CN106944088B - A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane - Google Patents
A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane, 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 B first, then reduction treatment is carried out to catalyst precarsor B, 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 B, it is reacted after solution D 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 propylene.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst for preparing propene by oxidative dehydrogenation of propane, more particularly, to a kind of propane oxygen
The preparation method of fluidized dehydrogenation propylene supported vanadium-based catalyst.
Background technique
Propylene is a kind of particularly important Organic Chemicals, be widely used to generate polypropylene, polyacrylonitrile, phenol,
The important chemical products of the series such as oxo alcohol, propylene oxide, methacrylaldehyde and acrylic acid.
Currently, propylene is mainly produced by petroleum catalytic cracking, propane catalytic dehydrogenation.The production of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane
Control of the process by thermodynamical equilibrium, severe reaction conditions, and exist because carbon distribution leads to rapid catalyst deactivation.And
Oxidative dehydrogenation of propane is a kind of new way for preparing propylene, compared with catalytic dehydrogenation processes, can overcome the limit of thermodynamical equilibrium
System, carries out, no carbon distribution, catalyst is not required to frequent regeneration at a lower temperature.
The research of catalyst for preparing propene by oxidative dehydrogenation of propane system is quite deep.For the reported height of goal response
Performance catalyst system mainly includes vanadium-based catalyst systems (V-Mg-O, barium oxide of load etc.) and catalyst with base of molybdenum system
(Mo-Mg-O, Ni-Mo-O etc.).CN 1396146 discloses one kind using mesoporous molecular sieve SBA-15 as carrier, using V as active group
The loaded catalyst divided, the conversion of propane at 600 DEG C are 50%, and the selectivity of propylene is 72% at this time, yield 36%.
CN 1073893A discloses the composite catalyst of a kind of fluoride containing Rare-Earth Ce and oxide, when reaction temperature is 500 DEG C
When, conversion of propane 53.4%, the selectivity of propylene is 67.5% at this time, and the yield of propylene is 36%.
And (this fast reaction is typically at mass transfer control for preparing propene by oxidative dehydrogenation of propane reaction or a fast reaction
Carried out under conditions of system), reactant reacts while reaching catalyst external surface to be completed, thus the interior table of catalyst
Less in face of goal response contribution, this has resulted in lower metal utilization in carrier duct, increases catalyst cost, together
When can also accelerate the deep oxidation of product.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of catalyst for preparing propene by oxidative dehydrogenation of propane
Preparation method, the catalyst of this method preparation have the characteristics that low in cost, metal component utilization rate is high and selectivity is good.
The present invention provides a kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane, 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, the second active group
It is divided into V, the first auxiliary agent is W, and the second auxiliary agent is one or more of Mo, Co, Mg, Fe, Ce or La, and preferably Mo and Co are carried
Body is any one of aluminium oxide, silica, SBA-15；It is with the percentage that each element quality in catalyst accounts for catalyst quality
Benchmark, the content of the first active component Ni are 1wt%~5wt%, and the content of the second active component V is 1wt%~15wt%, preferably
5wt%~10wt%, the content of the first auxiliary agent are 1wt%~3wt%, and the content of the second auxiliary agent is 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 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 catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, active component forerunner described in step (1)
Body is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；The first auxiliary agent presoma
For the soluble-salt of tungstenic, it is specifically as follows ammonium tungstate and/or ammonium metatungstate；In the solution A, the first active component is with element
Meter, mass fraction in solution A are 1%~7%, the first adjuvant component based on the element, the mass fraction in solution A is 1%~
5%。
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, dipping described in step (2) is to wait bodies
Product dipping, dip time are 1~3h；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, is done
The dry 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 catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, carrier described in step (2) is oxidation
Any one of aluminium, silica, SBA-15；The carrier can use commercially available product, can also be by side well known in the art
Method preparation；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt, load
Tungsten is 1wt%~3wt% of final catalyst in terms of element wt.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, reducing atmosphere described in step (3) is
The mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specifically
Reduction treatment process is as follows: catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then pass to hydrogen or hydrogen with
The mixed gas of 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 catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, before the second auxiliary agent described in step (4)
Drive body is ammonium molybdate, in cobalt nitrate, cobaltous sulfate, cobalt chloride, magnesium nitrate, magnesium chloride, ferric nitrate, ferric sulfate, cerous nitrate, lanthanum nitrate
One or more, preferably ammonium molybdate and cobalt nitrate；The mass fraction of furfural is 30%~50% in the furfural aqueous solution；Step
Suddenly furfural aqueous solution described in (4) and the mass ratio of solution C are 3 ~ 5, the gross mass and step of the solution C and furfural aqueous solution
(3) mass ratio of the reduction rear catalyst precursor B obtained is 3~6.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, water soluble polymer described in step (5)
Polymer is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；Described
Two active component presomas are ammonium metavanadate and/or vanadic sulfate, preferably ammonium metavanadate；In the solution D, the second active group
The mass fraction in solution D is 0.1%~1.5% to contained vanadium based on the element in point presoma, and water soluble polymer exists
Mass fraction in solution D is 3~6 times of V element mass fraction.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, dehydrated alcohol is added described in (6) in step
Or the quality of citric acid and the mass ratio of water soluble polymer are 2 ~ 4；The mass fraction of the aqueous citric acid solution is
10%~20%.
