CN106944087B - 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 PDFInfo
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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 includes the following steps: to prepare catalyst precarsor A first, then reduction treatment is carried out to catalyst precarsor A, it is uniformly mixed with furfural aqueous solution by auxiliary agent presoma is soluble in water, then it is added in autoclave together with catalyst precarsor A, it is reacted after solution C is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.The catalyst reaction activity of this method preparation is high, not only reduces metal consumption, but also improve the selectivity of isobutene.
Description
Technical field
The present invention relates to a kind of preparation methods of producing isobutene from oxidative dehydrogenation of isobutane catalyst, more particularly, to a kind of different
The preparation method of butane oxidation dehydrogenation preparing isobutene loaded catalyst.
Background technique
With the development of petrochemical technology, isobutene has become in alkene the most important basis in addition to ethylene, propylene
Industrial chemicals.Using isobutene as the development of the downstream product of resource, increase China to the demand of isobutene rapidly.
Iso-butane is mainly derived from petroleum catalytic cracking production process, the demand day with refinery to maximization of economic benefit
It is becoming tight urgent, iso-butane produces isobutene project and causes to pay attention to extensively.Currently, industrially mainly being produced using catalytic dehydrogenation of isobutane
Isobutene.The method of preparing isobutene through dehydrogenation of iso-butane, exists the problems such as being easy carbon distribution due to reaction temperature height and catalyst surface
Not the problems such as target product selectivity is not high and catalyst easy in inactivation.The method of producing isobutene from oxidative dehydrogenation of isobutane, although also
In conceptual phase, but the advantages of this method is: oxidative dehydrogenation is not limited by thermodynamical equilibrium, and there is no catalyst
Carbon distribution problem, and the reaction is exothermic reaction, can be carried out at a lower temperature, it is energy saving.
Currently, for isobutene for oxo-dehydrogenation reaction catalyst mainly include catalytic component based on vanadium, catalyst with base of molybdenum and its
Its type catalyst.Wherein, catalytic component based on vanadium catalytic activity usually with higher.Using vanadium as the 10%V-UVM-7 of active component
Catalyst, iso-butane conversion ratio at 490 DEG C are 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%, selective isobutene 66%(Appl.
Catal. A, 2003,250:143).Composite oxides Mg containing vanadium1.8V2Co0.2OxAlso there is preferable catalytic performance, 450
DEG C when iso-butane conversion ratio be 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 of this catalyst at 500 DEG C
Conversion ratio is 8%, selective isobutene be 40%(Appl. Catal. A, 1998,166:L259).NiMoO is modified with K, Ca, P4
The selectivity for generating isobutene, such as K-NiMoO can be improved in catalyst4Iso-butane conversion ratio of the catalyst at 480 DEG C is 8%,
Selective isobutene is about 70%(Appl. Catal. A, and 1998,169:L3).In addition, related isobutene for oxo-dehydrogenation catalytic body
System 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, 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 be silica, titanium oxide, vanadic anhydride,
One of copper oxide, cobaltosic oxide, cerium oxide, tellurium oxide etc., at reaction temperature be 300~600 DEG C, iso-butane turns
Rate is 7%~31%, and isobutene yield is up to 6%~18%.
However, the target product and iso-butane of isobutene for oxo-dehydrogenation reaction are easy to happen under oxygen existence condition
Deep oxidation leads to problems such as the waste of raw material and target product selectivity lower.Producing isobutene from oxidative dehydrogenation of isobutane reaction
Or fast reaction (this fast reaction be typically at carry out under conditions of mass transport limitation), reactant is urged in arrival
Reaction is completed while agent outer surface, thus the inner surface of catalyst contributes less goal response, this is resulted in
Lower metal utilization in carrier duct increases catalyst cost, while can also accelerate the deep oxidation of product.Therefore,
The catalyst for researching and developing a kind of high conversion and highly selective producing isobutene from oxidative dehydrogenation of isobutane is of great significance.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of catalysis of producing isobutene from oxidative dehydrogenation of isobutane
The preparation method of agent, the catalyst of this method preparation have the spy that low in cost, metal component utilization rate is high and selectivity is good
Point.
