CN106944087A - A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst - Google Patents

A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst Download PDF

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CN106944087A
CN106944087A CN201610003106.6A CN201610003106A CN106944087A CN 106944087 A CN106944087 A CN 106944087A CN 201610003106 A CN201610003106 A CN 201610003106A CN 106944087 A CN106944087 A CN 106944087A
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catalyst
solution
accordance
auxiliary agent
active component
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CN106944087B (en
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张舒冬
孙晓丹
刘继华
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B01J29/0358—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/888—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • C07C2529/035—Crystalline silica polymorphs, e.g. silicalites

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Abstract

The present invention relates to a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst, the catalyst includes the first active component, the second active component, the first auxiliary agent, the second auxiliary agent and carrier；The preparation method of the catalyst comprises the following steps：Catalyst precarsor A is prepared first, then reduction treatment is carried out to catalyst precarsor A, it is well mixed auxiliary agent presoma is soluble in water with furfural aqueous solution, then it is added to together with catalyst precarsor A in autoclave, reacted after adding solution C, 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 isobutene is improved again.

Description

A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst
Technical field
The present invention relates to a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst, more particularly, to a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane loaded catalyst.
Background technology
With the development of petrochemical technology, isobutene has become in alkene the most important basic chemical industry raw material in addition to ethene, propylene.Using isobutene as the development of the downstream product of resource, China is set to increase the demand of isobutene rapidly.
Iso-butane is mainly derived from petroleum catalytic cracking production process, and as refinery is increasingly urgent to the demand of maximization of economic benefit, iso-butane produces isobutene project and causes extensive attention.At present, it is industrial that isobutene is mainly produced using catalytic dehydrogenation of isobutane.The method of preparing isobutene through dehydrogenation of iso-butane, because reaction temperature is high and the problems such as catalyst surface easy carbon distribution, has that target product selectivity is not high and catalyst.The method of producing isobutene from oxidative dehydrogenation of isobutane, although the advantage also in conceptual phase, but this method is：Oxidative dehydrogenation is not limited by thermodynamical equilibrium, and in the absence of the carbon distribution problem of catalyst, and the reaction is exothermic reaction, can be carried out at a lower temperature, saves the energy.
Being presently used for the catalyst of isobutene for oxo-dehydrogenation reaction mainly includes catalytic component based on vanadium, catalyst with base of molybdenum and other type catalysts.Wherein, catalytic component based on vanadium generally has higher catalytic activity.10%V-UVM-7 catalyst by active component of vanadium, the iso-butane conversion ratio at 490 DEG C is 12%, and selective isobutene is 41%（Catal. Today, 2006:, 117：180）.V-Sb-Ni/Al2O3Iso-butane conversion ratio of the catalyst at 550 DEG C is 46%, and selective isobutene is 66%（Appl. Catal. A, 2003,250：143）.Composite oxides Mg containing vanadium1.8V2Co0.2OxAlso there is preferable catalytic performance, the iso-butane conversion ratio at 450 DEG C is 8.4%, the selectivity of isobutene is 86%（J. Jpn. Petrol. Inst., 2003,46:87）.The catalyst with base of molybdenum of dehydrogenation of isobutane reaction is mainly NiMoO4Catalyst, iso-butane conversion ratio of this catalyst at 500 DEG C is 8%, and selective isobutene is 40%（Appl. Catal. A, 1998,166：L259）.NiMoO is modified with K, Ca, P4Catalyst can improve the selectivity of generation isobutene, such as K-NiMoO4Iso-butane conversion ratio of the catalyst at 480 DEG C is 8%, and selective isobutene is about 70%（Appl. Catal. A, 1998,169：L3）.In addition, relevant isobutene for oxo-dehydrogenation catalyst system and catalyzing further relates to Cr-Ce-O, heteropolyacid salt and RE phosphate etc..
CN101618319A discloses a kind of CrOx/ mesoporous CaO catalyst of efficient producing isobutene from oxidative dehydrogenation of isobutane, when reaction temperature is 500 DEG C, and selective isobutene is 81% on 10%CrOx/ mesoporous CaO catalyst, and iso-butane conversion ratio is 10%.CN101439292A discloses a kind of solid catalyst of producing isobutene from oxidative dehydrogenation of isobutane, and the major ingredient of the catalyst is phosphato-molybdic heteropolyacid alkali metal（Alkaline-earth metal）Salt-nickel oxide composite material, additive is one kind in silica, titanium oxide, vanadic anhydride, cupric oxide, cobaltosic oxide, cerium oxide, tellurium oxide etc., in reaction temperature be 300~600 DEG C, iso-butane conversion ratio is 7%~31%, and isobutene yield is up to 6%~18%.
