CN109731594A - A kind of preparation and application of vanadyl phosphate catalyst - Google Patents
A kind of preparation and application of vanadyl phosphate catalyst Download PDFInfo
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Abstract
The invention belongs to catalysis technical fields, relate generally to a kind of preparation method of vanadyl phosphate catalyst comprising following steps: (1) mixing vanadium source, benzyl alcohol, the monohydric alcohol of C3~C8 and Heat Conduction Material, obtain mixture, react；(2) reaction product obtained by step (1) is mixed with phosphorus source, is warming up to 100 DEG C~200 DEG C, the reaction was continued, obtains vanadyl phosphate presoma；(3) it roasts, obtains the vanadyl phosphate catalyst；Wherein, the Heat Conduction Material is at least one of SiC, graphite, graphene and carbon nanotube.And provide application of the obtained vanadium-phosphor oxide catalyst in normal butane selective oxidation cis-butenedioic anhydride.This method adds Heat Conduction Material during the preparation process, can effectively realize heat transfer, solve the problems, such as hot-spot；The mutually uniform and stable formation of activity is effectively facilitated simultaneously, is promoted catalyst thermally equivalent during the reaction, is improved the performance of catalyst.
Description
Technical field
The present invention relates to chemical catalysis fields, relate generally to a kind of preparation method and application of vanadium-phosphor oxide catalyst.
Background technique
Maleic anhydride is called maleic anhydride, abbreviation cis-butenedioic anhydride, is a kind of economically very important organic chemical industry and essence
The third-largest acid anhydrides of phthalic anhydride and aceticanhydride is only second in refinement work intermediate product and anhydride product.It is widely used in
Unsaturated polyester resin, gamma-butyrolacton, 1,4-butanediol, tetrahydro are barked the production of numerous chemical products such as mutter, and market extensively and needs
Ask vigorous.And the requirement with the country to environment is continuously improved.It is right in raw material and production process for current benzene oxidatoin method
The pollution of environment and the status of cost.How benzene oxidatoin is improved into maleic anhydride production technique to improve maleic anhydride yield and quality
There is great meaning to the development of entire chemical industry.Normal butane fixed bed preparing cis-butenedioic anhydride by oxidation is low by feat of raw material (normal butane)
The features such as honest and clean, atom utilization is high and good product quality, is rapidly developed.Currently, normal butane fixed bed preparing cis-butenedioic anhydride by oxidation
Either catalyst preparation or production technology have all had evolved to a more mature stage.It is matched and industrial
Upper widely applied catalyst is then the catalyst based on vanadium phosphorus oxygen (VPO) series.The preparation of vpo catalyst mainly uses organic
Xiang Fa restores 5 valence vanadium with organic reducing medium, and using the combination of primary or secondary aliphatic alcohol or aromatic alcohols, such as isobutanol
And benzyl alcohol.Isobutanol is the organic reducing agent at most used, because optimum solvent and redox character can be combined with it,
Therefore be conducive to complete redox reaction, form tetravalence vanadium, vanadyl acid orthophosphates can be formed after phosphatase reaction is added
(vanadyl acid orthophosphate) semihydrate (VO) HPO4·0.5H2O, then further heat treatment is undergone with can be with
Form catalyst.
According to the C of the propositions such as Ballarini4H10+3.5O2→C4H2O3+4H2O△H0 298K=-1268kJ/mol, normal butane
Oxidation reaction is the reaction of a strongly exothermic process, therefore catalyst is easy to because of uneven heating and part during the reaction
The stability and selectivity of catalyst are overheated and affected, catalyst hot-spot is industrially easy to and is sintered.
Summary of the invention
For the above-mentioned problems in the prior art, the present invention provide a kind of vanadyl phosphate catalyst preparation method and
Using.Method of the invention adds Heat Conduction Material during preparing vanadyl phosphate catalyst, both can be in activation process
The mutually uniform and stable formation of activity is effectively facilitated, and promotes catalyst thermally equivalent during the reaction, is conducive to improve catalysis
Agent performance.There is good selectivity by catalyst prepared by the method, preparation method is simple, and production cost is low, is suitble to extensive
Preparation.
