CN106622316B - A kind of vanadium-phosphor oxide catalyst, preparation method and application - Google Patents
A kind of vanadium-phosphor oxide catalyst, preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of vanadium-phosphor oxide catalysts and preparation method thereof.In the vanadium-phosphor oxide catalyst (VO)2P2O7Its content is 80%~95% by volume, and it is the dual pore distribution of 10 ~ 20nm and 20 ~ 35nm that the vanadium-phosphor oxide catalyst, which has aperture, wherein the duct of 10 ~ 20nm accounts for total pore volume 29% ~ 36%, the duct of 20 ~ 35nm accounts for the 34% ~ 45% of total pore volume.The vanadium-phosphor oxide catalyst preparation method includes: ionic liquid I and II to be added in the synthesis process the sediment of generation is filtered, dries and is roasted after reaction, obtains vanadium-phosphor oxide catalyst presoma, then carries out activation molding and obtain catalyst.Vanadium-phosphor oxide catalyst made from the method for the present invention has dual pore distribution, and the catalyst being suitable as in preparing cis-anhydride by n-butane oxidation reaction, n-butane conversion is high, and Selectivity of maleic anhydride is good.
Description
Technical field
The present invention relates to a kind of vanadium-phosphor oxide catalyst and preparation method thereof, which is suitable as normal butane oxygen
Change the catalyst of cis-butenedioic anhydride reaction processed.
Background technique
Maleic anhydride abbreviation cis-butenedioic anhydride also known as maleic anhydride are a kind of important Organic Chemicals and fine chemistry industry
Product, is the third-largest acid anhydrides for being only second to phthalic anhydride and aceticanhydride in the world at present, and exploitation prospect is very wide.
Three kinds of basic lines of maleic anhydride production have: benzene oxidatoin method, butane oxidation method, butylene (C4Fraction) oxidizing process.With just
Butane is that raw material produces cis-butenedioic anhydride technology due to inexpensive with raw material, and environmental pollution is small, the low advantage of cis-butenedioic anhydride manufacturing cost, at present
Through the main route for becoming maleic anhydride production.Selective oxidation of n -butane cis-butenedioic anhydride is the currently the only lower alkanes for realizing industrial application
Hydrocarbon Selective Oxidation, catalyst are the key that technique, and vanadium phosphorus oxygen (VPO) catalyst is the most effective catalyst of the reaction.
Vpo catalyst is a kind of composite oxide catalysts with complicated microstructure, and each object is all mutually by forerunner
Body VOHPO4·0.5H2O is activated to be transformed, the brilliant looks and crystallite dimension of presoma directly affect catalyst brilliant looks and
Object phase composition.The catalytic activity and precursor preparation method of catalyst have much relations, and preparation process has catalytic performance non-
Often big influence.In order to improve the activity and selectivity of vanadium-phosphor oxide catalyst, improve the economic benefit of existing apparatus, people are to it
Preparation method has made intensive studies.
USP4,632,915 propose a kind of vanadium-phosphor oxide catalyst preparation method, in being stirred to react with reflux cooler
In kettle, cooling lower addition isobutanol, phosphoric acid (100%), vanadic anhydride, lithium chloride and iron powder, then it is passed through hydrogen chloride gas, so
Reflux is greater than 2.5 hours under conditions of 102 DEG C afterwards, obtains catalyst precursor, then passes through drying, roasts, and forms, activation
After prepare vanadium-phosphor oxide catalyst.The catalytic activity of the catalyst is high, butanes conversion > 78.1%, and cis-butenedioic anhydride molar yield is
54.5%。
CN1090224A proposes a kind of preparation method for improving vanadium-phosphor oxide catalyst performance, by vanadic anhydride and sulfuric acid
Zinc is placed in the there-necked flask of a belt stirrer and spherical reflux condenser, and the appropriate concentrated sulfuric acid is added and alcohols solvent is mixed
It closes, is heated to reflux 2 hours, phosphoric acid solution is then added dropwise, continue reflux 8 hours；The 4th component is added dropwise into bottle again or other are dilute
Earth metal compound or transistion metal compound flow back 5 hours, lake catalyst precursor blue are obtained after filtering.After molding
Carry out activation of catalyst and evaluation test using fixed-bed tube reactor: butanes conversion > 90%, cis-butenedioic anhydride molar yield are
62%。
[" influence of the addition auxiliary agent Mo to vpo catalyst cis-butenedioic anhydride catalytic performance ", Jiang great Lin etc., Inner Mongol petrochemical industry,
2006,9:25~27] a kind of preparation method of vpo catalyst is described in.By a certain amount of V2O5It is added to benzyl alcohol solvent
In, the metallic elements such as Mo, Zr, Cr, Co are added by certain atomic ratio, makees reducing agent with isobutanol, reacts 6h at a reflux temperature,
A certain amount of 85% H is added dropwise in the ratio of atomic ratio V:P=1:1.2 again3PO4, continue heating reaction 6h, obtain blackish green solution.
