CN104607219B - A kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride and preparation method thereof - Google Patents
A kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of vanadium-phosphor oxide catalyst and preparation method thereof.It should be made using nanometer vanadium phosphorus oxide as precursor through first activating aftershaping or being first molded post activation；The grain size of described nanometer vanadium phosphorus oxide is less than 100nm, and its Grain size distribution is as follows on the basis of volume,<15nm particle proportion is that 9~15%, 15 30nm particle proportion is that 62~80%, 30 100nm particles proportions are 11~23%.The nanometer vanadium phosphorus oxide is using the circulating impact flow reactor of submergence, is made by adding silane coupler.Catalyst of the present invention is prepared in cis-butenedioic anhydride catalytic reaction for n butane oxidation, and n-butane conversion is up to 90~95 mol%, and Selectivity of maleic anhydride is up to 75~88mol%.
Description
Technical field
The present invention relates to a kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride and preparation method thereof, the catalyst is suitable for
In the catalytic reaction process of preparing cis-anhydride by n-butane oxidation.
Background technology
Maleic anhydride abbreviation cis-butenedioic anhydride, also known as maleic anhydride, it is a kind of important Organic Chemicals, is only secondary
In the big organic acid anhydride in the third place in the world of phthalic anhydride and aceticanhydride, the industries such as petrochemical industry, food processing, medicine, building materials are widely used in.Its
Concrete application includes manufacture unsaturated polyester resin, alkyd resin, maleic acid（Maleic acid）, fumaric acid（Anti- butylene two
Acid）, and agricultural chemicals, coating, fiberglass, lube oil additive, papermaking chemical product additive, surfactant etc..New method cis-butenedioic anhydride
The appearance of esterified low-voltage hydrogenation production BDO technique, make the fine-chemical intermediate Isosorbide-5-Nitrae with high added value-
The important source material of butanediol, tetrahydrofuran, γ-fourth lactones, application field are expanded rapidly.
Benzene oxidatoin method, n butane oxidation method, butylene (C4Fraction) oxidizing process be maleic anhydride production 3 kinds of basic line (phthalic anhydrides
By-product can also produce cis-butenedioic anhydride), wherein benzene oxidatoin method is the technique applied earliest, and its reactor and catalyst technology are ripe, but former
Expect that benzene price is relatively expensive, caused environmental pollution is also more serious than latter two technique, increasingly shows its weak point.Butylene oxygen
Change method utilizes the thick C of naphtha pyrolysis cutting4Fraction (active principle 1- butylene, 2- butylene, butadiene account for 70v% altogether), can have
Effect improves the synthesis utilization rate of naphtha pyrolysis gas.From Monsanto companies n butane oxidation legal system maleic anhydride process in 1974 first
Realize industrialization, due to the advantages of technique has raw material inexpensive, and environmental pollution is small, and cis-butenedioic anhydride manufacturing cost is low, at present into
For the main route of maleic anhydride production.Selective oxidation of n -butane cis-butenedioic anhydride is the currently the only low-carbon alkanes choosing for realizing commercial Application
Select oxidation reaction, vanadium phosphorus oxygen（Vanadium phosphorus oxygen）Catalyst is the maximally effective catalyst of the reaction, since its successful commercialization, people
A large amount of further investigations have been carried out to its preparation method, substantial amounts of paper and patent application have been delivered, referring to CATAL.REV.-
SCI.ENG .27(1985)：373.
The reaction of vanadium-phosphor oxide catalyst selective oxidation normal butane is the major class carried out by redox (Re-dox) mechanism
Hydrocarbon selective oxidation reacts Typical Representative, and the process of chemical reaction is related to the transfer of 14 electronics, including 8 hydrogen atoms
The insertion sloughed with electronics on 3 oxygen atoms of upper electronics, the exploration of its reaction mechanism is always vanadium-phosphor oxide catalyst research
Focus, at present, different scholars still have different view and opinion to the specific reaction mechanism mechanism of reaction, and not up to consistent are total to
Know.Therefore, vanadium-phosphor oxide catalyst is a kind of complicated catalyst system, and its physical property and structure has very high point with preparation method
System, its preparation process have very big influence to catalytic performance,
The catalyst preparation of early stage is to use water as solvent, hydrochloric acid（Including hydrogen chloride gas）, oxalic acid etc. be reducing agent；Gained
The specific surface area of catalyst is smaller（< 10 m2/g）.The method developed later is that catalyst is prepared in organic phase, and use is gone back
Former agent is alcohols, aldehydes, esters etc..The specific surface area of the catalyst prepared in organic phase is larger（The m of ＞ 202/g）, and it is organic
The catalytic performance that catalyst is prepared in phase generally to be preferred over catalyst obtained by water as solvent.
It is many for the economic benefit for further improving the activity and selectivity of vanadium-phosphor oxide catalyst, improving existing apparatus
Substantial amounts of basic research or technology development work have done in research institution, competitively publish thesis and apply for a patent.
USP4,632,915 propose a kind of vanadium-phosphor oxide catalyst preparation method, in the stirring reaction with reflux cooler
In kettle, lower addition isobutanol, phosphoric acid are cooled down（100%）, vanadic anhydride, lithium chloride and iron powder, then be passed through hydrogen chloride gas, so
Backflow is more than 2.5 hours under conditions of 102 DEG C afterwards, obtains catalyst precursor, then by drying, is calcined, is molded, 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%。
Chinese patent CN1090224A proposes a kind of preparation method for improving vanadium-phosphor oxide catalyst performance, and two are aoxidized by five
Vanadium and zinc sulfate are placed in the there-necked flask of a belt stirrer and spherical reflux condenser, add the appropriate concentrated sulfuric acid and alcohols solvent
Mixed, be heated to reflux 2 hours, phosphoric acid solution is then added dropwise, continue backflow 8 hours；Again into bottle be added dropwise the 4th component or
Other rare earth compounds or transistion metal compound, flow back 5 hours, the catalyst precursor of lake blue is obtained after filtering.
Activation of catalyst and evaluation test are carried out using fixed-bed tube reactor after shaping：Butanes conversion ＞ 90%, cis-butenedioic anhydride mole are received
Rate is 62%.
