CN105413725B - Vanadium phosphorus catalyst and preparation method thereof - Google Patents
Vanadium phosphorus catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of vanadium phosphorus catalysts for hydro carbons gas phase catalytic oxidation reaction, mainly solve the low technical problem of existing catalyst activity low selectivity, the present invention is by using the catalyst for the combination of compounds containing vanadium, phosphorus, oxygen and one or more of other elements, it is characterized in that the XRD diffracting spectrum of the compound has main diffractive features peak, the diffraction maximum peak height (I at 2 θ=12.5 at 2 θ=12.5,18.5,22.8,28.4,29.3,29.9,43.21) and 2 θ=22.8 at diffraction maximum peak height (I2) ratio I1:I2=0.3~3, the catalyst has the performance of more preferably catalytic hydrocarbon gas-like phase selective oxidation, and catalyst obtained can use hydro carbons gas phase catalytic oxidation reaction.
Description
Technical field
The present invention relates to a kind of vanadium phosphorus oxide catalysts and preparation method thereof.It is anti-that the catalyst can be used for a variety of oxidations
It answers, produces maleic anhydride especially suitable for gas phase hydrocarbon selective oxidation.
Technical background
Maleic anhydride, abbreviation cis-butenedioic anhydride, that is, maleic anhydride (Maleic anhydride, MA) are a kind of common
Important Organic Chemicals, the in the world the third-largest acid anhydrides kind of consumption figure.Cis-butenedioic anhydride is currently used primarily in production unsaturated polyester (UP)
Resin, the chemicals such as alkyd resin, 1,4-butanediol (BDO), gamma-butyrolacton (GBL), tetrahydrofuran (THF).In addition, each
Class Field of Fine Chemicals is also widely used.
The production of cis-butenedioic anhydride is mainly divided to two classes, and earliest production method uses benzene as a raw material for production, but due to raw material itself
With the influence of harmfulness and economic factor to environment, the production technology of benzene method ratio shared in maleic anhydride production is increasingly
Reduce；The mainstream production method of cis-butenedioic anhydride uses normal butane as a raw material for production at present, including fixed bed, fluidized bed, moving bed etc.,
These techniques respectively have feature, there is actual industrial application mostly, but identical is the work of these preparing cis-anhydride by n-butane oxidation
Skill is all made of same class catalyst, i.e. vanadium phosphorus oxygen (VPO) catalyst.
Think that vpo catalyst is still to produce so far to catalyzed gas hydro carbons especially normal butane by years of researches
The maximally efficient catalyst system of maleic anhydride.Industrialized vpo catalyst generallys use aqueous solvent or organic solvent method
Presoma is made, gained presoma obtains final catalyst by calcination activation and molding.For in vpo catalyst mechanism
Active phase, most researchers still support early stage study viewpoint, i.e., vpo catalyst catalysis selective oxidation of n -butane generate
The main activity of cis-butenedioic anhydride is mutually (VO)2P2O7；In most of higher vpo catalysts of activity, the master of VPO in XRD characterization result
Wanting object is mutually (VO)2P2O7, mainly pass through presoma VOHPO4·0.5H2O heat treatment dehydration is formed.
(VO)2P2O7V is mainly V in phase4+Species, but usually vpo catalyst object phase composition is changeable, through different preparation and
Processing method can obtain different object phase composition states, often corresponding containing there are many V (V of valence state5+/V4+/V3+).This is amplified out
The problem of be, whether the catalytic performance of vpo catalyst only by (VO)2P2O7Main body mutually provides, or have other activity mutually or
The participation of active specy acts on.A part of researcher thinks, in the reaction that selective oxidation of n -butane generates cis-butenedioic anhydride, rises and mainly urges
Change effect is corresponding V4+(VO) of species2P2O7Phase；And V certain in catalyst is then thought there are also some researchers5+Species,
It can be improved the selectivity of cis-butenedioic anhydride, V in catalyst system4+And V5+Certain synergistic effect can be generated by existing simultaneously.And for
V5+/V4+Optimal proportion also exist dispute.This explanation, the crystal phase structure of vpo catalyst have its catalytic performance particularly significant
Influence.