The solution is filtered, washed again, then the solution after evaporation is put into baking oven, in 110 DEG C of at a temperature of drying, can be obtained
Blackish green catalyst precursor.Precursor powder is the gaseous mixture of 1.5% normal butane and air in volume fraction after forming,
Activation air speed is 1500h-1, reaction temperature is after reacting activation 24 hours at 400 DEG C, to measure the yield of cis-butenedioic anhydride 60% or more.
In the above method, organic solvent is all introduced in the synthesis process, is inevitably introduced in the catalyst not
The impurity of benefit, and the solvent and reducing agent thermal stability that use are low, have the shortcomings that volatile, and being easy to produce largely toxic has
Harmful waste liquid, exhaust gas, cause environmental pollution.
Summary of the invention
For excessive organic solvent is used in the preparation of vanadium-phosphor oxide catalyst in the prior art, impurity is not only introduced, also
The deficiency for causing environmental pollution, the present invention provides a kind of vanadium-phosphor oxide catalysts and preparation method thereof.The vanadium phosphorus of this method preparation
VPO catalysts have the characteristics that dual pore distribution, use ionic liquid as solvent and reducing agent, reduce environmental pollution.
Technical purpose of the invention is achieved through the following technical solutions:
A kind of vanadium-phosphor oxide catalyst, in the vanadium-phosphor oxide catalyst (VO)2P2O7Its content is 80%~95% by volume,
It is the dual pore distribution of 10 ~ 20nm and 20 ~ 35nm that the vanadium-phosphor oxide catalyst, which has aperture, wherein the duct of 10 ~ 20nm accounts for
Total pore volume 29% ~ 36%, the duct of 20 ~ 35nm account for the 34% ~ 45% of total pore volume.
Further, in the vanadium-phosphor oxide catalyst molar ratio of phosphorus and vanadium be 0.85~1.35, preferably 0.95~
1.20, specific surface area is 42~64m20.04 ~ 0.1mL/g of/g, Kong Rongwei.
Further, in the vanadium-phosphor oxide catalyst (VO)2P2O7Its content is 85~90% by volume.
Further, further include metal oxide in the vanadium-phosphor oxide catalyst, the metal oxide be selected from Co, Ni,
At least one of steady oxide of Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce, the gold
Belonging to the molar ratio of metallic element and V in oxide is 0.001~0.2.
The present invention separately provides the preparation method of the vanadium-phosphor oxide catalyst, including following content:
(1) by M1And M2It is added to the water, stirs, heating, isothermal reaction is after reaction, cooling, is centrifuged, and filtering obtains
Ionic liquid I；
By M3And M4Mixing, isothermal reaction obtains intermediate product, be cooled to, wash, dry after be added in acetone, then
M is added1, reaction is stirred at room temperature, filters, washing, cleaning solution merges with filtrate, with anhydrous MgSO4It is dried overnight, rotary evaporation goes out
Acetone and moisture obtain ionic liquid II；
(2) vanadic anhydride is added in ionic liquid I, is heated, 95~130 DEG C of 2 ~ 4h of back flow reaction, then
Concentrated phosphoric acid is added dropwise into reaction system, then ionic liquid II 4 ~ 8h of back flow reaction is added in the reaction was continued 4 ~ 6h, reaction terminates
Afterwards, through filtering, drying and roasting, vanadium-phosphor oxide catalyst presoma is obtained；
(3) vanadium-phosphor oxide catalyst presoma first activated, after form, or first formed, the processing of post activation obtains institute
State vanadium-phosphor oxide catalyst；
If including metal oxide in vanadium-phosphor oxide catalyst, the metal oxide can be introduced by following three kinds of modes: I
In step (2), the soluble-salt of metal is added into ionic liquid I together with vanadic anhydride；II is catalyzed in vanadium phosphorus oxygen
Before agent molding or forming process introduces；III after vanadium-phosphor oxide catalyst molding, is introduced with impregnation method；
The M1For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluoro phosphate or hexafluoro
At least one of potassium phosphate；
The M2It is (R with general formula1R2R3R4) N+Z-Structure, wherein R1、R2、R3And R4Separately selected from H or C1 ~
The alkyl of C4, and R1、R2、R3And R4The sum of C atom≤4, Z be halogen；
The M3For at least one of imidazoles, alkyl imidazole, pyridine, alkyl pyridine；
The M4For halogenated alkyl alcohol, having general formula is Z (CH2)nCH2OH、Z(CH2)nCHOHCH2OH or Z (CH2)nCHOHCH2CH2The structure of OH, the integer that wherein n is 0 ~ 9, Z is halogen, is one of F, Cl or Br.
Further, the M1Preferably ammonium hexafluorophosphate and/or ammonium tetrafluoroborate.