In order to improve the specific surface area of catalyst, CN99114080.X proposes a kind of vanadium phosphorus oxygen of supercritical drying process
The preparation process of catalyst, it can obtain specific surface area using supercritical drying process and be more than 50m2/ g vanadium phosphorus oxygen sample, but
It is these methods general more difficult operation and control, when especially being mass produced, and its principal crystalline phase composition is different from
Generally acknowledged active phase ［ (VO2)2P2O7.
It was found from the research of early stage, adding auxiliary agent can increase the specific surface area of catalyst, improve the conversion ratio of normal butane
With the yield of cis-butenedioic anhydride, also have in addition many methods such as add dispersant referring to SCI, 2002,
Vol.23：620~623 ］, the specific surface area of catalyst is improved, so as to improving catalyst activity.
CN 101157048A propose a kind of preparation method of the vanadium-phosphor oxide catalyst with nanostructured, are by changing
Enter conventional organic solvent method, introduced during vanadium-phosphor oxide catalyst presoma is prepared the auxiliary agent such as bismuth salt, dimethyl sulfoxide (DMSO) and
Polyethylene glycol, directly prepares the vanadium-phosphor oxide catalyst with nanostructured, although the nano V phosphorus of little crystal grain has been made in this method
VPO catalysts, but it is not high there is course of reaction butanes conversion, it is extra to add dimethyl sulfoxide (DMSO) and polyethylene glycol, add
The deficiencies of manufacturing cost of catalyst.
CN 1311058A disclose a kind of small granular size vanadium-phosphorus-oxygen catalyst, and it is made up of vanadium, phosphorus and oxygen atom, its particle diameter
Less than 100nm, specific surface area is 40~60m2/ g, principal crystalline phase are pyrophosphoric vanadyl.The catalyst preparation process is as follows：By 3.2g
Vanadic anhydride mixes with 120mL isobutanols-phenmethylol mixed solvent, is heated to reflux, and then adds 4.9g phosphoric acid（85%）, then
3.2g polyethylene glycol is added, continues to flow back, separates out precipitation, it is filtered, dry, vanadium-phosphor oxide catalyst precursor is obtained, using preceding 400
Activated at DEG C in reaction mixture gas, obtain fresh vanadium-phosphor oxide catalyst.The catalyst can be used as normal butane air oxidation to prepare
The catalyst of maleic acid anhydride reactant, its selectivity reach more than 72mol%, conversion per pass ＞ 85%.It is prepared by this method
Journey adds substantial amounts of polyethylene glycol dispersant, and obtained product has what Grain size distribution inequality was not enough concentrated with size distribution
Problem, and the deficiency that raw material polyethylene glycol additionally increases catalyst manufacturing cost be present.Although obtain the anti-of vanadium-phosphor oxide catalyst
Better performances are answered, but the activity and selectivity of catalyst still needs further raising.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of improved vanadium-phosphor oxide catalyst and preparation method thereof.The catalysis
Agent is used in the catalytic reaction of preparing cis-anhydride by n-butane oxidation, and n-butane conversion is high, and Selectivity of maleic anhydride is good.
The invention provides a kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride, with nanometer vanadium phosphorus oxide VOHPO
0.5H2O is precursor, is made through first activating aftershaping or being first molded post activation, wherein described nanometer vanadium phosphorus oxide tool
There is following property：Grain size is less than 100nm, and on the basis of the volume of vanadium phosphorus oxide, its Grain size distribution is as follows, ＜ 15nm's
The particle proportion that particle proportion is 9~15%, 15-30nm is that 62~80%, 30-100nm particles proportion is 11
~23%.
The vanadium-phosphor oxide catalyst crystal phase structure of the present invention is more regular, and active crystallographic plane diffraction peak intensity is than I (020)/I
(204) it is high, generally more than 1.0, preferably 1.0~1.5；Active crystal face（020 crystal face）Its big (020) crystal face half-peak breadth of exposure
FWHM/ ° general up to more than 0.75, preferably 0.8~1.1.Grain size and Grain size distribution are determined using laser particle analyzer,
Crystal phase structure is characterized using XRD analysis.
The crystal phase structure of vanadium-phosphor oxide catalyst of the present invention is mainly Vanadyl pyrophosphate（(VO2)2P2O7）Phase, (VO2)2P2O7Volume content be generally greater than 75%, preferably 80%~99%.The specific surface area of catalyst is at least 35m2/ g, pore volume are
At least 0.035mL/g.
Compared with the precursor of other vanadium-phosphor oxide catalysts, precursor-nanometer vanadium phosphorus oxide of catalyst of the present invention
Grain size distribution more concentrate, pore structure stable homogeneous, active crystal face（020 crystal face）Exposure is greatly as vanadium made from precursor
During phosphor oxide catalyst is used for preparing cis-anhydride by n-butane oxidation, reactivity is more preferable, and with preferably selectivity.
In vanadium-phosphor oxide catalyst of the present invention, the mol ratio of phosphorus and vanadium is 0.85~1.35, preferably 0.95~
1.20。
Can also contain conventional auxiliary agent in the vanadium-phosphor oxide catalyst of the present invention, for example, Co, Ni, Zn, Bi, Zr, Cu, Li,
K, the one or more in the element such as Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce.Described auxiliary agent is with elemental metal（Rub
You）Content be generally 0.001~0.2 times of V atoms.
Present invention also offers a kind of preparation method of above-mentioned vanadium-phosphor oxide catalyst, methods described includes：
（1）Isobutanol and phenmethylol are mixed in certain proportion, first added a part of isobutanol and benzyl alcohol solution
Enter to submerging in circulating impact flow reactor, be then proportionally added into silane coupler, start impact flow reactor, propeller
Revolution is the r/min of 1500r/min~3500, is warming up to 95~120 DEG C；By another part isobutanol and benzyl alcohol solution, five oxygen
Change two vanadium and be beaten in high speed shear refiner and form suspension, make concentrated phosphoric acid and above-mentioned suspension with certain stream rate of acceleration point
It is not added to from the side entrance of impact flow reactor two in reactor, forms impinging stream reaction, is kept reaction temperature, continue reaction 4
~8 hours, blue pulpous state reaction solution is obtained, filtered, dry and roasting, obtains vanadium phosphorus oxide powder；
（2）Gained vanadium phosphorus oxide is through first activating, aftershaping, or through being first molded, post activation obtain the vanadium phosphorus oxygen
Catalyst.