In research in recent years, aforementioned two kinds of customary preparation methods are defined as VPA and VPO method by Hutchings etc., and
They report using by pentavalent barium oxide and water and phosphatase reaction, obtain VOPO4·2H2O, then by VOPO4·2H2O is gone back
Original obtains VOHPO4·0.5H2VPO presoma obtained by the VPD method of O has bigger specific surface area, can generate more preferable
Catalytic performance (Vanadium phosphate:a new look at the active components of
catalysts for the oxidation of butane,G J Hutchings,J Mater Chem,2004,14,
3385).Pass through VOPO4Route high-specific surface area VPO preparation method obtains bigger specific surface area and more reasonable catalyst knot
Structure, so as to obtain better catalyst performance.And VOPO4And VOHPO4All be layer structure, this make its structure there is
The possibility of modulation is carried out by intercalation compound.
Summary of the invention
The problem of the first technical problem to be solved by the present invention is that existing catalyst activity is low, poor selectivity；This hair
Bright to provide a kind of vanadium phosphorus oxide catalyst and preparation method thereof, which there is excellent n butane oxidation to produce maleic
The catalytic performance of dicarboxylic anhydride.
The second technical problem to be solved by the present invention is to provide a kind of catalyst one of to solve above-mentioned technical problem
Preparation method.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of vanadium phosphorus oxide catalyst,
Its XRD diffracting spectrum has main diffractive features peak at 2 θ=12.5,18.5,22.8,28.4,29.3,29.9,43.2,
The diffraction maximum peak height I at 2 θ=12.51With the diffraction maximum peak height I at 2 θ=22.82Ratio I1:I2=0.3~3.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the vanadium phosphorus oxide is catalyzed
The preparation method of agent, comprising the following steps:
1) vfanadium compound is mixed with the compound of organic solvent, cocatalytic element as reducing agent and solvent and phosphoric acid
Afterwards, it is heated to reflux 1~20h；
2) gained precipitation solution is filtered and is used organic solvent washing, filter cake is dry at 110~180 DEG C；
3) by filter cake and the secondary solvent after drying reflux or lower than the secondary solvent boiling point at a temperature of mix 1~
After 10h, step 2) is repeated, wherein washing process uses the secondary solvent；
4) after the filter cake compressing tablet process after drying, calcination activation is carried out under certain temperature and atmosphere.
In above-mentioned technical proposal, used vfanadium compound is phosphorus pentoxide, ammonium metavanadate or organic acid vanadium；Step 1)
In organic solvent, using organic alcohols and polyalcohols solvent；The cocatalytic element is in Mo, Co, Nb, Zn, Cr
It is at least one；Product has good intermiscibility after secondary solvent in step 3) and the organic solvent in step 1) and its reduction；
Dielectric constant is between 10-50.
Preferred technical solution is, vfanadium compound is selected from vanadic anhydride, and organic solvent is using isobutanol and benzyl alcohol
The molar ratio of mixed solvent system, isobutanol and benzyl alcohol is any.
Preferred technical solution is that isobutanol and benzyl alcohol molar ratio are 5:1；The compound of cocatalytic element, which refers to, accordingly to be helped
Catalytic elements can be dissolved in the compound of organic solvent in step 1).
Preferred technical solution is that the phosphoric acid concentration is 85wt%~110wt%；Organic solvent in step 2),
Using alcohols and polyalcohols or low boiling point solvent.
Preferred technical solution is the phosphoric acid for using phosphoric acid concentration as 105wt%, and organic solvent uses isobutanol.
Preferred technical solution is that used secondary solvent is at least one of acetone, methanol, ethyl alcohol, ethylene glycol.
Preferred technical solution is that the heat treatment activation process in step 4) refers in oxygen-containing gas, inert gas, water
The one or more of steam and other special gases are formed by under atmosphere and carry out 1~20h's to catalyst at 370~480 DEG C
Heat treatment activation；It is heat-treated activation process, inert gas therein is at least one of nitrogen, helium and argon gas；Other are special
Other gas is oxycarbide.
Preferred technical solution is that other the special gases being heat-treated in activation process are carbon dioxide.
The catalyst is in addition to having typical (VO)2P2O7Crystal phase also has other special crystal phase structures, to be
The vpo catalyst of obtained preceding feature, the technical solution adopted in the present invention include following key step:
1. vfanadium compound is mixed with the compound of organic solvent, cocatalytic element as reducing agent and solvent and phosphoric acid
After be heated to reflux 1-10h；
2. gained precipitation solution is filtered and is used organic solvent washing, filter cake is dry at 120-170 DEG C；
3. by filter cake and the secondary solvent after drying reflux or lower than the secondary solvent boiling point at a temperature of mix 1-8h
After wash；
4. carrying out calcination activation under certain temperature and atmosphere after the filter cake compressing tablet process after dry.
