CN105727955B - 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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- CN105727955B CN105727955B CN201410732120.0A CN201410732120A CN105727955B CN 105727955 B CN105727955 B CN 105727955B CN 201410732120 A CN201410732120 A CN 201410732120A CN 105727955 B CN105727955 B CN 105727955B
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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, and the preparation method is soluble in water by active component presoma first, obtains solution A；Then carrier is added, catalyst precarsor B is obtained after aging, drying, calcination process；Reduction treatment is carried out to catalyst precarsor B using reducing atmosphere；Catalyst precarsor B after reduction and polyhydric alcohol solutions are added in reactor and carry out hydrogenation reaction, reaction effluent is placed, then filtration drying obtains catalyst precarsor C；Active component presoma and auxiliary agent presoma is soluble in water, solution D is obtained, catalyst precarsor C is then added, after drying, calcination process, obtains catalyst.The inventive method promotes more multiple active components and disperseed in carrier surface, had both improved the utilization rate of active metal, and had improved the conversion ratio of methane and the selectivity of product 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 methane water
The preparation method of vapour reforming hydrogen producing loading type nickel-based catalyst.
Background technology
Methane resource enriches, and hydrogen-carbon ratio is high, is good hydrogen feedstock.And hydrogen is as secondary energy sources efficiently, clean
By one of main energy sources as future society.In recent years, raw material of the hydrogen as fuel cell, have compared with other fuel
There is unrivaled superiority, such as hydrogen calorific value is high, on the one hand solves energy shortage without air pollution, the application of Hydrogen Energy and asks
Topic, on the other hand do not cause environmental pollution again.
At present, mainly two kinds of approach are passed through using methane as raw material for preparing hydrogen：One kind is by preparing synthesis gas（H2With
CO gaseous mixture）So as to obtain hydrogen；Another kind is to obtain hydrogen by the direct decomposition of methane.The method of methane preparing synthetic gas
Mainly there are three kinds：
Steam reforming method（SRM）：H=+206KJ/mol；
CO 2 reformation method（DMR）： H=+247 KJ/mol；
Partial oxidation process（POM）：H=-36 KJ/mol.
The steam reforming method of methane, in theory H2/ CO=3, it is hydrogen-rich synthetic gas, CO contents are smaller, and can be by suitable
Catalyst cause H2Ratio further increases, can be as the desirable route of fuel cell hydrogen source.Methane vapor reforming is anti-
It should be strong endothermic reaction, it is desirable to carry out at high temperature, in general reaction temperature is at 700 ~ 900 DEG C.Currently used methane water steams
The carrier of gas reforming catalyst is aluminum oxide, zirconium oxide, cerium oxide, magnesia, lanthana, niobium oxide, zeolite, perovskite, two
Silica clay, yittrium oxide, cobalt oxide, iron oxide and its mixture or one of.Research shows, noble metal Ru, Rh, Pd etc. is negative
When being loaded on suitable carrier, all there is higher reactivity and anti-carbon performance, but price is that the shortcomings that noble metal
It is expensive；In base metal, Raney nickel has higher reactivity, typically using Ni/Al2O3Catalyst, reaction condition are
1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio between/CO is about 3.
Although in the prior art, for prepare the method for methane vapor reforming nickel-base catalyst can obtain with compared with
The catalyst of good activity, but because the reaction is a fast reaction（This fast reaction is typically at mass transfer limited bar
Carried out under part）, reactant reacts while catalyst external surface is reached have been completed, thus the inner surface of catalyst is to mesh
Mark reaction contribution is little, and this has resulted in rate of metal relatively low in carrier duct, adds catalyst cost, 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 catalyst for hydrogen production from methane vapor reforming
Preparation method, this method prepare catalyst have cost is cheap, metal component utilization rate is high, selectivity good, anti-carbon deposition ability
The characteristics of strong and stability is good.
The preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, the catalyst include activearm
Point, auxiliary agent and carrier, active component Ni；Auxiliary agent is the one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce or La, is carried
Body is any one in aluminum oxide, silica, SBA-15；Using in catalyst each element quality account for the percentage of carrier quality as
Benchmark, the content of active component are 20wt%~30wt%, and the content of auxiliary agent is 1wt%~10wt%, preferably 3wt%~8wt%, surplus
For 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 aging, drying, calcination process, catalyst is obtained
Precursor B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B 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；
（5）By step（4）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 C；
（6）Active component presoma and auxiliary agent presoma is soluble in water, solution D is obtained, then adds step（5）Obtain
Catalyst precarsor C, after drying, calcination process, obtain catalyst.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（1）Described in active component forerunner
Body is the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or nickel acetate；In the solution A
The concentration of active component nickel is 0.15~1.15mol/L.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（2）Described in aging temperature be 10
~90 DEG C, preferably 20~60 DEG C, ageing time are 1~24h, preferably 4~12h；The drying temperature is 70~150 DEG C,
Preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；The sintering temperature is 500~900 DEG C, is preferably
600~800 DEG C, roasting time is 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 carrier be aluminum oxide,
One kind in silica, SBA-15；The carrier can use commercially available product, can also be by method system well known in the art
It is standby；In the catalyst precarsor B, nickel counts weight content in the carrier as 1wt%~5wt% using element.
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.Specifically
Reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then pass to hydrogen or hydrogen with
The mixed gas of nitrogen, in 0.1~0.5MPa（Absolute pressure）After handling 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 polyalcohol can be with
It is the one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%~10%；
Polyhydric alcohol solutions and step（3）Obtained reduction rear catalyst precursor B volume ratio is 5~10.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, step（6）In, the active component forerunner
Body is the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or nickel acetate；Auxiliary agent presoma
For sodium nitrate, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, nitre
One or more in sour cerium, lanthanum nitrate, preferably magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate and lanthanum nitrate；In the solution D
The concentration of active component nickel is 2~6.5mol/L, and the concentration of promoter metal is 0.2~3mol/L.The tool of auxiliary agent and active component
Body dipping process is to use method well known to those skilled in the art.
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 hydrogen production from methane vapor reforming reaction.Catalyst is before use
In a hydrogen atmosphere, 700~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method is applied to methane vapor reforming
Hydrogen production reaction, preferable process conditions are：The composition H of unstripped gas2O/CH4Mol ratio is 1~4, can contain in unstripped gas Ar,
N2Or the dilution such as He property gas, 1000~3000h of unstripped gas air speed-1, reaction pressure is 0.2~3Mpa, reaction temperature is 600~
800℃。
Catalyst of the present invention, using aluminum oxide, silica or SBA-15 carriers, first load a small amount of active metal
Component Ni, obtained catalyst precarsor is after reduction treatment, and catalytic polyol aqueous phase is hydrogenated with autoclave, generation
Product C5And C6Liquid alkane can be used as atent solvent to the further processing of catalyst precarsor；Before catalyst after treatment
Body load active component and adjuvant component again, the active metal amount loaded in carrier duct is preferably controlled, promoted more
Active component is disperseed carrier surface, had both been improved the utilization rate of active metal, and had been reduced catalyst cost, is accelerated again anti-
The adsorption desorption speed of thing and product in catalyst surface and hole is answered, so as to avoid the further oxidation of product, improves first
The conversion ratio of alkane and the selectivity of product.
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.In continuous sample introduction fixed bed
Reacted in quartz reactor, 750 DEG C of reaction temperature, unstripped gas composition H2O/CH4/N2=6.75/2.25/1（Mol ratio）, it is empty
Fast 2000h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Reaction starts sampling analysis, evaluation knot after 1 ~ 3 hour
Fruit is shown in Table 1.Average activity of the reaction result for catalyst after 750 DEG C of 100h that work in table 1.
