CN105289743B - It is a kind of to be used to produce vanadium-phosphor oxide catalyst of maleic anhydride and preparation method thereof - Google Patents
It is a kind of to be used to produce vanadium-phosphor oxide catalyst of maleic anhydride and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of vanadium-phosphor oxide catalyst for being used to produce maleic anhydride and preparation method thereof, the preparation method includes preparing heteropoly acid solution, prepares the steps such as catalyst precursor, shaping and roasting.Vpo catalyst preparation method of the present invention is to add heteropoly acid in catalyst precursor is prepared first, effectively improves catalyst activity and selectivity, and compared with prior art, n-butane conversion improves 1~2%, and Selectivity of maleic anhydride improves 2~3%.Catalyst preparation mode of the present invention simplifies preparation process, solve the problems, such as that bed temperature is unmanageable during vpo catalyst activation simultaneously, the vpo catalyst reaction temperature prepared through the inventive method is lower than existing commercial catalysts reaction temperature about 30 DEG C, has a good application prospect.
Description
【Technical field】
The invention belongs to technical field of compound preparation.More particularly it relates to a kind of be used to produce maleic two
The vanadium-phosphor oxide catalyst of acid anhydrides, further relate to the preparation method of the vanadium-phosphor oxide catalyst.
【Background technology】
Maleic anhydride (abbreviation cis-butenedioic anhydride) also known as maleic anhydride, it is widely used in synthetic resin, coating, lubricating oil addition
Agent, medicine and technical field of food additives, it is the third-largest organic acid anhydride outside aceticanhydride and phthalic anhydride.Because the structure of uniqueness is special
Point, cis-butenedioic anhydride have very strong reactivity worth, can further react synthesis unsaturated polyester resin, while can also be used as and prepare
The raw material of BDO and tetrahydrofuran derivatives organic compound, it is a kind of important industrial chemicals and intermediate.In recent years, by
To downstream BDO and the influence of unsaturated polyester resin increase in demand, China Maleic Anhydrite product consumption cumulative year after year,
With good market prospects.
From the point of view of the raw material of production cis-butenedioic anhydride, in the market main production has benzene oxidatoin method, n butane oxidation method, C4Alkene
Oxidizing process.Benzene oxidatoin method is the method for being used to produce cis-butenedioic anhydride earliest, there is complete production Technology, reactor and catalyst
The research of technology is also quite ripe, but for other techniques, and benzene oxidatoin method uses expensive raw material price, while
Serious environmental pollution can be also produced in production process, it is further perfect recently as environmental regulation, its advantage by
Gradually lose, in the industry being phased out.C4Olefin oxidation method uses thick C obtained by naphtha pyrolysis4Cut as raw material,
Can effectively improve the utilization rate of naphtha pyrolysis gas to a certain extent, but due in the method products therefrom accessory substance it is more, after
Continuous separation costs are higher, and economically without too many advantage, therefore, it is difficult to large-scale application.N butane oxidation method was from head in 1974
Since secondary application, due to its have low in raw material price, environmental pollution are relatively low, carbon atom utilization rate is high, production cost compared with
Low advantage, progressively start to occupy the leading position in new market as new not only economic but also environmental protection technique.
In n butane oxidation method, although incomplete same in terms of type of reactor, fluid bed, fixed bed and moving bed are equal
There is corresponding research, but field scientific research personnel almost unanimously thinks that maximally effective catalyst is vanadium phosphorus oxygen (VPO) catalyst system and catalyzing.
In recent years, scientific research personnel is directed to improving always the activity and selectivity of vpo catalyst, and main research direction is：(1) auxiliary agent
The doping vario-property of element, conventional auxiliary element have iron, molybdenum, rare earth element etc.；(2) regulation of catalyst structure is modified, wherein
Change including catalyst macro morphology and catalytic inner pore structure is adjusted.
CN103691466A proposes a kind of preparation method of new vpo catalyst presoma, and the preparation method is toward isobutyl
Concentrated phosphoric acid, Bronsted acid and corresponding metal salt or oxide are added in alcohol and benzyl alcohol solvent, is heated to reflux, then adds
Rare earth element, continue to be heated to reflux, then cool down, filter, dry, obtain vpo catalyst presoma, the presoma contain vanadium, phosphorus,
Zinc, rare earth element and elements A and element B.The vpo catalyst prepared in this way has a preferable catalytic activity, but
Reaction temperature is higher during use, and the Selectivity of maleic anhydride of the catalyst is also relatively low.
CN103537310A discloses a kind of TiO with acid treatment2-ZrO2The support type VPO that composite oxides make carrier is urged
Agent.Composite oxides are made first by coprecipitation, are then handled with phosphoric acid, obtain acid treatment Ti-Zr composite oxides
Powder；Secondly vanadic anhydride is added in phenmethylol and isobutanol in the mixed solvent, is heated to reflux, adds the carrier powder
End, continue to heat, then add concentrated phosphoric acid and reacted, filtered, dry, roasting obtains support type vpo catalyst presoma.
The vpo catalyst being prepared can reach high n-butane conversion after activation process, but the catalyst equally exists institute
Need reaction temperature higher, and the technical problem that Selectivity of maleic anhydride is relatively low.
CN103357446A provides a kind of method for producing high pore volume vpo catalyst.The use of dielectric constant is 10~50
Organic solvent (such as butanol, acetone, DMF, ethylene glycol) with prepare vpo catalyst presoma contacted, formation has
At least micropore of 0.2cc/g Micropore volumes, about more than 20% can be increased by so handling the catalyst total pore volume of catalyst, although
So processing can improve the activity of catalyst to a certain extent, but overall lifting effect is extremely limited.
CN104549392A discloses a kind of method for being used to preparing, post-process and activating vpo catalyst by ebullated bed.Will
Isobutanol, phenmethylol, vanadic anhydride and promoter metal are added in fluidized bed reactor together is reacted, and is then added dense
Phosphoric acid continues reaction a period of time, carries out dried in place and roasting after obtaining blue slurry, is then passed through activated gas and is lived
Change is handled, the vpo catalyst powder finally given, then obtains required catalyst through forming processes.VPO prepared by the method is urged
Agent has preferable catalytic activity, but for catalyst prepared by the conventional method using low cost, the two entirety
Activity does not have too big difference, so " ebullated bed " system of high cost does not have too many advantage.
Although the researcher of numerous this areas has done substantial amounts of related work, as described above, it is existing
Following technological deficiency also be present in disclosed vpo catalyst technology of preparing：(1) catalyst component is complicated, can be increased using rare element
Add catalyst preparation cost；(2) catalyst preparation process is complicated；(3) catalyst activity is relatively low, cause reaction temperature generally compared with
Height, while Selectivity of maleic anhydride is relatively low；(4) application of part novel process causes input cost and output disproportionate.
For these technological deficiencies existing for the art, the present invention proposes a kind of high efficiency, low cost vpo catalyst
Preparation and activation method..