However, under oxygen existence condition, deep oxidation easily occurs for the target product and iso-butane of isobutene for oxo-dehydrogenation reaction, the problems such as causing waste and the relatively low target product selectivity of raw material.Producing isobutene from oxidative dehydrogenation of isobutane reaction or a fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）Reactant reaction while catalyst external surface is reached has been completed, thus the inner surface of catalyst contributes little to goal response, and this has resulted in rate of metal relatively low in carrier duct, catalyst cost is added, while can also accelerate the deep oxidation of product.Therefore, the catalyst for researching and developing a kind of high conversion and the producing isobutene from oxidative dehydrogenation of isobutane of high selectivity is significant.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane 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 producing isobutene from oxidative dehydrogenation of isobutane catalyst, the catalyst includes the first active component, the second active component, the first auxiliary agent, the second auxiliary agent and carrier；First active component is Ni, and the second active component is V, and the first auxiliary agent is W, and the second auxiliary agent is the one or more in Mo, Mg, Ca, K, Cr, Ce or La, preferably Mo；Carrier is any of aluminum oxide, silica, SBA-15, preferably aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, first active component Ni content is 1wt%~5wt%, second active component V content is 1wt%~10wt%, preferably 3wt%~8wt%, the content of first auxiliary agent is 1wt%~3wt%, the content of second auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）First 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, the second 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 absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, step（1）Described in the first 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 the soluble-salt containing W, is specifically as follows ammonium tungstate and/or ammonium metatungstate；In the solution A, the first active component is in terms of element, and the mass fraction in solution A is 1%~5%, and the first adjuvant component is in terms of element, and the mass fraction in solution A is 1%~3%.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, step（2）Described in dipping be incipient impregnation；The aging temperature is 10~90 DEG C, and preferably 20~60 DEG C, ageing time is 1~24h, preferably 4~12h；Step（2）With step（6）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h；Step（2）With step（6）Described in sintering temperature be 500~900 DEG C, preferably 600~800 DEG C, roasting time be 2~12h, preferably 4~8h.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, step（2）Described in carrier any of for aluminum oxide, silica, SBA-15；The carrier can use commercially available product, can also be prepared by method well known in the art；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt, and the tungsten of load is 1wt%~3wt% of final catalyst in terms of element wt.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, step（3）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specific reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, in 0.1~0.5MPa（Absolute pressure）Handle after 4~8h, room temperature is down in a nitrogen atmosphere.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, step（4）Described in the second auxiliary agent presoma be one or more in ammonium molybdate, magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate, preferably ammonium molybdate；In the solution C, the second auxiliary agent is in terms of element, and mass fraction in the solution 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 producing isobutene from oxidative dehydrogenation of isobutane 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 second active component presoma is ammonium metavanadate and/or vanadic sulfate, preferably ammonium metavanadate；In the solution D, contained vanadium counts mass fraction in solution D as 0.1%~1% using element in the second active component presoma, and mass fraction of the high molecular weight water soluble polymer in solution D is 3~6 times of V element mass fraction.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane 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 reacts applied to producing isobutene from oxidative dehydrogenation of isobutane, and preferable process conditions are：The composition i-C of unstripped gas4H10/O2Mol ratio is 0.5~1, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 3000~9000mLg of unstripped gas air speedcat -1·h-1, reaction pressure is normal pressure, and reaction temperature is 500~700 DEG C.