Using the distribution situation of active component on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.This
The scanning electron microscope analysis of catalyst activity component nickel the results are shown in Table 2 in inventive embodiments.
Embodiment 1
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, is designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Silica（Pore volume is 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm）Carrier, aging 6h at room temperature,
110 DEG C of dry 10h, 600 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；Before catalyst
Body B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 90% in mixed gas, and reducing condition is 400 DEG C,
0.2MPa（Absolute pressure）, recovery time 8h；By the sorbierite that the catalyst precarsor B after reduction activation and 300mL mass concentrations are 10%
Solution is added in autoclave, is replaced 4 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 2MPa, anti-at 300 DEG C
Answer 2h；Reacted mixture in above-mentioned autoclave is placed into 1h, filtering, gained solid sample is dried at room temperature for sample table
Face obtains catalyst precarsor C without liquid phase；Catalyst precarsor C is added to the water containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In solution, be evaporated in 80 DEG C of stirrings to solution, be put into baking oven at 100 DEG C and dry 12h, 6h is calcined at 600 DEG C, that is, be made with
It is 25%Ni that element meter quality, which accounts for carrier percentage composition, 6%Mg catalyst, is designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；It is carried on using equi-volume impregnating
20gSBA-15（Pore volume is 1.23ml/g, specific surface area 701m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, at room temperature aging
8h, 120 DEG C of dry 6h, 600 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；Catalyst
Precursor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 10% in mixed gas, and reducing condition is 500 DEG C,
0.2MPa（Absolute pressure）, recovery time 6h；By the sorbierite that the catalyst precarsor B after reduction activation and 300mL mass concentrations are 10%
Solution is added in autoclave, is replaced 2 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, anti-at 220 DEG C
Answer 4h；Reacted mixture in above-mentioned autoclave is placed into 3h, filtering, gained solid sample is dried at room temperature for sample table
Face obtains catalyst precarsor C without liquid phase；Catalyst precarsor C is added to the water containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In solution, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 120 DEG C and dries 6h, 4h is calcined at 600 DEG C, be molded, that is, make
It is 25%Ni to be able to element meter quality and account for carrier percentage composition, 6%Mg catalyst, is designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 1% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 18.81g nickel nitrates and 6.33g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 20%Ni, 3%Mg catalyst, is designated as C-4.
Embodiment 5
Weigh 4.95g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 5% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to water-soluble containing 24.75g nickel nitrates and 16.88g magnesium nitrates
In liquid, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, make
It is 30%Ni to be able to element meter quality and account for carrier percentage composition, 8%Mg catalyst, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 7.07g calcium nitrate
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Ca catalyst, is designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 5.65g zirconium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Zr catalyst, is designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 3.72g cerous nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Ce catalyst, is designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 3.74g lanthanum nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%La catalyst, is designated as C-9.
Embodiment 10
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The xylitol solution that catalyst precarsor B and 400mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, is designated as C-10.
Embodiment 11
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The mannitol solution that catalyst precarsor B and 200mL mass concentrations after reduction activation are 10% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, is designated as C-11.
Embodiment 12
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；By the arabite solution that the catalyst precarsor B after reduction activation and 300mL mass concentrations are 10%
It is added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, reacted at 220 DEG C
4h；Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample is dried at room temperature for sample surfaces
Without liquid phase, catalyst precarsor C is obtained；Catalyst precarsor C is added to water-soluble containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In liquid, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, make
It is 25%Ni to be able to element meter quality and account for carrier percentage composition, 6%Mg catalyst, is designated as C-12.
Embodiment 13
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 5% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, is designated as C-13.
Embodiment 14
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；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；The sorbitol solution that catalyst precarsor B and 300mL mass concentrations after reduction activation are 8% is added
Enter into autoclave, replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；
Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, gained solid sample be dried at room temperature for sample surfaces without
Liquid phase, obtain catalyst precarsor C；Catalyst precarsor C is added to the aqueous solution containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, is made
Quality is counted using element and accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, is designated as C-14.
