CN106475103A - A kind of preparation method of methane portion oxidation synthesis gas catalyst - Google Patents
A kind of preparation method of methane portion oxidation synthesis gas catalyst Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/76—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 methane portion oxidation synthesis gas catalyst, described catalyst includes active component, auxiliary agent and carrier, and the preparation method of described catalyst comprises the steps：Prepare catalyst precarsor B first, then reduction treatment is carried out to catalyst precarsor B, mix homogeneously soluble in water for auxiliary agent presoma with furfural aqueous solution, then it is added in autoclave together with catalyst precarsor B, reacted after adding solution D, the solidliquid mixture that obtains process filter after separating gained solid sample again drying, after calcination process, obtain catalyst.The catalyst reaction activity of this method preparation is high, has both reduced metal consumption, inhibits the focus generation during methane portion oxidation again.
Description
Technical field
The present invention relates to a kind of preparation method of methane portion oxidation synthesis gas catalyst, especially relate to a kind of preparation method of methane portion oxidation synthesis gas loaded catalyst.
Background technology
More than the 90% of gas component is methane, by methane through synthesis gas resynthesis fuels and chemicals, is one of effective way of gas utilization.With traditional vapour reforming ratio, methane portion oxidation synthesis gas have the advantages that required reaction vessel volume is little, reaction rate is fast, energy consumption is low and the synthesis gas that generates is suitable as the unstripped gas of methanol and Fiscber-Tropscb synthesis.In addition, exploitation methane portion oxidation technology is possible to replace highly endothermic methane steam reformation technique and is used for producing synthesis gas, especially for remote or offshore natural gas resource using being significant.
The main catalyst system of methane portion oxidation synthesis gas is by active component noble metal（Pt, Pd, Rh, Ru, Ir）, nickel or cobalt be supported on the carriers such as aluminium oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, alkali metal, alkaline-earth metal or rare-earth oxide can be adopted to be modified to improve the reactivity worth of catalyst simultaneously.
CN
101049566A discloses a kind of Ni base catalyst for methane portion oxidation synthesis gas and preparation method thereof.The carrier of catalyst is complex carrier Mg-Al-Ce-Zr-O, and active component is NiO.This patent adopts coprecipitation method that complex carrier is obtained, and prepared carrier is dipped in Ni (NO3)2In solution, on obtained catalyst, methane conversion reaches more than 84%, CO selectivity and reaches more than 99%.
CN
101219393A discloses a kind of cobalt-based loaded catalyst for methane portion oxidation synthesis gas and preparation method thereof.Catalyst takes step impregnation method to prepare, and with Co as active component, with a kind of alkaline-earth metal or rare earth metal as auxiliary agent, with HZSM-5 as carrier, prepared catalyst activity is high, coking resistivity is strong, good stability.
CN
101284241A discloses a kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof.With transition metal Co and noble metal as active component, with a kind of element selected from alkaline-earth metal as auxiliary agent, with γ-Al2O3For carrier, the catalyst of methane portion oxidation synthesis gas is obtained using infusion process.Catalyst has the advantages that high activity, excellent coking resistivity, high stability.
Although the catalyst that above-mentioned patented method is obtained all obtains preferable methane portion oxidation synthesis gas reactivity worth, because this reaction is a fast reaction（This fast reaction is carried out under conditions of being typically at mass transport limitation）, reactant reaction while reaching catalyst external surface completes, thus the inner surface of catalyst is to target response contribution less, and this has resulted in relatively low rate of metal in carrier duct, also can accelerate the deep oxidation of product simultaneously.
Content of the invention
For overcoming weak point of the prior art, the invention provides a kind of preparation method of methane portion oxidation synthesis gas catalyst, the catalyst of the method preparation has the characteristics that with low cost, metal component utilization rate is high and selectivity is good.
