CN104549393B - Vanadium-phosphorus oxide and preparation method thereof - Google Patents
Vanadium-phosphorus oxide and preparation method thereof Download PDFInfo
- Publication number
- CN104549393B CN104549393B CN201310495721.XA CN201310495721A CN104549393B CN 104549393 B CN104549393 B CN 104549393B CN 201310495721 A CN201310495721 A CN 201310495721A CN 104549393 B CN104549393 B CN 104549393B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- phosphorus oxide
- vanadium phosphorus
- reactor
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a vanadium-phosphorus oxide and a preparation method thereof. Based on the volume of VOHPO4.0.5H2O, the content of the vanadium-phosphorus oxide is 75 to 99 percent; phosphorus and vanadium are in the molar ratio of 0.85 to 1.35; the particle size is 30 to 120 nm; the specific surface area of the vanadium-phosphorus oxide is 110 to 230 m<2>/g. The vanadium-phosphorus oxide prepared by the method disclosed by the invention has the characteristics of small grain size, large specific surface area, and centralized grain size distribution, and is suitable to serve as a precursor of a catalyst in a reaction for preparing maleic anhydride by oxidizing n-butane. According to the method, a mass transfer effect is good, the reaction efficiency is high, the reaction time is shortened, the production capacity is high, so that the method can be used for continuous production of the catalyst.
Description
Technical field
The present invention relates to a kind of vanadium phosphorus oxide and preparation method thereof, this vanadium phosphorus oxide is suitable as n butane oxidation system
The presoma of cis-butenedioic anhydride reacting middle catalyst.
Background technology
Maleic anhydride abbreviation cis-butenedioic anhydride, also known as maleic anhydride, are a kind of important Organic Chemicals and fine chemistry industry
Product, is the third-largest anhydride being only second to phthalic anhydride and acetic anhydride at present in the world, and its concrete application mainly includes producing unsaturated gathering
Ester resin, alkyd resin, and pesticide, medicine, coating, ink, lube oil additive, papermaking chemical product, textile finish,
Food additive and surfactant etc..Additionally, BDO, oxolane, Malaysia can also be produced for raw material with cis-butenedioic anhydride
A series of broad-spectrum fine chemical products such as acid, fumaric acid and tetrahydrochysene anhydride, exploitation prospect is very wide.
Three kinds of basic lines of maleic anhydride production have: benzene oxidatoin method, butane oxidation method, butylene (c4Fraction) oxidizing process.Wherein,
Benzene oxidatoin method is technique, its reactor and the catalyst technology comparative maturity of earliest application, but, due to the price phase of benzene feedstock
To expensive and poisonous, easily cause environmental pollution.So, for the requirement of environmental conservation aspect, countries in the world are competitively developed and are answered
It is raw material production cis-butenedioic anhydride technology with normal butane, and obtains remarkable break-throughs, raw material is inexpensive because this technique has, and environmental pollution is little,
The advantage of cis-butenedioic anhydride low cost of manufacture, has become as the main route of maleic anhydride production at present.Selective oxidation of n -butane cis-butenedioic anhydride is mesh
The front low-carbon alkanes Selective Oxidation uniquely realizing commercial Application, catalyst is the key of technique, and vanadium phosphorus oxygen (vpo) is catalyzed
Agent is the maximally effective catalyst of this reaction.
Vpo catalyst is a kind of composite oxide catalysts with complicated microstructure, and its each thing is mutually all by forerunner
Body vohpo4·0.5h2O is activated to be transformed, the brilliant looks of presoma and crystallite dimension directly affect catalyst brilliant looks and
Thing phase composition.The catalysis activity of catalyst and forerunner's preparation have much relations, and its preparation process has non-to catalytic performance
Often big impact.In order to improve the activity and selectivity of vanadium-phosphor oxide catalyst, improve the economic benefit of existing apparatus, people are to it
Preparation method has made intensive studies.