Comparative example 1
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；Before catalyst
Body B is added to 50mLC6In alkane solvent, 20min is impregnated, then filters, is dried at room temperature for, until catalyst precursor surface
Without liquid phase, catalyst precarsor C is made；Catalyst precarsor C is added to water-soluble containing 21.8g nickel nitrates and 12.66g magnesium nitrates
In liquid, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, make
It is 25%Ni to be able to element meter quality and account for carrier percentage composition, 6%Mg catalyst, is designated as D-1.
Comparative example 2
Weigh 2.97g nickel nitrates to be dissolved in appropriate amount of deionized water, obtain solution A；20g is carried on using equi-volume impregnating
Aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, aging 4h at room temperature,
80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight 3% are accounted in terms of element；Before catalyst
Body B is added in the sorbitol solution that 300mL mass concentrations are 10%, is impregnated 20min, is then filtered, be dried at room temperature for, directly
To catalyst precursor surface without liquid phase, catalyst precarsor C is made；Catalyst precarsor C is added to containing 21.8g nickel nitrates and
In the aqueous solution of 12.66g magnesium nitrates, it is evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C and dries 12h, 700 DEG C
Lower roasting 6h, shaping, that is, it is made and quality is counted using element accounts for carrier percentage composition as 25%Ni, 6%Mg catalyst, be designated as D-2.
Comparative example 3
Weigh 24.77g nickel nitrates and 12.66g magnesium nitrates are dissolved in deionized water, the aqueous solution is made；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 6h at room temperature, 110 DEG C of dry 12h, 700 DEG C of roasting 6h, that is, be made and count quality using element and account for catalyst percentage composition as 25%
Ni, 6%Mg catalyst, are designated as D-3.
The reactivity worth of the catalyst of table 1
| Catalyst | CH4Conversion ratio, % | CO selectivity, % |
| C-1 | 95.8 | 85.3 |
| C-2 | 92.7 | 83.1 |
| C-3 | 96.4 | 87.2 |
| C-4 | 88.6 | 80.4 |
| C-5 | 97.3 | 88.7 |
| C-6 | 92.2 | 81.5 |
| C-7 | 93.4 | 82.9 |
| C-8 | 96.7 | 84.1 |
| C-9 | 97.1 | 85.7 |
| C-10 | 96.6 | 87.2 |
| C-11 | 93.1 | 83.6 |
| C-12 | 92.4 | 81.9 |
| C-13 | 93.8 | 82.7 |
| C-14 | 94.4 | 84.3 |
| D-1 | 83.6 | 79.2 |
| D-2 | 80.2 | 75.9 |
| D-3 | 76.1 | 70.4 |
The catalyst activity component nickel content of table 2 is distributed（wt%）
| Catalyst | Center is to 1/4 radius | 1/4 radius to 2/4 radius | 2/4 radius to 3/4 radius | 3/4 radius is to appearance |
| C-1 | 4.01 | 1.87 | 3.23 | 34.58 |
| C-2 | 4.32 | 2.49 | 3.06 | 34.12 |
| C-3 | 4.18 | 2.26 | 3.15 | 34.31 |
| C-4 | 3.14 | 1.08 | 1.92 | 30.01 |
| C-5 | 4.58 | 1.57 | 2.79 | 39.45 |
| C-6 | 4.58 | 2.76 | 2.83 | 33.98 |
| C-7 | 4.37 | 2.18 | 3.13 | 34.09 |
| C-8 | 3.89 | 1.64 | 3.49 | 35.06 |
| C-9 | 3.94 | 1.53 | 3.67 | 35.15 |
| C-10 | 3.91 | 1.44 | 3.72 | 35.19 |
| C-11 | 4.22 | 2.03 | 2.89 | 33.97 |
| C-12 | 4.17 | 1.92 | 3.06 | 34.28 |
| C-13 | 4.43 | 2.29 | 2.69 | 33.89 |
| C-14 | 4.18 | 1.96 | 3.01 | 34.17 |
| D-1 | 16.67 | 16.67 | 13.79 | 25.53 |
| D-2 | 28.57 | 21.05 | 19.35 | 18.60 |
| D-3 | 6.25 | 18.75 | 31.25 | 43.75 |
Claims (15)
1. a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and load
Body, active component Ni；Auxiliary agent be Na, K, Mg, Ca, Sr, Ba, Zr, Ce or La in one or more, carrier be aluminum oxide,
Any one in silica, SBA-15；On the basis of each element quality accounts for the percentage of carrier quality in catalyst, activearm
The content divided is 20wt%~30wt%, and the content of auxiliary agent is 1wt%~10wt%, and surplus is carrier；The preparation side of the catalyst
