains synthesis gas first（H2With CO gaseous mixture）, then pass through transformationreation（WGS）And pressure-variable adsorption（PSA）Obtain hydrogen.Wherein hydrogen production from methane vapor reforming can obtain hydrogen-carbon ratio（H2/CO）For 3 synthesis gas, therefore it is more suitable for for hydrogen manufacturing.Hydrogen production from methane vapor reforming is a kind of ripe industrialization hydrogen producing technology, and process is highly endothermic, generally in high temperature（800~1100 DEG C）Under the conditions of carry out, using high steam/hydrocarbons ratio operate（VH2O/VCH4>3）, to prevent catalyst carbon deposit.At present, the research of hydrogen production from methane vapor reforming is laid particular emphasis under the conditions of low steam carbon ratio high activity and the catalyst preparation of high stability, to seek the investment and the technical scheme of production cost that reduce natural gas steam reforming process.
Conventional SMR catalyst be loaded catalyst, carrier be aluminum oxide, zirconium oxide, cerium oxide, magnesia, lanthana, niobium oxide, zeolite, perovskite, silica clay, yittrium oxide, cobalt oxide, iron oxide and its mixture or one of.In group VIII non-radioactive metal can as SMR catalyst active metal.Research shows, by group VIII noble metals Ru, Rh, Pd even load when on suitable carrier, all with higher reactivity and anti-carbon performance, but noble metal shortcoming be that it is expensive；In group VIII base metal, Raney nickel has higher reactivity, typically using Ni/Al2O3Catalyst, reaction condition is 1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio between/CO is about 3.
Although existing catalyst can obtain preferable hydrogen production from methane vapor reforming reactivity worth, still suffer from that cost is higher, catalyst easy carbon distribution the problems such as.Particularly work as reactant（Methane and water）Molecule during mass transfer, due to the difference of diffusion velocity, causes two kinds of reactant molecule ratios gradient radially occur in catalyst granules, particle inside steam/hydrocarbons ratio, which is much smaller than inside stoichiometry, therefore catalyst granules, is more easy to carbon distribution in catalyst granules.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, 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 of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, auxiliary agent is the one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce, La, and carrier is any of aluminum oxide, silica, SBA-15；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 10wt%~20wt%, and the content of auxiliary agent is 1wt%~5wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after impregnated, aging, drying, calcination process, catalyst precarsor B is obtained；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）Auxiliary agent presoma is soluble in water, solution C is obtained, and be well mixed with furfural aqueous solution, then with step（3）Obtained catalyst precarsor B is added in autoclave together；
（5）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step（4）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；
（6）Treat step（5）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.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（1）Described in active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate；In the solution A, active component is in terms of element, and the mass fraction in solution A is 1%~7%.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（2）Described in dipping be incipient impregnation, dip time be 1~3h；The aging temperature is 10~90 DEG C, and preferably 20~60 DEG C, ageing time is 1~24h, preferably 4~12h；Step（2）With step（6）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h；Step（2）With step（6）Described in sintering temperature be 500~900 DEG C, preferably 600~800 DEG C, roasting time be 2~12h, preferably 4~8h.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（2）Described in carrier any of for aluminum oxide, silica, SBA-15；The carrier can use commercially available product, can also be prepared by method well known in the art；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（3）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, 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, 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.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（4）Described in auxiliary agent presoma be one or more in sodium nitrate, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate, preferably magnesium nitrate；In the solution C, auxiliary agent is in terms of element, and the mass fraction in solution C is 1%~4%；The mass fraction of furfural is 30%~50% in the furfural aqueous solution；Step（4）Described in furfural aqueous solution and the mass ratio of solution C be 3~5, the gross mass and step of the solution C and furfural aqueous solution（3）Obtained reduction rear catalyst precursor B mass ratio is 3~6.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（5）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 D, in active component presoma it is nickeliferous mass fraction in solution D is counted as 0.3%~2% using element, mass fraction of the high molecular weight water soluble polymer in solution D is 3~6 times of Ni element mass fractions.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（6）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%.