For the preparation of vanadium-phosphor oxide catalyst, the document report of early stage is usually to make reducing agent with hcl in aqueous medium, but
Less (＜ 10 m of specific surface area of catalyst of gained2/ g), and the specific surface area of catalyst of organic phase method preparation is high (generally higher than
20 m2/ g), active at low temperature, and reactivity and selectivity also high.Due to catalyst specific surface area with available
One of closely related in the active bits number of catalytic reaction, and improve the effective way of active bits number, it is by vanadium phosphorus oxide
Make the ultramicron of Large ratio surface.Existing traditional preparation method or the colloidal sol ~ gel method of routine, prepared vanadium phosphorus oxide
Particle is larger, is micron order, and particle size distribution is uneven, and specific surface is less, typically in 2 ~ 20 m2/g.
【tribomechanical pretreatment of vanadium phosphates: structural and
Catalytic effects, catalyst letters, 2000,68 (1-2), 13-18] described in physical grinding side
Method is although can make particle diameter reduce, specific surface area increases, but not easy to operate in large-scale production, and the collection of sample is more tired
Difficulty, and the poor repeatability prepared.
A kind of preparation method of supermicro particles of vanadium phosphorus oxide is disclosed, the method is by v in cn1264619a2o5, salt
Acid, phosphoric acid one react, and add citric acid after completion of the reaction, water-bath is evaporated to gel, then are processed with dehydrated alcohol exchange,
Then carry out supercritical fluid drying in ethanol medium, finally activate, prepared supermicro particles of vanadium phosphorus oxide (particle diameter is 30～
200nm, specific surface area is 7～176m2/ g), the oxidation state of surface vanadium is+4 valencys.But its principal crystalline phase is different from usual vanadium phosphorus oxygen
Composite oxides and all kinds of intermediate.Meanwhile, preparation method is complicated, and supercritical reaction conditions are also harsher, are unfavorable for industry
Application.
Boiling bed technique is a kind of new multiphase fluidisation state reaction technology.Fluidisation state technology is to instigate solid particle and stream
Body medium contacts, and using the effect of streaming flow, promotes a large amount of solid particles to be suspended in fluid media (medium) so as to change from static
Becoming the state similar to fluid boiling, thus considerably increasing the touch opportunity of granule and fluid, so that various unit operations is reached
Perfect degree.
In prior art, using reaction engineering principle, using boiling bed technique preparation vpo catalyst precursor there is not yet literary composition
Offer report.
Content of the invention
For the deficiencies in the prior art, the invention provides what a kind of high-specific surface area, small particle, Grain size distribution were concentrated
Vanadium phosphorus oxide and preparation method thereof.
The vanadium phosphorus oxide of the present invention, the volume content of vanadium phosphorus oxide is with vohpo4·0.5h2O is calculated as 75%～99%, excellent
Elect 85～99% as, phosphorus is 0.85～1.35 with the mol ratio of vanadium, preferably 0.95～1.20；Particle diameter is 30 ~ 120nm, and grain size is divided
Cloth is as follows: on the basis of volume, the particle proportion of 30～60nm is 5%～12%, and the particle proportion of 60～90nm is
46%～80%, 90 ~ 120nm particle proportion is 10%～40%；The specific surface area of vanadium phosphorus oxide is 110～230m2/ g, excellent
Select 180～230m2/g.
Conventional auxiliary agent can also be contained in described vanadium phosphorus oxide.Auxiliary agent be selected from co, ni, zn, bi, zr, cu, li,
One or more of elements such as k, ca, mg, ti, la, mo, nb, b, fe, cr and ce.Described auxiliary agent is with elemental metal
Content can be 0.001～0.2 times of v atom.
The preparation method of vanadium phosphorus oxide of the present invention: by the mixed solution of isobutanol and benzyl alcohol, vanadic anhydride and help
Agent is added in fluidized bed reactor, is passed through fluid in reactor, makes material be in " boiling-like " tumbling state, by reactor
It is warming up to reaction temperature to be reacted；Then be passed through a certain amount of strong phosphoric acid toward in reactor, keep " boiling-like ", obtain blue or
Sky-blue pulpous state reactant liquor；Gained reactant liquor through filtering, washing, be dried and roasting, that is, obtains described vanadium phosphorus oxide.
