CN105727955A - Preparation method of catalyst for methane reforming with vapor to natural gas - Google Patents
Preparation method of catalyst for methane reforming with vapor to natural gas Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst for methane reforming with vapor to natural gas. The catalyst comprises an active ingredient, a first additive, and a carrier. The preparation method is as below: dissolving an active ingredient precursor into water to obtain a solution A; adding the carrier, ageing, drying and calcining to obtain a catalyst precursor B; reducing the catalyst precursor B in a reducing atmosphere; adding the reduced catalyst precursor B and a polyol solution into a reactor, and carrying out a hydrogenation reaction; placing a reaction effluent, filtering and dying to obtain a catalyst precursor C; and dissolving an active ingredient precursor and an additive precursor in water to obtain a solution D, then adding the catalyst precursor C, drying and calcining to obtain the catalyst. The method of the present invention promotes dispersion of more active ingredients on the surface of the carrier, improves the utilization of the active metal, as well as improves the conversion of methane and the selectivity of products.
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst for hydrogen production from methane vapor reforming, the preparation method especially relating to a kind of hydrogen production from methane vapor reforming loading type nickel-based catalyst.
Background technology
Methane resource enriches, and hydrogen-carbon ratio is high, is good hydrogen feedstock.And hydrogen as efficient, clean secondary energy sources by one of main energy sources becoming Future Society.In recent years, hydrogen, as the raw material of fuel cell, has unrivaled superiority compared with other fuel, and such as hydrogen calorific value height, without air pollution etc., the application of Hydrogen Energy solves energy shortage problem on the one hand, does not cause again environmental pollution on the other hand.
At present, with methane for raw material for preparing hydrogen mainly by two kinds of approach: one is by preparing synthesis gas (H2Gaseous mixture with CO) thus obtaining hydrogen；The Direct Resolution that another kind is by methane obtains hydrogen.The method of methane synthesis gas mainly has three kinds:
Steam reforming method (SRM): H=+206KJ/mol；
CO 2 reformation method (DMR): H=+247KJ/mol；
Partial oxidation process (POM): H=-36KJ/mol.
The steam reforming method of methane, H in theory2/ CO=3, for hydrogen-rich synthetic gas, CO content is less, and can make H by suitable catalyst2Ratio increases further, it is possible to as the desirable route of fuel cell hydrogen source.Methane-steam reforming is strong endothermic reaction, it is desirable at high temperature carry out, and general reaction temperature is at 700 ~ 900 DEG C.The carrier of at present conventional SMR catalyst be aluminium oxide, zirconium oxide, cerium oxide, magnesium oxide, lanthana, niobium oxide, zeolite, perovskite, silicon dioxide clay, yittrium oxide, cobalt oxide, ferrum oxide and mixture thereof or one of.Research shows, during by noble metal Ru, Rh, Pd even load on suitable carrier, all has higher reactivity and anti-carbon performance, but the shortcoming of noble metal is that expensive；In base metal, Raney nickel has higher reactivity, is generally adopted Ni/Al2O3Catalyst, reaction condition is 1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio of/CO is about 3.
Although in prior art, method for preparing methane vapor reforming nickel-base catalyst all can obtain the catalyst with better activity, but owing to this reaction is a fast reaction (this fast reaction be typically under mass transfer limited condition carry out), namely reactant completes at the simultaneous reactions arriving catalyst external surface, thus the inner surface of catalyst is little to target response contribution, this has resulted in using rate of metal relatively low in carrier duct, add catalyst cost, also can accelerate the deep oxidation of product simultaneously.
Summary of the invention
For overcoming weak point of the prior art, the preparation method that the invention provides a kind of catalyst for hydrogen production from methane vapor reforming, catalyst prepared by the method has that with low cost, metal component utilization rate is high, selectivity is good, anti-carbon deposition ability is strong and the feature of good stability.
The preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni；Auxiliary agent is one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce or La, and carrier is any one in aluminium oxide, silicon oxide, SBA-15；In catalyst, each element quality accounts for the percentage ratio of carrier quality is benchmark, and the content of active component is 20wt%～30wt%, and the content of auxiliary agent is 1wt%～10wt%, it is preferable that 3wt%～8wt%, and surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) by soluble in water for active component presoma, solution A is obtained；
(2) carrier is joined in the solution A that step (1) obtains, after aging, dry, calcination process, obtain catalyst precarsor B；
(3) the catalyst precarsor B that step (2) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(4) the catalyst precarsor B after reduction step (3) obtained and polyhydric alcohol solutions join in autoclave, use hydrogen exchange 2～5 times after sealing, then regulate Hydrogen Vapor Pressure to 2～4MPa, react 2～5h at 200～300 DEG C；
(5) reaction effluent step (4) obtained places 1～3h, then filters, and gained solid sample is at room temperature dried, until sample surfaces is without liquid phase, obtains catalyst precarsor C；
(6) by soluble in water to active component presoma and auxiliary agent presoma, obtain solution D, be subsequently adding the catalyst precarsor C that step (5) obtains, after drying, calcination process, obtain catalyst.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, active component presoma described in step (1) is one or more in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride., it is preferable that nickel nitrate or nickel acetate；In described 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, aging temperature described in step (2) is 10～90 DEG C, it is preferred to 20～60 DEG C, and ageing time is 1～24h, it is preferred to 4～12h；Described baking temperature is 70～150 DEG C, it is preferred to 80～120 DEG C, and drying time is 2～12h, it is preferred to 4～8h；Described sintering temperature is 500～900 DEG C, it is preferred to 600～800 DEG C, and roasting time is 2～12h, it is preferred to 4～8h.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, the carrier described in step (2) is the one in aluminium oxide, silicon oxide, SBA-15；Described carrier can adopt commercially available product, it is also possible to prepares by method well known in the art；In described catalyst precarsor B, nickel counts weight content in the carrier for 1wt%～5wt% with element.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (3), in described mixing gas, hydrogen volume percentage composition is 10%～95%.Concrete reduction treatment process is as follows: under nitrogen atmosphere, catalyst precarsor is warming up to 300～600 DEG C, then passes to the mixing gas of hydrogen or hydrogen and nitrogen, in 0.1～0.5MPa(absolute pressure) process 4～8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, the polyhydric alcohol described in step (4) can be one or more in xylitol, sorbitol, mannitol, arabitol；The mass concentration of polyhydric alcohol solutions is 5%～10%；The volume ratio of the reduction rear catalyst precursor B that polyhydric alcohol solutions and step (3) obtain is 5～10.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, in step (6), described active component presoma is one or more in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride., it is preferable that nickel nitrate or nickel acetate；Auxiliary agent presoma is 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 (III) nitrate, it is preferable that magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate and Lanthanum (III) nitrate；In described 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 concrete dipping process of auxiliary agent and active component is for adopting method well known to those skilled in the art.
Catalyst prepared by the inventive method can also make suitable particle shape according to the needs used, as made bar shaped, sheet-shaped, cylindricality etc..
Catalyst prepared by the inventive method can apply to hydrogen production from methane vapor reforming reaction.Catalyst before use in a hydrogen atmosphere, 700～800 DEG C of prereduction 2～5h.Catalyst prepared by the inventive method is applied to hydrogen production from methane vapor reforming reaction, and good 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, unstripped gas air speed 1000～3000h-1, reaction pressure is 0.2～3Mpa, and reaction temperature is 600～800 DEG C.
The catalyst that the present invention relates to, adopts aluminium oxide, silicon oxide or SBA-15 carrier, the active metal component Ni that first load is a small amount of, and the catalyst precarsor obtained is after reduction treatment, and in autoclave, catalytic polyol aqueous phase is hydrogenated with, the product C of generation5And C6Catalyst precarsor can be processed further by liquid alkane as atent solvent；The load active component again of catalyst precarsor after treatment and adjuvant component, control the active metal amount of load in carrier duct preferably, promote that more multiple active components is in the dispersion of carrier surface, both improve the utilization rate of active metal, reduce catalyst cost, accelerating again reactant and the product adsorption desorption speed in catalyst surface and hole, thus avoiding the further oxidation of product, improve the conversion ratio of methane and the selectivity of product.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not so limited the present invention.
Appreciation condition: use hydrogen reducing 3 hours at 700 DEG C before catalyst reaction of the present invention.Continuous sample introduction fixed-bed quartz reactor reacts, reaction temperature 750 DEG C, unstripped gas composition H2O/CH4/N2=6.75/2.25/1(mol ratio), air speed 2000h-1, product is condensed dewater after use gas chromatogram on-line analysis.Starting sample analysis after reacting 1 ~ 3 hour, evaluation result is in Table 1.Reaction result in table 1 is the average activity after catalyst works 100h at 750 DEG C.