Catalyst prepared by the inventive method can apply to hydrogen production from methane vapor reforming reaction.Catalyst using before in a hydrogen atmosphere, 700~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method reacts applied to hydrogen production from methane vapor reforming, and preferable process conditions are：The composition H of unstripped gas2O/CH4Mol ratio is 1~4, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 1000~3000h of unstripped gas air speed-1, reaction pressure is 0.2~3Mpa, and reaction temperature is 600~800 DEG C.
Compared with prior art, the catalyst for hydrogen production from methane vapor reforming that a kind of active metal outer layer is distributed can be obtained by preparation method of the present invention.In the present invention, pre-soaked a part of active metal is to carry out furfural aqueous phase hydrogenation reaction.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.Catalyst reaction activity prepared by this method is high, both reduces metal consumption, the selectivity of product is improved 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 3 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 H2O/CH4/N2=6.75/2.25/1（Mol ratio）, air speed 2000h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Reaction starts sampling analysis after 1 ~ 3 hour, and evaluation result is shown in Table 1.Average activity of the reaction result for catalyst after 750 DEG C of 100h that work 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
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.2g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；6.41g magnesium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 12.7%Ni, 1.9%Mg catalyst, is designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.2g silica supports are carried on using equi-volume impregnating（Pore volume is 0.97mL/g, and specific surface area is 372m2/ g, spherical, equivalent diameter 0.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；6.41g magnesium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 12.3%Ni, 1.8%Mg catalyst, is designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.2g SBA-15 carriers are carried on using equi-volume impregnating（Pore volume is 1.23mL/g, and specific surface area is 701m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；6.41g magnesium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 12.9%Ni, 2.1%Mg catalyst, is designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrates to be dissolved in 16mL deionized waters, obtain solution A；17.1g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 1% of final catalyst in terms of element wt；Catalyst precarsor B 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；2.14g magnesium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；8.1g polyethylene glycol, 8.92g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 8.6%Ni, 0.5%Mg catalyst, is designated as C-4.
Embodiment 5
Weigh 4.96g nickel nitrates to be dissolved in 11mL deionized waters, obtain solution A；13.2g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 5% of final catalyst in terms of element wt；Catalyst precarsor B 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；10.68g magnesium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；13.5g polyethylene glycol, 14.87g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 41g 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 17.3%Ni, 3.7%Mg catalyst, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.4g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；2.22g sodium nitrate is dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；By 10.8g polyvinylpyrrolidones（k30）, 11.89g nickel nitrates be dissolved in 200mL deionized waters, obtain solution D；Solution D 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 12.2%Ni, 1.9%Na catalyst, is designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.5g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；1.45g strontium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyvinyl alcohol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 165g mass fractions are 20%, 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 12.4%Ni, 1.7%Sr catalyst, is designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.4g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；2.82g zirconium nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 12.5%Ni, 2.1%Zr catalyst, is designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrates to be dissolved in 14mL deionized waters, obtain solution A；15.4g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, 2h, aging 4h, 80 DEG C of dry 12h are impregnated at room temperature, and 700 DEG C of roastings 4h, obtained catalyst precarsor B, the Ni of load are the 3% of final catalyst in terms of element wt；Catalyst precarsor B 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；1.87g lanthanum nitrates are dissolved in 16mL deionized waters, solution C 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 B after reduction activation in autoclave；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters, solution D is obtained；Solution D 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 12.6%Ni, 2.1%La catalyst, is designated as C-9.
Comparative example
Weigh 14.87g nickel nitrates, 6.41g magnesium nitrates to be dissolved in deionized water, the aqueous solution is made；15.2g alumina supports are carried on using equi-volume impregnating（Pore volume is 0.73mL/g, and specific surface area is 253m2/ g, bar shaped, equivalent diameter 1.5mm）, impregnate 2h at room temperature, aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h are made and count quality using element and account for catalyst percentage composition as 14.1%Ni, 2.4%Mg 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 (19)
1. a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, auxiliary agent is the one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce, La, and carrier is any of aluminum oxide, silica, SBA-15；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 10wt%~20wt%, and the content of auxiliary agent is 1wt%~5wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after impregnated, aging, drying, calcination process, catalyst precarsor B is obtained；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）Auxiliary agent presoma is soluble in water, solution C is obtained, and be well mixed with furfural aqueous solution, then with step（3）Obtained catalyst precarsor B is added in autoclave together；
（5）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step（4）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；
（6）Treat step（5）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 active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in solution A, active component is in terms of element, and the mass fraction in solution A is 1%~7%.
4. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in aging temperature be 10~90 DEG C, preferably 20~60 DEG C, ageing time be 1~24h, preferably 4~12h.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）With step（6）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）With step（6）Described in sintering temperature be 500~900 DEG C, preferably 600~800 DEG C, roasting time be 2~12h, preferably 4~8h.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in catalyst precarsor B in, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
9. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in auxiliary agent presoma be one or more in sodium nitrate, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate, preferably magnesium nitrate.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in solution C, auxiliary agent is in terms of element, and the mass fraction in solution C is 1%~4%.
11. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in furfural aqueous solution the mass fraction of furfural be 30%~50%.
12. in accordance with the method for claim 1, it is characterised in that：Step（4）Middle step（4）Described in furfural aqueous solution and the mass ratio of solution C be 3~5.
13. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in solution C and the gross mass and step of furfural aqueous solution（3）Obtained reduction rear catalyst precursor B mass ratio is 3~6.
14. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in high molecular weight water soluble polymer be polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）In one or more.
15. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate.
16. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in solution D, in active component presoma nickeliferous mass fraction in solution D is counted as 0.3%~2% using element.
17. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in mass fraction of the high molecular weight water soluble polymer in solution D be 3~6 times of Ni element mass fractions.
18. in accordance with the method for claim 1, it is characterised in that：Step（6）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.
19. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in aqueous citric acid solution mass fraction be 10%~20%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866261A (en) * | 2017-11-14 | 2018-04-03 | 北京赛诺时飞石化科技有限公司 | A kind of hydrocarbons reforming catalyst of the molecular sieves of modified SBA 15 and its preparation method and application |
| CN110586111A (en) * | 2019-09-17 | 2019-12-20 | 大连海事大学 | Preparation method of composite catalyst for hydrogen production by methane steam reforming |
| CN111545215A (en) * | 2020-06-22 | 2020-08-18 | 中国科学技术大学 | Perovskite loaded monatomic catalyst and preparation method and application thereof |
| CN112916015A (en) * | 2021-01-27 | 2021-06-08 | 成都理工大学 | Strontium-zirconium perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114772552A (en) * | 2022-03-23 | 2022-07-22 | 浙江浙能技术研究院有限公司 | Structured oxygen carrier for hydrogen production by chemical chain methane reforming and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139897A (en) * | 1978-04-22 | 1979-10-30 | Jgc Corp | Low temperature steam reforming catalyst for hydrocarbon |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
-
2016
- 2016-01-07 CN CN201610003115.5A patent/CN106944159B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139897A (en) * | 1978-04-22 | 1979-10-30 | Jgc Corp | Low temperature steam reforming catalyst for hydrocarbon |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866261A (en) * | 2017-11-14 | 2018-04-03 | 北京赛诺时飞石化科技有限公司 | A kind of hydrocarbons reforming catalyst of the molecular sieves of modified SBA 15 and its preparation method and application |
| CN107866261B (en) * | 2017-11-14 | 2020-10-27 | 北京赛诺时飞石化科技有限公司 | Hydrocarbon reforming catalyst of modified SBA-15 molecular sieve and preparation method and application thereof |
| CN110586111A (en) * | 2019-09-17 | 2019-12-20 | 大连海事大学 | Preparation method of composite catalyst for hydrogen production by methane steam reforming |
| CN111545215A (en) * | 2020-06-22 | 2020-08-18 | 中国科学技术大学 | Perovskite loaded monatomic catalyst and preparation method and application thereof |
| CN111545215B (en) * | 2020-06-22 | 2022-09-30 | 中国科学技术大学 | Perovskite-loaded monatomic catalyst and preparation method and application thereof |
| CN112916015A (en) * | 2021-01-27 | 2021-06-08 | 成都理工大学 | Strontium-zirconium perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN112916015B (en) * | 2021-01-27 | 2022-07-01 | 成都理工大学 | Strontium-zirconium perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114772552A (en) * | 2022-03-23 | 2022-07-22 | 浙江浙能技术研究院有限公司 | Structured oxygen carrier for hydrogen production by chemical chain methane reforming and preparation method thereof |
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