The mixed volume of wherein said isobutanol and benzyl alcohol is than for 1:1～100:1, preferably 10:1～25:1.
The mixed weight of described isobutanol and benzyl alcohol mixture and vanadic anhydride than for 5:1～25:1, preferably
10:1～20:1.
The concentration expressed in percentage by weight of described strong phosphoric acid is 85%～100%.The addition of strong phosphoric acid is with phosphorus in system and vanadium
Molar ratio computing is 0.85～1.35, preferably 0.90～1.20.
Described range of reaction temperature is 90～120 DEG C, and the described response time is 2～4 hours.Add strong phosphoric acid follow-up
Continuation of insurance is held " boiling-like " and is reacted 6～8 hours.
Described drying condition excessively is as follows: is dried 8～12 hours at a temperature of 95～160 DEG C, preferred baking temperature is 120
～150 DEG C；
Described roasting condition is as follows: in 200～280 DEG C of roasting temperatures 4～8 hours, preferred sintering temperature was 230
～250 DEG C.
In the preparation process of vanadium phosphorus oxide of the present invention, may be incorporated into auxiliary agent, such as co, ni, zn, bi, zr, cu, li,
One or more of elements such as k, ca, mg, ti, la, mo, nb, b, fe, cr, ce.The addition of described auxiliary agent is with metallic element
It is calculated as 0.001～0.2 times of v atom.
In the inventive method, described fluidized bed reactor is vertical reactor, and reactor bottom is provided with baffle plate
Fluid distribution plate, fluid distribution plate carries throttling pore, and small aperture is 60 ~ 100 mesh, and baffle plate is become with the centrage of aperture
45 °～90 °.
In the inventive method, described fluid can adopt n2, one or more of air or noble gases.
In the inventive method, in the preparation process of vanadium phosphorus oxide, after reaction a period of time in mixing alcoholic solution, one
Part vanadic anhydride is gradually reduced in alcoholic solution and dissolves.With the addition of phosphoric acid, remaining vanadic anhydride is fast
Instant solution, and fast reaction crystallization becomes vanadium phosphorus oxide vohpo4·0.5h2o.High-specific surface area to be obtained, small particle
vohpo4·0.5h2O must is fulfilled for two conditions: one is vohpo4·0.5h2O nucleus should be formed simultaneously, and two are as
vohpo4·0.5h2O grows up, and there will be no nucleation process, simultaneously the gathering of also granule to be avoided.
Fluidized bed reactor can very well meet above-mentioned two condition.This is because the ultimate principle of ebullated bed is
Using circulating pump, fluid media (medium) is directly entered fluidized-bed reactor, fluidized bed device through heat exchanger or without heat exchanger
Bottom is provided with baffled fluid distribution plate, in the presence of throttling pore and baffle plate on distribution grid, makes fluid with uniform
Flow is radial to enter reactor by each aperture.When fluid is gone out from throttling pore, its impulsive force is by solid
Granule holds up, and orders about a large amount of solid particles and fluid is sufficiently mixed and is in that " boiling-like " is stirred up and down, impinging one another with mix,
So fluid just can contact with solid particle for a long time.Due to high-velocity fluid continuous Ground shock waves solid particle, the consolidating of floating
Body granule is in the flowing shape of fast scroll, and speed quickly and forms turbulent flow, and 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 tradition stirring means, is greatly promoted microcosmic and mixes
Close.This high turbulence and very big alternate relative velocity have effectively facilitated the microcosmic mixing on molecular scale, so that can
Dissolubility vanadium species produce very high moment degree of supersaturation, and strong microcosmic mixing can ensure that high degree of supersaturation reaches pole
High uniform state, substantial amounts of vohpo4·0.5h2O nucleus is formed simultaneously, and crystal is grown up rapidly, such that it is able to thinner, grain is obtained
Narrower nanometer vanadium phosphorus oxide crystal (the i.e. vohpo of footpath distribution4·0.5h2O).