The present invention provides a kind of preparation method of vanadyl phosphate catalyst comprising following steps:
(1) vanadium source, benzyl alcohol, the monohydric alcohol of C3~C8 and Heat Conduction Material are mixed, obtains mixture, reacted；
(2) reaction product obtained by step (1) is mixed with phosphorus source, is warming up to 100 DEG C~200 DEG C, the reaction was continued, obtains phosphorus
Sour vanadyl presoma；
(3) it roasts, obtains the vanadyl phosphate catalyst；
Wherein, the Heat Conduction Material is at least one of SiC, graphite, graphene and carbon nanotube.
The present invention also provides the vanadyl phosphate catalyst of above method acquisition in normal butane selective oxidation cis-butenedioic anhydride
Using.
The preparation method and application of provided by the invention kind of vanadyl phosphate catalyst adds Heat Conduction Material in preparation process,
It can effectively realize heat transfer, solve the problems, such as whether macroscopic view or it is microcosmic on reflect existing hot-spot；In addition, heat conduction material
Material is added can not only effectively facilitate the mutually uniform and stable formation of activity in activation process, but also promote catalyst equal during the reaction
It is even heated, be conducive to improve catalyst performance.Compared to traditional impregnating metal method, method of the invention simplifies the system of catalyst
Standby process, it is at low cost, it is easy to operate, it is suitble to industrialized production.Moreover, Heat Conduction Material can be effective with the progress of catalysis reaction
The excessive oxidation for inhibiting catalyst, reduces the generation of by-product.Meanwhile thermal conducting material SiC, graphite, graphene and carbon nanotube
The advantageous generation for promoting intermediate product, inhibits the generation of side reaction, improves the selectivity of catalyst.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the catalyst precursor that the embodiment of the present invention 2 obtains；
Fig. 2 is the scanning electron microscope (SEM) photograph for the catalyst precursor that the embodiment of the present invention 5 obtains；
Fig. 3 is the embodiment of the present invention 2, and the X of the vanadyl phosphate catalyst for the activation that embodiment 5 and comparative example 1 obtain is penetrated
Ray diffraction diagram；
Fig. 4 is the cyclic voltammogram for the catalyst that the embodiment of the present invention 5 and comparative example 1 obtain.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of preparation method of vanadyl phosphate catalyst comprising following steps:
(1) vanadium source, benzyl alcohol, the monohydric alcohol of C3~C8 and Heat Conduction Material are mixed, obtains mixture, reacted；
(2) reaction product obtained by step (1) is mixed with phosphorus source, is warming up to 100 DEG C~200 DEG C, the reaction was continued, obtains phosphorus
Sour vanadyl presoma；
(3) it roasts, obtains the vanadyl phosphate catalyst；
Wherein, the Heat Conduction Material is at least one of SiC, graphite, graphene and carbon nanotube.
Specifically, the volume ratio of the monohydric alcohol of the C3~C8 and benzyl alcohol is (3~5): 1, such as 3:1,4:1,5:1
Deng.Preferably, in the mixture, the concentration in vanadium source is 0.02g/mL~0.12g/mL, such as 0.02g/mL, 0.04g/mL,
0.06g/mL, 0.07g/mL, 0.08g/mL, 0.09g/mL, 0.1g/mL or 0.12g/mL etc..If concentration is lower than 0.02g/mL, meeting
Cause vanadium phosphorus than reducing, active crystal phase can not be formed；If concentration is higher than 0.12g/mL, it will form more miscellaneous phase, cause to select
Property reduce.