【The content of the invention】
[technical problems to be solved]
It is an object of the invention to provide a kind of vanadium-phosphor oxide catalyst for being used to produce maleic anhydride.
It is a further object to provide a kind of production for being used to produce the vanadium-phosphor oxide catalyst of maleic anhydride
Method.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method for being used to produce the vanadium-phosphor oxide catalyst of maleic anhydride.The vanadium phosphorus oxygen is urged
The step of agent production method, is as follows：
A, heteropoly acid solution is prepared
At 10~100 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of water or organic solvent：5~50 will have Keggin
The heteropoly acid of structure is dissolved in water or organic solvent, obtains a kind of heteropoly acid solution；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.001~0.1, heteropoly acid solution that step A is obtained with
Vanadic anhydride is added to the in the mixed solvent being made up of phenmethylol and isobutanol, well mixed to obtain a kind of reactant mixture, connects
And allow described reactant mixture progress first paragraph to be heated to reflux 6~24h, concentrated phosphoric acid is then added dropwise, then carry out second segment heating
Flow back 9~24h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using water, ethanol, isobutanol or
Methanol solvate is washed, and is done in temperature with being selected under conditions of air, nitrogen, argon gas or vacuum atmosphere for 100~150 DEG C
Dry, screening obtains a kind of catalyst precursor；
C, it is molded
The catalyst precursor that step B is obtained is with the remover selected from graphite, talcum powder or ethylene glycol according to weight ratio
100：0.1~10 is well mixed, then beats sheetmolding using tablet machine；
D, it is calcined
The sheetmolding catalyst precursor of beating for allowing step C to obtain mixes in normal butane and air Mixture or vapor with air
In the activation phenomenon for closing gas, in gaseous mixture with 500~2000h of air speed-1Under conditions of 0.1~1.0MPa of reaction pressure, to rise
Warm 1~10 DEG C/min of speed is heated to 200~350 DEG C of temperature, and 1~3h of activation process in this temperature range by room temperature；
Then；In the activation phenomenon of water vapour and air Mixture or vapor with inert gas gaseous mixture, in gaseous mixture with air speed
500~2000h-1Under conditions of 0.1~1.0MPa of reaction pressure, with 2~20 DEG C/min of heating rate be heated to temperature 350~
550 DEG C, and 0.1~3.0h of activation process in this temperature range, obtain described vanadium-phosphor oxide catalyst.
According to another preferred embodiment of the present invention, in step, described organic solvent is one or more choosings
From the organic solvent of methanol, ethanol, acetic acid, isobutanol, phenmethylol, ethylene glycol or citric acid.
According to another preferred embodiment of the present invention, in stepb, in the in the mixed solvent phenmethylol and isobutyl
The volume ratio of alcohol is 1：10~10：1.
According to another preferred embodiment of the present invention, in stepb, mixed solvent and five oxygen in gram in terms of milliliter
The ratio for changing two vanadium is 1：0.01~0.2.
According to another preferred embodiment of the present invention, in stepb, described reactant mixture is allowed with heating rate
1~10 DEG C/min is heated to 100~150 DEG C of progress first paragraphs of temperature and is heated to reflux.
According to another preferred embodiment of the present invention, in stepb, the concentration of the concentrated phosphoric acid is by weight 70
~100%.
According to another preferred embodiment of the present invention, in stepb, the reactant mixture for allowing first paragraph to be heated to reflux
90~140 DEG C of progress second segments of temperature are heated to 1~10 DEG C/min of heating rate to be heated to reflux.
According to another preferred embodiment of the present invention, in step C, its shape being molded is cylinder, bar shaped, three
Clover shape or annular.
According to another preferred embodiment of the present invention, in step D, in normal butane and air Mixture or vapor
With the activation in the activation phenomenon of air Mixture and in water vapour and air Mixture or vapor and inert gas gaseous mixture
In atmosphere, molar fraction of the normal butane in the gaseous mixture is 0.5~2.0%；Mole of the vapor in the gaseous mixture
Fraction is 20~60%；Molar fraction of the inert gas in the gaseous mixture is 40~80%；Described inert gas is one
Kind or a variety of inert gases selected from nitrogen, argon gas or helium.
The invention further relates to the vanadium-phosphor oxide catalyst obtained using the preparation method.It has following characteristics：
Chemical composition：Structure with Keggin heteropoly acid or salt [XM12O40]n-/ vpo catalyst, in formula X represent P, Si, Ge or
As elements；M represents Mo or W elements；
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
[XM12O40]n-；
Specific surface area：15~35m2/g；
Pore volume：0.1~0.6ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is more than 85%, and Selectivity of maleic anhydride is more than 68%.
The present invention is described in more detail below.
The present invention relates to a kind of preparation method for being used to produce the vanadium-phosphor oxide catalyst of maleic anhydride.The vanadium phosphorus oxygen is urged
The step of agent production method, is as follows：
A, heteropoly acid solution is prepared
At 10~100 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of water or organic solvent：5~1：50 will have
The heteropoly acid of structure with Keggin is dissolved in water or organic solvent, obtains a kind of heteropoly acid solution；
Heteropoly acid (HPA) is with one by central atom (such as P, Si, As, Ge etc.) and coordination atom (such as Mo, V, W etc.)
Determine the general name for the oxygen-containing polyacid that structure is made up of Atomic coordinate bridging.At present, most importantly have in catalytic reaction
The heteropoly acid of structure with Keggin, i.e. structural formula are [XM12O40]n-(X=P, Si, As, Ge etc.；M=Mo, W etc.) molybdenum and tungsten it is miscellaneous more
Acid, such as 12 phosphotungstic acid (H3PW12O40·xH2O, PW12), 12 silico-tungstic acid (H3SiW12O40·xH2O, SiW12)。
In the present invention, it is miscellaneous selected from phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid, silicon molybdenum using the heteropoly acid with structure with Keggin
Polyacid, phosphato-molybdic heteropolyacid or their salt etc. are current market sales of product, such as are had by Aladdin reagent (Shanghai)
Phosphorus heteropoly tungstic acid that limit company is sold with trade name phosphotungstic acid hydrate, by lark prestige Science and Technology Ltd. with trade name silico-tungstic acid
The silicotungstic heteropolyacid of sale, by lark prestige Science and Technology Ltd. with trade name 12-Molybdophosphoric acid
The phosphato-molybdic heteropolyacid of hydrate sale, the silicon sold by lark prestige Science and Technology Ltd. with trade name 12- molybdenum heteropolyacids hydrate
Molybdenum heteropolyacid etc..
According to the present invention, described organic solvent is one or more selected from methanol, ethanol, acetic acid, isobutanol, benzene first
The organic solvent of alcohol, ethylene glycol or citric acid.
Preferably, described organic solvent is that one or more are selected from ethanol, isobutanol, phenmethylol, ethylene glycol or lemon
The organic solvent of acid.