Compared with prior art, vanadium phosphorus oxide catalyst of the present invention and preparation method thereof have the characteristics that following:
1st, the vohpo prepared by conventional method4·0.5h2O is micron order, and its own crystallite dimension is larger, in activation process
In only top layer crystal can lose water of crystallization, its body phase is difficult to lose water of crystallization, then results in body phase vohpo4·0.5h2O exists
In reaction atmosphere, final transformation generates vopo4Phase.And the vohpo prepared by this method4·0.5h2O presoma crystallite dimension
Little, easily lose water of crystallization completely in activation process, be directly translated into (vo)2p2o7Phase.(vo)2p2o7Crystalline phase is considered as vpo
The chief active phase of catalyst, it is rhombic system.In activation process, presoma vohpo4·5h2O is to (vo)2p2o7Crystalline phase
Phase in version is carried out under substantially holding mother crystal shape, and the catalyst after activation remains the structure before activation.This phase turns
Become and be referred to as topotactic transformation (local structured's transformation).The activity of vpo catalyst and this (vo)2p2o7The octahedral of crystal
Body structure is closely related.Therefore, size of microcrystal is distributed greater concentration of nanometer vanadium phosphorus oxide crystal (i.e. vohpo4·0.5h2O)
(vo) obtaining after activated2p2o7The octahedral structure of crystalline phase will more regular so that prepared catalyst structure is more stable,
Catalysis activity is higher.
2nd, the ebullating bed reactor mode in the present invention makes the contact area between reactant liquor and granular solids material increase
Plus, promote the carrying out of mass-and heat-transfer；Meanwhile, reaction mass is in the kinestate of rolling, can keeping temperature uniform, it is to avoid locally
Overheated.
3rd, the vanadium phosphorus oxide particle diameter that prepared by the inventive method is little, Grain size distribution is concentrated, and specific surface area is big.
4th, the granule flowing in the inventive method, is readily incorporated into or takes out and will not affect the carrying out reacting, can make preparation
Process continuous.
5th, the ebullated bed in the present invention enhances alternate transmission effect, improves mass tranfer coefficient, improves reaction efficiency, contracting
The short response time, simultaneously simple to operate, process control steadily, is suitable to large-scale production.
Brief description
Fig. 1 is the fluidized bed reactor structural representation used by the present invention.1st, charging aperture, 2, charging aperture (gas access),
3rd, discharge port, 4, gas outlet's (recycling), 5, fluid distribution plate.
Fig. 2 is x-ray diffraction (xrd) spectrogram of the vanadium phosphorus oxide of embodiment 1 preparation.
Specific embodiment
The concrete preparation process of vanadium phosphorus oxide of the present invention is as follows:
In fluidized bed reactor shown in Fig. 1, vanadic anhydride and auxiliary agent, isobutanol, benzyl alcohol are added by charge door 1
Mixed liquor, isobutanol and benzyl alcohol volume ratio 1:1～100:1；Then fluid is blasted in reactor by charging aperture 2, make reaction
Liquid and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 90～120 DEG C, keep the response time 2
～4 hours；It is passed through strong phosphoric acid (concentration 85%～100%) in again from charge door 1 to reactor, phosphorus and vanadium mol ratio be 0.85～
1.35, continue to keep " boiling-like " to react 6～8 hours, reaction terminates to be discharged by reacting material outlet 3.Reactant liquor is cooled to room
Wen Hou, is filtered, and filter cake is with, after a small amount of isobutanol drip washing three times, preferably first by filter cake, natural air drying 10～24 is little at room temperature
When, then it is dried in an oven 8～12 hours, finally at 200～280 DEG C in Muffle furnace, roasting 4～8 hours, obtain dark brown
The vanadium phosphorus oxide of color.
With reference to specific embodiment, technical scheme is described in further detail.Following examples are not
It is limiting the scope of the invention, those skilled in the art can do suitable expansion with reference to description of the invention and full text
Exhibition, these extensions should be all the protection domain of technical solution of the present invention.