The present invention provides a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst, the catalyst includes
First active component, the second active component, the first auxiliary agent, the second auxiliary agent and carrier；First active component is Ni, and second is living
Property group be divided into V, the first auxiliary agent is W, and the second auxiliary agent is one or more of Mo, Mg, Ca, K, Cr, Ce or La, preferably Mo；
Carrier is any one of aluminium oxide, silica, SBA-15, preferably aluminium oxide；Catalysis is accounted for each element quality in catalyst
On the basis of the percentage of agent quality, the content of the first active component Ni is 1wt%~5wt%, and the content of the second active component V is
1wt%~10wt%, preferably 3wt%~8wt%, the content of the first auxiliary agent are 1wt%~3wt%, and the content of the second auxiliary agent is 1wt%
~3wt%, surplus are carrier；The preparation method of the catalyst includes the following steps:
(1) the first active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is obtained
Catalyst precarsor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
Suddenly the catalyst precarsor B that (3) obtain is added in autoclave together；
(5) water soluble polymer, the second active component presoma is soluble in water, solution D is obtained, by solution D
Be added in autoclave described in step (4), replaced 2~5 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 2~
4MPa reacts 1~3h at 100~200 DEG C；
(6) solidliquid mixture obtained to step (5) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added,
1~2h is placed, is then filtered, obtained 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, the first activity described in step (1)
Component presoma is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；Described first helps
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 group
Divide based on the element, the mass fraction in solution A is 1%~5%, and the first adjuvant component based on the element, divide by the quality in solution A
Number is 1%~3%.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, dipping described in step (2) is
Incipient impregnation；The aging temperature be 10~90 DEG C, preferably 20~60 DEG C, ageing time be 1~for 24 hours, preferably 4~
12h；Drying temperature described in step (2) and step (6) is 70~150 DEG C, preferably 80~120 DEG C, drying time is 2~
12h, preferably 4~8h；Maturing temperature described in step (2) and step (6) is 500~900 DEG C, preferably 600~800 DEG C,
Calcining time is 2~12h, preferably 4~8h.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, carrier described in step (2) is
Any one of aluminium oxide, silica, SBA-15；The carrier can use commercially available product, can also by it is well known that
Method preparation；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst, is born in terms of element wt
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, Primordial Qi is gone back described in step (3)
Atmosphere is the mixed gas of hydrogen or hydrogen and nitrogen, and hydrogen volume percentage composition is 10%~95% in the mixed gas.Tool
The reduction treatment process of body is as follows: catalyst precarsor being warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen
The mixed gas of gas and nitrogen, in 0.1~0.5MPa(absolute pressure) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, second is helped described in step (4)
Agent presoma be one of ammonium molybdate, magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate or a variety of, preferably
For ammonium molybdate；In the solution C, based on the element, mass fraction in the solution is 1%~4% to the second auxiliary agent；The furfural is water-soluble
The mass fraction of furfural is 30%~50% in liquid；Furfural aqueous solution described in step (4) and the mass ratio of solution C are 3~5, institute
The mass ratio for the reduction rear catalyst precursor B that the gross mass and step (3) for stating solution C and furfural aqueous solution obtain is 3~6.
In the preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst of the present invention, high water solubility described in step (5)
Molecularly Imprinted Polymer is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；Institute
Stating the second active component presoma is ammonium metavanadate and/or vanadic sulfate, preferably ammonium metavanadate；In the solution D, second is living
Property component presoma in contained vanadium based on the element the mass fraction in solution D be 0.1%~1%, water soluble polymer
Mass fraction 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, addition described in step (6) is anhydrous
The mass ratio of the quality and water soluble polymer of ethyl alcohol or citric acid is 2~4；The quality of the aqueous citric acid solution point
Number is 10%~20%.
The catalyst of the method for the present invention preparation is reacted applied to producing isobutene from oxidative dehydrogenation of isobutane, preferable process conditions
Are as follows: the composition i-C of unstripped gas4H10/O2Molar ratio is 0.5~1, can contain Ar, N in unstripped gas2Or the dilution property gas such as He,
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, a kind of available active metal outer layer distribution of the preparation method being related to through the invention
Producing isobutene from oxidative dehydrogenation of isobutane catalyst.In the present invention, pre-soaked a part of active metal is to carry out furfural water phase
Hydrogenation reaction.Active metal predecessor and water soluble polymer is added 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, active metal forerunner is utilized
Coordination between object and water soluble polymer, reduce solution in active metallic ion inside and outside catalyst granules
Concentration difference slows down active metal to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both
Metal consumption is reduced, and improves the selectivity of isobutene.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation,
Preparation process is simple, is conducive to industrial amplification.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Evaluation condition: isobutene for oxo-dehydrogenation reaction carries out on atmospheric fixed bed micro-reaction equipment, catalyst loading
0.2g, 650 DEG C of reaction temperature, reaction gas forms i-C4H10/O2/N2=1/1/4(molar ratio), flow velocity: 20mL/min, air speed
6000mL·gcat -1·h-1, product is after condensation water removal with gas chromatograph on-line analysis.Reaction starts sampling point after 1 hour
Analysis, evaluation results are shown in Table 1.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention
The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example
The scanning electron microscope analysis of component vanadium the results are shown in Table 2.