The Heat Conduction Material and the mass ratio in vanadium source are 0.001~0.5, it is preferable that the mass ratio of Heat Conduction Material and vanadium source
It is 0.01~0.05, Heat Conduction Material is excessively few not to have corresponding effect then, if excessively then diluting active component and covering phase
The active crystal face answered, the system of the Heat Conduction Materials of the carbon elements of thermal coefficient larger (at least more than 100W/mK) in vanadyl phosphate
Have great importance during standby.Wherein, graphite and carbon nanotube effect are relatively prominent.It is highly preferred that the Heat Conduction Material
For graphite, VPO is grown on graphite in synthesis process, since the lamellar structure and broken edge of graphite promote pyrophosphoric acid
The exposure of 020 crystal face of vanadyl, meanwhile, graphite can promote butane to generate butylene intermediate product, reduce the activation energy of reaction conversion.
It is highly preferred that the graphite and the mass ratio in vanadium source are 0.02~0.1.Carbon material, high thermal conductivity coefficient and electron transmission, for
The dehydrogenation of alkene can be catalyzed the rate determining step of dehydrating alkanes and butane oxidation cis-butenedioic anhydride especially containing the carbon of functional group
Suddenly.
Specifically, described " monohydric alcohol of C3~C8 " refers to: any one in the monohydric alcohol that carbon atom number is 3~8 or two
The combination of kind, such as may is that propyl alcohol, isobutanol, n-butanol, amylalcohol, hexanol, enanthol, octanol, the group of propyl alcohol and isobutanol
Close, the combination of propyl alcohol and amylalcohol, the combination of n-butanol and hexanol, the combination of n-butanol and octanol, propyl alcohol, isobutanol, amylalcohol and
The combination etc. of octanol, preferably isobutanol.Step (1) the vanadium source includes at least one of vanadic salts or barium oxide, preferably
Including V2O5、NH4VO3、V2O4And V2O3At least one of.But be not limited to the above-mentioned vanadium source enumerated, other it is commonly used in the art can
The vanadium source for reaching same effect can also be used for the present invention, preferably V2O5.Preferably, the temperature of step (1) described reaction is 100
DEG C~180 DEG C, such as 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 165 DEG C, 170 DEG C or
180 DEG C etc., preferably 130 DEG C~140 DEG C.Preferably, the time of step (1) described reaction be 2h~8h, such as 2h, 3h, 4h,
5h, 5.5h, 6h, 7h or 8h etc., preferably 3h~5h.Preferably, after step (1) described reaction, 30 DEG C~80 DEG C are cooled to, example
Such as 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C.
As the optimal technical scheme of the method for the invention, the method also includes: in the process that Heat Conduction Material is added
Any one middle being added in metal oxide or metal salt or two kinds of combination.
Preferably, the metallic element in the metal oxide or metal salt independently selected from Fe, Cu, Co, Mn, Ni, Zr,
In Zn, Ce or Mo any one or at least two combination, preferably Zr and Mo.
Preferably, the metallic element and the atomic molar of vanadium ratio be 0.0005~0.035, such as 0.0005,
0.0008,0.001,0.002,0.003,0.005,0.01,0.015,0.02,0.03 or 0.035 etc..
Preferably, the molar ratio of the phosphorus in phosphorus source and the vanadium in vanadium source is (0.8~1.5): 1, such as 0.8:1,
0.9:1,1:1,1.1:1,1.2:1,1.3:1,1.4:1 or 1.5:1 etc., preferably (0.9~1.2): 1.If molar ratio is less than
0.8:1, will lead to phosphorus in catalyst system can comparatively fast be lost, and catalyst life reduces；If molar ratio be greater than 1.5:1, will lead to compared with
More miscellaneous phases are formed.
As the optimal technical scheme of the method for the invention, step (1) the mixed mode are as follows: be first placed in vanadium source
In container, the mixed liquor of benzyl alcohol and the monohydric alcohol of C3~C8 is then added.
Preferably, step (2) phosphorus source includes at least one of phosphoric acid, phosphate and phosphorous oxides, is preferably included
Any one in the phosphoric acid (such as commercially available concentrated phosphoric acid) of mass fraction 85%, phosphate or phosphoric acid oxide or at least two
Combination further preferably includes the phosphoric acid, (NH of mass fraction 85%4)3PO4、(NH4)2HPO4、NH4H2PO4、P2O5Or P2O3In
Any one or at least two combination.But be not limited to the above-mentioned phosphorus source enumerated, other are commonly used in the art can reach it is identical
The phosphorus source of effect can also be used for the present invention.