Agents useful for same in embodiment and comparative example, (fine chemistry industry institute is recovered in Tianjin to isobutanol, analyzes pure, content
＞ 99.0%), benzyl alcohol (Tianjin recover fine chemistry industry institute, analyze pure, content ＞ 99.0%), vanadic anhydride (Tianjin
City's good fortune morning chemical reagent factory, analyze pure, content ＞ 99.0%), phosphoric acid (Shenyang Big Dipper chemical reagent factory, analyze pure, content ＞
99.0%).The grain size of vanadium phosphorus oxide of the present invention and Grain size distribution are to be measured using laser particle analyzer.Vanadium phosphorus oxygen
Vohpo in compound4·0.5h2O crystalline phase volume content is fitted according to the peak area in xrd spectrogram.
Embodiment 1
In fluidized bed reactor shown in Fig. 1, vanadic anhydride 30.0g is added by charge door 1；Isobutanol, benzyl alcohol
Mixed liquor 690ml, isobutanol/benzyl alcohol volume ratio 10:1.By n2Blasted in reactor by charging aperture 2, make reactant liquor and solid
Granule keeps " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 110 ± 2 DEG C, keep 3 hours response time；Again by
Charge door 1 is passed through strong phosphoric acid 38.0g that concentration is 85% in reactor, and phosphorus/vanadium mol ratio is 1.0.Continue to keep " boiling-like "
Reaction 6 hours, reaction terminates to be discharged by reacting material outlet 3.After reactant liquor is cooled to room temperature, filtered, filter cake is with a small quantity
After isobutanol drip washing three times, filter cake is put into natural air drying under room temperature in enamel tray, is then dried 8 hours in 130 DEG C of baking ovens,
At last 250 DEG C in Muffle furnace, roasting 5 hours, obtains the vanadium phosphorus oxide powder of pitchy.Gained vanadium phosphorus oxide is through dividing
Analysis: specific surface area is 180m2/g；Its Grain size distribution is as follows by volume: 30～60nm proportion is 10%, 60～90nm
Proportion is 61%, and 90 ~ 120nm proportion is 29%.Through xrd, gained vanadium phosphorus oxide detects that its crystalline phase is vohpo4·
0.5h2O phase (volume content is 90%).
Embodiment 2
In fluidized bed reactor shown in Fig. 1, vanadic anhydride 30g, auxiliary agent zirconium nitrate 0.5g are added by charge door 1,
Auxiliary agent six water nickel nitrate 0.95g；Isobutanol, benzyl alcohol mixed liquor 690ml, isobutanol/benzyl alcohol volume ratio 15:1.By n2By entering
Material mouth 2 blasts in reactor, makes reactant liquor and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at
100 ± 2 DEG C, keep 4 hours response time；It is passed through, in again from charge door 1 to reactor, strong phosphoric acid 35.5g that concentration is 100%,
Phosphorus/vanadium mol ratio is 1.1, continues to keep " boiling-like " to react 6 hours, reaction terminates to be discharged by reacting material outlet 3.Reactant liquor
After being cooled to room temperature, filtered, filter cake is with, after a small amount of isobutanol drip washing three times, filter cake being put into natural under room temperature in enamel tray
Air-dry, be then dried in 130 DEG C of baking ovens 8 hours, finally roasting 6 hours at 250 DEG C in Muffle furnace, obtain the vanadium of pitchy
Phosphorous oxides powder.Gained vanadium phosphorus oxide is through analysis: specific surface area is 210m2/ g, its Grain size distribution is as follows by volume:
30～60nm proportion is 7%, and 60～90nm proportion is 62%, and 90 ~ 120nm proportion is 31%.Gained vanadium phosphorus oxidation
Through xrd, thing detects that its crystalline phase is vohpo4·0.5h2O phase (volume content is 96%).