It is highly preferred that described organic solvent is one or more organic solvents for being selected from ethanol, ethylene glycol or citric acid.
In the present invention, prepare heteropoly acid solution the factors such as solubility limit due to and need temperature 10~
Carried out at 100 DEG C, if prepare temperature less than 10 DEG C, be difficult to form stable solution quickly.If it is high to prepare temperature
When 100 DEG C, a large amount of evaporations of solvent cause the increase of running cost.Therefore prepare temperature is all no more than this temperature range
Allow, preferably 25~80 DEG C, more preferably 35~60 DEG C.
Because heteropoly acid concentration is very big to catalyst precursor performance impact, therefore it should be controlled when preparing heteropoly acid
Heteropoly acid and water or the mass ratio of organic solvent.If heteropoly acid is more than 1 with the mass ratio of water or organic solvent：When 5, institute is prepared
It is higher to obtain solution concentration, it is difficult to be stabilized and preserve for a long time.If heteropoly acid is less than 1 with the mass ratio of water or organic solvent：
When 50, preparation resulting solution concentration is too low, and substantial amounts of solvent can be introduced while introducing a certain amount of heteropoly acid, and then to follow-up
Catalyst preparation process produces negative impact.Therefore, heteropoly acid and the mass ratio of water or organic solvent are 1：5~1：50 be to close
Reason, preferably 1：10~1：40, more preferably 1：18~1：30.
B, catalyst precursor is prepared
According to the mol ratio 1 of vanadic anhydride and heteropoly acid：0.001~0.1, heteropoly acid solution that step A is obtained with
Vanadic anhydride is added to the in the mixed solvent being made up of phenmethylol and isobutanol, well mixed to obtain a kind of reactant mixture, connects
And allow described reactant mixture progress first paragraph to be heated to reflux 6~24h, concentrated phosphoric acid is then added dropwise, then carry out second segment heating
Flow back 9~24h, obtains a kind of blue slurry, is cooled to room temperature.
In the present invention, organic phase reducing catalyst, isobutanol conduct are used as using phenmethylol and isobutanol mixed solvent
Solvent, phenmethylol is as reducing agent.Phenmethylol has an impact with isobutanol ratio to catalyst activity.The in the mixed solvent benzene first
The volume ratio of alcohol and isobutanol is 1：10~10：1, preferably 1：5~5：1, more preferably 1：2~2：1.
When preparing catalyst precursor, heteropoly acid and vanadic anhydride mol ratio are influence its presoma performance main
Factor, therefore its mol ratio should be controlled in a zone of reasonableness.According to the present invention, heteropoly acid and vanadic anhydride rub
Your ratio is 1：0.001~0.1, if the mol ratio of heteropoly acid and vanadic anhydride is less than 1：0.001, the too low shadow of heteropoly acid content
Ring catalyst activity；If the mol ratio of heteropoly acid and vanadic anhydride is more than 1：0.1, heteropoly acid too high levels are lived to catalyst
Property influences little, but can cause the increase of catalyst cost.Therefore, the mol ratio 1 of heteropoly acid and vanadic anhydride：0.001~0.1
Be it is appropriate, preferably 1：0.01~0.0.08, more preferably 1：0.02~0.0.06.
According to the present invention, the ratio of mixed solvent and vanadic anhydride in gram is 1 in terms of milliliter：0.01~0.2.It is if mixed
The ratio of bonding solvent and vanadic anhydride is more than 1：0.01, solvent can not be effectively utilized on the premise of properties of product are ensured, is made
Into the increase of cost；If the ratio of mixed solvent and vanadic anhydride is less than 1：0.2, vanadic anhydride and subsequent reactions generate
Vpo catalyst presoma can not disperse well in a solvent, products obtained therefrom can not reach preferable performance；Preferably 1：
0.05~0.16, more preferably 1：0.08~0.12.
In this step, first paragraph heating reflux reaction is carried out first, is then added phosphoric acid progress first paragraph and is heated back
Stream reaction.
The purpose of first paragraph heating reflux reaction is to enable vanadic anhydride preferably in a solvent to be disperseed, be molten
Solution.
Described reactant mixture is allowed to be heated to 100~150 DEG C of progress first paragraphs of temperature with 1~10 DEG C/min of heating rate
It is heated to reflux 6~24h.Section and second is heated to reflux first to be heated to reflux in section, heating ramp rate is too fast or is all slowly excessively
Unfavorable, solution can be caused to stablize formation and produce bumping phenomenon because heating is too fast, and excessively slow heating rate meeting
Cause the increase of running cost.
Preferably, described reactant mixture is heated to 120~140 DEG C of temperature with 2~5 DEG C/min of heating rate and carries out the
One section is heated to reflux 11~18h.
In this step, the effect for adding concentrated phosphoric acid is to make P with disperseing in a solvent before and dissociating abundant
V-arrangement into VPO presoma.
The concentration of addition concentrated phosphoric acid is 70~100%, preferably 85~95% by weight.
The amount of addition concentrated phosphoric acid is to be controlled with P/V moles in the reaction system for 0.9~1.3, preferably
1.0~1.2, more preferably 1.05~1.15.
The purpose of second segment heating reflux reaction is to enable P and V fully to react under certain temperature and solvent atmosphere
VPO presomas required for generation.
In this step, the reactant mixture that first paragraph is heated to reflux is allowed to be heated to 1~10 DEG C/min of heating rate
90~140 DEG C of temperature carries out second segment and is heated to reflux 9~24h.
Preferably, the reactant mixture that first paragraph is heated to reflux is allowed to be heated to temperature 120 with 2~5 DEG C/min of heating rate
~135 DEG C carry out second segment and are heated to reflux 11~20h, obtain a kind of blue slurry.
Then, the blue slurry is cooled to room temperature, generation grey black precipitation, then filters, use one or more
Solvent selected from water, ethanol, isobutanol or methanol is washed, 100~150 DEG C of temperature with selected from air, nitrogen, argon gas or
It is dried under conditions of vacuum atmosphere, screening obtains a kind of catalyst precursor；
In grey black washing of precipitate, grey black precipitation and the weight ratio of cleaning solvent are 1：2~5；Preferably 1：3~
4；Washing times are usually 2~4 times.
When drying grey black precipitation, common using those skilled in the art and known baking oven or tube furnace etc. are dry
Dry equipment is in 100~150 DEG C of temperature with being dried under air, nitrogen or argon gas atmosphere in terms of the complex catalyst precursor body weight
Less than 5%.
When being dried under vacuum atmosphere, using vacuum drying oven common to those skilled in the art 100~150 DEG C of temperature with
Dried under conditions of vacuum 0.001-0.01MPa to less than 5% in terms of the complex catalyst precursor body weight.
Preferably, drying temperature is 110~135 DEG C.
Using conventional grinding machine in the art and disintegrating apparatus, dry grey black sediment is ground,
Screening, the grey black sediment that granularity is 10~40 mesh is collected, is described catalyst precursor.