Further, the M2General formula in, R1、R2、R3And R4It is separately selected from H, methyl or ethyl, Z is preferably
Chlorine, it is further preferable that the M2Selected from alkyl dimethyl ammonium chloride and/or diethylammonium chloride.
Further, the halogenated alkyl alcohol is most preferably chlorethanol.
In the method for the present invention, M in step (1)1With M2Molar ratio be 1:1~1:2, reaction temperature be 60~150 DEG C, it is excellent
70~100 DEG C are selected, the isothermal reaction time is 1~4h, preferably 1~2h.
In the method for the present invention, M in step (1)3With M4Molar ratio be 1:1~1:2, reaction temperature be 70 ~ 100 DEG C, preferably
70~90 DEG C, the isothermal reaction time is 20~30h, preferably 20~for 24 hours.
In the method for the present invention, intermediate product drying temperature described in step (1) be 60 DEG C~100 DEG C, preferably 70 DEG C~90
℃；Drying time is 24~50h, preferably 30~48h.
In the method for the present invention, intermediate product and M described in step (1)1Weight ratio be 0.5:1~3:1, preferably 1:1~
2:1；The weight ratio of the intermediate product and acetone is 0.1:1~1:1, preferably 0.2:1~0.5:1.
In the method for the present invention, the weight ratio of ionic liquid I described in step (2) and vanadic anhydride is 5:1~15:1；
The weight ratio of ionic liquid II and vanadic anhydride is 1:1~10:1.
In the method for the present invention, the mass percentage concentration of concentrated phosphoric acid described in step (2) is 85%~100%；Concentrated phosphoric acid adds
Enter amount with the molar ratio computing of phosphorus in system and vanadium for 0.85:1~1.35:1.
In the method for the present invention, reaction temperature described in step (2) is 95 DEG C~130 DEG C, and the reaction time is 2~4h.Add
4~the 6h that enters after concentrated phosphoric acid that the reaction was continued.The reaction was continued 4~8h after ionic liquid II is added.
In the method for the present invention, drying condition described in step (2) are as follows: 8~12 hours dry at a temperature of 95~170 DEG C；
The roasting condition are as follows: 200~280 DEG C roasting temperature 4~8 hours.
In the method for the present invention, activation described in step (3) is in nitrogen/air gaseous mixture, vapor/air gaseous mixture
Or carried out under the atmosphere of the one or more combination of butane/air gaseous mixture, activation temperature be 350~450 DEG C, preferably 375
~425 DEG C；Activation time is 5~40 hours, preferably 12~20 hours.
In the method for the present invention, molding mode described in step (3) is extrusion, plays piece or balling-up.
Vanadium-phosphor oxide catalyst of the present invention can be used in the reaction of preparing cis-anhydride by n-butane oxidation as catalyst, positive fourth
Alkane high conversion rate, Selectivity of maleic anhydride are good.Wherein the reaction of the preparing cis-anhydride by n-butane oxidation can take fixed bed, fluidized bed or
Moving bed reaction mode；The reaction condition of the preparing cis-anhydride by n-butane oxidation is general are as follows: 380~450 DEG C of reaction temperature, pressure is
Normal pressure~0.5MPa, normal butane gaseous mixture air speed are 1000~3500h-1, concentration of n-butane is 1.0%~1.8%(volume basis
Than).
Compared with prior art, vanadium-phosphor oxide catalyst and preparation method thereof of the invention has the characteristics that following:
1, vanadium phosphorus oxidation catalyst of the present invention contains dual pore structure, and duct is more abundant, and specific surface area increased, instead
Diffusion of the molecule in duct is answered to accelerate, and accessible active site also increases, therefore duct utilization rate improves.While by
In dual duct abundant, molecule diffusion path shortens, and coking deactivation rate can also slow down, and macromolecular is also easily spread, from
And effectively extend catalyst life.
2, in the method for the present invention, by the way that two kinds of ionic liquids, different ionic liquids are added during precursor synthesis
With different space sizes, so that prepared catalyst has different size of dual cellular structure.Hydroxyl is used simultaneously
Ionic liquid direct-reduction prepares vanadium-phosphor oxide catalyst presoma, compared with the ordinary method, significantly reduces the use of reducing agent
Amount.Conventional preparation method is needed using a large amount of solvent and reducing agent, and thermal stability is low, volatile, is easy to produce a large amount of
Poisonous and hazardous waste liquid, exhaust gas, so as to cause environmental pollution.This method avoids the impurity introducings unfavorable to catalyst, and
Ionic liquid at room temperature has the advantages that non-volatile, thermal stability is good, and a large amount of poisonous and hazardous give up is not used and discharged in reaction
Liquid, exhaust gas.
3, in the method for the present invention, ionic liquid is easy to be separated with product after reaction, can recycle, thus
Reduce production cost.