Embodiment 3
In fluidized bed reactor shown in Fig. 1, vanadic anhydride 30.0g is added by charge door 1；Isobutanol, benzyl alcohol
Mixed liquor 690ml, isobutanol/benzyl alcohol volume ratio 20:1.By n2Blasted in reactor by charging aperture 2, make reactant liquor and solid
Granule keeps " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 98 ± 2 DEG C, keep 4 hours response time；Again by plus
Material mouth 1 is passed through strong phosphoric acid 34.0g that concentration is 95% in reactor, and phosphorus/vanadium mol ratio is 1.0.Continue to keep " boiling-like " anti-
Answer 8 hours, reaction terminates to be discharged by reacting material outlet 3.After reactant liquor is cooled to room temperature, filtered, filter cake is used different on a small quantity
After butanol drip washing three times, filter cake is put into natural air drying under room temperature in enamel tray, then dry 7 hours in 120 DEG C of baking ovens,
Roasting 5 hours at 240 DEG C in Muffle furnace, obtain the vanadium phosphorus oxide powder of pitchy afterwards.Gained vanadium phosphorus oxide is through analysis:
Specific surface area is 190m2/ g, its Grain size distribution is as follows by volume, and 30～60nm proportion is 9%, shared by 60～90nm
Ratio is 70%, 90nm ~ 120nm proportion is 21%.Through xrd, gained vanadium phosphorus oxide detects that its crystalline phase is vohpo4·
0.5h2O phase (volume content is 92%).
Embodiment 4
In fluidized bed reactor shown in Fig. 1, vanadic anhydride 30.0g is added by charge door 1；Isobutanol, benzyl alcohol
Mixed liquor 600ml, isobutanol/benzyl alcohol volume ratio 15:1.Helium is blasted in reactor by charging aperture 2, makes reactant liquor and consolidate
Body granule keeps " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 100 ± 2 DEG C, keep 4 hours response time；Again
It is passed through strong phosphoric acid 32.3g that concentration is 100%, phosphorus/vanadium mol ratio is 1.0 in from charge door 1 to reactor.Continue to keep " boiling
Shape " reacts 6 hours, and reaction terminates to be discharged by reacting material outlet 3.After reactant liquor is cooled to room temperature, filtered, filter cake is with less
After amount isobutanol drip washing three times, filter cake is put into natural air drying under room temperature in enamel tray, in 120 DEG C of baking ovens, be then dried 8 little
When, finally roasting 5 hours at 250 DEG C in Muffle furnace, obtain the vanadium phosphorus oxide powder of pitchy.Gained vanadium phosphorus oxide warp
Analysis: specific surface area is 206m2/ g, its Grain size distribution is as follows by volume: 30～60nm proportion is 11%, 60～
90nm proportion is 59%, and 90 ~ 120nm proportion is 30%.Through xrd, gained vanadium phosphorus oxide detects that its crystalline phase is
vohpo4·0.5h2O phase (volume content is 89%).
Comparative example 1
In the four-hole boiling flask with agitator, add vanadic anhydride 30.0g, the mixed liquor of isobutanol and benzyl alcohol
For 1.5:1, stirring heats up the mixed volume of 690ml, isobutanol and benzyl alcohol ratio, flows back 4 hours at 110 ± 2 DEG C；Then weigh
100% phosphoric acid 35.5g, phosphorus/vanadium mol ratio is 1.1, is added in flask, continues backflow 6 hours, obtains reactant liquor.Reactant liquor
It is cooled to room temperature, vacuum filtration, filter cake a small amount of isobutanol drip washing three times, in 120 DEG C of air dryings 12 hours, in Muffle furnace
In at 250 DEG C, roasting 5 hours, obtain the vanadium phosphorus oxide powder of pitchy.Gained vanadium phosphorus oxide is through analysis: specific surface area
For 48m2/g；Its Grain size distribution is as follows by volume: 180 ~ 210nm proportion is 12%, and 210 ~ 250nm proportion is
33%, ＞ 250nm proportion is 55%.Through xrd, gained vanadium phosphorus oxide detects that its crystalline phase is vohpo4·0.5h2O phase (volume
Content is 82%).