Compared with prior art, the producing isobutene from oxidative dehydrogenation of isobutane 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 isobutene 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：Isobutene for oxo-dehydrogenation reaction is carried out on atmospheric fixed bed micro-reaction equipment, catalyst loading amount 0.2g, 650 DEG C of reaction temperature, reaction gas composition i-C4H10/O2/N2=1/1/4（Mol ratio）, flow velocity：20mL/min, air speed 6000mLgcat -1·h-1, gas chromatograph on-line analysis is used after the condensed water removal of product.Reaction starts sampling analysis after 1 hour, and evaluation result is shown 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 vanadium 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, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；0.74g ammonium molybdates are dissolved in 15mL 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；5.4g polyethylene glycol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.4%Ni, 4.8%V, 1.5%W, 1.4%Mo catalyst, is designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；0.74g ammonium molybdates are dissolved in 15mL 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；5.4g polyethylene glycol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.5%Ni, 4.6%V, 1.6%W, 1.3%Mo catalyst, is designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；0.74g ammonium molybdates are dissolved in 15mL 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；5.4g polyethylene glycol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.6%Ni, 5.1%V, 1.6%W, 1.5%Mo catalyst, is designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrates, 0.28g ammonium tungstates to be dissolved in 17mL deionized waters, obtain solution A；18g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 1% of final catalyst in terms of element wt, and the W of load is the 1% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；0.37g ammonium molybdates are dissolved in 15mL 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；2.7g polyethylene glycol, 1.38g ammonium metavanadates 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 8.1g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 0.7%Ni, 2.1%V, 0.6%W, 0.5%Mo catalyst, is designated as C-4.
Embodiment 5
Weigh 4.96g nickel nitrates, 0.83g ammonium tungstates to be dissolved in 11mL deionized waters, obtain solution A；14.2g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 5% of final catalyst in terms of element wt, and the W of load is the 3% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.1g ammonium molybdates are dissolved in 15mL 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；7.2g polyethylene glycol, 3.67g ammonium metavanadates 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 22g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 4.3%Ni, 6.9%V, 2.5%W, 2.2%Mo catalyst, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；4.27g magnesium nitrates are dissolved in 15mL 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；5.4g polyethylene glycol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.2%Ni, 4.4%V, 1.6%W, 1.5%Mg catalyst, is designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.03g potassium nitrate is dissolved in 15mL deionized waters, solution C is obtained, and is well mixed with the mass fraction of its 5 times of quality for 50% furfural aqueous solution, is then added to together with the catalyst precarsor B after reduction activation in autoclave；5.4g polyethylene glycol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.5%Ni, 4.5%V, 1.7%W, 1.4%K catalyst, is designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；3.08g chromic nitrates are dissolved in 15mL 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；5.4g polyvinyl alcohol, 2.76g ammonium metavanadates 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 17g absolute ethyl alcohols, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.5%Ni, 4.6%V, 1.6%W, 1.5%Cr catalyst, is designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates to be dissolved in 14mL deionized waters, obtain solution A；16g 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 are calcined 4h, and catalyst precarsor B are made, wherein, the Ni of load is the 3% of final catalyst in terms of element wt, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.25g lanthanum nitrates are dissolved in 15mL 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；By 5.4g polyvinylpyrrolidones（k30）, 2.76g ammonium metavanadates 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 114g mass fractions are 15%, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 2.5%Ni, 5.1%V, 1.6%W, 1.5%La catalyst, is designated as C-9.
Comparative example
Weigh 2.97g nickel nitrates, 0.55g ammonium tungstates, 0.74g ammonium molybdates and 2.76g ammonium metavanadates to be dissolved in deionized water, the aqueous solution is made；16g 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 2.7%Ni, 5.6%V, 1.5%W, 1.7%Mo catalyst are designated as D-1.
The reactivity worth of the catalyst of table 1
The catalyst activity component V content of table 2 is distributed（wt%）

