CN104549392B - A kind of preparation method of vanadium-phosphor oxide catalyst - Google Patents
A kind of preparation method of vanadium-phosphor oxide catalyst Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of vanadium-phosphor oxide catalyst, the method includes following content: isobutanol and the mixture of benzyl alcohol, vanadic anhydride and auxiliary agent are joined in fluidized bed reactor by (1), fluid it is passed through in reactor, make material be in " boiling-like " tumbling state, reactor is warming up to reaction temperature and reacts；Then in reactor, it is passed through a certain amount of strong phosphoric acid, keeps " boiling-like ", obtain blue or sky-blue pulpous state reactant liquor；(2) material in step (1) is dried, calcination process, obtain the presoma of vanadium-phosphor oxide catalyst, during this material keep " boiling-like "；(3) being passed through activated gas in reactor, catalyst precursor is carried out activation processing, obtains vanadium-phosphor oxide catalyst, during this, material keeps " boiling-like ".The method technique is simple, production efficiency is high, reproducible, prepared catalyst grain size is little, specific surface area is big, intensity is high, it is little to wear away, and for the catalytic reaction of preparing cis-anhydride by n-butane oxidation, n-butane conversion is high, and Selectivity of maleic anhydride is good.
Description
Technical field
The invention belongs to catalyst preparation technology, be specifically related to the preparation method of a kind of vanadium-phosphor oxide catalyst.
Background technology
Maleic anhydride is called for short cis-butenedioic anhydride, have another name called maleic anhydride, it is a kind of important Organic Chemicals and fine chemical product, it it is the third-largest anhydride being only second to phthalic anhydride and acetic anhydride at present in the world, its concrete application mainly includes producing unsaturated polyester resin, alkyd resin, and pesticide, medicine, coating, ink, lube oil additive, papermaking chemical product, textile finish, food additive and surfactant etc..Additionally, can also produce a series of broad-spectrum fine chemical products such as BDO, oxolane, maleic acid, fumaric acid and tetrahydrochysene anhydride with cis-butenedioic anhydride for raw material, exploitation prospect is the most 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 the technique applied the earliest, its reactor and catalyst technology comparative maturity, but, owing to the price of benzene feedstock is relatively costly and poisonous, easily cause environmental pollution.So, for the requirement in terms of environmental conservation, countries in the world competitively development and application normal butane is raw material production cis-butenedioic anhydride technology; and obtain remarkable break-throughs, due to this technique, to have raw material inexpensive, 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 the currently the only low-carbon alkanes Selective Oxidation realizing commercial Application, and catalyst is the key of technique, and vanadium phosphorus oxide (VPO) catalyst is the maximally effective catalyst of this reaction.
Vpo catalyst is a kind of composite oxide catalysts with complicated microstructure, and its catalysis activity has much relations with preparation method, and its preparation process has the biggest impact to catalytic performance.In order to improve the activity and selectivity of vanadium-phosphor oxide catalyst, improve the economic benefit of existing apparatus, its preparation method is conducted in-depth research by people.
For the preparation of vanadium-phosphor oxide catalyst, document report in early days is usually in aqueous medium and makees reducing agent with HCl, but less (＜ 10 m of the specific surface area of catalyst of gained2/ g), and high (＞ 20 m of specific surface area of catalyst prepared by organic phase method2/ g), the most active, and reactivity and selectivity the highest.Owing to the specific surface area of catalyst is closely related with the active sites number that can be used for catalytic reaction, and one of improve the effective way of active sites number, be the ultramicron that vanadium phosphorus oxide is made Large ratio surface.Existing traditional preparation method or the colloidal sol ~ gel method of routine, prepared vanadium phosphorus oxide particle is relatively big, and for micron order, and particle size distribution is uneven, and specific surface is less, typically at 2 ~ 20 m2/g。
Disclosing the preparation method of a kind of supermicro particles of vanadium phosphorus oxide in CN1264619A, the method is by V2O5, hydrochloric acid, phosphoric acid one reacts, add citric acid after completion of the reaction, gel it is evaporated in water-bath, process with dehydrated alcohol exchange again, then in ethanol medium, carry out supercritical fluid drying, finally activating, (particle diameter is 30～200nm, and specific surface area is 7～176m to prepare supermicro particles of vanadium phosphorus oxide2/ g).This preparation method is complicated, and supercritical reaction conditions is the harshest, is unfavorable for commercial Application.And its principal crystalline phase composition is different from generally acknowledged active phase ［ (VO2)2P2O7?.
【Tribomechanical pretreatment of
Vanadium phosphates:structural and catalytic effects, Catalyst Letters, 2000,68 (1-2), 13-18] described in the method for physical grinding, although particle diameter can be made to reduce, specific surface area increases, but be difficult to operation when large-scale production, the collection of sample is relatively difficult, and the poor repeatability prepared.