Preferably, step (2) is warming up to 100 DEG C~150 DEG C, such as 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C etc..
Preferably, step (2) time that the reaction was continued is 10h~for 24 hours, for example, 10h, 12h, 13h, 15h, 17h, 18h, 20h,
21h, 22h, 23h or for 24 hours etc..Preferably, step (2) step for after the completion of the reaction was continued, being filtered, washing and drying
Suddenly.
Preferably, the atmosphere of step (3) described roasting be nitrogen atmosphere or normal butane and air mixed atmosphere or
The volume ratio of the mixed atmosphere of person's normal butane, oxygen and nitrogen, the normal butane and air is preferably (0.8~1.8): 100；Institute
The volume ratio for stating normal butane, oxygen and nitrogen is (0.8~1.8): (10~25): (75~85).Preferably, step (3) is described
The temperature of roasting be 350 DEG C~550 DEG C, such as 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 430 DEG C, 450 DEG C,
475 DEG C, 500 DEG C, 515 DEG C, 530 DEG C or 550 DEG C etc..Preferably, the time of step (3) described roasting is 10h~for 24 hours, such as
10h, 12h, 13.5h, 15h, 16h, 18h, 20h, 22h or for 24 hours etc..
For the ease of the effect assessment of catalyst, calcination steps of the present invention can be after vanadyl phosphate forerunner be body formed
It carries out, catalyst effect evaluation is directly used in after roasting；Reshaping can also be first roasted, catalyst effect evaluation is subsequently used for.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps:
(1) first vanadic anhydride is placed in container, benzyl alcohol, isobutanol and Heat Conduction Material mixing is then added, obtains
Mixture is subsequently cooled to 30~80 DEG C in 130 DEG C~140 DEG C reaction 3h~5h, wherein the Heat Conduction Material is SiC, stone
At least one of ink, graphene, carbon nanotube；
(2) phosphorus source is added into container again, is warming up to 100 DEG C~150 DEG C, the reaction was continued 10h~for 24 hours, it is filtered, washed simultaneously
It is dry, obtain vanadyl phosphate presoma；
(3) in the mixing of nitrogen atmosphere or the mixed atmosphere or normal butane, oxygen and nitrogen of normal butane and air
In atmosphere, 350 DEG C~550 DEG C of roasting 10h~are realized in-situ activation for 24 hours, obtain vanadyl phosphate catalyst；
The Heat Conduction Material and the mass ratio in vanadium source are 0.001~0.5, and the volume ratio of the isopropanol and benzyl alcohol is (3
~5): 1；Isobutanol and benzyl alcohol and vanadic anhydride and phosphatizing, facilitate to stablize 4 valence of vanadium and guarantor in the proportional region
The formation for demonstrate,proving active phase precursor, to improve the activity of catalyst.In the mixture, the concentration of vanadic anhydride is 0.02g/
ML~0.12g/mL；The molar ratio of phosphorus in phosphorus source and the vanadium in vanadium source is (0.9~1.2): 1.
The present invention mentions the preparation method vanadyl phosphate catalyst obtained of the also above-mentioned vanadyl phosphate catalyst of embodiment
Application in normal butane selective oxidation cis-butenedioic anhydride.
Preferably, the reaction condition of the normal butane selective oxidation cis-butenedioic anhydride are as follows: 400 DEG C~550 DEG C of reaction temperature, pressure
Power is 0.1MPa~0.3MPa, and normal butane gaseous mixture air speed is 1000h-1~3000h-1, concentration of n-butane be 1.3wt%~
1.8wt%.
The preparation method of vanadium-phosphor oxide catalyst is illustrated below by way of specific embodiment.Chemical combination in following example
Object can be directly prepared according to existing method respectively, certainly, can also directly be bought from the market in other embodiments, and
It is without being limited thereto.