Catalyst of the present invention, used vfanadium compound can use phosphorus pentoxide, ammonium metavanadate or organic acid vanadium,
Wherein preferred vanadic anhydride；Used phosphoric acid weight concentration can be 85wt.%-110wt.%, wherein it is preferred that 105wt%
Phosphoric acid.
Organic solvent in the preparation method step 1 of catalyst of the present invention, can be used organic alcohols and polyalcohols
Solvent, it is preferred to use the molar ratio of the mixed solvent system of isobutanol and benzyl alcohol, isobutanol and benzyl alcohol can arbitrarily change, special
The mixed system that not preferred isobutanol and benzyl alcohol molar ratio are 4:1.
Alcohols and polyalcohols and low can be used in organic solvent in the preparation method step 2 of catalyst of the present invention
Boiling point solvent, it is preferred to use isobutanol.
Secondary solvent in the preparation method step 3 of catalyst of the present invention has characteristics that 1) and in step 1
Organic solvent and its reduction after product have good intermiscibility；2) dielectric constant is between 10-50.Used secondary solvent
But such as acetone, methanol, ethyl alcohol, ethylene glycol meet one kind or mixture of the solvent of afore-mentioned characteristics.
Heat treatment activation process of the present invention refers to and is containing oxygen, inert gas, vapor and other special gas
The one or more of body are formed by the process for carrying out heat treatment activation under atmosphere to catalyst at 370-480 DEG C.Described is lazy
Property gas, can be one or more of nitrogen, helium and argon gas.Other described special gases, can be oxycarbide,
It is preferable to use carbon dioxide.Wherein, oxygen volume content should be no more than 50% in total gas composition, other described special gas
Body volume content in total gas composition should be no more than 40%.
Catalyst of the present invention forms a kind of combination phase structure, such composition can by X-ray diffraction (XRD) technology into
Row detecting and definition, the main XRD diffractive features peak having include 2 θ=28.4, at 29.9,22.8,43.2,18.5, corresponding
(VO)2P2O7Characteristic feature peak in addition to this have a characteristic peak simultaneously at 2 θ=12.5,29.3, a kind of corresponding vanadium phosphorus mica
The crystal phase structure of phase.Experiments prove that the vanadium-phosphor oxide catalyst of such crystal phase composition has preferable catalyzed gas hydro carbons such as
Selective oxidation of n -butane produces the performance of cis-butenedioic anhydride, specific preparation method and under the conditions of, control 2 θ=12.5 at diffraction maximum peak
Height (I1) and 2 θ=22.8 at diffraction maximum peak height (I2) ratio I1:I2Catalyst between=0.3~3 has optimal catalysis
Performance.It by catalyst prepared by the preparation process, is characterized, is had foregoing brilliant through XRD polycrystalline diffractive technology
Phase structure.
The present invention, but content not thereby limiting the invention are further illustrated with example below.
Specific embodiment
[embodiment 1]
By 25g vanadic anhydride be added 250ml isobutanol and 100ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
It filters and is washed with isobutanol, gained filter cake dry 20h at 120 DEG C obtains precursor A.Precursor A and 300ml ethylene glycol are mixed
It is heated to 100 DEG C of stirring 3h after conjunction, cooled and filtered and with acetone washing, gained filter cake dry 20h at 120 DEG C obtains forerunner
Body B.By precursor B in air atmosphere 250 DEG C of roasting 3h, then in 20% air of volume ratio/20% nitrogen/10% titanium dioxide
425 DEG C of roasting 3h are warming up in carbon/50% vapor atmosphere, finally in 40% nitrogen/10% carbon dioxide/50% vapor
450 DEG C of roasting 3h obtain active catalyst C1 in atmosphere.Gained catalyst is fed in 1.5vol% butane, 2000hr-1Under air speed
It is checked and rated in fixed bed reactors, measuring butanes conversion is 85.8%, yield of maleic anhydride 59.7%.