Adopt active component distribution situation on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.In the embodiment of the present invention, the scanning electron microscope analysis result of catalyst activity component nickel is in Table 2.
Embodiment 1
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 1.06ml/g, and specific surface area is 387m to adopt equi-volume impregnating to be carried on 20g silicon oxide2/ g, spherical, equivalent diameter 0.5mm) carrier, aged at room temperature 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa(absolute pressure), recovery time 8h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 4 times, then regulate Hydrogen Vapor Pressure to 2MPa, at 300 DEG C, react 2h；Reacted mixture in above-mentioned autoclave being placed 1h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 100 DEG C, roasting 6h at 600 DEG C, namely prepare and count quality with element and account for carrier percentage composition for 25%Ni, the catalyst of 6%Mg, is designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；Adopting equi-volume impregnating to be carried on 20gSBA-15(pore volume is 1.23ml/g, and specific surface area is 701m2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 8h, 120 DEG C of dry 6h, 600 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 10%, and reducing condition is 500 DEG C, 0.2MPa(absolute pressure), recovery time 6h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 2 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 3h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 6h at 120 DEG C, roasting 4h at 600 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 1% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 18.81g nickel nitrate and 6.33g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 20%Ni, 3%Mg, be designated as C-4.
Embodiment 5
Weigh 4.95g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 5% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 24.75g nickel nitrate and 16.88g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 30%Ni, 8%Mg, be designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 7.07g calcium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Ca, be designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 5.65g zirconium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Zr, be designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 3.72g cerous nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Ce, be designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 3.74g Lanthanum (III) nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%La, be designated as C-9.
Embodiment 10
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the xylitol solution that 400mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-10.
Embodiment 11
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the mannitol solution that 200mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-11.
Embodiment 12
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the arabitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-12.
Embodiment 13
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 5%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-13.
Embodiment 14
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 8%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as C-14.
Comparative example 1
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B is joined 50mLC6In alkane solvent, impregnate 20min, then filter, at room temperature dry, until catalyst precursor surface is without liquid phase, prepare catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as D-1.
Comparative example 2
Weigh 2.97g nickel nitrate and be dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element；Catalyst precarsor B is joined in the sorbitol solution that 300mL mass concentration is 10%, impregnate 20min, then filter, at room temperature dry, until catalyst precursor surface is without liquid phase, prepare catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 21.8g nickel nitrate and 12.66g magnesium nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 25%Ni, 6%Mg, be designated as D-2.
Comparative example 3
Weigh 24.77g nickel nitrate and 12.66g magnesium nitrate is dissolved in deionized water, prepare aqueous solution；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 6h, 110 DEG C of dry 12h, 700 DEG C of roasting 6h, namely prepare and count quality with element and account for the catalyst that catalyst percentage composition is 25%Ni, 6%Mg, be designated as D-3.
The reactivity worth of table 1 catalyst
| 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 |
Table 2 catalyst activity component nickel content distribution (wt%)
| Catalyst | Center is to 1/4 radius | 1/4 radius is to 2/4 radius | 2/4 radius is 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 (14)
1. a preparation method for catalyst for hydrogen production from methane vapor reforming, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni；Auxiliary agent is one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce or La, and carrier is any one in aluminium oxide, silicon oxide, SBA-15；In catalyst, each element quality accounts for the percentage ratio of carrier quality is benchmark, and the content of active component is 20wt%～30wt%, and the content of auxiliary agent is 1wt%～10wt%, it is preferable that 3wt%～8wt%, and surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) by soluble in water for active component presoma, solution A is obtained；
(2) carrier is joined in the solution A that step (1) obtains, after aging, dry, calcination process, obtain catalyst precarsor B；
(3) the catalyst precarsor B that step (2) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(4) the catalyst precarsor B after reduction step (3) obtained and polyhydric alcohol solutions join in autoclave, use hydrogen exchange 2～5 times after sealing, then regulate Hydrogen Vapor Pressure to 2～4MPa, react 2～5h at 200～300 DEG C；
(5) reaction effluent step (4) obtained places 1～3h, then filters, and gained solid sample is at room temperature dried, until sample surfaces is without liquid phase, obtains catalyst precarsor C；
(6) by soluble in water to active component presoma and auxiliary agent presoma, obtain solution D, be subsequently adding the catalyst precarsor C that step (5) obtains, after drying, calcination process, obtain catalyst.
2. in accordance with the method for claim 1, it is characterised in that: step (1) and active component presoma described in step (6) they are one or more in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride..