The catalyst of the method for the present invention preparation is reacted applied to preparing propene by oxidative dehydrogenation of propane, preferable process conditions are as follows:
The composition C of unstripped gas3H8/O2Molar ratio is 1~3, can contain Ar, N in unstripped gas2Or the dilution property gas such as He, unstripped gas are empty
3000~9000mLg of speedcat -1·h-1, reaction pressure is normal pressure, and reaction temperature is 400~600 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
Catalyst for preparing propene by oxidative dehydrogenation of propane.In the present invention, pre-soaked a part of active metal adds hydrogen to carry out furfural water phase
Reaction.Active metal predecessor and water soluble polymer is added simultaneously in the system of furfural hydrogenation, on the one hand utilizes
Furfural hydrogenation product hinders active metal to the diffusion inside catalyst granules；On the other hand, using active metal predecessor and
Coordination between water soluble polymer reduces concentration of the active metallic ion inside and outside catalyst granules in solution
Difference slows down active metal to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both reduces
Metal consumption, and improve the selectivity of propylene.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, prepares work
Skill 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: oxidative dehydrogenation of propane reaction carries out on atmospheric fixed bed micro-reaction equipment, catalyst loading
0.2g, 500 DEG C of reaction temperature, reaction gas forms C3H8/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 13mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.3g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, 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, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；7.2g polyethylene glycol, 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
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 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 2.4%Ni, 6.3%V, 1.3%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 13mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.3g silica support (Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter
0.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, 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, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；7.2g polyethylene glycol, 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
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 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 2.6%Ni, 6.6%V, 1.5%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 13mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.3gSBA-15 carrier (Kong Rongwei 1.23mL/g, specific surface area 701m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, 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, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；7.2g polyethylene glycol, 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
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 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 2.8%Ni, 6.9%V, 1.4%W, and the catalyst of 1.2%Mo is denoted as C-3.
Embodiment 4
Weigh 0.99g nickel nitrate, 0.28g ammonium tungstate is dissolved in 16mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 17.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa
(absolute pressure), recovery time 4h；0.99g cobalt nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；4.5g polyethylene glycol, 2.3g 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 13.5g 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 0.8%Ni, 3.7%V, 0.6%W, and the catalyst of 0.4%Co 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 13.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 5% of final catalyst, and the W of load is the 3% of final catalyst in terms of element wt；Catalyst precarsor B
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa
(absolute pressure), recovery time 4h；6.41g magnesium nitrate is dissolved in 15mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；9g polyethylene glycol, 4.59g 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 27g 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 4.1%Ni, 8.2%V, 2.4%W, and the catalyst of 1.8%Mg is denoted as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 13mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.3g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa
(absolute pressure), recovery time 4h；2.86g ferric nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 3 times of quality are obtained
It measures the furfural aqueous solution that score is 30% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；7.2g polyvinylpyrrolidone (k30), 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；
Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, 150
2h is reacted at DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the lemon that 147g mass fraction is 15% is added
Lemon 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 is burnt, obtaining quality based on the element and accounting for catalyst percentage composition is 2.6%Ni, 6.5%V, 1.5%W, the catalyst of 1.3%Fe, note
For C-6.
Embodiment 7
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate is dissolved in 13mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, 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
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa
(absolute pressure), recovery time 4h；1.24g cerous nitrate is dissolved in 15mL deionized water, solution C, and the matter with its 5 times of quality are obtained
It measures the furfural aqueous solution that score is 50% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；7.2g polyvinyl alcohol, 3.67g ammonium metavanadate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
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 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 2.7%Ni, 6.6%V, 1.6%W, and the catalyst of 1.2%Ce is denoted as C-7.