Wherein step（1）In, wherein described isobutanol and the mixed volume ratio of phenmethylol are 10:1~100:1, it is described
Isobutanol and the weight of phenmethylol mixture and vanadic anhydride ratio be 10:1~35:1.
Described isobutanol and the mixed weight of phenmethylol mixture and vanadic anhydride ratio can be 5:1~30:1, most
It is well 10:1~25:1.
The part isobutanol and benzyl alcohol solution of described first addition reactor account for isobutanol and the total dosage of benzyl alcohol solution
50%~80%, remaining isobutanol and benzyl alcohol solution add in pulping process.
Described silane coupler can be selected from one kind in A-143, A-151, A-171, A-174, A-186 and A-187
It is or several.The adding proportion of silane coupler is the 0.5%~5% of vanadic anhydride addition.Preferably 1%~2.5%.
The concentration expressed in percentage by weight of the concentrated phosphoric acid is 85%~100%.Described percussion flow propeller revolution is 750 r/min
The r/min of~4500r/min, preferably 1500r/min~3500.
Described range of reaction temperature is 95~120 DEG C, and the described reaction time is 2~4 hours, and preferably 6~8 is small
When.
Drying condition after the filtering is as follows：It is small that 8~12 are dried at 95~170 DEG C of temperature, preferably 120~150 DEG C
When；Described roasting condition is as follows：It is calcined 4~8 hours at 200~285 DEG C of temperature, preferably 230~260 DEG C.
Described activation can be in the mixed of the gaseous mixture of nitrogen/air, the gaseous mixture of vapor/air or butane/air
Close and carried out under the atmosphere of the one or more combination of gas.Activation temperature is generally 350~450 DEG C, preferably 375~425 DEG C；It is living
The change time is generally 5~40 hours, preferably 12~20 hours.
Described molding mode can be extrusion, beat piece or the conventional forming method in this area such as balling-up.
In the preparation process of vanadium-phosphor oxide catalyst of the present invention, auxiliary agent may be incorporated into.Described auxiliary agent be selected from Co, Ni,
One or more in Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce element.The auxiliary agent can be with
It is introduced into one of in the following manner in catalyst：（1）It is the preparation process of nanometer vanadium phosphorus oxide in vanadium-phosphor oxide catalyst precursor
Middle introducing；（2）Before vanadium-phosphor oxide catalyst shaping or forming process introduces；（3）After vanadium-phosphor oxide catalyst activation, then with dipping
Mode introduces.
Present invention also offers a kind of reaction method of preparing cis-anhydride by n-butane oxidation, it is characterised in that oxidizing process uses
Above-mentioned vanadium-phosphor oxide catalyst.Vanadium-phosphor oxide catalyst provided by the invention is applied to preparing cis-anhydride by n-butane oxidation course of reaction
In, n-butane conversion is high, and Selectivity of maleic anhydride is good.The reaction method of wherein described preparing cis-anhydride by n-butane oxidation can take fixation
Bed reactive mode, fluid bed or moving bed reaction mode.
The reaction condition of the preparing cis-anhydride by n-butane oxidation is generally：380~450 DEG C of reaction temperature, pressure be normal pressure~
0.5MPa, normal butane gaseous mixture volume space velocity are 1000~3500h-1, concentration of n-butane is 1.0%~1.8%（Percent by volume）.
In the preparation process of vanadium-phosphor oxide catalyst of the present invention, vanadic anhydride a part of first gradual quilt in alcoholic solution
Reduction and dissolving, with the remaining vanadic anhydride of the addition of phosphoric acid quickly dissolved and further crystallization turn into vanadium phosphorus oxygen catalysis
Agent precursor VOHPO0.5H2O.Obtain the VOHPO0.5H of nanostructured2O must is fulfilled for two conditions：When
VOHPO4·0.5H2O nucleus should be formed simultaneously, second, with precursor VOHPO4·0.5H2O's grows up, and there will be no and was nucleated
Journey, also to avoid the aggregation of particle.
It has been unexpectedly discovered that impinging stream reaction can very well meet two above-mentioned conditions, because hitting
The general principle for hitting stream is that the opposite flow at high speed of two strands of two-phase fluids is hit, and as a result causes a height rapid between two accelerating tubes
Dynamic impingement region.Fluid axial velocity on striking face goes to zero and switchs to Radial Flow.Medium can penetrate into reverse flow by inertia
And reach maximum in the moment alternate relative velocity for starting to penetrate into；Then slow down under frictional resistance effect until axial velocity
Zero is decayed to, acceleration is then reversed again and is moved to striking face, impingement region high turbulence and very big alternate relative velocity provide
Splendid condition of transmitting.Carry-over factor improves several times to more than ten times than traditional stirring means, and percussion flow is greatly promoted
Microcosmic mixing.
It has been found that nanometer VOHPO in vanadium phosphorus oxide preparation process4·0.5H2O specific surface area is big, surface energy
It is high and be easy to reunite, it is not easy to disperse in isobutanol and benzyl alcohol solution, after silane coupler modified processing, nanometer
VOHPO4·0.5H2The silane coupled agent molecule of O adsorptions, effectively reduces its surface energy, beneficial to nanometer VOHPO4·
0.5H2O's is scattered；The hydroxyl of modified coupling agent and nanometer VOHPO simultaneously4·0.5H2The hydroxy combining on O surfaces, organic matter base
Cumularsharolith is in VOHPO4·0.5H2Outside O, larger steric hindrance is formed, prevents a nanometer VOHPO4·0.5H2O reunion.From
And the nanometer VOHPO that grain size is smaller, particle diameter distribution is more concentrated can be made4·0.5H2O crystal.
Compared with prior art, vanadium-phosphor oxide catalyst provided by the invention and preparation method thereof has the characteristics that：
1st, vanadium-phosphor oxide catalyst of the invention, due to be using the nanometer vanadium phosphorus oxide with good Grain size distribution as
Precursor is made, and activity of the nanometer vanadium phosphorus oxide in preformed catalyst is mutually (VO)2P2O7The octahedral structure of crystalline phase is more
Regular, then the active center distribution of gained catalyst evenly, is improved so as to obtain the reactivity of vanadium-phosphor oxide catalyst.