Specific embodiment
The specific preparation process of vanadium phosphorus oxide of the present invention is as follows:
(1) preparation of ionic liquid
By M1And M2It is added to the water, M1With M2Molar ratio be 1:1~1:2, be heated to reaction temperature under agitation,
Reaction temperature is 60~150 DEG C, and 1~4h of isothermal reaction is cooled to room temperature after reaction, and ionic liquid is obtained by filtration in centrifugation
I。
By M3And M4Mixing, M3With M4Molar ratio be 1:1~1:2, at 70 ~ 100 DEG C of reaction temperature isothermal reaction 20 ~
30h obtains colourless viscous liquid, is cooled to room temperature, and is washed 2 ~ 6 times with ether, and dry 24 ~ 50h, obtains intermediate at 60 ~ 100 DEG C
Product adds it in acetone, adds M1, it is stirred at room temperature, filters, washing, cleaning solution merges with filtrate, with anhydrous MgSO4
It is dried overnight, rotary evaporation goes out acetone and moisture, obtains ionic liquid II.
(2) preparation of vanadium phosphorus oxidation catalyst precursor
Vanadic anhydride and auxiliary agent are added in ionic liquid I, it is 95 DEG C which, which is heated to reaction temperature,
~130 DEG C, 2~4h of reflux time；Concentrated phosphoric acid is added dropwise into reaction system, continues 4~6h of reflux；Then ionic liquid is added
Body II, the reaction was continued 4~8h, after reaction, reaction solution is cooled to room temperature, is filtered, preferably first by filter cake at room temperature
It is natural air drying 10~24 hours, then 8~12 hours dry in 95~170 DEG C of baking ovens, finally 200~280 in Muffle furnace
At DEG C, roasts 4~8 hours, obtain the vanadium phosphorus oxide i.e. vanadium-phosphor oxide catalyst presoma of dark brown.
(3) preparation of vanadium-phosphor oxide catalyst
Vanadium-phosphor oxide catalyst presoma obtained by step (2) is first formed, and obtains vanadium-phosphor oxide catalyst intermediate, then carry out
Activation；Or gained vanadium-phosphor oxide catalyst presoma is first activated, and vanadium-phosphor oxide catalyst intermediate is obtained, and is using molding
Obtain vanadium-phosphor oxide catalyst.
The shape of obtained vanadium-phosphor oxide catalyst can be that shapes, the objects of catalyst such as tabletting, spherical shape, extrusion mutually be mainly
Vanadyl pyrophosphate ((VO)2P2O7) phase.
Above-mentioned forming process generally may include: by vanadium-phosphor oxide catalyst precursor powder (or the vanadium after overactivation
Phosphorus catalyst intermediate) graphite powder that mass fraction is 3%~5% is added, after being sufficiently mixed, using rotary tablet machine, suitably
Impact dynamics is adjusted, is squeezed into the such as column or other special-shaped catalyst of certain shapes, what this method was prepared urges
Agent is suitable for using in fixed bed reactors.
For the people for being proficient in this technology, vanadium-phosphor oxide catalyst precursor powder above-mentioned (or the catalyst after activation
Intermediate) different types of catalyst can also be prepared using other molding modes, and can apply to fixed bed, heat friendship
It changes in reactor, fluidized-bed reactor or moving-burden bed reactor.Than vanadium-phosphor oxide catalyst precursor powder as the aforementioned (or through work
Catalyst intermediate after change) adhesive appropriate is added, lubricant can also be formed by the way of extrusion, be suitble to bond
Agent, lubricant substance include starch, calcium stearate, stearic acid or graphite etc..Similarly, the parent of preformed catalyst can also be with
Catalyst microspheres are made to use in fluidized bed and moving bed, the details of operation of these above-mentioned reactors has been in the industry
Personage is grasped.
The activation method are as follows: set vanadium phosphorus oxidation catalyst precursor powder (or catalyst intermediate after molding)
In a pipe type calciner with activation phenomenon.Activation phenomenon can be butane/air gaseous mixture (butane volumetric concentration
It is 0.5%~1.5%, preferably 0.8%~1.2%), activation phenomenon can also be air/water steam gaseous mixture, and (vapor volume is dense
Degree be 25%~75%, preferably 35%~55%), nitrogen/vapor gaseous mixture (vapor volumetric concentration be 25%~75%, it is best
It is 35%~55%) etc..By activation temperature from room temperature to 350~450 DEG C, preferably 375~425 DEG C；Keep activation time one
As be 5~40 hours, preferably 12~20 hours.Activation process terminates to get to by vanadium-phosphor oxide catalyst of the invention.