Comparative example
2.97g nickel nitrate, 0.55g ammonium tungstate, 0.74g ammonium molybdate and 3.67g ammonium metavanadate is weighed to be dissolved in deionized water,
Aqueous solution is made；Being carried on 15.3g 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 2.6%Ni, 7.2%V, 1.4%W, and the catalyst of 1.6%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 (27)
1. a kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane, the catalyst includes 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, and first helps
Agent is W, and the second auxiliary agent is one or more of Mo, Co, Mg, Fe, Ce or La, and carrier is aluminium oxide, in silica, SBA-15
It is any；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of the first active component Ni
For 1wt%~5wt%, the content of the second active component V is 1wt%~15wt%, and the content of the first auxiliary agent is 1wt%~3wt%, second
The content of auxiliary agent is 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 Co.
3. according to the method for claim 1, it is characterised in that: the content of the second active component V is 5wt%~10wt%.
4. 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.
5. according to method described in claim 1 or 4, it is characterised in that: the first active component presoma described in step (1) is
Nickel nitrate.
6. according to the method for claim 1, it is characterised in that: the first auxiliary agent presoma described in step (1) is tungstenic
Soluble-salt.
7. according to method described in claim 1 or 6, it is characterised in that: the first auxiliary agent presoma described in step (1) is wolframic acid
Ammonium and/or ammonium metatungstate.
8. 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%~7%, and based on the element, the mass fraction in solution A is the first adjuvant component
1%~5%.
9. according to the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10~90 DEG C, aging
Time be 1~for 24 hours.
10. according to method described in claim 1 or 9, it is characterised in that: aging temperature described in step (2) is 20~60 DEG C,
Ageing time is 4~12h.
11. 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.
12. according to method described in claim 1 or 11, 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.
13. 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.
14. according to method described in claim 1 or 13, 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.
15. 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%.
16. 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.
17. 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, cobalt nitrate, cobaltous sulfate, cobalt chloride, magnesium nitrate, magnesium chloride, ferric nitrate, ferric sulfate, cerous nitrate, lanthanum nitrate are more
Kind.
18. according to method described in claim 1 or 17, it is characterised in that: the second auxiliary agent presoma described in step (4) is
Ammonium molybdate and cobalt nitrate.
19. according to the method for claim 1, it is characterised in that: the mass fraction of furfural is 30% in the furfural aqueous solution
~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 be ammonium metavanadate and/
Or vanadic sulfate.
23. according to method described in claims 1 or 22, it is characterised in that: the second active component presoma is metavanadic acid
Ammonium.
24. according to the method for claim 1, it is characterised in that: in the solution D, institute in the second active component presoma
Containing vanadium, the mass fraction in solution D is 0.1%~1.5% based on the element.
25. according to the method for claim 1, it is characterised in that: quality of the water soluble polymer in solution D point
Number is 3~6 times of V element mass fraction.
26. 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.
27. 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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Citations (5)
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|---|---|---|---|---|
| EP1516666A1 (en) * | 2000-06-27 | 2005-03-23 | Saudi Basic Industries Corporation | Catalysts for production of olefins by oxidative dehydrogenation |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| CN101309889A (en) * | 2005-11-24 | 2008-11-19 | 巴斯夫欧洲公司 | Process for preparing acrolein or acrylic acid or a mixture thereof from propane |
| CN101543781A (en) * | 2009-05-04 | 2009-09-30 | 厦门大学 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
| CN102019178A (en) * | 2009-09-14 | 2011-04-20 | 卓润生 | Propane dehydrogenation to propylene catalyst and preparation and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8609568B2 (en) * | 2010-10-04 | 2013-12-17 | King Fahd University Of Petroleum And Minerals | Catalyst for oxidative dehydrogenation of propane to propylene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1516666A1 (en) * | 2000-06-27 | 2005-03-23 | Saudi Basic Industries Corporation | Catalysts for production of olefins by oxidative dehydrogenation |
| CN101309889A (en) * | 2005-11-24 | 2008-11-19 | 巴斯夫欧洲公司 | Process for preparing acrolein or acrylic acid or a mixture thereof from propane |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| CN101543781A (en) * | 2009-05-04 | 2009-09-30 | 厦门大学 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
| CN102019178A (en) * | 2009-09-14 | 2011-04-20 | 卓润生 | Propane dehydrogenation to propylene catalyst and preparation and applications thereof |
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