The invention provides a kind of preparation method of methane portion oxidation synthesis gas catalyst, described catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is one or more of Ca, Mg, Zr, Ce or La, and carrier is aluminium oxide, any one in silicon oxide；On the basis of in catalyst, each element quality accounts for the percentage ratio of catalyst quality, the content of active component is 10wt%～25wt%, preferably 10wt%～20wt%, and the content of auxiliary agent is 1wt%～5wt%, preferably 3wt%～5wt%, balance of carrier；The preparation method of described catalyst comprises the steps：
（1）Will be soluble in water for active component presoma, obtain solution A；
（2）Carrier is added to step（1）In the solution A obtaining, after impregnated, aging, dry, calcination process, obtain catalyst precarsor B；
（3）Using reducing atmosphere to step（2）The catalyst precarsor B obtaining carries out reduction treatment；
（4）Will be soluble in water for auxiliary agent presoma, obtain solution C, and mix homogeneously with furfural aqueous solution, then with step（3）The catalyst precarsor B obtaining is added in autoclave together；
（5）Will be soluble in water to high molecular weight water soluble polymer, active component presoma, obtain solution D；Solution D is added to step（4）In described autoclave, after sealing, use hydrogen exchange 2～5 times, then adjust Hydrogen Vapor Pressure to 2～4MPa, react 1～3h at 100～200 DEG C；
（6）Treat step（5）The solidliquid mixture obtaining is down to 20～30 DEG C, adds dehydrated alcohol or aqueous citric acid solution, places 1～2h, then filters, gained solid sample again drying, after calcination process, obtain catalyst.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（1）Described in active component presoma be one or more of nickel nitrate, nickel acetate, nickel sulfate, Nickel dichloride., preferably nickel nitrate；In described solution A, in terms of element, mass fraction in the solution is 1%～7% to active component.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（2）Described in dipping be incipient impregnation, dip time be 1～3h；Described aging can aging at room temperature it is also possible to aging at a constant temperature, aging temperature is 10～90 DEG C, preferably 20～60 DEG C, ageing time is 1～24h, preferably 4～12h；Step（2）With step（6）Described in baking 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 methane portion oxidation synthesis gas catalyst of the present invention, step（2）Described in carrier be aluminium oxide, any one in silicon oxide, described carrier can be using commercially available product it is also possible to by method preparation well known in the art；In described catalyst precarsor B, the nickel of load in terms of element wt, for the 1wt%～5wt% of final catalyst.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（3）Described in reducing atmosphere be hydrogen or hydrogen and nitrogen mixed gas, in described mixed gas, hydrogen volume content is 10%～95%.Specific reduction treatment process is as follows：Under nitrogen atmosphere, catalyst precarsor B is warming up to 300～600 DEG C, then passes to the mixed gas of hydrogen or hydrogen and nitrogen, in 0.1～0.5MPa（Absolute pressure）After processing 4～8h, it is down to room temperature in a nitrogen atmosphere.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（4）Described in auxiliary agent presoma be one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, Lanthanum (III) nitrate, preferably magnesium nitrate；In described solution C, in terms of element, mass fraction in the solution is 1%～4% to auxiliary agent；In described furfural aqueous solution, the mass fraction of furfural is 30%～50%；Step（4）Described in the mass ratio of furfural aqueous solution and solution C be 3～5, the gross mass of described solution C and furfuryl aldehyde solution and step（3）The mass ratio of the reduction rear catalyst precursor B obtaining is 3～6.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（5）Described in high molecular weight water soluble polymer be Polyethylene Glycol（PEG）, Polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）One or more of；Described active component presoma is one or more of nickel nitrate, nickel acetate, nickel sulfate, Nickel dichloride., preferably nickel nitrate；In described solution D, in active component presoma nickeliferous mass fraction in solution D is counted for 0.4%～2% with element, mass fraction in solution D for the high molecular weight water soluble polymer is 3～6 times of Ni element mass fraction.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（6）Described in add the quality of dehydrated alcohol or citric acid to be 2～4 with the mass ratio of high molecular weight water soluble polymer；The mass fraction of described aqueous citric acid solution is 10%～20%.
The catalyst of the inventive method preparation can apply to methane portion oxidation synthesis gas reaction.Catalyst before use in a hydrogen atmosphere, 700～800 DEG C of prereduction 1～3h.The catalyst of the inventive method preparation is applied to methane portion oxidation synthesis gas reaction, and preferable process conditions are：The composition CH of unstripped gas4/O2Mol ratio is 1.75～2.2, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, unstripped gas air speed 20000～200000h-1, reaction pressure is 0.1～1Mpa, and reaction temperature is 600～900 DEG C.
Compared with prior art, a kind of methane portion oxidation synthesis gas nickel-base catalyst of active metal outer layer distribution can be obtained by preparation method according to the present invention.In the present invention, pre-soaked a part of active metal is to carry out furfural aqueous phase hydrogenation reaction.It is simultaneously introduced active metal predecessor and high molecular weight water soluble polymer in the system of furfural hydrogenation, on the one hand utilize furfural hydrogenation product to hinder diffusion within to catalyst granules for the active metal；On the other hand, using the coordination between active metal predecessor and high molecular weight water soluble polymer, reduce concentration difference inside and outside catalyst granules for the active metallic ion in solution, slow down diffusion velocity within to catalyst granules for the active metal.The catalyst reaction activity of this method preparation is high, has both reduced metal consumption, inhibits the focus generation during methane portion oxidation again.Catalyst precarsor is processed and is completed with catalyst preparation one step simultaneously, preparation process is simple, is conducive to industry amplification.
Specific embodiment
Further illustrate technology contents and the effect of the present invention with reference to embodiment, but be not so limited the present invention.
Appreciation condition：Hydrogen reducing is used 2 hours at 700 DEG C before catalyst reaction of the present invention.Continuous sample introduction fixed-bed quartz reactor is reacted, 750 DEG C of reaction temperature, unstripped gas forms CH4/O2/Ar
= 2/1/4（Mol ratio）, air speed 1 × 105h-1, after the condensed eliminating water of product, use gas chromatogram on-line analyses.Sample analysis after reacting 1 hour, evaluation result is shown in Table 1.
Metal element content in the catalyst using XRF analysis technical measurement.Using active component distribution situation on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.The scanning electron microscope analysis of the embodiment of the present invention and comparative example gained catalyst activity component nickel the results are shown in Table 2.
Embodiment 1
Weigh 2.97g nickel nitrate to be dissolved in 13mL deionized water, obtain solution A；14.9g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 3% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；8.55g magnesium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 4 times of quality is 40%, be then added in autoclave together with the catalyst precarsor B after reduction activation；10.8g Polyethylene Glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 33g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 12.6%Ni, the catalyst of 3.7%Mg, is designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate to be dissolved in 12mL deionized water, obtain solution A；14.9g silica support is carried on using equi-volume impregnating（Pore volume is 0.97mL/g, and specific surface area is 372m2/ g, spherical, equivalent diameter 0.5mm）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 3% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；8.55g magnesium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 4 times of quality is 40%, be then added in autoclave together with the catalyst precarsor B after reduction activation；10.8g Polyethylene Glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 33g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 11.8%Ni, the catalyst of 3.1%Mg, is designated as C-2.
Embodiment 3
Weigh 0.99g nickel nitrate to be dissolved in 15mL deionized water, obtain solution A；16.5g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 1% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；6.41g magnesium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 4 times of quality is 40%, be then added in autoclave together with the catalyst precarsor B after reduction activation；8.1g Polyethylene Glycol, 8.92g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 25g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 8.7%Ni, the catalyst of 2.2%Mg, is designated as C-3.
Embodiment 4
Weigh 4.96g nickel nitrate to be dissolved in 11mL deionized water, obtain solution A；13.3g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 5% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；10.68g magnesium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 4 times of quality is 40%, be then added in autoclave together with the catalyst precarsor B after reduction activation；13.5g Polyethylene Glycol, 14.87g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 41g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 17.3%Ni, the catalyst of 4.1%Mg, is designated as C-4.
Embodiment 5
Weigh 2.97g nickel nitrate to be dissolved in 13mL deionized water, obtain solution A；14.9g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 3% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；3.77g zirconium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 4 times of quality is 40%, be then added in autoclave together with the catalyst precarsor B after reduction activation；10.8g Polyethylene Glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 33g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 12.1%Ni, the catalyst of 3.2%Zr, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate to be dissolved in 13mL deionized water, obtain solution A；14.9g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 3% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；4.72g calcium nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 3 times of quality is 30%, be then added in autoclave together with the catalyst precarsor B after reduction activation；By 10.8g Polyvinylpyrrolidone（k30）, 11.89g nickel nitrate be dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add the aqueous citric acid solution that 220g mass fraction is 15%, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 13.1%Ni, the catalyst of 3.5%Ca, is designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrate to be dissolved in 13mL deionized water, obtain solution A；14.9g alumina support is 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）, under room temperature impregnate 2h, aging 4h, 80 DEG C are dried 12h, 700 DEG C of roasting 4h, prepared catalyst precarsor B, the Ni of load in terms of element wt, for the 3% of final catalyst；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.48g Lanthanum (III) nitrate is dissolved in 16mL deionized water, obtains solution C, and mix homogeneously with the furfural aqueous solution that the mass fraction of its 5 times of quality is 50%, be then added in autoclave together with the catalyst precarsor B after reduction activation；10.8g polyvinyl alcohol, 11.89g nickel nitrate are dissolved in 200mL deionized water, obtain solution D；Solution D is also added in autoclave, after sealing, uses hydrogen exchange 3 times, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；Treat that in above-mentioned autoclave, reacted solidliquid mixture is down to 25 DEG C, add 33g dehydrated alcohol, place 1.5h, then filter, gained solid sample is put in baking oven and 6h is dried at 110 DEG C, roasting 6h at 700 DEG C, that is, be obtained and count quality with element and account for catalyst percentage composition as 12.6%Ni, the catalyst of 3.7%La, is designated as C-7.