C, it is molded
The catalyst precursor that step B is obtained is with the remover selected from graphite, talcum powder or ethylene glycol according to weight ratio
100：0.1~10 is well mixed, then beats sheetmolding using tablet machine.
Releasing agent is used in an interface coating of two body surfaces for being easy to adhesion each other, and it can make body surface easy
In depart from, it is smooth and clean.Releasing agent is widely used in die cast metal, polyurethane foam and elastomer, glass fiber reinforcement modeling
In the various coining operations such as material, injection molded thermoplastic's plastics, vacuum foam sheet material and extrudate.In molding, other are moulded sometimes
Material compound such as plasticizer can be exuded on interface, at this moment just need a surface scavenger to remove it.
The present invention is that reduce material is stripped successfully in the adhesion strength of die surface so as to improve using the effect of remover
Rate and the frequency for reducing burn failure.In the present invention, if the weight of catalyst precursor and remover ratio is less than 100：
0.1, then active ingredient is relatively low in the shaped article obtained, reduces the performance of catalyst；If catalyst precursor and remover
Weight ratio be more than 100：10, the adhesion strength of material and die surface can not significantly reduce, the spoilage increase of mould；Therefore,
The weight of catalyst precursor and remover ratio is 100：0.1~10 is feasible；Preferably 100：1~8, more preferably
100：2~6.
The tablet machine that the present invention uses is current market sales of product, such as by Shanghai Tianfan Pharmaceutical Machinery Factory with business
Name of an article ZP17D rotates the product of continuous tablet press machine sale automatically.
According to the present invention, its shape being molded is cylinder, bar shaped, cloverleaf pattern or annular.
D, it is calcined
The sheetmolding catalyst precursor of beating for allowing step C to obtain mixes in normal butane and air Mixture or vapor with air
In the activation phenomenon for closing gas, in gaseous mixture with 500~2000h of air speed-1Under conditions of 0.1~1.0MPa of reaction pressure, to rise
Warm 1~10 DEG C/min of speed is heated to 200~350 DEG C of temperature, and 1~3h of activation process in this temperature range by room temperature；
Then；In the activation phenomenon of water vapour and air Mixture or vapor with inert gas gaseous mixture, in gaseous mixture with air speed
500~2000h-1Under conditions of 0.1~1.0MPa of reaction pressure, with 2~20 DEG C/min of heating rate be heated to temperature 350~
550 DEG C, and 0.1~3.0h of activation process in this temperature range, obtain described vanadium-phosphor oxide catalyst.
In the present invention, the sheetmolding catalyst precursor of beating is carried out in two steps activation process.
The purpose of first step activation process is that catalyst precursor is formed catalysis as much as possible under the atmosphere lives
Property phase, while remove there is no the organic impurities of catalytic activity in sample at a lower temperature.
According to the present invention, in normal butane and the activation phenomenon of air Mixture, normal butane rubbing in the gaseous mixture
Your fraction is 0.5~2.0%；Preferably 1.5~1.8%.
In water vapour and the activation phenomenon of air Mixture, molar fraction of the water vapour in the gaseous mixture be 20~
60%；Preferably 35~45%.
Preferably, beat sheetmolding catalyst precursor in activation phenomenon gaseous mixture with 800~1400h of air speed-1With reaction
Under conditions of 0.3~0.6MPa of pressure, 260~300 DEG C of temperature is heated to by room temperature with 3~6 DEG C/min of heating rate, and at this
1.6~2.5h of activation process in individual temperature range.
The purpose of second step activation process in activation process in guarantee catalyst on the premise of it will not occur temperature runaway, surely
Determine the catalytic activity phase of first step activation generation, while promote the generation of more catalyst activity phases.
According to the present invention, in water vapour and the activation phenomenon of air Mixture, water vapour rubbing in the gaseous mixture
Your fraction is 20~600%；Preferably 35~45%.
In the activation phenomenon of vapor and inert gas gaseous mixture, molar fraction of the inert gas in the gaseous mixture
It is 40~80%；Preferably 48~68%；Described inert gas is one or more selected from the lazy of nitrogen, argon gas or helium
Property gas.
Preferably, the preformed catalyst presoma through first step activation process activation phenomenon in, in gaseous mixture with sky
800~1600h of speed-1Under conditions of 0.3~0.6MPa of reaction pressure, temperature 400 is heated to 6~14 DEG C/min of heating rate
~500 DEG C, and 1.0~2.0h of activation process in this temperature range.
The invention further relates to the vanadium-phosphor oxide catalyst obtained using the preparation method.
Described vanadium-phosphor oxide catalyst has following characteristics：
Determined using x-ray fluorescence analysis method, its P, Si, Ge, As, Mo, content of element W are with oxide mass content meter
It is 38.80%, 0.03%, 0.06%, 0.05%, 0.7% or 1.13% respectively.It can be determined by these element oxide contents
Vanadium-phosphor oxide catalyst prepared by the present invention has following chemical compositions, and wherein Si (Ge, As) and Mo (W) mol ratio are about 1:12,
Prove [XM12O40] still keeping structure with Keggin after heteropoly acid and vpo catalyst are compound, X represents P, Si, Ge or As member in formula
Element；M represents Mo or W elements；
X-ray diffraction analysis (XRD) use the x-ray powder diffraction instrument of Dutch PANalytical companies, in following conditions
Lower test：CuK α, graphite monochromator, operating voltage 30kV, operating current 30mA, 10~80 ° of scanning range, vanadium phosphorus of the invention
VPO catalysts X-ray diffractogram is listed in accompanying drawing 1.X-ray diffractogram result shows that vanadium-phosphor oxide catalyst prepared by the present invention is main
For (VO)2P2O7Phase, amorphous phase, and have no structure with Keggin heteropoly acid or salt [XM12O40]n-Crystalline phase peak, illustrates heteropoly acid
It is highly dispersed on vpo catalyst.
Nitrogen physisorption desorption measure vanadium-phosphor oxide catalyst surface property specific surface area is used as 15~35m2/g；Hole body
Product is 0.1~0.6ml/g.
Activation vpo catalyst is loaded into shell and tube fused salt heat exchanging reactor well-known in the art, utilizes heat exchange
Medium fused salt controls temperature of reactor.Vpo catalyst of the present invention is reacted under following process conditions：Contained with normal butane mole
Measure and make raw material for 1~2% normal butane and the gaseous mixture of air, 370~420 DEG C of reaction temperature, volume space velocity 1000~
2000h-1With being reacted under conditions of 0.05~0.20MPa of reaction pressure, by analyzing tail gas gas phase composition and tail gas absorption
Liquid composition can calculate n-butane conversion and Selectivity of maleic anhydride according to formula.