Prepared vanadium-phosphor oxide catalyst can carry out as follows performance evaluation: by the vanadium phosphorus oxygen of above-mentioned preparation
Catalyst is fitted into fixed bed reactors, is passed through reaction mixture gas body, utilizes the composition of gas chromatographic analysis reaction product.It comments
Covalent reaction condition is as follows: 380~450 DEG C of reaction temperature, pressure be normal pressure~0.5MPa, normal butane gaseous mixture air speed be 1000~
3500h-1, butane concentration is 1.0%~1.8%(percent by volume), carry out the active evaluation test of catalyst.
Technical solution of the present invention is described in further detail combined with specific embodiments below.Following embodiment is not
It is limiting the scope of the invention, those skilled in the art combines description of the invention and full text that can do expansion appropriate
Exhibition, these extensions all should be the protection scopes of technical solution of the present invention.
Agents useful for same in Examples and Comparative Examples, ammonium tetrafluoroborate, sodium tetrafluoroborate, the limited public affairs of Wuhan sea moral development of chemical industry
Department；Alkyl dimethyl ammonium chloride, ammonio methacrylate, diethylammonium chloride, Qingdao Golden Horse Chemical Co., Ltd.；Chlorethanol, Yixing City prestige
Letter Chemical Co., Ltd.；Methaform, Jiangsu Yonghua Fine Chemical Co., Ltd.；Mecoral, the limited public affairs of Zibo sage's promise chemical industry
Department；Imidazoles, methylimidazole, Ya Bang chemical industry (Shanghai) Co., Ltd.；Fine chemistry industry research institute is recovered in isobutanol, Tianjin；Benzene first
Fine chemistry industry research institute is recovered in alcohol, Tianjin；Vanadic anhydride, Tianjin good fortune morning chemical reagent factory；Phosphoric acid, Shenyang Big Dipper chemistry
Chemical reagent work.Specific surface area, Kong Rong and the measurement in aperture of vanadium phosphorus oxide of the present invention are using U.S. Quantachrome
The full-automatic specific surface area of Autosorb3b type and pore-size distribution instrument of company measure.In vanadium-phosphor oxide catalyst (VO)2P2O7Crystal phase body
Product content is fitted according to the peak area in XRD spectra.
Embodiment 1
Alkyl dimethyl ammonium chloride 300g, ammonium tetrafluoroborate 190g, pure water 450g, mixing are heated to 80 DEG C, constant temperature under stiring
After 1h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, yield
73wt%。
1.92 mol chlorethanols and 1.28mol methylimidazole is taken to flow back for 24 hours, after reaction for 80 DEG C under conditions of microwave heating
Thick colorless transparency liquid is obtained, is cooled to room temperature, is washed four times with ether, clear crystal 1- ethoxy -3- methyl miaow is obtained
Azoles chloride ion liquid, 80 DEG C of dry 48h in vacuum oven.1- ethoxy -3- methylimidazole chloride ion liquid after taking drying
100g(0.6mol) it is added in 600ml acetone, adds 72g(0.68mol) sodium tetrafluoroborate, it is stirred at room temperature for 24 hours, filters, filter
Slag is waxy solid, and twice with acetone washing, cleaning solution merges with filtrate, with anhydrous MgSO4It is dried overnight, 40 DEG C of rotary evaporations
Acetone out, then 100 DEG C of oil bath rotary evaporation moisture 2h, obtain pure 1- ethoxy -3- methylimidazole borofluoride ion
Liquid.
300g ionic liquid I is added in the four-hole boiling flask with blender, vanadic anhydride 30.0g is added, by this
It is 98 DEG C that reaction system, which is heated to reaction temperature, reflux time 3h；The concentrated phosphoric acid that concentration is 85% is added dropwise into reaction system
38.0g, phosphorus/vanadium molar ratio are 1.0, continue the 4h that flows back；Then be added 100g 1- ethoxy -3- methylimidazole borofluoride from
Sub- liquid, the reaction was continued 5h, after reaction, reaction solution is cooled to room temperature, is filtered, by filter cake natural wind at room temperature
Dry, then the dry 8h in 120 DEG C of baking ovens, finally in Muffle furnace at 250 DEG C, roasts 6h, the vanadium phosphorus oxygen for obtaining dark brown is urged
Agent presoma.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 400 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 90%).Specific surface area is 60m2/ g, Kong Rongwei 0.06ml/g, and there is dual pore distribution,
Aperture is 10 ~ 20nm and 20 ~ 35nm；Wherein the pore size distribution of 10 ~ 20nm accounts for total pore volume 29%, and the pore size distribution of 20 ~ 35nm accounts for total pore volume
40%.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 380 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas volume air speed be 1750h-1Reaction condition under into
Row catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 91%(moles), Selectivity of maleic anhydride reaches 74%(moles).
Embodiment 2
Diethylammonium chloride 250g, ammonium tetrafluoroborate 180g, pure water 400g, mixing are heated to 90 DEG C, constant temperature under stiring
After 1.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 260g, aqueous about 3.5wt%, receives
Rate 73wt%.
1-(4 '-hydroxyl) butyl -3- methylimidazole borofluoride ion liquid preparation step with embodiment 1.
250g ionic liquid I is added in the four-hole boiling flask with blender, vanadic anhydride 30.0g, auxiliary agent is added
Six water ferric nitrate 0.3g, auxiliary agent zirconium nitrate 0.5g, it is 96 DEG C which, which is heated to reaction temperature, reflux time
3h；The concentrated phosphoric acid 35.5g that concentration is 100% is added dropwise into reaction system, phosphorus/vanadium molar ratio is 1.1, continues the 5h that flows back；Then plus
Enter the 1-(4 '-hydroxyl of 150g) butyl -3- methylimidazole borofluoride ion liquid, the reaction was continued, and 5h reacts after reaction
Liquid is cooled to room temperature, is filtered, by filter cake natural air drying at room temperature, the then dry 8h in 110 DEG C of baking ovens, finally in horse
Not in furnace at 240 DEG C, 6h is roasted, the vanadium-phosphor oxide catalyst presoma of dark brown is obtained.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 92%).Specific surface area is 58m2/ g, Kong Rongwei 0.06ml/g, and there is dual pore distribution,
Aperture is 10 ~ 20nm and 20 ~ 35nm；Wherein the pore size distribution of 10 ~ 20nm accounts for total pore volume 31%, and the pore size distribution of 20 ~ 35nm accounts for total pore volume
44%.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 94%(moles), Selectivity of maleic anhydride reaches 71%(moles).
Embodiment 3
Ammonio methacrylate 250g, ammonium tetrafluoroborate 150g, pure water 300g, mixing are heated to 90 DEG C, constant temperature under stiring
After 1.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, receives
Rate 73wt%.
The preparation step of 1- ethoxy -3- methylimidazole borofluoride ion liquid is the same as embodiment 1.
300g ionic liquid I is added in the four-hole boiling flask with blender, vanadic anhydride 30.0g, auxiliary agent is added
Zirconium nitrate 0.5g, six water nickel nitrate 0.95g of auxiliary agent, it is 110 DEG C which, which is heated to reaction temperature, reflux time
2.5h；The concentrated phosphoric acid 34.0g that concentration is 95% is added dropwise into reaction system, phosphorus/vanadium molar ratio is 1.0, continues the 5h that flows back；Then
1- ethoxy -3- methylimidazole borofluoride ion the liquid of 120g is added, the reaction was continued, and 4h reacts liquid cooling after reaction
But it to after room temperature, is filtered, by filter cake natural air drying at room temperature, the then dry 9h in 150 DEG C of baking ovens, finally in Muffle
In furnace at 260 DEG C, 6h is roasted, dark brown vanadium-phosphor oxide catalyst presoma is obtained.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 89%).Specific surface area is 55m2/ g, Kong Rongwei 0.05ml/g, and there is dual pore distribution,
Aperture is 10 ~ 20nm and 20 ~ 35nm；Wherein the pore size distribution of 10 ~ 20nm accounts for total pore volume 33%, and the pore size distribution of 20 ~ 35nm accounts for total pore volume
40%.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 91%(moles), Selectivity of maleic anhydride reaches 70%(moles).
Embodiment 4
The preparation step of ionic liquid I is the same as embodiment 1.
1-(6 '-hydroxyl) hexyl -3- methylimidazole borofluoride ion liquid preparation step with embodiment 1.
250g ionic liquid I is added in the four-hole boiling flask with blender, vanadic anhydride 30.0g, auxiliary agent is added
Six water ferric nitrate 0.3g, auxiliary agent zirconium nitrate 0.5g, it is 120 DEG C which, which is heated to reaction temperature, reflux time
3h；The concentrated phosphoric acid 32.3g that concentration is 100% is added dropwise into reaction system, phosphorus/vanadium molar ratio is 1.0, continues the 6h that flows back；Then plus
Enter the 1-(6 '-hydroxyl of 80g) hexyl -3- methylimidazole borofluoride ion liquid, the reaction was continued, and 7h reacts after reaction
It after liquid is cooled to room temperature, is filtered, by filter cake natural air drying at room temperature, then the dry 6h in 140 DEG C of baking ovens, finally exists
In Muffle furnace at 250 DEG C, 6h is roasted, the vanadium-phosphor oxide catalyst presoma of dark brown is obtained.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 90%).Specific surface area is 61m2/ g, Kong Rongwei 0.09ml/g, and there is dual pore distribution,
Aperture is 10 ~ 20nm and 20 ~ 35nm；Wherein the pore size distribution of 10 ~ 20nm accounts for total pore volume 30%, and the pore size distribution of 20 ~ 35nm accounts for total pore volume
44%.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 94%(moles), Selectivity of maleic anhydride reaches 69%(moles).