Method 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 aging, drying, calcination process, catalyst precarsor is obtained
B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B 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, described is more
First alcohol is the one or more in xylitol, sorbierite, mannitol, arabite；
（5）By step（4）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 C；
（6）Active component presoma and auxiliary agent presoma is soluble in water, solution D is obtained, then adds step（5）What is obtained urges
Agent precursor C, after drying, calcination process, obtains catalyst.
2. in accordance with the method for claim 1, it is characterised in that：The percentage of carrier quality is accounted for each element quality in catalyst
Than on the basis of, the content of auxiliary agent is 3wt%~8wt%.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）And step（6）Described in active component presoma
For the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
4. in accordance with the method for claim 3, it is characterised in that：Step（1）And step（6）Described in active component presoma
For nickel nitrate or nickel acetate.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in solution A active component nickel concentration
For 0.15~1.15mol/L.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in aging temperature be 10~90 DEG C, aging
Time is 1~24h, and the drying temperature is 70~150 DEG C, and drying time is 2~12h, and the sintering temperature is 500~900
DEG C, roasting time is 2~12h.
7. in accordance with the method for claim 6, it is characterised in that：Step（2）Described in aging temperature be 20~60 DEG C, aging
Time is 4~12h, and the drying temperature is 80~120 DEG C, and drying time is 4~8h, and the sintering temperature is 600~800
DEG C, roasting time is 4~8h.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）In the catalyst precarsor B, nickel is in terms of element
Weight content in the carrier is 1wt%~5wt%.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in reduction treatment process it is as follows：Nitrogen
Catalyst precarsor B is warming up to 300~600 DEG C under 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.
11. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in the mass concentrations of polyhydric alcohol solutions be
5%~10%.
12. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in polyhydric alcohol solutions and step（3）
The reduction rear catalyst precursor B arrived volume ratio is 5~10.
13. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in auxiliary agent presoma be sodium nitrate, nitre
Sour potassium, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate
In one or more.
14. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in auxiliary agent presoma be magnesium nitrate, nitre
Sour calcium, zirconium nitrate, cerous nitrate and lanthanum nitrate.
15. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in solution D active component nickel it is dense
Spend for 2~6.5mol/L, the concentration of promoter metal is 0.2~3mol/L.
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| CN108043448A (en) * | 2017-11-09 | 2018-05-18 | 大连大学 | It is a kind of using molecular sieve as the preparation method of the catalyst for hydrogen production from methane vapor reforming of carrier |
| CN108134102B (en) * | 2018-01-04 | 2020-10-09 | 西南化工研究设计院有限公司 | Catalyst for methane steam reforming in fuel cell |
| CN109987582B (en) * | 2019-04-15 | 2020-01-07 | 余菲 | Full liquid phase hydrogenation technology |
| CN113842918B (en) * | 2021-09-15 | 2023-03-24 | 大连理工大学 | High-activity anti-sintering methane steam reforming catalyst and preparation method and application thereof |
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| CN102299345A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of methane reforming catalyst to molten carbonate fuel cell |
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