Claims (20)

1. a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst, the catalyst includes the first active component, the second active component, the first auxiliary agent, the second auxiliary agent and carrier；First active component is Ni, and the second active component is V, and the first auxiliary agent is W, and the second auxiliary agent is the one or more in Mo, Mg, Ca, K, Cr, Ce or La, preferably Mo；Carrier is any of aluminum oxide, silica, SBA-15, preferably aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, first active component Ni content is 1wt%~5wt%, second active component V content is 1wt%~10wt%, preferably 3wt%~8wt%, the content of first auxiliary agent is 1wt%~3wt%, the content of second auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）First 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, the second 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 absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in the first active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be the soluble-salt containing W.
4. in accordance with the method for claim 3, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be ammonium tungstate and/or ammonium metatungstate.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in solution A, the first active component is in terms of element, and the mass fraction in solution A is 1%~5%, and the first adjuvant component is in terms of element, and the mass fraction in solution A is 1%~3%.
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 drying 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（2）Described in catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt, and the tungsten of load is 1wt%~3wt% of final catalyst in terms of element wt.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
11. 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 ammonium molybdate, magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate, preferably ammonium molybdate.
12. 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 mass fraction in the solution is 1%~4%.
13. 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%.
14. 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.
15. 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.
16. 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.
17. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in the second active component presoma be ammonium metavanadate and/or vanadic sulfate, preferably ammonium metavanadate.
18. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in solution D, contained vanadium counts mass fraction in solution D as 0.1%~1% using element in the second active component presoma, and mass fraction of the high molecular weight water soluble polymer in solution D is 3~6 times of V element mass fraction.
19. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in add the quality of absolute ethyl alcohol or citric acid and the mass ratio of high molecular weight water soluble polymer be 2~4.
20. in accordance with the method for claim 1, it is characterised in that：Step（6）Described in aqueous citric acid solution mass fraction be 10%~20%.
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CN108479792A (en) * 2018-03-23 2018-09-04 安徽理工大学 It is a kind of to prepare higher olefins catalyst and Catalytic processes by the microwave radiation technology of carrier of aluminium oxide
RU2722837C1 (en) * 2019-12-27 2020-06-04 Федеральное государственное автономное образовательное учреждение высшего образования "Новосибирский национальный исследовательский государственный университет" (Новосибирский государственный университет, НГУ) Method of preparing a hydrogenation catalyst for furfurol and furfuryl alcohol to 2-methylfuran
CN115400748A (en) * 2022-09-20 2022-11-29 中国科学院山西煤炭化学研究所 Isobutane CO 2 Vanadium-based catalyst for preparing isobutene by oxidative dehydrogenation and preparation method thereof
CN116060024A (en) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 Ester hydrogenation catalyst, preparation method and application thereof

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CN101439292A (en) * 2008-12-26 2009-05-27 厦门大学 Solid catalyst for producing isobutene from oxidative dehydrogenation of isobutane and preparation method thereof
WO2015198351A2 (en) * 2014-06-25 2015-12-30 Council Of Scientific & Industrial Research Ni containing anionic clay catalyst useful for selective hydrogenation of furfural to furfuryl alcohol and its preparation thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108479792A (en) * 2018-03-23 2018-09-04 安徽理工大学 It is a kind of to prepare higher olefins catalyst and Catalytic processes by the microwave radiation technology of carrier of aluminium oxide
CN108479792B (en) * 2018-03-23 2020-10-13 安徽理工大学 Microwave-assisted catalyst for preparing high-carbon olefin by using alumina as carrier and catalytic process
RU2722837C1 (en) * 2019-12-27 2020-06-04 Федеральное государственное автономное образовательное учреждение высшего образования "Новосибирский национальный исследовательский государственный университет" (Новосибирский государственный университет, НГУ) Method of preparing a hydrogenation catalyst for furfurol and furfuryl alcohol to 2-methylfuran
CN116060024A (en) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 Ester hydrogenation catalyst, preparation method and application thereof
CN116060024B (en) * 2021-10-31 2024-05-10 中国石油化工股份有限公司 Ester hydrogenation catalyst, preparation method and application thereof
CN115400748A (en) * 2022-09-20 2022-11-29 中国科学院山西煤炭化学研究所 Isobutane CO 2 Vanadium-based catalyst for preparing isobutene by oxidative dehydrogenation and preparation method thereof
CN115400748B (en) * 2022-09-20 2023-09-08 中国科学院山西煤炭化学研究所 Isobutane CO 2 Vanadium-based catalyst for oxidative dehydrogenation to prepare isobutene and preparation thereof

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