[comparative example 1]
By 25g vanadic anhydride be added 250ml isobutanol and 100ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
It filters and is washed with isobutanol, gained filter cake dry 20h at 120 DEG C obtains precursor A.By precursor A 250 in air atmosphere
DEG C roasting 3h, be then warming up in 20% air of volume ratio/20% nitrogen/10% carbon dioxide/50% vapor atmosphere
425 DEG C of roasting 3h, finally 450 DEG C of roasting 3h obtain active catalytic in 40% nitrogen/10% carbon dioxide/50% steam atmosphere
Agent C1A.Gained catalyst is fed in 1.5vol% butane, 2000hr-1It is checked and rated in fixed bed reactors under air speed, obtains butane and turn
Rate 83.9%, yield of maleic anhydride 55.9%.
[comparative example 2]
By 25g vanadic anhydride be added 250ml isobutanol and 100ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
Acetone washing is filtered and uses, gained filter cake dry 20h at 120 DEG C obtains precursor A.By precursor A 250 DEG C in air atmosphere
3h is roasted, 425 DEG C of roasting 3h are then warming up in 50% air/50% steam atmosphere, finally in 25% air/25% nitrogen
425 DEG C of roasting 3h obtain active catalyst C1B in gas/50% steam atmosphere.Gained catalyst is fed in 1.5vol% butane,
2000hr-1It is checked and rated in fixed bed reactors under air speed, obtains butanes conversion 78.4%, yield of maleic anhydride 51.2%.
[comparative example 3]
By 25g vanadic anhydride be added 250ml isobutanol and 100ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
It filters and is washed with isobutanol, gained filter cake dry 20h at 120 DEG C obtains precursor A.By precursor A 250 in air atmosphere
DEG C roasting 3h, then in butane/air Mixture of butane ratio 1.5vol% in 420 DEG C activation for 24 hours active catalyst
C1C.Gained catalyst is fed in 1.5vol% butane, 2000hr-1It is checked and rated in fixed bed reactors under air speed, measures butane and turn
Rate is 83.5%, yield of maleic anhydride 55.2%.
[embodiment 2]
By 25g vanadic anhydride be added 200ml isobutanol and 200ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
It filters and is washed with isobutanol, gained filter cake dry 20h at 120 DEG C obtains precursor A.Precursor A and 300ml ethylene glycol are mixed
It is heated to 100 DEG C of stirring 3h after conjunction, cooled and filtered and with acetone washing, gained filter cake dry 20h at 120 DEG C obtains forerunner
Body B.By precursor B in air atmosphere 250 DEG C of roasting 3h, then in 20% air of volume ratio/20% nitrogen/10% titanium dioxide
425 DEG C of roasting 3h are warming up in carbon/50% vapor atmosphere, finally in 40% nitrogen/10% carbon dioxide/50% vapor
450 DEG C of roasting 3h obtain active catalyst C2 in atmosphere.Gained catalyst is fed in 1.5vol% butane, 2000hr-1Under air speed
It is checked and rated in fixed bed reactors, measuring butanes conversion is 84.2%, yield of maleic anhydride 55.5%.
[embodiment 3]
By 25g vanadic anhydride be added 250ml isobutanol and 100ml benzyl alcohol mixed solution, open stir and slowly
The phosphoric acid of about 29.5g105wt.% is added, flow back 16h after heating mixed solution to reflux, by mixed solution mistake after stopping heating
It filters and is washed with isobutanol, gained filter cake dry 20h at 120 DEG C obtains precursor A.Precursor A is mixed with 300ml acetone
After be heated to reflux stirring 3h, filter and use acetone washing, gained filter cake at 120 DEG C dry 20h, obtain precursor B.By presoma
B 250 DEG C of roasting 3h in air atmosphere are then steamed in 20% air of volume ratio/20% nitrogen/10% carbon dioxide/50% water
425 DEG C of roasting 3h are warming up in the atmosphere of gas, finally 450 DEG C in 40% nitrogen/10% carbon dioxide/50% steam atmosphere
Roasting 3h obtains active catalyst C3.Gained catalyst is fed in 1.5vol% butane, 2000hr-1In fixed bed reactors under air speed
Middle examination, measuring butanes conversion is 79.5%, yield of maleic anhydride 50.9%.
Claims (5)
1. the preparation method of vanadium phosphorus oxide catalyst, comprising the following steps:
1) after vfanadium compound being mixed with the compound of organic solvent, cocatalytic element as reducing agent and solvent and phosphoric acid,
It is heated to reflux 1~20h；The organic solvent of step 1) uses the mixed solvent system of isobutanol and benzyl alcohol；
2) gained mixture is filtered and is used organic solvent washing, filter cake is dry at 110~180 DEG C；
3) by filter cake and the secondary solvent after drying reflux or lower than the secondary solvent boiling point at a temperature of mix 1~10h after,
Step 2) is repeated, wherein washing process uses the secondary solvent；Used secondary solvent is methanol, in ethyl alcohol, ethylene glycol
It is at least one；
4) after the filter cake compressing tablet process after drying, calcination activation is carried out under certain temperature and atmosphere；Calcination activation process, refers to
In the case where the one or more of oxygen-containing gas, inert gas, vapor and other special gases are formed by atmosphere 370~480
DEG C to catalyst carry out 1~20h calcination activation；Calcination activation process, inert gas therein are in nitrogen, helium and argon gas
At least one；Other special gases are carbon dioxide；
Its XRD diffracting spectrum has main diffractive features at 2 θ=12.5,18.5,22.8,28.4,29.3,29.9,43.2
Peak, the diffraction maximum peak height I at 2 θ=12.51With the diffraction maximum peak height I at 2 θ=22.82Ratio I1:I2=0.3~3.
2. preparation method according to claim 1, it is characterised in that used vfanadium compound is vanadic anhydride, inclined vanadium
Sour ammonium or organic acid vanadium；The cocatalytic element is at least one of Mo, Co, Nb, Zn, Cr；It is secondary molten in step 3)
Product has good intermiscibility after organic solvent and its reduction in agent and step 1)；Dielectric constant is between 10-50.
3. preparation method according to claim 1, it is characterised in that isobutanol is 5:1 with benzyl alcohol molar ratio；Co-catalysis
The compound of element refers to that corresponding cocatalytic element can be dissolved in the compound of organic solvent in step 1).
4. preparation method according to claim 1, it is characterised in that the phosphoric acid concentration is 85wt%~110wt%；
Organic solvent in step 2), using alcohols.
5. preparation method according to claim 1, it is characterised in that used phosphoric acid concentration is the phosphoric acid of 105wt%, step
It is rapid 2) in organic solvent use isobutanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106000434A (en) * | 2016-05-23 | 2016-10-12 | 刘阳 | Maleic anhydride catalyst and preparation method thereof |
| CN107866240B (en) * | 2016-09-23 | 2020-12-01 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride and preparation method thereof |
| CN107866246B (en) * | 2016-09-23 | 2021-02-09 | 中国石油化工股份有限公司 | Hydrocarbon selective oxidation catalyst and preparation method thereof |
| CN107866244B (en) * | 2016-09-23 | 2020-10-16 | 中国石油化工股份有限公司 | Vanadium phosphorus catalyst and preparation method thereof |
| CN107866247B (en) * | 2016-09-23 | 2021-02-09 | 中国石油化工股份有限公司 | Low-carbon hydrocarbon oxidation catalyst and preparation method thereof |
| CN107866248B (en) * | 2016-09-23 | 2020-11-27 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof |
| CN107866245B (en) * | 2016-09-23 | 2020-11-03 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof |
| 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 |
| CN107649155A (en) * | 2017-09-29 | 2018-02-02 | 吉林大学 | A kind of doping Nb vpo catalyst, preparation method and its application in acrylic acid is produced |
| CN109261221A (en) * | 2018-11-08 | 2019-01-25 | 中触媒新材料股份有限公司 | A method of for removing reductive organic matter in vanadium silver molybdophosphate catalyst |
| DE102019100983A1 (en) * | 2019-01-16 | 2020-07-16 | Clariant International Ltd | METHOD FOR PRODUCING A VPO CATALYST |
| CN112691686B (en) * | 2019-10-23 | 2023-07-04 | 中国石油化工股份有限公司 | Vanadium phosphorus oxide catalyst and activation method and application thereof |
| CN111841590B (en) * | 2020-09-04 | 2023-02-10 | 兰州石化职业技术学院 | Method for controllably synthesizing vanadium phosphorus oxide catalyst by binary mixed solvent system |
| CN116020503B (en) * | 2021-10-25 | 2024-08-30 | 中国石油化工股份有限公司 | Shaped vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, preparation method thereof and preparation method of maleic anhydride |
| CN116020505A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst for hydrocarbon selective oxidation and preparation method and application thereof |
| 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 |
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