Embodiment 1:
Weigh V2O520g is placed in the flask of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
The SiC of 4.4g is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being warming up to 136 DEG C later.It is cooling
It to room temperature, refilters, with ethanol washing, obtains sky blue sediment after suction filtration, be dried overnight, obtain in 120 DEG C of air
Catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40 mesh to urge
Catalyst particles.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2 DEG C/
The heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst chief active
It is mutually mutually to be made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence becomes C with unstripped gas group4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure
0.12MPa, gas space velocity 2000h-1Under conditions of react, reaction end gas is obtained normal butane and is turned by gas-chromatography on-line analysis
Rate is 72%, and the selectivity of cis-butenedioic anhydride is 73%, yield of maleic anhydride 52.6%.
Embodiment 2:
Weigh V2O520g is placed in the flask of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
The SiC of 2.2g is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being warming up to 136 DEG C later.It is cooling
To room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment, product is dried overnight in 120 DEG C of air, obtains
To catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40 mesh
Catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2 DEG C/
The heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst chief active
It is mutually mutually to be made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
90%, the selectivity of cis-butenedioic anhydride is 72%, yield of maleic anhydride 64.8%.
Embodiment 3:
Weigh V2O520g is placed in the flask of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
The SiC of 1.1g is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being warming up to 136 DEG C later.It is cooling
To room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment, product is dried overnight in 120 DEG C of air, obtains
To catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40 mesh
Catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2 DEG C/
The heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst chief active
It is mutually mutually to be made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 410 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
85%, the selectivity of cis-butenedioic anhydride is 63%, yield of maleic anhydride 53.6%.
Embodiment 4:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
2.64g graphite is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being just warming up to 136 DEG C later.It is cold
But to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment, product is dried overnight in 120 DEG C of air,
Obtain catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40
Mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2
DEG C/heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst is mainly lived
Property is mutually made of Vanadyl pyrophosphate object.
The vanadium-phosphor oxide catalyst of activation is crushed in the pressure lower sheeting of 15MPa, and sieve takes 20-40 mesh catalyst granules, is weighed
4.5g, is placed in the fixed bed reactors that internal diameter is 14mm and carries out catalyst performance evaluation, and unstripped gas group becomes C4H10/O2/N2=
1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa, gas space velocity 2000h-1Under conditions of it is anti-
It answers, for reaction end gas by gas-chromatography on-line analysis, obtaining n-butane conversion is 81.4%, and the selectivity of cis-butenedioic anhydride is 75%,
Yield of maleic anhydride is 61.1%.
Embodiment 5:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
1.32g graphite is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being just warming up to 136 DEG C later.It is cold
But to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment.Collection is dried overnight in 120 DEG C of air,
Obtain catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40
Mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2
DEG C/heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst is mainly lived
Property is mutually made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
92%, the selectivity of cis-butenedioic anhydride is 72%, yield of maleic anhydride 66.2%.
Embodiment 6:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50ml benzyl alcohol is added, with
0.66g graphite is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, at the uniform velocity dripping later after flowing back 3 hours under the conditions of 136 DEG C
Adding mass fraction is 85% H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being just warming up to 136 DEG C later.It is cold
But to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment.Collection is dried overnight in 120 DEG C of air,
Obtain catalyst precursor.Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40
Mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with 2
DEG C/heating rate of min rises to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst is mainly lived
Property is mutually made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
93%, the selectivity of cis-butenedioic anhydride is 63%, yield of maleic anhydride 58.6%.
Embodiment 7:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
2.64g carbon nanotube is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, even later after flowing back 3 hours under the conditions of 136 DEG C
The H that mass fraction is 85% is added dropwise in speed3PO415.5mL and stir, it is 16 small to continue reflux at a temperature of being just warming up to 136 DEG C later
When.Be cooled to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment.It collects in 120 DEG C of air overnight
It is dry, obtain catalyst precursor.Obtained catalyst precursor powder is crushed, sieve takes in the pressure lower sheeting of 20MPa again
20-40 mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room
Temperature rises to 430 DEG C of in-situ activations 12 hours with the heating rate of 2 DEG C/min, the vanadium-phosphor oxide catalyst activated.The catalyst
Chief active is mutually made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
83%, the selectivity of cis-butenedioic anhydride is 76%, yield of maleic anhydride 63.1%.