Result of the test shows, makees raw material by 1~2% normal butane and the gaseous mixture of air of normal butane molar content,
370~420 DEG C of reaction temperature, 1000~2000h of volume space velocity-1, normal butane turns under conditions of 0.05~0.20MPa of reaction pressure
Rate can reach 85%, and Selectivity of maleic anhydride reaches 68%.
Compared with existing other prior arts, vpo catalyst preparation method of the present invention has advantages below：(1) it is of the invention
The architectural feature of heteropoly acid, the existing complex of heteropoly acid and metal oxide is added in catalyst precursor is prepared first, also
Have redox property and acidity concurrently.So as to effectively improve catalyst activity and selectivity, such as compared with prior art, this
The n-butane conversion for inventing the vpo catalyst prepared improves 1~3%, and Selectivity of maleic anhydride improves 2~3%.Simultaneously as
Transition metal oxide auxiliary agent and surfactant are not introduced in preparation process, also simplify preparation process to a certain extent,
Also reduce catalyst preparation cost simultaneously；(2) present invention effectively solves VPO catalysis using vpo catalyst segmentation activation method
Bed temperature is unmanageable and the problem of finished catalyst activity is relatively low in agent single hop activation process；(3) according to present invention side
Vpo catalyst reaction temperature prepared by method is lower about 30 DEG C than existing catalysis catalyst.
The invention provides a kind of vanadium phosphorus oxygen catalysis that can be used for producing cis-butenedioic anhydride by n butane oxidation with industrially scalable
Agent, vpo catalyst prepared by the present invention have good market competitiveness, have boundless application compared with prior art
Prospect.
【Beneficial effect】
The beneficial effects of the invention are as follows：Compared with existing other prior arts, vpo catalyst preparation method of the present invention has
Advantages below：(1) present invention adds heteropoly acid in catalyst precursor is prepared first, and preparation technology is simple and cost is cheap,
The activity and selectivity of catalyst is effectively improved, compared with prior art, n-butane conversion improves 1~3%, cis-butenedioic anhydride choosing
Selecting property improves 2~3%；(2) solve the problems, such as that bed temperature is unmanageable during vpo catalyst activation in the prior art；(3) with
Prior art is compared, and vpo catalyst reaction temperature prepared by the inventive method is lower than existing catalyst reaction temperatures about 30 DEG C, drop
Low energy consumption, cost is saved for enterprise.
【Brief description of the drawings】
Accompanying drawing 1 is the x-ray diffraction pattern of vanadium-phosphor oxide catalyst of the present invention.
【Embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
At 25 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of methanol organic solvent：30, will be limited by lark prestige science and technology
The phosphorus heteropoly tungstic acid that company of company is sold with trade name phosphotungstic acid is dissolved in described organic solvent, and it is molten to obtain a kind of heteropoly acid
Liquid；
B, catalyst precursor is prepared
According to the mol ratio 0.02 of phosphorus heteropoly tungstic acid and vanadic anhydride：1, the heteropoly acid solution and five that step A is obtained
V 2 O is added to by phenmethylol and isobutanol according to volume ratio 2：1 composition in the mixed solvent, in terms of milliliter mixed solvent with
The ratio of vanadic anhydride is 1 in gram：0.05, it is well mixed to obtain a kind of reactant mixture, then allow described reaction to mix
Thing is heated to 100 DEG C of progress first paragraphs of temperature with 2 DEG C/min of heating rate and is heated to reflux 11h, and concentration then is added dropwise by weight
70% concentrated phosphoric acid, it is 1.05 to reach P/V moles in the reaction system, then allow the reactant mixture that first paragraph is heated to reflux with
1 DEG C/min of heating rate is heated to 120 DEG C of progress second segments of temperature and is heated to reflux 15h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filters, is precipitated using water according to grey black
Weight with water is than 1：2 washings 2 times, are then dried to before with the catalyst under conditions of 135 DEG C of temperature and air atmosphere
Weight 5.0% is driven, screening, the grey black sediment that granularity is 10~20 mesh is collected, is described catalyst precursor；
C, it is molded
The catalyst precursor that step B is obtained is with being selected from graphite remover according to weight than 100：1 is well mixed, then
Using by Shanghai Tianfan Pharmaceutical Machinery Factory using trade name ZP17D rotate automatically the tablet machine that continuous tablet press machine sells beat sheetmolding as
Cylinder；
D, it is calcined
Allow step C obtains beat sheetmolding catalyst precursor the normal butane that normal butane molar fraction is 0.5% with it is empty
In the activation phenomenon of gas gaseous mixture, in gaseous mixture with air speed 1200h-1Under conditions of reaction pressure 0.2MPa, with heating rate 8
DEG C/min is heated to 260 DEG C of temperature, and activation process 2.0h at this temperature by room temperature；Then；In steam molar fraction
Water vapour for 20% and in the activation phenomenon of air Mixture, in gaseous mixture with air speed 800h-1With reaction pressure 0.2MPa's
Under the conditions of, 350 DEG C of temperature, and activation process 1.0h at this temperature are heated to 6 DEG C/min of heating rate, obtained described
Vanadium-phosphor oxide catalyst.
Determined using the method described in present specification：
Chemical composition：PW12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
PW12/VPO。
Specific surface area：15m2/g；
Pore volume：0.2ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is 85.6%, Selectivity of maleic anhydride 68.2%.
Embodiment 2：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
At 80 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of water：50, will be by Chinese medicines group company with trade name silicon tungsten
Acid, it is soluble in water to be hydrated the silicotungstic heteropolyacid of sale, obtains a kind of heteropoly acid solution；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.0.06, the obtained heteropoly acid solution of step A and five oxygen
Change two vanadium to be added to by phenmethylol and isobutanol according to volume ratio 8：10 composition in the mixed solvents, in terms of milliliter mixed solvent with
Gram meter vanadic anhydride ratio be 1：0.16, it is well mixed to obtain a kind of reactant mixture, then allow described reactant mixture
120 DEG C of progress first paragraphs of temperature are heated to 5 DEG C/min of heating rate and are heated to reflux 18h, concentration then is added dropwise by weight
85% concentrated phosphoric acid, it is 1.15 to reach P/V moles in the reaction system, then allow the reactant mixture that first paragraph is heated to reflux with
10 DEG C/min of heating rate is heated to 135 DEG C of progress second segments of temperature and is heated to reflux 11h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using alcohol solvent according to greyish black
Color precipitates the weight with cleaning solvent than 1：5 washings 3 times, in 100 DEG C of temperature with being dried extremely with described under conditions of nitrogen atmosphere
For complex catalyst precursor body weight meter below 5%, the grey black sediment that granularity is 20~40 mesh is collected in screening, is described catalysis
Agent presoma；
C, it is molded
The catalyst precursor that step B is obtained is with the remover selected from talcum powder remover according to weight than 100：8 is mixed
Close uniform, then use and beat piece by Shanghai Tianfan Pharmaceutical Machinery Factory with what trade name ZP17D rotated continuous tablet press machine sale automatically
Machine beats sheetmolding as annular；
D, it is calcined
Allow what step C obtained to beat sheetmolding catalyst precursor in the vapor and air that steam molar fraction is 60%
In the activation phenomenon of gaseous mixture, in gaseous mixture with air speed 500h-1Under conditions of reaction pressure 0.3MPa, with 1 DEG C of heating rate/
Min is heated to 300 DEG C of temperature, and activation process 1.0h at this temperature by room temperature；Then；It is in inert gas molar fraction
In 80% steam and the activation phenomenon of inert gas gaseous mixture, in gaseous mixture with air speed 1600h-1With reaction pressure 0.3MPa's
Under the conditions of, 400 DEG C of temperature, and activation process 0.1h at this temperature are heated to 14 DEG C/min of heating rate, obtained described
Vanadium-phosphor oxide catalyst.
Determined using the method described in present specification：
Chemical composition：SiW12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
SiW12/VPO。
Specific surface area：35m2/g；
Pore volume：0.3ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is 86.4%, Selectivity of maleic anhydride 66.8%.
Embodiment 3：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
At 10 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of isobutanol organic solvent：5, will be limited by lark prestige science and technology
The silicon-molybdenum heteropoly acid that company is sold with trade name 12- molybdenum heteropolyacids hydrate is dissolved in described organic solvent, is obtained a kind of miscellaneous
More acid solutions；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.001, the obtained heteropoly acid solution of step A and five are aoxidized
Two vanadium are added to by phenmethylol and isobutanol according to volume ratio 6：5 composition in the mixed solvents, in terms of milliliter mixed solvent with gram
The ratio for counting vanadic anhydride is 1：0.01, it is well mixed to obtain a kind of reactant mixture, then allow described reactant mixture with
1 DEG C/min of heating rate is heated to 140 DEG C of temperature carries out first paragraphs and is heated to reflux 6h, and concentration by weight 95% is then added dropwise
Concentrated phosphoric acid, it is 0.9 to reach P/V moles in the reaction system, then allows the reactant mixture that first paragraph is heated to reflux with the speed that heats up
6 DEG C/min of rate is heated to 90 DEG C of progress second segments of temperature and is heated to reflux 20h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using iso-butanol solvent according to ash
The weight of black precipitate and cleaning solvent is than 1：3 washings 4 times, are dried to institute under conditions of 110 DEG C of temperature and argon gas atmosphere
Complex catalyst precursor body weight meter is stated below 5%, the grey black sediment that granularity is 10~20 mesh is collected in screening, is described urge
Agent presoma；
C, it is molded
The catalyst precursor that step B is obtained is with ethylene glycol remover according to weight than 100：0.1 is well mixed, then
Using by Shanghai Tianfan Pharmaceutical Machinery Factory using trade name ZP17D rotate automatically the tablet machine that continuous tablet press machine sells beat sheetmolding as
Cylinder；
D, it is calcined
Allow step C obtains beat sheetmolding catalyst precursor the normal butane that normal butane molar fraction is 2.0% with it is empty
In the activation phenomenon of gas gaseous mixture, in gaseous mixture with air speed 2000h-1Under conditions of reaction pressure 0.6MPa, with heating rate 3
DEG C/min is heated to 200 DEG C of temperature, and activation process 3.0h at this temperature by room temperature；Then；In inert gas mole point
Number is in 40% steam and the activation phenomenon of inert gas gaseous mixture, in gaseous mixture with air speed 500h-1With reaction pressure
Under conditions of 0.6MPa, 550 DEG C of temperature, and activation process 0.1h at this temperature are heated to 2 DEG C/min of heating rate, obtained
To described vanadium-phosphor oxide catalyst.
Determined using the method described in present specification：
Chemical composition：SiMo12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
SiMo12/VPO。
Specific surface area：20m2/g；
Pore volume：0.3ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is more than 86.8%, Selectivity of maleic anhydride 65.2%.
Embodiment 4：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
At 100 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of isobutanol organic solvent：10, will be had by lark prestige science and technology
Limit company is dissolved in described organic with the trade name 12-Molybdophosphoric acid hydrate phosphato-molybdic heteropolyacids sold
In solvent, a kind of heteropoly acid solution is obtained；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.1, the obtained heteropoly acid solution of step A and five oxidations two
Vanadium is added to by phenmethylol and isobutanol according to volume ratio 10：7 composition in the mixed solvents, in terms of milliliter mixed solvent with gram
The ratio of vanadic anhydride is 1：0.2, it is well mixed to obtain a kind of reactant mixture, then allow described reactant mixture to heat up
10 DEG C/min of speed is heated to 150 DEG C of temperature carries out first paragraphs and is heated to reflux 24h, and concentration by weight 100% is then added dropwise
Concentrated phosphoric acid, it is 1.3 to reach P/V moles in the reaction system, then allows the reactant mixture that first paragraph is heated to reflux with the speed that heats up
2 DEG C/min of rate is heated to 140 DEG C of progress second segments of temperature and is heated to reflux 9h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using methanol solvate according to greyish black
Color precipitates the weight with cleaning solvent than 1：4 washings 3 times, in 140 DEG C of temperature with being dried extremely with described under conditions of nitrogen atmosphere
For complex catalyst precursor body weight meter below 5%, the grey black sediment that granularity is 20~30 mesh is collected in screening, is described catalysis
Agent presoma；
C, it is molded
The catalyst precursor that step B is obtained is with graphite remover according to weight than 100：10 is well mixed, then makes
Sheetmolding is beaten as ring with the tablet machine for rotating continuous tablet press machine sale automatically using trade name ZP17D by Shanghai Tianfan Pharmaceutical Machinery Factory
Shape；
D, it is calcined
Allow what step C obtained to beat sheetmolding catalyst precursor in the vapor and air that steam molar fraction is 30%
In the activation phenomenon of gaseous mixture, in gaseous mixture with air speed 800h-1Under conditions of reaction pressure 0.1MPa, with 6 DEG C of heating rate/
Min is heated to 350 DEG C of temperature, and activation process 1.6h at this temperature by room temperature；Then；It is in steam molar fraction
In 40% water vapour and the activation phenomenon of air Mixture, in gaseous mixture with air speed 1000h-1With reaction pressure 0.1MPa bar
Under part, 500 DEG C of temperature, and activation process 3.0h at this temperature are heated to 2 DEG C/min of heating rate, obtain described vanadium
Phosphor oxide catalyst.
Determined using the method described in present specification：
Chemical composition：PMo12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
PMo12/VPO。
Specific surface area：28m2/g；
Pore volume：0.6ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is more than 84.7%, Selectivity of maleic anhydride 68.6%.