Claims (13)
1. a kind of vanadium phosphorus oxide it is characterised in that: the volume content of vanadium phosphorus oxide is with vohpo4·0.5h2O is calculated as 75%～
99%, phosphorus is 0.85～1.35 with the mol ratio of vanadium；Particle diameter is 30 ~ 120nm, the specific surface area of vanadium phosphorus oxide is 110～
230m2/g；The preparation method of vanadium phosphorus oxide, including following content: by the mixed solution of isobutanol and benzyl alcohol, five oxidations two
Vanadium and auxiliary agent are added in fluidized bed reactor, are passed through fluid in reactor, make material be in " boiling-like " tumbling state, will
Reactor is warming up to reaction temperature and is reacted；Then be passed through strong phosphoric acid toward in reactor, keep " boiling-like ", obtain blue or
Sky-blue pulpous state reactant liquor, gained reactant liquor, through filtering, washing, be dried and roasting, obtains vanadium phosphorus oxide.
2. according to the vanadium phosphorus oxide described in claim 1 it is characterised in that: the specific surface area of vanadium phosphorus oxide be 180 ~ 230
m2/g.
3. according to the vanadium phosphorus oxide described in claim 1 it is characterised in that: the Grain size distribution of vanadium phosphorus oxide is as follows: with
On the basis of volume, the particle proportion of 30～60nm is 5%～12%, and the particle proportion of 60～90nm is 46%～80%,
90 ~ 120nm particle proportion is 10%～40%.
4. according to the vanadium phosphorus oxide described in claim 1 it is characterised in that: in described vanadium phosphorus oxide contain co, ni,
One or more of zn, bi, zr, cu, li, k, ca, mg, ti, la, mo, nb, b, fe, cr and ce element, described auxiliary agent with
The content of elemental metal is 0.001～0.2 times of v atom.
5. the preparation method of the vanadium phosphorus oxide described in claim 1 is it is characterised in that include following content: by isobutanol and benzene
The mixed solution of methanol, vanadic anhydride and auxiliary agent are added in fluidized bed reactor, be passed through fluid, make material in reactor
It is in " boiling-like " tumbling state, reactor is warming up to reaction temperature and is reacted；Then it is passed through strong phosphoric acid toward in reactor,
Keep " boiling-like ", obtain blue or sky-blue pulpous state reactant liquor, gained reactant liquor, through filtering, washing, be dried and roasting, obtains
Vanadium phosphorus oxide.
6. in accordance with the method for claim 5 it is characterised in that: the mixed volume of described isobutanol and benzyl alcohol is than for 1:
1～100:1.
7. in accordance with the method for claim 5 it is characterised in that: described isobutanol and benzyl alcohol mixture and five oxidation two
The mixed weight of vanadium is than for 5:1～25:1.
8. in accordance with the method for claim 5 it is characterised in that: the concentration expressed in percentage by weight of described strong phosphoric acid be 85%～
100%；The addition of strong phosphoric acid is with the molar ratio computing of phosphorus in system and vanadium for 0.85～1.35.
9. in accordance with the method for claim 5 it is characterised in that: described reaction temperature is 90～120 DEG C, and the response time is
2～4 hours.
10. in accordance with the method for claim 5 it is characterised in that: add strong phosphoric acid after continue keep " boiling-like " 6～8 little
When.
11. in accordance with the method for claim 5 it is characterised in that: described drying condition is as follows: in 95～160 DEG C of temperature
Lower drying 8～12 hours；Described roasting condition was as follows: in 200～280 DEG C of roasting temperatures 4～8 hours.
12. in accordance with the method for claim 5 it is characterised in that: described fluidized bed reactor be vertical reactor, reaction
Device bottom is provided with the fluid distribution plate of baffle plate, and fluid distribution plate carries throttling pore, and small aperture is 60 ~ 100 mesh, gear
The centrage of plate and aperture is at 45 °～and 90 °.