Comparative example
Weigh 14.86g nickel nitrate and 8.55g magnesium nitrate is dissolved in deionized water, prepared aqueous solution；16.2g alumina support is 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, aging 6h under room temperature, 110 DEG C are dried 6h, 700 DEG C of roasting 6h, that is, be obtained and quality is counted with element account for catalyst percentage composition as 14.7%Ni, the catalyst of 3.6%Mg, it is designated as D-1.
The reactivity worth of table 1 catalyst
Table 2 catalyst activity component Ni content distribution（wt%）
Claims (18)
1. a kind of preparation method of methane portion oxidation synthesis gas catalyst, described catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is one or more of Ca, Mg, Zr, Ce or La, and carrier is aluminium oxide, any one in silicon oxide；On the basis of in catalyst, each element quality accounts for the percentage ratio of catalyst quality, the content of active component is 10wt%～25wt%, preferably 10wt%～20wt%, and the content of auxiliary agent is 1wt%～5wt%, preferably 3wt%～5wt%, balance of carrier；The preparation method of described catalyst comprises the steps：
（1）Will be soluble in water for active component presoma, obtain solution A；
（2）Carrier is added to step（1）In the solution A obtaining, after impregnated, aging, dry, calcination process, obtain catalyst precarsor B；
（3）Using reducing atmosphere to step（2）The catalyst precarsor B obtaining carries out reduction treatment；
（4）Will be soluble in water for auxiliary agent presoma, obtain solution C, and mix homogeneously with furfural aqueous solution, then with step（3）The catalyst precarsor B obtaining is added in autoclave together；
（5）Will be soluble in water to high molecular weight water soluble polymer, active component presoma, obtain solution D；Solution D is added to step（4）In described autoclave, after sealing, use hydrogen exchange 2～5 times, then adjust Hydrogen Vapor Pressure to 2～4MPa, react 1～3h at 100～200 DEG C；
（6）Treat step（5）The solidliquid mixture obtaining is down to 20～30 DEG C, is subsequently adding dehydrated alcohol or aqueous citric acid solution, places 1～2h, then filters, gained solid sample again drying, after calcination process, obtain catalyst.
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 of nickel nitrate, nickel acetate, nickel sulfate, Nickel dichloride., preferably nickel nitrate.
3. in accordance with the method for claim 1 it is characterised in that：Step（1）Described in solution A, in terms of element, the mass fraction in solution A is 1%～7% to active component.
4. in accordance with the method for claim 1 it is characterised in that：Step（2）Described in catalyst precarsor B, the nickel of load in terms of element wt, for the 1wt%～5wt% of final catalyst.
5. in accordance with the method for claim 1 it is characterised in that：Step（2）Described in dipping be incipient impregnation, dip time be 1～3h.
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, preferably 20～60 DEG C, ageing time be 1～24h, preferably 4～12h.
7. in accordance with the method for claim 1 it is characterised in that：Step（2）With step（6）Described in baking temperature be 70～150 DEG C, preferably 80～120 DEG C, drying time be 2～12h, preferably 4～8h.
8. 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.
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, in described mixed gas, hydrogen volume content is 10%～95%.
10. in accordance with the method for claim 1 it is characterised in that：Step（4）Described in auxiliary agent presoma be one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, Lanthanum (III) nitrate, preferably magnesium nitrate.
11. in accordance with the method for claim 1 it is characterised in that：Step（4）Described in solution C, in terms of element, the mass fraction in solution C is 1%～4% to auxiliary agent.
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 the mass ratio of furfural aqueous solution and solution C be 3～5.
14. in accordance with the method for claim 1 it is characterised in that：Step（4）Described in the gross mass of solution C and furfural aqueous solution and step（3）The mass ratio of the reduction rear catalyst precursor B obtaining 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 one or more of Polyethylene Glycol, Polyvinylpyrrolidone, polyvinyl alcohol.
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 of nickel nitrate, nickel acetate, nickel sulfate, Nickel dichloride., 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 for 0.4%～2% with element, mass fraction in solution D for the high molecular weight water soluble polymer is 3～6 times of Ni element mass fraction.
18. in accordance with the method for claim 1 it is characterised in that：Step（6）Described in add the quality of dehydrated alcohol or citric acid to be 2～4 with the mass ratio of high molecular weight water soluble polymer；The mass fraction of described aqueous citric acid solution is 10%～20%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111036196A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing indole |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1419814A1 (en) * | 2002-11-15 | 2004-05-19 | L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des | Perovskite catalyst for the partial oxidation of natural gas |
| CN103801299A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for syngas preparation by methane partial oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1419814A1 (en) * | 2002-11-15 | 2004-05-19 | L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des | Perovskite catalyst for the partial oxidation of natural gas |
| CN103801299A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for syngas preparation by methane partial oxidation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036196A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing indole |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
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