Embodiment 5：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
At 35 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of ethylene glycol organic solvent：40, will by Aladdin reagent (on
Sea) phosphorus heteropoly tungstic acid sell with trade name 12- tungstophosphoric acids hydrate of Co., Ltd be dissolved in described in organic solvent in, obtain one
Kind heteropoly acid solution；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.01, the obtained heteropoly acid solution of step A and five are aoxidized
Two vanadium are added to by phenmethylol and isobutanol according to volume ratio 5：4 composition in the mixed solvents, in terms of milliliter mixed solvent with gram
The ratio for counting vanadic anhydride is 1：0.08, it is well mixed to obtain a kind of reactant mixture, then allow described reactant mixture with
6 DEG C/min of heating rate, which is heated to 110 DEG C of temperature, to carry out first paragraphs and is heated to reflux 20h, and concentration by weight 80% is then added dropwise
Concentrated phosphoric acid, it is 1.0 to reach P/V moles in the reaction system, then allows the reactant mixture that first paragraph is heated to reflux to heat up
5 DEG C/min of speed is heated to 110 DEG C of progress second segments of temperature and is heated to reflux 18h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using alcohol solvent according to greyish black
Color precipitates the weight with cleaning solvent than 1：2 washings 4 times, are dried extremely under conditions of 150 DEG C of temperature and vacuum 0.001MPa
Less than 5% in terms of the complex catalyst precursor body weight, the grey black sediment that granularity is 20~40 mesh is collected in screening, is described
Catalyst precursor；
C, it is molded
The catalyst precursor that step B is obtained is with talcum powder remover according to weight than 100：2 is well mixed, then makes
Sheetmolding is beaten to be round with the tablet machine for rotating continuous tablet press machine sale automatically using trade name ZP17D by Shanghai Tianfan Pharmaceutical Machinery Factory
Cylindricality；
D, it is calcined
Allow step C obtains beat sheetmolding catalyst precursor the normal butane that normal butane molar fraction is 0.8% with it is empty
In the activation phenomenon of gas gaseous mixture, in gaseous mixture with air speed 1800h-1Under conditions of reaction pressure 0.8MPa, with heating rate
10 DEG C/min is heated to 240 DEG C of temperature, and activation process 2.5h at this temperature by room temperature；Then；In steam molar point
Number is in 50% water vapour and the activation phenomenon of air Mixture, in gaseous mixture with air speed 2000h-1With reaction pressure 1.0MPa
Under conditions of, 450 DEG C of temperature, and activation process 1.6h at this temperature are heated to 20 DEG C/min of heating rate, obtain institute
The vanadium-phosphor oxide catalyst stated.
Determined using the method described in present specification：
Chemical composition：PW12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
PW12/VPO。
Specific surface area：30m2/g；
Pore volume：0.1ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is more than 82.2%, Selectivity of maleic anhydride 70.2%.
Embodiment 6：
Prepare the vanadium-phosphor oxide catalyst of the present invention
The implementation steps of the embodiment are as follows：
A, heteropoly acid solution is prepared
Under temperature 60 C, according to heteropoly acid and the mass ratio 1 of citric acid organic solvent：18, clever biology will be breathed out by Shanghai
The silicotungstic heteropolyacid that Science and Technology Ltd. is sold with trade name Silicotungstic acid hydrate is dissolved in described organic solvent, obtains one kind
Heteropoly acid solution；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.0.08, the obtained heteropoly acid solution of step A and five oxygen
Change two vanadium to be added to by phenmethylol and isobutanol according to volume ratio 1：2 composition in the mixed solvents, in terms of milliliter mixed solvent with
Gram meter vanadic anhydride ratio be 1：0.12, it is well mixed to obtain a kind of reactant mixture, then allow described reactant mixture
120 DEG C of progress first paragraphs of temperature are heated to 8 DEG C/min of heating rate and are heated to reflux 16h, concentration then is added dropwise by weight
90% concentrated phosphoric acid, it is 1.2 to reach P/V moles in the reaction system, then allow the reactant mixture that first paragraph is heated to reflux with
8 DEG C/min of heating rate is heated to 100 DEG C of progress second segments of temperature and is heated to reflux 24h, obtains a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filtered, using iso-butanol solvent according to ash
The weight of black precipitate and cleaning solvent is than 1：4 washings 2 times, are dried extremely under conditions of 125 DEG C of temperature and vacuum 0.01MPa
Less than 5% in terms of the complex catalyst precursor body weight, the grey black sediment that granularity is 10~40 mesh is collected in screening, is described
Catalyst precursor；
C, it is molded
The catalyst precursor that step B is obtained is with graphite remover according to weight than 100：6 is well mixed, then uses
The tablet machine for rotating continuous tablet press machine sale automatically using trade name ZP17D by Shanghai Tianfan Pharmaceutical Machinery Factory beats sheetmolding as ring
Shape；
D, it is calcined
Allow step C obtains beat sheetmolding catalyst precursor the normal butane that normal butane molar fraction is 1.4% with it is empty
In the activation phenomenon of gas gaseous mixture, in gaseous mixture with air speed 1800h-1Under conditions of reaction pressure 0.8MPa, with heating rate 5
DEG C/min is heated to 320 DEG C of temperature, and activation process 1.8h at this temperature by room temperature；Then；In inert gas mole point
Number is in 60% steam and the activation phenomenon of inert gas gaseous mixture, in gaseous mixture with air speed 1800h-1With reaction pressure
Under conditions of 0.8MPa, 480 DEG C of temperature, and activation process 2.4h at this temperature are heated to 10 DEG C/min of heating rate,
Obtain described vanadium-phosphor oxide catalyst.
Determined using the method described in present specification：
Chemical composition：SiWo12(heteropoly acid or salt)/VPO
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
SiW12/VPO。
Specific surface area：18m2/g；
Pore volume：0.4ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, reacting
370~420 DEG C of temperature, 1000~2000h of volume space velocity-1Converted with normal butane under conditions of 0.05~0.20MPa of reaction pressure
Rate is more than 83.6%, Selectivity of maleic anhydride 68.9%.
Comparative example 1
It is catalyzed from the vanadium phosphorus oxygen commercial catalysts produced by German South Chemical Company described in background section
Agent sample, code name A, catalyst performance evaluation condition is identical with the method described in embodiment 1-6, and catalyst performance is the same as implementation
Example is together listed in table 1.
Comparative example 2
From the vanadium-phosphor oxide catalyst production piece produced by Shandong enterprise described in background section, code name is
B, catalyst performance evaluation condition is identical with the method described in embodiment 1-6, and catalyst performance is together listed in table with embodiment
1。
Table 1：The operating temperature and reaction result of different catalysts
The result of table 1 clearly shows that vpo catalyst prepared by the present invention has preferable n-butane conversion and cis-butenedioic anhydride selection
Property, n-butane conversion and Selectivity of maleic anhydride have been respectively increased 1~3% and 2~3%, and low 30 DEG C or so of reaction temperature, had
There is very good application prospect.