Embodiment 8:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
1.32g carbon nanotube is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, even later after flowing back 3 hours under the conditions of 136 DEG C
The H that mass fraction is 85% is added dropwise in speed3PO415.5mL is simultaneously stirred, and it is small to continue reflux 16 at a temperature of being just warming up to 136 DEG C later
When.Be cooled to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment.It collects in 120 DEG C of air overnight
It is dry, obtain catalyst precursor.Obtained catalyst precursor powder is crushed, sieve takes in the pressure lower sheeting of 20MPa again
20-40 mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room
Temperature rises to 430 DEG C of in-situ activations 12 hours with the heating rate of 2 DEG C/min, the vanadium-phosphor oxide catalyst activated.The catalyst
Chief active is mutually made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
88%, the selectivity of cis-butenedioic anhydride is 73%, yield of maleic anhydride 64.2%.
Embodiment 9:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, with
0.66g carbon nanotube is added afterwards, is uniformly mixed, is cooled to 90 DEG C hereinafter, even later after flowing back 3 hours under the conditions of 136 DEG C
The H that mass fraction is 85% is added dropwise in speed3PO415.5mL is simultaneously stirred, and it is small to continue reflux 16 at a temperature of being just warming up to 136 DEG C later
When.Be cooled to room temperature, refilter, filtered with ethanol washing after obtain sky blue sediment.It collects in 120 DEG C of air overnight
It is dry, obtain catalyst precursor.Obtained catalyst precursor powder is crushed, sieve takes in the pressure lower sheeting of 20MPa again
20-40 mesh catalyst granules.Later by catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room
Temperature rises to 430 DEG C of in-situ activations 12 hours with the heating rate of 2 DEG C/min, the vanadium-phosphor oxide catalyst activated.The catalyst
Chief active is mutually made of Vanadyl pyrophosphate object.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure
0.12MPa, gas space velocity 2000h-1Under conditions of react, reaction end gas is obtained normal butane and is turned by gas-chromatography on-line analysis
Rate is 90%, and the selectivity of cis-butenedioic anhydride is 61%, yield of maleic anhydride 54.9%.
Comparative example 1:
Weigh V2O520g is placed in the container of 500mL, and the isobutanol of 200mL and the mixed liquor of 50mL benzyl alcohol is added, stirs
It mixes uniformly mixed, 90 DEG C is cooled to after flowing back 3 hours under the conditions of 136 DEG C hereinafter, it is 85% that mass fraction is at the uniform velocity added dropwise later
H3PO415.5mL is simultaneously stirred, and continues reflux 16 hours at a temperature of being just warming up to 136 DEG C later.It is cooled to room temperature, refilters, uses
Ethanol washing obtains sky blue sediment after filtering.Collection is dried overnight in 120 DEG C of air, obtains catalyst precursor.
Obtained catalyst precursor powder is crushed in the pressure lower sheeting of 20MPa again, sieve takes 20-40 mesh catalyst granules.Later
By catalyst granules in reaction atmosphere (C4H10/O2/N2=1.4/19.5/79.1) by room temperature with the heating rate of 2 DEG C/min
Rise to 430 DEG C of in-situ activations 12 hours, the vanadium-phosphor oxide catalyst activated.The catalyst chief active is mutually by pyrophosphoric acid oxygen
Vanadium object is mutually constituted.
Catalyst 4.5g after weighing activation is placed in progress catalyst performance in the fixed bed reactors that internal diameter is 14mm and comments
Valence, unstripped gas group become C4H10/O2/N2=1.4/19.5/79.1 (v/v/v), 420 DEG C of reaction temperature, reaction pressure 0.12MPa,
Gas space velocity 2000h-1Under conditions of react, by gas-chromatography on-line analysis, obtain n-butane conversion is reaction end gas
82%, the selectivity of cis-butenedioic anhydride is 56%, yield of maleic anhydride 45.9%.