At the same time, it is purpose product maleic anhydride that dispersed activated centre, which is more beneficial for normal butane conversion, and reduces generation
Accessory substance COx（CO and CO2）Trend.
2nd, it is modified by the surface of silane coupler, changes a nanometer VOHPO4·0.5H2O surface polarity, the vanadium of preparation
Phosphorous oxides crystal phase structure is more regular, and active crystallographic plane diffraction peak intensity compares I(020)/I(204)Height, active crystal face（020 crystal face）
Exposure is big, and the catalyst activity that thus prepared by presoma is higher.
3rd, micron VOHPO made from conventional method4·0.5H2O precursors were activating because itself crystallite dimension is larger
Top layer crystal can lose the crystallization water in journey, but body phase is difficult to lose the crystallization water, then result in body phase VOHPO4·0.5H2O is anti-
Final transformation in atmosphere is answered to generate VOPO4Phase.And the nanometer vanadium phosphorus oxide VOHPO of the present invention4·0.5H2O crystallite dimensions are more
It is small, the crystallization water is easily lost completely in activation process, is directly translated into (VO)2P2O7, so as to obtain the reaction of vanadium-phosphor oxide catalyst
Activity is improved.
4th, the impinging stream reaction used in the inventive method is simple to operate, and process control is steady, is suitable for mass producing.
Brief description of the drawings
Fig. 1 is the structural representation of the circulating impact flow reactor of submergence used in the present invention.
Fig. 2 is the XRD spectra of the gained vanadium-phosphor oxide catalyst of embodiment 2.
Embodiment
The specific preparation process of vanadium-phosphor oxide catalyst provided by the invention is as follows：
（1）Catalyst precursor --- the synthesis of nanometer vanadium phosphorus oxide
In the impact flow reactor shown in Fig. 1, a part of isobutanol, phenmethylol mixed liquor are added to by charge door 5
In impact flow reactor, silane coupling A -174 are then proportionally added into, start impact flow reactor, adjust the revolution of propeller 2
Reach 750r/min~4500r/min, raise reaction temperature and be maintained at 95~120 DEG C, by another part isobutanol, phenmethylol
Mixed liquor, vanadic anhydride are beaten in high speed shear refiner and form suspension, make phosphoric acid with certain stream rate of acceleration by adding
Material mouth 5 is added, and above-mentioned suspension is added with certain stream rate of acceleration by charge door 6, and reaction solution enters impingement region by guide shell 1
3 form percussion flow, when keeping being reacted at 95~120 DEG C of reaction temperature in impact flow reactor, and maintaining to continue reaction
Between 4~8 hours, reaction end obtain blue pulpous state reaction solution, discharged by reacting material outlet 4.After reaction solution is cooled to room temperature,
Filtered.After filter cake is eluted three times with a small amount of isobutanol, then filter cake natural air drying 12~24 hours at room temperature are being dried
Dried 8~12 hours in case, finally in Muffle furnace at 200~285 DEG C, be calcined 4~8 hours, obtain the catalyst of dark brown
Precursor-nanometer vanadium phosphorus oxide.
（2）The preparation of vanadium-phosphor oxide catalyst
Step（1）Gained vanadium phosphorus oxide is first molded, and obtains vanadium-phosphor oxide catalyst intermediate, then activated；Or
Vanadium phosphorus oxide obtained by person is first activated, and obtains vanadium-phosphor oxide catalyst intermediate, then produce the catalysis of vanadium phosphorus oxygen through overmolding
Agent.
The shape of obtained vanadium-phosphor oxide catalyst can be that shape, the things of catalyst such as tabletting, spherical, extrusion are mainly mutually
Super vanadyl phosphate（(VO2)2P2O7）Phase.
Above-mentioned forming process can typically include：By vanadium phosphorus oxide powder（Or the vanadium phosphorus catalyst after overactivation
Intermediate）The graphite powder that mass fraction is 3%~5% is added, after being sufficiently mixed, using rotary tablet machine, appropriate adjustment impact
Dynamics, the such as column of definite shape is squeezed into, or other special-shaped catalyst, the catalyst that this method is prepared are adapted to
Used in fixed bed reactors.
For the people for being proficient in this technology, foregoing vanadium phosphorus oxide powder（Or the catalyst intermediate after activation）Also
Different types of catalyst can be prepared using other molding modes, and can apply to fixed bed, heat exchange reactor,
In fluidized-bed reactor or moving-burden bed reactor.Than vanadium phosphorus oxide powder as the aforementioned（Or it is activated after catalyst among
Body）Adding appropriate adhesive, lubricant can also be molded by the way of extrusion, be adapted to the material for doing adhesive, lubricant
Including starch, calcium stearate, stearic acid or graphite etc..Similarly, catalyst microspheres can also be made in the parent of preformed catalyst
To be used in fluid bed and moving bed, the details of operation of these above-mentioned reactors is grasped by professional.
Described activation method is：By vanadium phosphorus oxide powder（Or the catalyst intermediate after shaping）One is placed in carry
In the pipe type calciner of activation phenomenon.Activation phenomenon can be the gaseous mixture of butane/air（Butane volumetric concentration be 0.5%~
1.5%, preferably 0.8%~1.2%）, activation phenomenon can also be air/water steam gaseous mixture（Vapor volumetric concentration is 25%
~75%, preferably 35%~55%）, nitrogen/vapor gaseous mixture（Vapor volumetric concentration be 25%~75%, preferably 35%~
55%）Deng.By activation temperature from room temperature to 350~450 DEG C, preferably 375~425 DEG C；Keep soak time be generally 5~
40 hours, preferably 12~20 hours.Activation process terminates, that is, obtains by the vanadium-phosphor oxide catalyst of the present invention.
Prepared vanadium-phosphor oxide catalyst, performance evaluation can be carried out as follows：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.Comment
Covalent reaction condition is as follows：380~450 DEG C of reaction temperature, pressure are normal pressure~0.5MPa, and normal butane gaseous mixture volume space velocity is
1000~3500h-1, butane concentration is 1.0%~1.8%（Percent by volume）, carry out the active evaluation test of catalyst.