Comparative example 1
In the four-hole boiling flask with blender, vanadic anhydride 30.0g, the mixed liquor of isobutanol and benzyl alcohol is added
The mixed volume ratio of 600mL, isobutanol and benzyl alcohol is 15:1, and stirring heats up, and flow back 4h at 110 ± 2 DEG C；Then 100% is weighed
Phosphoric acid 35.5g, phosphorus/vanadium molar ratio be 1.1, be added in flask, continue flow back 6h, obtain reaction solution.Reaction solution is cooled to
Room temperature, vacuum filtration, a small amount of isobutanol of filter cake elute three times, the dry 12h in 120 DEG C of baking ovens, 250 DEG C in Muffle furnace
Under, 5h is roasted, the vanadium-phosphor oxide catalyst presoma of dark brown is obtained.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 90%).Specific surface area is 27m2/g；Kong Rongwei 0.05ml/g, aperture 17nm.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 72%(moles), 52%(moles of Selectivity of maleic anhydride).
Comparative example 2
Alkyl dimethyl ammonium chloride 300g, ammonium tetrafluoroborate 190g, pure water 450g, mixing are heated to 80 DEG C, constant temperature under stiring
After 1h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, yield
73wt%。
300g ionic liquid I is added in the four-hole boiling flask with blender, isobutanol 200mL, five oxidations two are added
Vanadium 30.0g, it is 90 DEG C which, which is heated to reaction temperature, reflux time 6h；Concentration is added dropwise into reaction system
For 85% concentrated phosphoric acid 38.0g, phosphorus/vanadium molar ratio is 1.0, continues the 4h that flows back；After reaction, reaction solution is cooled to room temperature, into
Row filtering, a small amount of isobutanol of filter cake elute three times, then filter cake natural air drying at room temperature are dried in 130 DEG C of baking ovens
8h finally in Muffle furnace at 250 DEG C, roasts 6h, obtains the vanadium-phosphor oxide catalyst presoma of dark brown.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 90%).Specific surface area is 28m2/ g, Kong Rongwei 0.05ml/g, aperture 16nm.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 76%(moles), 55%(moles of Selectivity of maleic anhydride).
Comparative example 3
1.92 mol chlorethanols and 1.28mol methylimidazole 85 DEG C of reflux 8h under conditions of microwave heating are taken, after reaction
Thick colorless transparency liquid is obtained, is cooled to room temperature, is washed four times with ether, clear crystal 1- ethoxy -3- methyl miaow is obtained
Azoles chloride ion liquid, 80 DEG C of dry 48h in vacuum oven.1- ethoxy -3- methylimidazole chloride ion liquid after taking drying
100g(0.6mol) it is added in 600ml acetone, adds 72g(0.68mol) sodium tetrafluoroborate, it is stirred at room temperature for 24 hours, filters, filter
Slag is waxy solid, and twice with acetone washing, cleaning solution merges with filtrate, with anhydrous MgSO4It is dried overnight, 40 DEG C of rotary evaporations
Acetone out, then 100 DEG C of oil bath rotary evaporation moisture 2h, obtain pure 1- ethoxy -3- methylimidazole borofluoride ion
Liquid.
In the four-hole boiling flask with blender, vanadic anhydride 30.0g, 1- ethoxy -3- methylimidazole fluorine boron is added
Hydrochlorate ionic liquid 500g.It is 95 DEG C that the reaction system, which is heated to reaction temperature, reflux time 5h；Into reaction system
The concentrated phosphoric acid 34.0g that concentration is 95% is added dropwise, phosphorus/vanadium molar ratio is 1.0, continues the 4h that flows back；After reaction, reaction solution is cooling
To after room temperature, it is filtered, by filter cake natural air drying at room temperature, the then dry 8h in 120 DEG C of baking ovens, finally in Muffle furnace
In at 250 DEG C, roast 7h, obtain the vanadium-phosphor oxide catalyst presoma of dark brown.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is mixed to be passed through butane/air
Gas (butane volumetric concentration is 0.8%) is closed, activation temperature is quickly increased to 250 DEG C from room temperature, is then slowly warming up to 420 DEG C
And kept for 20 hours, activation process terminates to arrive vanadium-phosphor oxide catalyst.Gained catalyst detects its crystal phase through XRD
(VO)2P2O7Phase (volume content 89%).Specific surface area is 32m2/ g, Kong Rongwei 0.07ml/g, aperture 30nm.
The graphite powder that mass fraction is 4% is added in catalyst above-mentioned, after being sufficiently mixed, using rotary tablet machine, is fitted
When adjustment impact dynamics, it is squeezed into column.It is crushed and is sieved, be prepared into catalyst granules.Measure 5mL catalyst particles
Grain (5~10 mesh) is placed in the stainless steel reaction pipe that internal diameter is 10mm.At 395 DEG C of reaction temperature, reaction pressure 0.25MPa, instead
Should gas be butane volumetric concentration 1.5% normal butane/air Mixture, gas space velocity 3500h-1Reaction condition under urged
Change performance evaluation.Through gas chromatographic analysis, n-butane conversion is 86%(moles), 62%(moles of Selectivity of maleic anhydride).
Claims (10)
1. a kind of vanadium-phosphor oxide catalyst, it is characterised in that: in the vanadium-phosphor oxide catalyst (VO)2P2O7Its content is by volume
80%~95%, it is the dual pore distribution of 10 ~ 20nm and 20 ~ 35nm that the vanadium-phosphor oxide catalyst, which has aperture, wherein 10 ~ 20nm
Duct account for total pore volume 29% ~ 36%, the duct of 20 ~ 35nm accounts for the 34% ~ 45% of total pore volume.
2. vanadium-phosphor oxide catalyst described in accordance with the claim 1, it is characterised in that: the molar ratio of phosphorus and vanadium in vanadium-phosphor oxide catalyst
It is 0.85~1.35, specific surface area is 42~64m20.04 ~ 0.1mL/g of/g, Kong Rongwei.
3. vanadium-phosphor oxide catalyst described in accordance with the claim 1, it is characterised in that: further include metal in the vanadium-phosphor oxide catalyst
Oxide, the metal oxide are selected from Co, Ni, Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, Fe, Cr and Ce
At least one of steady oxide, the molar ratio of metallic element and V are 0.001~0.2 in the metal oxide.
4. a kind of preparation method of vanadium-phosphor oxide catalyst described in claim 1 ~ 3 any one, it is characterised in that including as follows
Content:
(1) by M1And M2It is added to the water, stirs, heating, isothermal reaction is after reaction, cooling, is centrifuged, and filtering obtains ion
Liquid I；
By M3And M4Mixing, isothermal reaction obtains intermediate product, be cooled to, wash, dry after be added in acetone, add
M1, reaction is stirred at room temperature, filters, washing, cleaning solution merges with filtrate, with anhydrous MgSO4It is dried overnight, rotary evaporation goes out acetone
And moisture, obtain ionic liquid II；
(2) vanadic anhydride is added in ionic liquid I, is heated, 95~130 DEG C of 2 ~ 4h of back flow reaction, then to anti-
It answering and concentrated phosphoric acid is added dropwise in system, then ionic liquid II 4 ~ 8h of back flow reaction is added in the reaction was continued 4 ~ 6h, after reaction, warp
Filtering, dry and roasting, obtain vanadium-phosphor oxide catalyst presoma；
(3) vanadium-phosphor oxide catalyst presoma first activated, after form, or first formed, the processing of post activation obtains the vanadium
Phosphor oxide catalyst；
If including metal oxide in vanadium-phosphor oxide catalyst, the metal oxide can be introduced by following three kinds of modes: I in step
Suddenly in (2), the soluble-salt of metal is added into ionic liquid I together with vanadic anhydride；II vanadium-phosphor oxide catalyst at
Before type or forming process introduces；III after vanadium-phosphor oxide catalyst molding, is introduced with impregnation method；
The M1For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluoro phosphate or Potassium Hexafluorophosphate
At least one of；
The M2It is (R with general formula1R2R3R4) N+Z-Structure, wherein R1、R2、R3And R4Separately selected from H or C1 ~ C4
Alkyl, and R1、R2、R3And R4One of the sum of C atom≤4, Z F, Cl or Br；
The M3For at least one of imidazoles, alkyl imidazole, pyridine, alkyl pyridine；
The M4For halogenated alkyl alcohol, having general formula is Z (CH2)nCH2OH、Z(CH2)nCHOHCH2OH or Z (CH2)nCHOHCH2CH2The structure of OH, the integer that wherein n is 0 ~ 9, one of Z F, Cl or Br.
5. according to the method for claim 4, it is characterised in that: M in step (1)1With M2Molar ratio be 1:1~1:2, instead
Answering temperature is 60~150 DEG C, and the isothermal reaction time is 1~4h.
6. according to the method for claim 4, it is characterised in that: M in step (1)3With M4Molar ratio be 1:1~1:2, instead
Answering temperature is 70 ~ 100 DEG C, and the isothermal reaction time is 20 ~ 30h.
7. according to the method for claim 4, it is characterised in that: intermediate product and M described in step (1)1Weight ratio be
0.5:1 ~ 3:1；The weight ratio of the intermediate product and acetone is 0.1:1 ~ 1:1.
8. according to the method for claim 4, it is characterised in that: ionic liquid I and vanadic anhydride described in step (2)
Weight ratio be 5:1~15:1.
9. according to the method for claim 4, it is characterised in that: ionic liquid II and vanadic anhydride described in step (2)
Weight ratio be 1:1~10:1.
10. vanadium-phosphor oxide catalyst described in claim 1 ~ 3 any one is in preparing cis-anhydride by n-butane oxidation reaction as catalysis
The application of agent.
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