Claims (8)
1. a kind of preparation method for being used to produce the vanadium-phosphor oxide catalyst of maleic anhydride, it is characterised in that the step of this method
It is as follows：
A, heteropoly acid solution is prepared
At 10~100 DEG C of temperature, according to heteropoly acid and the mass ratio 1 of water or organic solvent：5~50 will have structure with Keggin
Heteropoly acid be dissolved in water or organic solvent, obtain a kind of heteropoly acid solution；Described organic solvent is that one or more are selected from
Methanol, ethanol, acetic acid, isobutanol, phenmethylol, the organic solvent of ethylene glycol or citric acid；
B, catalyst precursor is prepared
According to the mol ratio 1 of heteropoly acid and vanadic anhydride：0.001~0.1, the obtained heteropoly acid solution of step A and five oxygen
Change two vanadium to be added to by phenmethylol and isobutanol according to volume ratio 1：10~10：The in the mixed solvent of 1 composition, it is well mixed to obtain one
Kind reactant mixture, then allow described reactant mixture to carry out first paragraph and be heated to reflux 6~24h, concentrated phosphoric acid is then added dropwise, then
Carry out second segment and be heated to reflux 9~24h, obtain a kind of blue slurry；
The blue slurry is cooled to room temperature, generation grey black precipitation, then filters, uses water, ethanol, isobutanol or methanol
Solvent is washed, and in temperature, 100~150 DEG C are dried with being selected under conditions of air, nitrogen, argon gas atmosphere or vacuum,
Screening obtains a kind of catalyst precursor；
C, it is molded
The catalyst precursor that step B is obtained is with the remover selected from graphite, talcum powder or ethylene glycol according to weight than 100：
0.1~10 is well mixed, then beats sheetmolding using tablet machine；
D, it is calcined
Allow what step C obtained to beat sheetmolding catalyst precursor in normal butane and air Mixture or vapor and air Mixture
Activation phenomenon in, in gaseous mixture with 500~2000h of air speed-1Under conditions of 0.1~1.0MPa of reaction pressure, with the speed that heats up
1~10 DEG C/min of rate is heated to 200~350 DEG C of temperature, and 1~3h of activation process in this temperature range by room temperature；Then,
In the activation phenomenon of water vapour and air Mixture or vapor with inert gas gaseous mixture, gaseous mixture with air speed 500~
2000h-1Under conditions of 0.1~1.0MPa of reaction pressure, temperature 350~550 is heated to 2~20 DEG C/min of heating rate
DEG C, and 0.1~3.0h of activation process in this temperature range, obtain described vanadium-phosphor oxide catalyst.
2. preparation method according to claim 1, it is characterised in that in stepb, in terms of milliliter mixed solvent with gram
The ratio for counting vanadic anhydride is 1：0.01~0.2.
3. preparation method according to claim 1, it is characterised in that in stepb, allow described reactant mixture to rise
Warm 1~10 DEG C/min of speed is heated to 100~150 DEG C of progress first paragraphs of temperature and is heated to reflux.
4. preparation method according to claim 1, it is characterised in that in stepb, the concentration of the concentrated phosphoric acid is with weight
Gauge 70~100%.
5. preparation method according to claim 1, it is characterised in that in stepb, the reaction for allowing first paragraph to be heated to reflux
Mixture is heated to 90~140 DEG C of progress second segments of temperature with 1~10 DEG C/min of heating rate and is heated to reflux.
6. preparation method according to claim 1, it is characterised in that in step C, its shape being molded is cylinder, bar
Shape, cloverleaf pattern or annular.
7. preparation method according to claim 1, it is characterised in that in step D, in normal butane and air Mixture or
In vapor and the activation phenomenon of air Mixture and in water vapour and air Mixture or vapor and inert gas gaseous mixture
Activation phenomenon in, molar fraction of the normal butane in the gaseous mixture is 0.5~2.0%；Vapor is in the gaseous mixture
Molar fraction be 20~60%；Molar fraction of the inert gas in the gaseous mixture is 40~80%；Described indifferent gas
Body is one or more inert gases for being selected from nitrogen, argon gas or helium.
8. according to preparation method described in any one of claim 1-7 claim obtain be used for produce maleic anhydride
Vanadium-phosphor oxide catalyst, it is characterised in that it has following characteristics：
Chemical composition：Structure with Keggin heteropoly acid or salt [XM12O40]n-/ vpo catalyst, X represents P, Si, Ge or As member in formula
Element；M represents Mo or W elements；
Crystal structure：In catalyst predominantly (VO)2P2O7Phase, amorphous phase and structure with Keggin heteropoly acid or salt
[XM12O40]n-；
Specific surface area：15~35m2/g；
Pore volume：0.1~0.6ml/g；
Catalytic performance：Make raw material in the normal butane and the gaseous mixture of air that normal butane molar content is 1~2%, in reaction temperature
370~420 DEG C, 1000~2000h of volume space velocity-1It is with n-butane conversion under conditions of 0.05~0.20MPa of reaction pressure
More than 85%, Selectivity of maleic anhydride is more than 68%.
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| CN106552656A (en) * | 2016-11-07 | 2017-04-05 | 山东齐鲁科力化工研究院有限公司 | Loaded catalyst and application thereof |
| CN108101872B (en) * | 2016-11-24 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst grading method for producing maleic anhydride by oxidizing n-butane |
| CN108339558B (en) * | 2017-01-24 | 2020-12-18 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst for preparing maleic anhydride by oxidizing n-butane and preparation method thereof |
| CN108355690B (en) * | 2018-02-09 | 2021-01-26 | 中国科学院过程工程研究所 | Vanadyl phosphate catalyst, preparation method and application thereof |
| CN109053647B (en) * | 2018-08-23 | 2022-06-10 | 常州新日催化剂股份有限公司 | Production process for preparing maleic anhydride by oxidizing n-butane |
| CN111054409B (en) * | 2018-10-16 | 2022-12-13 | 中国石油化工股份有限公司 | Activation method of catalyst for preparing maleic anhydride by oxidizing n-butane |
| CN114797921B (en) * | 2022-04-20 | 2023-08-08 | 润和催化剂股份有限公司 | Maleic anhydride catalyst and preparation method and application thereof |
| CN115770618A (en) * | 2022-11-29 | 2023-03-10 | 安徽工业大学 | Supported vanadium phosphorus oxo heteropoly acid catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1132689C (en) * | 2000-12-29 | 2003-12-31 | 南京大学 | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use |
| DE10211449A1 (en) * | 2002-03-15 | 2003-09-25 | Basf Ag | Production of a vanadium, phosphorous and oxygen catalyst precursor for the production of maleic acid anhydride comprises controlled mixing and/or heating of vanadium pentoxide with a phosphorous compound in the presence of an alcohol |
| CN103769181B (en) * | 2012-10-24 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of vanadium-phosphor oxide catalyst and preparation method thereof |
| CN103769183B (en) * | 2012-10-24 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of vanadium phosphorus oxide and preparation method thereof |
| CN103769182B (en) * | 2012-10-24 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of load-type vanadium phosphorous oxides and its production and use |
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