With reference to embodiment, the present invention is described in further detail, and following examples are not that the present invention is protected
The limitation of scope, those skilled in the art combine description of the invention and can do appropriate extension in full, and these extensions are all
It should be protection scope of the present invention.
In embodiment and comparative example, the laser particle analyzer that grain size and Grain size distribution measurement use is Britain
The particle size analyzers of Mastersizer 2000；Crystalline phase detection is entered using the D/max-2500X x ray diffractometer xs of Japanese RIGAKU companies
OK, specific surface area uses the full-automatic specific surface area of AUTOSORB3B types and pore-size distribution instrument of Quantachrome companies of the U.S..
Embodiment 1
In the impact flow reactor shown in Fig. 1, isobutanol, phenmethylol mixed liquor 500mL, isobutanol/phenmethylol are added
Volume ratio 10:1, the 0.29g of silane coupling A -147, start impact flow reactor, agitating paddle revolution is reached 1500r/min,
Reaction solution forms percussion flow by guide shell.Rise reaction temperature is simultaneously maintained at 110 ± 2 DEG C, by vanadic anhydride 29.53g and
Isobutanol, phenmethylol mixed liquor 149mL are beaten in FSH-2 type high-speed homogenization machines and form suspension, make the phosphoric acid of concentration 85%
44.7g and above-mentioned suspension are added in reactor from impact flow reactor two entrances respectively with certain stream rate of acceleration, are protected
The reaction of 6 hours reaction time is held to terminate.After reaction solution is cooled to room temperature, vacuum filtration, filter cake is eluted three times with a small amount of isobutanol
Afterwards, filter cake is put into enamel tray natural air drying at room temperature, dried 8 hours in 105 DEG C of baking ovens, finally 250 in Muffle furnace
It is calcined 5 hours at DEG C, obtains the vanadium phosphorus oxide powder of dark brown（That is catalyst precursor）.Gained vanadium phosphorus oxide is through analysis
Grain size is less than 100nm, and Grain size distribution analysis result is shown in Table 1.
Vanadium phosphorus oxide powder obtained above is placed in a pipe type calciner, is passed through the gaseous mixture of butane/air
（Butane volumetric concentration is 0.8%）, activation temperature is quickly increased to 250 DEG C from room temperature, 400 DEG C is then slowly warming up to and protects
Hold 20 hours, activation process terminates, that is, obtains catalyst intermediate.It is 4% that foregoing catalyst intermediate is added into mass fraction
Graphite powder, it is appropriate to adjust impact dynamics using rotary tablet machine after being sufficiently mixed, be squeezed into cylindrical catalyst finished product.
XRD crystal phase analysis result and specific surface area of catalyst analysis result are shown in Table 1.
Gained catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）Be placed in internal diameter for 10mm not
Become rusty in steel reaction tube, in 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is the positive fourth of butane volumetric concentration 1.5%
Alkane/air Mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test.Reaction result is shown in Table 2.
Embodiment 2
In the impact flow reactor shown in Fig. 1, isobutanol, phenmethylol mixed liquor 500mL, isobutanol/phenmethylol are added
Volume ratio 15:1, the 0.29g of silane coupling A -151, auxiliary agent six water ferric nitrate 0.3g, auxiliary agent zirconium nitrate 0.5g, start percussion flow
Reactor, makes agitating paddle revolution reach 2500r/min, and reaction solution forms percussion flow by guide shell.Rise reaction temperature is simultaneously protected
Hold at 100 ± 2 DEG C, by vanadic anhydride 29.53g and isobutanol, phenmethylol mixed liquor 149mL in FSH-2 type high-speed homogenization machines
Middle mashing forms suspension, make concentration 100% phosphoric acid 34.98g and above-mentioned suspension with certain stream rate of acceleration respectively from shock
Flow reactor two entrances are added in reactor, keep the reaction of 6 hours reaction time to terminate.After reaction solution is cooled to room temperature,
Vacuum filtration, after filter cake is eluted three times with a small amount of isobutanol, filter cake is put into enamel tray natural air drying at room temperature, at 100 DEG C
Dried 10 hours in baking oven, be finally calcined 5 hours at 250 DEG C in Muffle furnace, obtain the vanadium phosphorus oxide powder of dark brown（I.e.
Catalyst precursor）.Gained vanadium phosphorus oxide is less than 100nm through analyzing grain size, and Grain size distribution analysis result is shown in Table 1.
Vanadium phosphorus oxide powder obtained above is placed in a pipe type calciner, is passed through the gaseous mixture of butane/air
（Butane volumetric concentration is 0.8%）, activation temperature is quickly increased to 250 DEG C from room temperature, 390 DEG C is then slowly warming up to and protects
Hold 30 hours, activation process terminates, that is, obtains catalyst intermediate.It is 4% that foregoing catalyst intermediate is added into mass fraction
Graphite powder, it is appropriate to adjust impact dynamics using rotary tablet machine after being sufficiently mixed, be squeezed into cylindrical catalyst finished product.
XRD crystal phase analysis result and specific surface area of catalyst analysis result are shown in Table 1.
Gained catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）Be placed in internal diameter for 10mm not
Become rusty in steel reaction tube, in 395 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is the positive fourth of butane volumetric concentration 1.5%
Alkane/air Mixture, volume space velocity 3500h-1Reaction condition under carry out catalytic performance test.Reaction result is shown in Table 2.
Embodiment 3
In the impact flow reactor shown in Fig. 1, isobutanol, phenmethylol mixed liquor 500mL, isobutanol/phenmethylol are added
Volume ratio 20:1, the 0.44g of silane coupling A -147, start impact flow reactor, agitating paddle revolution is reached 3500r/min,
Reaction solution forms percussion flow by guide shell.Rise reaction temperature is simultaneously maintained at 97 ± 2 DEG C, by vanadic anhydride 29.53g and different
Butanol, phenmethylol mixed liquor 149mL are beaten in FSH-2 type high-speed homogenization machines and form suspension, make the phosphoric acid of concentration 95%
33.47g and above-mentioned suspension are added in reactor from impact flow reactor two entrances respectively with certain stream rate of acceleration, are protected
The reaction of 8 hours reaction time is held to terminate.After reaction solution is cooled to room temperature, vacuum filtration, filter cake is eluted three times with a small amount of isobutanol
Afterwards, filter cake is put into enamel tray natural air drying at room temperature, dried 8 hours in 100 DEG C of baking ovens, finally 250 in Muffle furnace
It is calcined 5 hours at DEG C, obtains the vanadium phosphorus oxide powder of dark brown（That is catalyst precursor）.Gained vanadium phosphorus oxide is through analysis
Grain size is less than 100nm, and Grain size distribution analysis result is shown in Table 1.