Embodiment 1
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；0.74g ammonium molybdate is dissolved in 15mL deionized water, solution C, and the quality with its 4 times of quality are obtained
The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyethylene glycol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 2.4%Ni, 4.8%V, 1.5%W, and the catalyst of 1.4%Mo is denoted as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g silica support (Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter 0.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；0.74g ammonium molybdate is dissolved in 15mL deionized water, solution C, and the quality with its 4 times of quality are obtained
The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyethylene glycol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 2.5%Ni, 4.6%V, 1.6%W, and the catalyst of 1.3%Mo is denoted as C-2.
Embodiment 3
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g SBA-15 carrier (Kong Rongwei 1.23mL/g, specific surface area 701m2/ g, bar shaped, equivalent diameter
1.5mm), 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B is made, wherein load
Ni in terms of element wt, be final catalyst 3%, the W of load in terms of element wt, be final catalyst 2%；Catalyst
Precursor 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 molybdate is dissolved in 15mL deionized water, obtains solution C, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor B after reduction activation
In autoclave；5.4g polyethylene glycol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；By solution
D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusting Hydrogen Vapor Pressure to 3MPa, anti-at 150 DEG C
Answer 2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 2.6%Ni, 5.1%V, 1.6%W, and the catalyst of 1.5%Mo is denoted as C-3.
Embodiment 4
Weigh 0.99g nickel nitrate, 0.28g ammonium tungstate is dissolved in 17mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 18g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 1% of final catalyst, and the W of load is the 1% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；0.37g ammonium molybdate is dissolved in 15mL deionized water, solution C, and the quality with its 4 times of quality are obtained
The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；2.7g polyethylene glycol, 1.38g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 8.1g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 0.7%Ni, 2.1%V, 0.6%W, and the catalyst of 0.5%Mo is denoted as C-4.
Embodiment 5
Weigh 4.96g nickel nitrate, 0.83g ammonium tungstate is dissolved in 11mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 14.2g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B is made, wherein load
Ni in terms of element wt, be final catalyst 5%, the W of load in terms of element wt, be final catalyst 3%；Catalyst
Precursor 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 molybdate is dissolved in 15mL deionized water, obtains solution C, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor B after reduction activation
In autoclave；7.2g polyethylene glycol, 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；By solution
D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusting Hydrogen Vapor Pressure to 3MPa, anti-at 150 DEG C
Answer 2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 22g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 4.3%Ni, 6.9%V, 2.5%W, and the catalyst of 2.2%Mo is denoted as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；4.27g magnesium nitrate is dissolved in 15mL deionized water, solution C, and the quality with its 3 times of quality are obtained
The furfural aqueous solution that score is 30% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyethylene glycol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 2.2%Ni, 4.4%V, 1.6%W, and the catalyst of 1.5%Mg is denoted as C-6.
Embodiment 7
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；1.03g potassium nitrate is dissolved in 15mL deionized water, solution C, and the quality with its 5 times of quality are obtained
The furfural aqueous solution that score is 50% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyethylene glycol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 2.5%Ni, 4.5%V, 1.7%W, and the catalyst of 1.4%K is denoted as C-7.
Embodiment 8
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；3.08g chromic nitrate is dissolved in 15mL deionized water, solution C, and the quality with its 4 times of quality are obtained
The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyvinyl alcohol, 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 17g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 2.5%Ni, 4.6%V, 1.6%W, and the catalyst of 1.5%Cr is denoted as C-8.
Embodiment 9
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 14mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated at room temperature, catalyst precarsor B are made, wherein the Ni of load is with member
Plain poidometer, is the 3% of final catalyst, and the W of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B exists
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, and 0.2MPa(is exhausted
Pressure), recovery time 4h；1.25g lanthanum nitrate is dissolved in 15mL deionized water, solution C, and the quality with its 4 times of quality are obtained
The furfural aqueous solution that score is 40% is uniformly mixed, and is then added to reaction under high pressure together with the catalyst precarsor B after reduction activation
In kettle；5.4g polyvinylpyrrolidone (k30), 2.76g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；It will
Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, at 150 DEG C
Lower reaction 2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the lemon that 114g mass fraction is 15% is added
Aqueous acid is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts at 700 DEG C
6h, obtaining quality based on the element and accounting for catalyst percentage composition is 2.5%Ni, 5.1%V, 1.6%W, and the catalyst of 1.5%La is denoted as
C-9。
Comparative example
2.97g nickel nitrate, 0.55g ammonium tungstate, 0.74g ammonium molybdate and 2.76g ammonium metavanadate is weighed to be dissolved in deionized water,
Aqueous solution is made；Being carried on 16g alumina support using equi-volume impregnating, (Kong Rongwei 0.73mL/g, specific surface area are
253m2/ g, bar shaped, equivalent diameter 1.5mm), 2h is impregnated at room temperature, and aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h make
Obtaining quality based on the element and accounting for catalyst percentage composition is 2.7%Ni, 5.6%V, 1.5%W, and the catalyst of 1.7%Mo is denoted as D-1.
The reactivity worth of 1 catalyst of table
2 catalyst activity component V content of table is distributed (wt%)
Claims (26)
1. a kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst, the catalyst include the first active component,
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, the
One auxiliary agent is W, and the second auxiliary agent is one or more of Mo, Mg, Ca, K, Cr, Ce or La, carrier be aluminium oxide, silica,
Any one of SBA-15；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the first active component
The content of Ni is 1wt%~5wt%, and the content of the second active component V is 1wt%~10wt%, the content of the first auxiliary agent be 1wt%~
The content of 3wt%, the second auxiliary agent are 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps:
(1) the first active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is catalyzed
Agent precursor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
(3) the catalyst precarsor B obtained is added in autoclave together；
(5) water soluble polymer, the second active component presoma is soluble in water, solution D is obtained, solution D is added
It into autoclave described in step (4), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C, the water soluble polymer is polyethylene glycol, polyvinylpyrrolidone, poly- second
One or more of enol；
(6) solidliquid mixture obtained to step (5) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, and places 1
~2h, is then filtered, and obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that: second auxiliary agent is Mo, and carrier is aluminium oxide, with catalysis
Each element quality accounts on the basis of the percentage of catalyst quality in agent, and the content of the second active component V is 3wt%~8wt%.
3. according to the method for claim 1, it is characterised in that: the first active component presoma described in step (1) is nitre
One of sour nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
4. according to the method for claim 1, it is characterised in that: the first active component presoma described in step (1) is nitre
Sour nickel.
5. according to the method for claim 1, it is characterised in that: the first auxiliary agent presoma described in step (1) be containing W can
Soluble.
6. according to the method for claim 5, it is characterised in that: the first auxiliary agent presoma described in step (1) is ammonium tungstate
And/or ammonium metatungstate.
7. according to the method for claim 1, it is characterised in that: in solution A described in step (1), the first active component with
Element meter, the mass fraction in solution A are 1%~5%, and based on the element, the mass fraction in solution A is the first adjuvant component
1%~3%.
8. according to the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10~90 DEG C, always
Change the time be 1~for 24 hours.
9. according to method described in claim 1 or 8, it is characterised in that: aging temperature described in step (2) is 20~60
DEG C, ageing time is 4~12h.
10. according to the method for claim 1, it is characterised in that: drying temperature described in step (2) and step (6) is 70
~150 DEG C, drying time is 2~12h.
11. according to method described in claim 1 or 10, it is characterised in that: drying temperature described in step (2) and step (6)
It is 80~120 DEG C, drying time is 4~8h.
12. according to the method for claim 1, it is characterised in that: maturing temperature described in step (2) and step (6) is 500
~900 DEG C, calcining time is 2~12h.
13. according to method described in claim 1 or 12, it is characterised in that: maturing temperature described in step (2) and step (6)
It is 600~800 DEG C, calcining time is 4~8h.
14. according to the method for claim 1, it is characterised in that: in catalyst precarsor B described in step (2), the nickel of load
It is 1wt%~5wt% of final catalyst in terms of element wt, the tungsten of load is the 1wt% of final catalyst in terms of element wt
~3wt%.
15. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (3) is hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
16. according to the method for claim 1, it is characterised in that: the second auxiliary agent presoma described in step (4) is molybdic acid
One of ammonium, magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate are a variety of.
17. according to method described in claim 1 or 16, it is characterised in that: the second auxiliary agent presoma described in step (4) is
Ammonium molybdate.
18. according to the method for claim 1, it is characterised in that: in solution C described in step (4), the second auxiliary agent is with element
Meter, mass fraction in the solution are 1%~4%.
19. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (4)
Score is 30%~50%.
20. according to the method for claim 1, it is characterised in that: the matter of furfural aqueous solution and solution C described in step (4)
Amount is than being 3~5.
21. according to the method for claim 1, it is characterised in that: solution C described in step (4) and furfural aqueous solution it is total
The mass ratio for the reduction rear catalyst precursor B that quality and step (3) obtain is 3~6.
22. according to the method for claim 1, it is characterised in that: the second active component presoma is inclined described in step (5)
Ammonium vanadate and/or vanadic sulfate.
23. according to method described in claims 1 or 22, it is characterised in that: the second active component presoma described in step (5)
For ammonium metavanadate.
24. according to the method for claim 1, it is characterised in that: in solution D described in step (5), before the second active component
Driving contained vanadium in body, the mass fraction in solution D is 0.1%~1% based on the element, and water soluble polymer is in solution D
Mass fraction be 3~6 times of V element mass fraction.
25. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (6)
The mass ratio of quality and water soluble polymer is 2~4.
26. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (6)
It is 10%~20%.
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