Figure 4, it is seen that it is the vanadyl phosphate that embodiment 5 obtains that oxidation peak current and reduction peak current, which are incremented by degree,
Catalyst is greater than the vanadyl phosphate catalyst that comparative example 1 obtains, therefore, vanadyl phosphate catalyst V (IV) after doped graphite/
Redox reaction of V (V) electricity between is easier to occur.Do not have the anode peak of the vanadyl phosphate catalyst of graphite dopping-
0.537V, the anode peak of vanadyl phosphate catalyst of the cathode peak after -0.469V, doped graphite in -0.353V, cathode peak -
0.094V is said it can thus be seen that the redox peaks of vanadyl phosphate catalyst are mobile to high voltage direction after doped graphite
Vpo catalyst after bright doped graphite is easier to that electronics transfer occurs, and preferably, catalyst activity is also therefore more for electrode catalyst activity
It is high.The vanadyl phosphate of the preparation of Heat Conduction Material is not added with relative to the vanadyl phosphate catalyst obtained in embodiment from comparative example 1
From the point of view of, Heat Conduction Material is added can not only effectively facilitate the mutually uniform and stable formation of activity in activation process, but also during the reaction
Promote catalyst thermally equivalent, is conducive to improve catalyst performance, with the progress of catalysis reaction, Heat Conduction Material can effectively inhibit
The excessive oxidation of catalyst reduces the generation of by-product.Part thermal conducting material favorably promotes the generation of intermediate product simultaneously, inhibits
The generation of side reaction improves the selectivity of catalyst.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of preparation method of vanadyl phosphate catalyst, which is characterized in that described method includes following steps:
(1) vanadium source, benzyl alcohol, the monohydric alcohol of C3~C8 and Heat Conduction Material are mixed, obtains mixture, reacted；
(2) reaction product obtained by step (1) is mixed with phosphorus source, is warming up to 100 DEG C~200 DEG C, the reaction was continued, obtains phosphoric acid oxygen
Vanadium presoma；
(3) it roasts, obtains the vanadyl phosphate catalyst；
Wherein, the Heat Conduction Material is at least one of SiC, graphite, graphene and carbon nanotube.
2. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the Heat Conduction Material and vanadium source
Mass ratio is 0.001~0.5.
3. the method for vanadyl phosphate catalyst according to claim 1 or 2, which is characterized in that the Heat Conduction Material and vanadium
The mass ratio in source is 0.02~0.1.
4. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the Heat Conduction Material is graphite
And/or carbon nanotube.
5. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the concentration in the vanadium source is
The monohydric alcohol of 0.02g/mL~0.12g/mL, the C3~C8 and the volume ratio of benzyl alcohol are (3~5): 1.
6. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the vanadium source is V2O5, the C3
The monohydric alcohol of~C8 is isobutanol.
7. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the step (1) reaction
Temperature be 100 DEG C~180 DEG C, the step (2) is warming up to 100 DEG C~150 DEG C.
8. the method for vanadyl phosphate catalyst according to claim 1, which is characterized in that the atmosphere of step (3) described roasting
It encloses for the mixed atmosphere of the mixed atmosphere or normal butane of nitrogen atmosphere or normal butane and air, oxygen and nitrogen.
9. the vanadium-phosphor oxide catalyst that a kind of preparation method of vanadyl phosphate catalyst as described in claim 1~8 obtains is just
Application in n-Butane Selective Oxidation cis-butenedioic anhydride.
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| CN111701624A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Regeneration method and application of deactivated vanadium phosphorus oxide catalyst |
| CN112439436A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by benzene oxidation and preparation method thereof |
| CN113522329A (en) * | 2020-04-15 | 2021-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method and application thereof |
| CN114100623A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
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| CN112439436A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by benzene oxidation and preparation method thereof |
| CN113522329A (en) * | 2020-04-15 | 2021-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method and application thereof |
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| CN114100623A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
| CN114100623B (en) * | 2020-08-26 | 2023-12-08 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
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