3. the method described in claim 1 or 2, it is characterised in that: step (1) and active component presoma described in step (6) they are nickel nitrate or nickel acetate.
4. in accordance with the method for claim 1, it is characterised in that: in solution A described in step (1), the concentration of active component nickel is 0.15～1.15mol/L.
5. in accordance with the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10～90 DEG C, and ageing time is 1～24h, described baking temperature is 70～150 DEG C, drying time is 2～12h, and described sintering temperature is 500～900 DEG C, and roasting time is 2～12h.
6. in accordance with the method for claim 5, it is characterised in that: aging temperature described in step (2) is 20～60 DEG C, and ageing time is 4～12h, described baking temperature is 80～120 DEG C, drying time is 4～8h, and described sintering temperature is 600～800 DEG C, and roasting time is 4～8h.
7. in accordance with the method for claim 1, it is characterised in that: in the described catalyst precarsor B of step (2), nickel counts weight content in the carrier for 1wt%～5wt% with element.
8. in accordance with the method for claim 1, it is characterised in that: the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (3), in described mixing gas, hydrogen volume percentage composition is 10%～95%.
9. in accordance with the method for claim 1, it is characterized in that: reduction treatment process described in step (3) is as follows: under nitrogen atmosphere, catalyst precarsor is warming up to 300～600 DEG C, then pass to the mixing gas of hydrogen or hydrogen and nitrogen, in 0.1～0.5MPa(absolute pressure) process 4～8h after, be down to room temperature in a nitrogen atmosphere.
10. in accordance with the method for claim 1, it is characterised in that: the polyhydric alcohol described in step (4) is one or more in xylitol, sorbitol, mannitol, arabitol.
11. in accordance with the method for claim 1, it is characterised in that: described in step (4), the mass concentration of polyhydric alcohol solutions is 5%～10%.
12. in accordance with the method for claim 1, it is characterised in that: the volume ratio of the reduction rear catalyst precursor B that polyhydric alcohol solutions described in step (4) and step (3) obtain is 5～10.
13. in accordance with the method for claim 1, it is characterized in that: auxiliary agent presoma described in step (6) is 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 (III) nitrate, it is preferable that magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate and Lanthanum (III) nitrate.
14. in accordance with the method for claim 1, it is characterised in that: in solution D described in step (6), the concentration of active component nickel is 2～6.5mol/L, and the concentration of promoter metal is 0.2～3mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107790170A (en) * | 2017-11-02 | 2018-03-13 | 中国科学院上海高等研究院 | Methane dry reforming catalyst and its production and use |
| 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 |
| CN108134102A (en) * | 2018-01-04 | 2018-06-08 | 四川天科技股份有限公司 | A kind of catalyst for methane steam reforming in fuel cell |
| CN109987582A (en) * | 2019-04-15 | 2019-07-09 | 余菲 | A kind of full liquid phase hydrogenation technology |
| CN113842918A (en) * | 2021-09-15 | 2021-12-28 | 大连理工大学 | High-activity anti-sintering methane steam reforming catalyst and preparation method and application thereof |
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| 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 |
| 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 |
| US20130116351A1 (en) * | 2011-11-08 | 2013-05-09 | Claudia Querner | Process for producing a methanation catalyst and a process for the methanation of synthesis gas |
| US20130116118A1 (en) * | 2011-11-09 | 2013-05-09 | Basf Se | Catalyst composition for the steam reforming of methane in fuel cells |
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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 |
| US20130116351A1 (en) * | 2011-11-08 | 2013-05-09 | Claudia Querner | Process for producing a methanation catalyst and a process for the methanation of synthesis gas |
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| CN107790170A (en) * | 2017-11-02 | 2018-03-13 | 中国科学院上海高等研究院 | Methane dry reforming catalyst and its production and use |
| 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 |
| CN108134102A (en) * | 2018-01-04 | 2018-06-08 | 四川天科技股份有限公司 | A kind of catalyst for methane steam reforming in fuel cell |
| 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 |
| CN109987582A (en) * | 2019-04-15 | 2019-07-09 | 余菲 | A kind of full liquid phase hydrogenation technology |
| CN109987582B (en) * | 2019-04-15 | 2020-01-07 | 余菲 | Full liquid phase hydrogenation technology |
| CN113842918A (en) * | 2021-09-15 | 2021-12-28 | 大连理工大学 | High-activity anti-sintering methane steam reforming catalyst and preparation method and application thereof |
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