13. in accordance with the method for claim 5 it is characterised in that: described fluid adopts n2, in air or noble gases
One or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495721.XA CN104549393B (en) | 2013-10-22 | 2013-10-22 | Vanadium-phosphorus oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495721.XA CN104549393B (en) | 2013-10-22 | 2013-10-22 | Vanadium-phosphorus oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549393A CN104549393A (en) | 2015-04-29 |
| CN104549393B true CN104549393B (en) | 2017-01-25 |
Family
ID=53067098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310495721.XA Active CN104549393B (en) | 2013-10-22 | 2013-10-22 | Vanadium-phosphorus oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549393B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337493B (en) * | 2019-08-09 | 2021-12-31 | 中国科学院过程工程研究所 | Preparation method and application of nano-thin-sheet vanadium-phosphorus-oxygen catalyst for enhancing micro mixing and reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241147A (en) * | 1997-06-04 | 2000-01-12 | 萨索尔技术(控股)有限公司 | Process for producing vanadium phosphorus oxide catalyst |
| CN1264619A (en) * | 1999-02-26 | 2000-08-30 | 中国石油化工集团公司 | Process for preparing supermicro particles of vanadium phosphorus oxide and its products |
| CN1453071A (en) * | 2003-05-19 | 2003-11-05 | 南京大学 | Loaded V-P-O catalyst and its prepn and use |
-
2013
- 2013-10-22 CN CN201310495721.XA patent/CN104549393B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241147A (en) * | 1997-06-04 | 2000-01-12 | 萨索尔技术(控股)有限公司 | Process for producing vanadium phosphorus oxide catalyst |
| CN1264619A (en) * | 1999-02-26 | 2000-08-30 | 中国石油化工集团公司 | Process for preparing supermicro particles of vanadium phosphorus oxide and its products |
| CN1453071A (en) * | 2003-05-19 | 2003-11-05 | 南京大学 | Loaded V-P-O catalyst and its prepn and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549393A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549391B (en) | Supported type vanadium phosphorus oxide catalyst and preparation method thereof | |
| CN104549394B (en) | A kind of vanadium-phosphor oxide catalyst and preparation method thereof | |
| CN104607219B (en) | A kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride and preparation method thereof | |
| CN101829580B (en) | Fischer-Tropsch synthetic catalyst, preparation method and application thereof | |
| CN103769183B (en) | A kind of vanadium phosphorus oxide and preparation method thereof | |
| CN103025424B (en) | For the catalyst making ortho-xylene and/or Fluidized bed become phthalic anhydride | |
| CN104549392B (en) | A kind of preparation method of vanadium-phosphor oxide catalyst | |
| CN104607221B (en) | Vanadium-phosphorus oxide and preparation method thereof | |
| CN102371154B (en) | Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof | |
| CN106622316B (en) | A kind of vanadium-phosphor oxide catalyst, preparation method and application | |
| CN102989490A (en) | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof | |
| CN103769182A (en) | Supported-type vanadium-phosphorus oxide, and preparation method and applications thereof | |
| CN104355995B (en) | A kind of synthetic method of medicinal ATOC | |
| CN107008473A (en) | A kind of three-dimensional structure bismuth titanates nanometer sheet/perite nanometer piece composite photo-catalyst and preparation method thereof | |
| CN104549393B (en) | Vanadium-phosphorus oxide and preparation method thereof | |
| WO2023071244A1 (en) | Catalyst for synthesizing carbon dioxide into methanol, preparation method therefor, and use thereof | |
| CN108722455B (en) | Preparation method of vanadium phosphorus oxide catalyst | |
| CN107175119B (en) | A kind of preparation method and applications of load-type vanadium phosphor oxide catalyst | |
| CN106622315A (en) | A vanadium phosphorous oxide and a preparing method thereof | |
| CN103230800B (en) | A kind of containing gallium iron-base fischer-tropsch Catalysts and its preparation method | |
| CN103769150B (en) | The catalyst of low-water ratio ethylbenzene dehydrogenation and method thereof | |
| CN107866244A (en) | Vanadium phosphorus catalyst and preparation method thereof | |
| CN106492861B (en) | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride | |
| CN102826568A (en) | Preparation method of nanocrystalline ZSM-5 zeolite cluster, and nanocrystalline ZSM-5 zeolite cluster prepared thereby | |
| CN104117373B (en) | Mixed metal oxide catalyst of P Modification and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |