CN106944060A - A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst - Google Patents
A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst Download PDFInfo
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- 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
- B01J23/74—Iron group metals
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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
- B01J23/76—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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- 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
- 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
- B01J23/83—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 rare earths or actinides
Abstract
The present invention relates to a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, the first auxiliary agent, the second 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 methane is improved again.
Description
Technical field
The present invention relates to a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, more particularly, to a kind of preparation method of synthesizing gas by reforming methane with co 2 loading type nickel-based catalyst.
Background technology
Methane and carbon dioxide is cheap in nature and resourceful carbon compound; using the reforming reaction producing synthesis gas of methane and carbon dioxide, for alleviating energy crisis, mitigate due to caused by the discharge of greenhouse gases global climate warm it is significant.The synthesis gas that methane is prepared with CO 2 reformation has H2The characteristics of/CO≤1, go for F- T synthesis, the high chemicals of added value such as production higher hydrocarbon.
The catalyst for being presently used for synthesizing gas by reforming methane with co 2 is more based on metal supported catalyst, is broadly divided into two major classes：Noble metal and non-precious metal catalyst.Although noble metal catalyst is with excellent reactivity worth, expensive, sintering is also easy under hot conditions and is lost in.Non-precious metal catalyst is that nickel or cobalt are carried on the carriers such as aluminum oxide, silica, magnesia, zirconium oxide, titanium oxide, the advantage of this system is that reactivity worth is good, catalyst preparation low cost, but catalyst carbon accumulation resisting ability is low, can cause inactivation because of carbon distribution, sintering.
CN
101352687A discloses a kind of bimetallic catalyst of modification, and the catalyst is with a kind of γ-Al of modification2O3For carrier, the Co using mass percent as 1% ~ 20% Ni and 1% ~ 20% is prepared for active component using infusion process.But the preparation technology is more complicated, cost is higher.
CN
102658145A discloses a kind of MgO（111）The preparation method of supported nickel based catalysts, first step carrier synthesis, is dissolved in absolute ethyl alcohol by magnesium rod, sequentially adds methoxy benzyl alcohol, methanol, is reacted in autoclave, roasting obtains carrier；Carrier impregnation is obtained metallic catalyst by second step in nickel acetylacetonate solution.But the preparation cost of the catalyst is too high, and preparation process is whard to control.
CN
1280882A discloses a kind of nickel-base catalyst of nano-crystal oxide load.The catalyst is that the aqueous solution of nickel nitrate is added in nanocrystal oxide, and stirring, dry, roasting are made.The reaction of gained catalyst is lasted a long time, but this method preparation process is complicated, and cost is higher.
Although catalyst made from above-mentioned patented method obtains preferable synthesizing gas by reforming methane with co 2 reactivity worth, still suffer from that cost is higher, catalyst easy carbon distribution the problems such as.Reactant molecule is in catalyst granules during mass transfer, due to the difference of diffusion velocity, two kinds of reactant molecule ratios are caused gradient radially occur in catalyst granules, particle inside methane is much larger than inside stoichiometry, therefore catalyst granules with carbon dioxide ratio and is more easy to carbon distribution.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the characteristics of catalyst prepared by this method has with low cost, metal component utilization rate high and is selective good.
The invention provides a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, the first auxiliary agent, the second auxiliary agent and carrier, active component is Ni, first auxiliary agent is Co, second auxiliary agent is the one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce or 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%~25wt%, preferably 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, and the content of the second auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma and the first auxiliary agent 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）Second 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, solution D is obtained, 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 ethanol 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 synthesizing gas by reforming methane with co 2 catalyst 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；The first auxiliary agent presoma is cobalt nitrate, cobalt chloride, the preferably one or more in cobaltous sulfate, cobalt nitrate；In the solution A, active component is in terms of element, and the mass fraction in solution A is 1%~7%, and the first adjuvant component is in terms of element, and the mass fraction in solution A is 1%~5%.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（2）Described in dipping be incipient impregnation, dip time be 1~3h；Described 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 synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（2）Described carrier is any of 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, and the cobalt of load is 1wt%~3wt% of final catalyst in terms of element wt.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（3）Described in reducing atmosphere be hydrogen, or hydrogen and nitrogen mixed gas, 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 synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（4）Described in the second 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, the second 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 synthesizing gas by reforming methane with co 2 catalyst 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%~2.5% 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 methane portion oxidation synthesis gas catalyst 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 synthesizing gas by reforming methane with co 2 reaction.Catalyst using before in a hydrogen atmosphere, 600~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method reacts applied to synthesizing gas by reforming methane with co 2, and preferable process conditions are：The composition CH of unstripped gas4/CO2Mol ratio is 1~1.5, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 2000~6000h of unstripped gas air speed-1, reaction pressure is 0.1~2Mpa, and reaction temperature is 700~900 DEG C.
Compared with prior art, the synthesizing gas by reforming methane with co 2 catalyst 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 4 hours at 700 DEG C before catalyst reaction of the present invention.Reacted in continuous sample introduction fixed-bed quartz reactor, 700 DEG C of reaction temperature, unstripped gas composition CH4/CO2/Ar
=1/1/4（Mol ratio）, air speed 4000h-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 800 DEG C of 50h 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, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15g 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, the Co of load is the 2% of final catalyst in terms of element wt 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；4.27g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 12.5%Ni, 1.6%Co, 1.3%Mg catalyst, are designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15g 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, the Co of load is the 2% of final catalyst in terms of element wt 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；4.27g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 11.8%Ni, 1.5%Co, 1.2%Mg catalyst, are designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15g 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, the Co of load is the 2% of final catalyst in terms of element wt 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；4.27g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 12.7%Ni, 1.7%Co, 1.4%Mg catalyst, are designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrates, 0.99g cobalt nitrates to be dissolved in 16mL deionized waters, obtain solution A；16.9g 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, the Co of load is the 1% of final catalyst in terms of element wt 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, it is made and quality is counted using element accounts for catalyst percentage composition as 8.4%Ni, 0.6%Co, 0.5%Mg catalyst, are designated as C-4.
Embodiment 5
Weigh 4.96g nickel nitrates, 2.96g cobalt nitrates to be dissolved in 16mL deionized waters, obtain solution A；13.1g 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 5% of final catalyst, the Co of load is the 3% of final catalyst in terms of element wt 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；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, it is made and quality is counted using element accounts for catalyst percentage composition as 17.2%Ni, 2.4%Co, 1.9%Mg catalyst, are designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15.1g 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 3% of final catalyst, the Co of load is the 2% of final catalyst in terms of element wt 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；1.48g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 12.9 %Ni, 1.7%Co, 1.4%Na catalyst, are designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL 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, the Co of load is the 2% of final catalyst in terms of element wt 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；0.97g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 12.1%Ni, 1.7%Co, 1.3%Sr catalyst, are designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15g.1 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, the Co of load is the 2% of final catalyst in terms of element wt 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；1.88g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 11.7 %Ni, 1.7%Co, 1.4%Zr catalyst, are designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrates, 1.98g cobalt nitrates to be dissolved in 13mL deionized waters, obtain solution A；15g.1 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, the Co of load is the 2% of final catalyst in terms of element wt 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；1.25g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 11.9%Ni, 1.6%Co, 1.4%La catalyst, are designated as C-9.
Comparative example
Weigh 14.87g nickel nitrates, 1.98g cobalt nitrates, 4.27g magnesium nitrates to be dissolved in deionized water, the aqueous solution is made；15g 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 13.8%Ni, 1.5%Co, 1.6%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 (18)
1. a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, the first auxiliary agent, the second auxiliary agent and carrier, active component is Ni, first auxiliary agent is Co, second auxiliary agent is the one or more in Na, K, Mg, Ca, Sr, Ba, Zr, Ce or 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%~25wt%, preferably 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, and the content of the second auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma and the first auxiliary agent 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）Second 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, solution D is obtained, 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 ethanol 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）The first auxiliary agent presoma is cobalt nitrate, cobalt chloride, the preferably one or more in cobaltous sulfate, cobalt nitrate.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）In the solution A, active component is in terms of element, and the mass fraction in solution A is 1%~7%, and the first adjuvant component is in terms of element, and the mass fraction in solution A is 1%~5%.
5. 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.
6. 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.
7. 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.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt, and the cobalt of load is 1wt%~3wt% of final catalyst in terms of element wt.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be hydrogen, or hydrogen and nitrogen mixed gas, 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（4）Described in the second 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.
11. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in solution C, the second auxiliary agent is in terms of element, and the mass fraction in solution C is 1%~4%.
12. 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%.
13. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in furfural aqueous solution and the mass ratio of solution C be 3 ~ 5.
14. 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.
15. 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, polyvinylpyrrolidone, polyvinyl alcohol in one or more.
16. 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.
17. 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%~2.5% using element.
18. in accordance with the method for claim 1, it is characterised in that：Step（5）Mass fraction of the middle high molecular weight water soluble polymer in solution D is 3~6 times of Ni element mass fractions.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110893346A (en) * | 2018-09-12 | 2020-03-20 | 华东理工大学 | Bimetallic low-temperature methanation catalyst and preparation method and application thereof |
| CN113457722A (en) * | 2021-07-05 | 2021-10-01 | 万华化学集团股份有限公司 | Methane carbon dioxide dry reforming catalyst and preparation method and application thereof |
| CN114522689A (en) * | 2022-02-26 | 2022-05-24 | 石河子大学 | Catalyst for preparing ethanol by hydrogenating oxalate and preparation method thereof |
| CN114700102A (en) * | 2022-04-07 | 2022-07-05 | 西安近代化学研究所 | Active metal-modified oxide catalyst, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280097A (en) * | 1999-07-09 | 2001-01-17 | 浙江大学 | Catalyst for synthesizing gas by reforming methane with co2 and its preparing method |
| US20080300130A1 (en) * | 2004-07-08 | 2008-12-04 | Air Products And Chemicals, Inc. | Catalyst For Improving The Adiabatic Steam Reforming Of Natural Gas |
-
2016
- 2016-01-07 CN CN201610003121.0A patent/CN106944060B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280097A (en) * | 1999-07-09 | 2001-01-17 | 浙江大学 | Catalyst for synthesizing gas by reforming methane with co2 and its preparing method |
| US20080300130A1 (en) * | 2004-07-08 | 2008-12-04 | Air Products And Chemicals, Inc. | Catalyst For Improving The Adiabatic Steam Reforming Of Natural Gas |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110893346A (en) * | 2018-09-12 | 2020-03-20 | 华东理工大学 | Bimetallic low-temperature methanation catalyst and preparation method and application thereof |
| CN113457722A (en) * | 2021-07-05 | 2021-10-01 | 万华化学集团股份有限公司 | Methane carbon dioxide dry reforming catalyst and preparation method and application thereof |
| CN113457722B (en) * | 2021-07-05 | 2022-08-05 | 万华化学集团股份有限公司 | Methane carbon dioxide dry reforming catalyst and preparation method and application thereof |
| CN114522689A (en) * | 2022-02-26 | 2022-05-24 | 石河子大学 | Catalyst for preparing ethanol by hydrogenating oxalate and preparation method thereof |
| CN114700102A (en) * | 2022-04-07 | 2022-07-05 | 西安近代化学研究所 | Active metal-modified oxide catalyst, preparation method and application thereof |
| CN114700102B (en) * | 2022-04-07 | 2024-03-26 | 西安近代化学研究所 | Active metal-modified oxide catalyst, preparation method and application thereof |
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