Vanadium phosphorus oxide powder obtained above is placed in a pipe type calciner, is passed through the gaseous mixture of butane/air
（Butane volumetric concentration is 0.8%）, activation temperature is quickly increased to 250 DEG C from room temperature, 400 DEG C is then slowly warming up to and protects
Hold 20 hours, activation process terminates, that is, obtains catalyst intermediate.It is 3% that foregoing catalyst intermediate is added into mass fraction
Graphite powder, it is appropriate to adjust impact dynamics using rotary tablet machine after being sufficiently mixed, be squeezed into cylindrical catalyst finished product.
XRD crystal phase analysis result and specific surface area of catalyst analysis result are shown in Table 1.
Gained catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）Be placed in internal diameter for 10mm not
Become rusty in steel reaction tube, in 390 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is the positive fourth of butane volumetric concentration 1.5%
Alkane/air Mixture, volume space velocity 3000h-1Reaction condition under carry out catalytic performance test.Reaction result is shown in Table 2.
Embodiment 4
In the impact flow reactor shown in Fig. 1, isobutanol, phenmethylol mixed liquor 500mL, isobutanol/phenmethylol are added
Volume ratio 15:1, the 0.29g of silane coupling A -187, start impact flow reactor, agitating paddle revolution is reached 2500r/min,
Reaction solution forms percussion flow by guide shell.Rise reaction temperature is simultaneously maintained at 100 ± 2 DEG C, by vanadic anhydride 29.53g and
Isobutanol, phenmethylol mixed liquor 149mL are beaten in FSH-2 type high-speed homogenization machines and form suspension, make the phosphoric acid of concentration 100%
34.98g and above-mentioned suspension are added in reactor from impact flow reactor two entrances respectively with certain stream rate of acceleration, are protected
The reaction of 6 hours reaction time is held to terminate.After reaction solution is cooled to room temperature, vacuum filtration, filter cake is eluted three times with a small amount of isobutanol
Afterwards, filter cake is put into enamel tray natural air drying at room temperature, dried 8 hours in 105 DEG C of baking ovens, finally 250 in Muffle furnace
It is calcined 5 hours at DEG C, obtains the vanadium phosphorus oxide powder of dark brown（That is catalyst precursor）.Gained vanadium phosphorus oxide is through analysis
Grain size is less than 100nm, and Grain size distribution analysis result is shown in Table 1.
Vanadium phosphorus oxide powder obtained above is placed in a pipe type calciner, is passed through the gaseous mixture of butane/air
（Butane volumetric concentration is 0.8%）, activation temperature is quickly increased to 250 DEG C from room temperature, 400 DEG C is then slowly warming up to and protects
Hold 20 hours, activation process terminates, that is, obtains catalyst intermediate.It is 3% that foregoing catalyst intermediate is added into mass fraction
Graphite powder, it is appropriate to adjust impact dynamics using rotary tablet machine after being sufficiently mixed, be squeezed into cylindrical catalyst finished product.
XRD crystal phase analysis result and specific surface area of catalyst analysis result are shown in Table 1.
Gained catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）Be placed in internal diameter for 10mm not
Become rusty in steel reaction tube, in 400 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is the positive fourth of butane volumetric concentration 1.8%
Alkane/air Mixture, volume space velocity 2000h-1Reaction condition under carry out catalytic performance test.Reaction result is shown in Table 2.
Comparative example 1
In the four-hole boiling flask with agitator, isobutanol, phenmethylol mixed liquor 421.8mL, isobutanol/phenmethylol are added
Volume ratio 10:1, vanadic anhydride 29.53g, stirring heating, are kept stirring for revolution 450r/min, at 100 ± 2 DEG C of reaction temperature
Flowed back, maintain the reflux for the time 4 hours, add the phosphoric acid 34.98g of concentration 100%, continue to maintain the reflux for the reaction time 4 small
When, reaction terminates.After reaction solution is cooled to room temperature, vacuum filtration, after filter cake is eluted three times with a small amount of isobutanol, filter cake is put into
Natural air drying at room temperature in enamel tray, dry 8 hours in 105 DEG C of baking oven, be finally calcined 5 hours at 250 DEG C in Muffle furnace,
Obtain the vanadium phosphorus oxide powder of dark brown（That is catalyst precursor）.Grain size is more than gained vanadium phosphorus oxide by analysis
100nm, Grain size distribution analysis result are shown in Table 1.
Vanadium phosphorus oxide powder obtained above is placed in pipe type calciner, is passed through the gaseous mixture of butane/air（Butane
Volumetric concentration is 0.8%）, activation temperature is quickly increased to 250 DEG C from room temperature, 400 DEG C is then slowly warming up to and holding 20 is small
When, activation process terminates, that is, obtains vanadium-phosphor oxide catalyst intermediate.It is 4% that foregoing catalyst intermediate is added into mass fraction
Graphite powder, it is appropriate to adjust impact dynamics using rotary tablet machine after being sufficiently mixed, cylindrical catalyst is squeezed into, through XRD
It is (VO to detect its crystalline phase2)2P2O7, XRD crystal phase analysis result and specific surface area of catalyst analysis result are shown in Table 1.
Gained catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）Be placed in internal diameter for 10mm not
Become rusty in steel reaction tube, in 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is the positive fourth of butane volumetric concentration 1.5%
Alkane/air Mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
Comparative example 2
Vanadium phosphorus oxide is prepared according to method disclosed in embodiment in CN1311058A 1.Vanadium phosphorus oxide is obtained, through analysis
Grain size is less than 100nm, and Grain size distribution analysis result is shown in Table 1.
Obtained vanadium phosphorus oxide powder is activated in reaction atmosphere, activation condition obtains with embodiment 1, then through tabletting
Vanadium-phosphor oxide catalyst.Detected through XRD, crystalline phase is mainly Vanadyl pyrophosphate, XRD crystal phase analysis result and specific surface area of catalyst point
Analysis the results are shown in Table 1.
Catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）It is placed in the stainless steel that internal diameter is 10mm
In reaction tube, in 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is normal butane/sky of butane volumetric concentration 1.5%
Gas gaseous mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
Comparative example 3
The preparation method of catalyst is carried out fully according to method disclosed in embodiment in CN1311058A 2.Obtain vanadium phosphorus oxygen
Compound is less than 100nm through analyzing grain size, and Grain size distribution analysis result is shown in Table 1.
Obtained vanadium phosphorus oxide powder is activated in reaction atmosphere, activation condition is the same as embodiment 1；Again through compression molding
Obtain vanadium-phosphor oxide catalyst.Detected through XRD, crystalline phase is mainly Vanadyl pyrophosphate, XRD crystal phase analysis result and catalyst specific surface
Integration analysis the results are shown in Table 1.
Catalyst is crushed and sieved, and measures 5mL catalyst granules（The mesh of 5 mesh~10）It is the stainless of 10mm to be placed in internal diameter
In steel reaction tube.In 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas for butane volumetric concentration 1.5% normal butane/
Air Mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
Comparative example 4
The preparation method of catalyst is carried out fully according to method disclosed in embodiment in CN1264619A 1.Obtain vanadium phosphorus oxygen
Compound is less than 100nm through analyzing grain size, and Grain size distribution analysis result is shown in Table 1.
Obtained vanadium phosphorus oxide powder is activated in reaction atmosphere, activation condition is the same as embodiment 1；And obtained through tabletting
Vanadium-phosphor oxide catalyst.Detected through XRD, crystalline phase has least a portion of (VO2)2P2O7, XRD crystal phase analysis result and catalyst specific surface
Integration analysis the results are shown in Table 1.
Catalyst is crushed and sieved, and measures 5mL catalyst granules（The mesh of 5 mesh~10）It is the stainless of 10mm to be placed in internal diameter
In steel reaction tube.In 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas for butane volumetric concentration 1.5% normal butane/
Air Mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
Comparative example 5
The preparation method of catalyst is carried out fully according to method disclosed in embodiment in CN1264619A 2.Obtain vanadium phosphorus oxygen
Grain size is less than 100nm to compound by analysis, and Grain size distribution analysis result is shown in Table 1.
Obtained vanadium phosphorus oxide powder is activated in reaction atmosphere, activation condition is the same as embodiment 1；Again by tabletting into
Type obtains vanadium-phosphor oxide catalyst.Detected through XRD, crystalline phase has least a portion of (VO2)2P2O7, XRD crystal phase analysis result and catalyst
Specific surface area analysis the results are shown in Table 1.
Catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）It is placed in the stainless steel that internal diameter is 10mm
In reaction tube, in 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is normal butane/sky of butane volumetric concentration 1.5%
Gas gaseous mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
Comparative example 6
The preparation method of catalyst is carried out fully according to method disclosed in embodiment in CN101157048A 1.Obtain vanadium phosphorus
Grain size is less than 100nm to oxide by analysis, and Grain size distribution analysis result is shown in Table 1.
Obtained vanadium phosphorus oxide powder is activated in reaction atmosphere, activation condition is the same as embodiment 1；Again by tabletting into
Type obtains vanadium-phosphor oxide catalyst.Detected through XRD, crystalline phase has the (VO of part2)2P2O7, XRD crystal phase analysis result and catalyst ratio
Surface area analysis is shown in Table 1.
Catalyst measures 5mL catalyst granules through broken and screening（The mesh of 5 mesh~10）It is placed in the stainless steel that internal diameter is 10mm
In reaction tube, in 385 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas is normal butane/sky of butane volumetric concentration 1.5%
Gas gaseous mixture, volume space velocity 1750h-1Reaction condition under carry out catalytic performance test, reaction result is shown in Table 2.
The distribution of the catalyst particle size of table 1, crystal phase analysis and Evaluation results.
The catalyst performance evaluation result of table 2.
Claims (25)
1. a kind of preparation method of vanadium-phosphor oxide catalyst, comprises the following steps：
（1）Mix by by isobutanol and phenmethylol, first add a part of isobutanol and benzyl alcohol solution in certain proportion
To submerging in circulating impact flow reactor, silane coupler is then proportionally added into, starts impact flow reactor, is warming up to 95
~120 DEG C, another part isobutanol and benzyl alcohol solution, vanadic anhydride are beaten in high speed shear refiner formed it is suspended
Liquid, concentrated phosphoric acid and above-mentioned suspension is set to be added to reactor from the side entrance of impact flow reactor two respectively with certain stream rate of acceleration
In, impinging stream reaction is formed, reaction temperature is kept, continues reaction 4~8 hours, obtain blue pulpous state reaction solution, it is filtered, dry
Dry and roasting, obtains vanadium phosphorus oxide powder；
（2）Gained vanadium phosphorus oxide is through first activating, aftershaping, or through being first molded, post activation obtain vanadium phosphorus oxygen catalysis
Agent；
Wherein, the vanadium phosphorus oxide has the following properties that：Grain size is less than 100nm, its Grain size distribution on the basis of volume
As follows, the particle proportion that ＜ 15nm particle proportion is 9~15%, 15-30nm is 62~80%, 30-100nm particles
Proportion is 11~23%.
2. in accordance with the method for claim 1, it is characterised in that described isobutanol and the mixed volume ratio of phenmethylol are
10:1~100:1, described isobutanol and the weight of phenmethylol mixture and vanadic anhydride ratio are 10:1~35:1.
3. in accordance with the method for claim 1, it is characterised in that first add the part isobutanol and benzyl alcohol solution of reactor
The 50%~80% of isobutanol and the total dosage of benzyl alcohol solution, remaining isobutanol and benzyl alcohol solution is accounted for add in pulping process.
4. in accordance with the method for claim 1, it is characterised in that the addition of described silane coupler is vanadic anhydride
The 0.5%~5% of addition.
5. in accordance with the method for claim 1, it is characterised in that described silane coupler be A-143, A-151, A-171,
One or more in A-174, A-186 or A-187.
6. in accordance with the method for claim 1, it is characterised in that the concentration expressed in percentage by weight of described concentrated phosphoric acid be 85%~
100%。
7. in accordance with the method for claim 1, it is characterised in that the propeller revolution of the impact flow reactor is 1500r/
The r/min of min~3500.
8. in accordance with the method for claim 1, it is characterised in that step（1）The condition of the drying is：At 95~170 DEG C
At a temperature of dry 8~12 hours；Described roasting condition is：In 200~285 DEG C of roasting temperatures 4~8 hours.
9. in accordance with the method for claim 8, it is characterised in that the temperature of the drying is 120~150 DEG C, the roasting
Temperature be 230~260 DEG C.
10. in accordance with the method for claim 1, it is characterised in that described activation is steamed in the mixing gas and water of nitrogen/air
Carried out under the atmosphere of the one or more combination of the gaseous mixture of gas/air or the gaseous mixture of butane/air, activation temperature 350
~450 DEG C, soak time is 5~40 hours.
11. in accordance with the method for claim 10, it is characterised in that 375~425 DEG C of described activation temperature, described work
It is 12~20 hours to change the time.
12. in accordance with the method for claim 1, it is characterised in that described molding mode is extrusion, plays piece or balling-up.
13. in accordance with the method for claim 1, it is characterised in that auxiliary agent is introduced in the preparation process of vanadium-phosphor oxide catalyst,
Promoter addition is calculated as 0.001~0.2 times of V atoms with element, described auxiliary agent be selected from Co, Ni, Zn, Bi, Zr, Cu, Li, K,
One or more in Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce element.
14. in accordance with the method for claim 13, it is characterised in that the auxiliary agent introduces catalyst one of in the following manner
In：（1）Introduced in the preparation process that vanadium-phosphor oxide catalyst precursor is vanadium phosphorus oxide；（2）It is molded in vanadium-phosphor oxide catalyst
Preceding or forming process introduces；（3）Introduced after vanadium-phosphor oxide catalyst activation, then with impregnation method.
15. in accordance with the method for claim 2, it is characterised in that described isobutanol and the mixed volume ratio of phenmethylol are
10:1~25:1, described isobutanol and the weight of phenmethylol mixture and vanadic anhydride ratio are 10:1~20:1.
16. in accordance with the method for claim 4, it is characterised in that the addition of described silane coupler is five oxidations two
The 1%~2.5% of vanadium addition.
17. vanadium-phosphor oxide catalyst prepared by claim 1-16 either method.
18. according to the vanadium-phosphor oxide catalyst described in claim 17, it is characterised in that the mol ratio of phosphorus and vanadium is in catalyst
0.85~1.35.
19. according to the vanadium-phosphor oxide catalyst described in claim 18, it is characterised in that the mol ratio of phosphorus and vanadium is in catalyst
0.95~1.20.
20. according to the vanadium-phosphor oxide catalyst described in claim 18, it is characterised in that Vanadyl pyrophosphate (VO) in catalyst2P2O7Volume content be higher than 75%.
21. according to the vanadium-phosphor oxide catalyst described in claim 18, it is characterised in that the specific surface area of the vanadium-phosphor oxide catalyst
It is at least 35m2/ g, pore volume are at least 0.035mL/g.
22. according to the vanadium-phosphor oxide catalyst described in claim 18, it is characterised in that the active crystallographic plane diffraction peak intensity of catalyst
Than I (020)/I (204) more than 1.0, active crystal face（020 crystal face）Half-peak breadth FWHM is more than 0.75 °.
23. according to the vanadium-phosphor oxide catalyst described in claim 22, it is characterised in that the active crystallographic plane diffraction peak intensity of catalyst
It is 1.0~1.5 than I (020)/I (204), active crystal face（020 crystal face）Half-peak breadth FWHM is 0.8~1.1 °.
24. a kind of n butane oxidation prepares the reaction method of cis-butenedioic anhydride, it is characterised in that claim has been used in course of reaction
Any described vanadium-phosphor oxide catalysts of 17-23.
25. according to the reaction method described in claim 24, it is characterised in that reaction condition is：380~450 DEG C of reaction temperature,
Pressure is normal pressure~0.5MPa, and normal butane gaseous mixture volume space velocity is 1000~3500h-1, concentration of n-butane is 1.0%~1.8%.
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| US9675966B2 (en) * | 2015-07-16 | 2017-06-13 | Ineos Europe Ag | Catalyst for n-butane oxidation to maleic anhydride |
| CN106582747B (en) * | 2015-10-19 | 2019-05-14 | 中国石油化工股份有限公司 | For producing the preparation method of the catalyst of cis-butenedioic anhydride |
| CN106582746B (en) * | 2015-10-19 | 2019-05-14 | 中国石油化工股份有限公司 | Catalyst for preparing cis-anhydride by n-butane oxidation |
| CN105536831A (en) * | 2015-12-14 | 2016-05-04 | 天津市天环精细化工研究所 | Method for preparing maleic anhydride VPO catalyst through n-butane oxidation method |
| CN106938197B (en) * | 2016-05-25 | 2019-12-13 | 中国科学院过程工程研究所 | Preparation method of vanadium phosphorus oxide catalyst |
| CN109248699B (en) * | 2017-07-14 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing KA oil by cyclohexane oxidation |
| CN111097465B (en) * | 2018-10-25 | 2022-10-11 | 中国石油化工股份有限公司 | Preparation method of vanadium phosphorus oxide catalyst |
| CN114433150B (en) * | 2020-10-30 | 2023-09-01 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst |
| CN114433149B (en) * | 2020-10-30 | 2023-09-01 | 中国石油化工股份有限公司 | Vanadium phosphorus oxide catalyst, preparation method and application thereof |
| CN115850214A (en) * | 2022-12-28 | 2023-03-28 | 常州新日催化剂股份有限公司 | Method for preparing maleic anhydride by oxidizing n-butane |
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| CN100446858C (en) * | 2006-10-13 | 2008-12-31 | 南京大学 | Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use |
| CN101157048B (en) * | 2007-11-20 | 2010-04-07 | 吐哈石油勘探开发指挥部石油天然气化工厂 | A high performance vanadium phosphorus oxygen catalyst with nanostructure as well as its preparing method |
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