CN 101157048A proposes the preparation method of a kind of vanadium-phosphor oxide catalyst with nanostructured, it is by improving conventional organic solvent method, auxiliary agent, dimethyl sulfoxide and the Polyethylene Glycol such as bismuth salt is introduced during preparing vanadium-phosphor oxide catalyst presoma, directly preparation has the vanadium-phosphor oxide catalyst of nanostructured, the method catalyst preparation process is more complicated, step is various, there is butanes conversion the highest simultaneously, extra add dimethyl sulfoxide and Polyethylene Glycol, add the deficiency such as production cost of catalyst.
CN 1311058A discloses a kind of small granular size vanadium-phosphorus-oxygen catalyst, and it is made up of vanadium, phosphorus and oxygen atom, and its particle diameter is less than 100nm, and specific surface area is 40～60m2/ g, principal crystalline phase is pyrophosphoric vanadyl.This catalyst preparation process is as follows: mixed with 120mL isobutanol-benzyl alcohol mixed solvent by 3.2g vanadic anhydride, it is heated to reflux, it is subsequently adding 4.9g phosphoric acid (85%), add 3.2g Polyethylene Glycol, continue backflow, separate out precipitation, through filtering, being dried, obtain vanadium-phosphor oxide catalyst presoma, at 400 DEG C, reaction mixture gas activates before using, obtain fresh vanadium-phosphor oxide catalyst.This catalyst can prepare the catalyst of maleic acid anhydride reactant as normal butane air oxidation, and selectivity reaches more than 72mol%, conversion per pass ＞ 85%.But the method preparation process adds substantial amounts of Polyethylene Glycol dispersant, there is the uneven problem concentrated not with particle size distribution of Grain size distribution in the product obtained, the activity and selectivity of catalyst need nonetheless remain for improving further.
Method for preparing catalyst described in the prior art is more complicated, and step is various, when producing high-quality catalyst in the scale required by commercial production, needs the strict operating condition controlling each step, thus the catalyst performance obtained is the most not ideal enough.Additionally, preparing cis-anhydride by n-butane oxidation fluidized bed process catalyst is higher than fixed bed process catalyst requirement, difficulty is big.First this catalyst should ensure that enough activity and intensity, has wearability and bears the performance of high concentration starting charge, and easy-formation processing characteristics to be had, the microspherical catalyst easy flow properties to be had made.
Ebullated bed technology is a kind of novel heterogeneous fluidisation state reaction technology.Fluidisation state technology is to instigate solid particle to contact with fluid media (medium), utilize the effect of streaming flow, a large amount of solid particle is promoted to be suspended in fluid media (medium), it is made to be transformed into the state being similar to fluid boiling from static state, thus considerably increase the touch opportunity of granule and fluid, make the operation of various unit tend to perfect.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of a kind of vanadium-phosphor oxide catalyst.The method technique is simple, production efficiency is high, reproducible, prepared catalyst grain size is little, specific surface area is high, and for the catalytic reaction of preparing cis-anhydride by n-butane oxidation, n-butane conversion is high, and Selectivity of maleic anhydride is good.
The preparation method of the vanadium-phosphor oxide catalyst of the present invention, including following content:
(1) isobutanol and the mixture of benzyl alcohol, vanadic anhydride and auxiliary agent are joined in fluidized bed reactor, in reactor, be passed through fluid, make material be in " boiling-like " tumbling state, reactor is warming up to reaction temperature and reacts；Then in reactor, it is passed through a certain amount of strong phosphoric acid, keeps " boiling-like ", obtain blue or sky-blue pulpous state reactant liquor；
(2) material in step (1) is dried, calcination process, obtain the presoma of vanadium-phosphor oxide catalyst, during this material keep " boiling-like "；
(3) being passed through activated gas in reactor, catalyst precursor is carried out activation processing, obtains vanadium-phosphor oxide catalyst, during this, material keeps " boiling-like ".
In the inventive method, isobutanol described in step (1) and the mixed volume of benzyl alcohol are than for 1:1～100:1, preferably 10:1～25:1.
In the inventive method, the mixed weight of isobutanol described in step (1) and benzyl alcohol mixture and vanadic anhydride is than for 5:1～25:1, preferably 10:1～20:1.
In the inventive method, the fluid described in step (1) can use N2, one or more in air or noble gas.
In the inventive method, the fluidized bed reactor described in step (1) is vertical reactor, and reactor bottom is provided with the fluid distribution plate of baffle plate, and with throttling pore on distribution grid, small aperture is 60 ~ 100 mesh, and the centrage of baffle plate and aperture is at 45 °～90 °.
In the inventive method, the mass percent concentration of the strong phosphoric acid described in step (1) is 85%～100%.The addition of strong phosphoric acid is 0.85～1.35 with the molar ratio computing of phosphorus in system Yu vanadium, preferably 0.9～1.2.
In the inventive method, the reaction temperature described in step (1) is 85～110 DEG C, and the response time is 2～4 hours；Continue after adding strong phosphoric acid to keep " boiling-like " to react 4～6 hours.
In the inventive method, the drying condition described in step (2) is as follows: being dried 6～10 hours at a temperature of 120～160 DEG C, preferred baking temperature is 120～140 DEG C；
In the inventive method, the roasting condition described in step (2) is as follows: roasting 4～8 hours at 200～300 DEG C, preferred sintering temperature is 220～260 DEG C.
In the inventive method, the combination of one or more in the gaseous mixture that activation gas is the gaseous mixture of nitrogen/air, the gaseous mixture of steam/air or butane/air described in step (3), activation temperature is 340～450 DEG C, and soak time is 8～40 hours, preferably 12～24 hours.
In the preparation process of vanadium-phosphor oxide catalyst of the present invention, may be incorporated into auxiliary agent, such as one or more in the elements such as Co, Ni, Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr, Ce, auxiliary element is 0.001:1～0.2:1 with the atomic ratio of v element.Described auxiliary agent introduces in catalyst one of in the following manner: (1) introduces in the preparation process of vanadium-phosphor oxide catalyst presoma；(2) before vanadium-phosphor oxide catalyst molding or forming process introduce；(3) after vanadium-phosphor oxide catalyst activates, then introduce with impregnation method.
Vanadium-phosphor oxide catalyst prepared by the inventive method, specific surface area is 110～230m2/ g, grain size is less than 120nm, and on the basis of volume, its Grain size distribution is as follows: the particle proportion of 30～60nm is 7%～13%, and the particle proportion of 60～90nm is 47%～80%, and 90 ~ 120nm particle proportion is 13%～40%.The side pressure strength of catalyst is 20 ~ 35N mm-1.Attrition of catalyst is less than 0.05%/h.
In catalyst of the present invention, the crystal phase structure of described vanadium-phosphor oxide catalyst is mainly Vanadyl pyrophosphate (VO2)2P2O7Phase, (VO2)2P2O7Volume content be 85%～99%.
In catalyst of the present invention, phosphorus is 0.85～1.35 with the mol ratio of vanadium, preferably 0.9～1.2.
In catalyst of the present invention, auxiliary agent can also be added according to actual needs, one or more in the elements such as Co, Ni, Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce of auxiliary agent, auxiliary element is 0.001:1～0.2:1 with the atomic ratio of v element.
The vanadium-phosphor oxide catalyst of the present invention is applied to preparing cis-anhydride by n-butane oxidation reaction, reactive mode can be to take fixed bed reaction mode, fluid bed or moving bed reaction mode, reaction condition is: reaction temperature 375～450 DEG C, pressure is normal pressure～0.5MPa, and normal butane gaseous mixture air speed is 1200～3500h-1, concentration of n-butane is 1.0%～1.8%(percent by volume).
In the preparation process of vanadium-phosphor oxide catalyst of the present invention, first, a part of vanadic anhydride is gradually reduced in mixed alcohol solution and dissolves.Along with the addition of phosphoric acid, remaining vanadic anhydride is by rapid solution, and fast reaction crystallization becomes vanadium-phosphor oxide catalyst presoma VOHPO4·0.5H2O.Obtain the VOHPO with nanostructured4·0.5H2O must is fulfilled for two conditions: one is VOHPO4·0.5H2O nucleus should concurrently form, and two are as VOHPO4·0.5H2O grows up, and there will be no nucleation process, simultaneously the gathering of 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 to utilize circulating pump that fluid media (medium) is directly entered fluidized-bed reactor through heat exchanger or without heat exchanger, baffled fluid distribution plate it is provided with bottom fluidized bed device, on distribution grid under the effect of throttling pore and baffle plate, fluid is made radially to enter reactor by each aperture with uniform flow.When fluid is gone out from throttling pore, its impulsive force by solid particle hold up, order about a large amount of solid particle and fluid be sufficiently mixed and stirs up and down in " boiling-like ", impinging one another with mix, such fluid just can contact with solid particle for a long time.Constantly impact solid particle due to high-velocity fluid, the solid particle of floating is the flowing shape of fast scroll, and speed quickly and forms turbulent flow, and high turbulence and the biggest alternate relative velocity provide splendid condition of transmitting.Carry-over factor improves several times to tens times than tradition stirring means, effectively facilitate the microcosmic mixing on molecular scale, so that soluble vanadium species produce the highest moment degree of supersaturation, and strong microcosmic mixing can ensure that high degree of supersaturation reaches high uniform state, substantial amounts of VOHPO4·0.5H2O nucleus concurrently forms, and crystal is grown up rapidly, such that it is able to prepare thinner, nano V phosphorous oxides crystal (the i.e. VOHPO of centralized particle diameter4·0.5H2O).
Compared with prior art, vanadium-phosphor oxide catalyst of the present invention and preparation method thereof has a following feature:
1, the vanadium-phosphor oxide catalyst particle diameter that prepared by the inventive method is little, Grain size distribution is concentrated, and specific surface area is big, and intensity is high, wears away little.VOHPO prepared by conventional method4·0.5H2O is micron order, and crystallite dimension is relatively big, and in activation process, only top layer crystal can lose water of crystallization, and body is difficult to lose water of crystallization mutually, then results in body phase VOHPO4·0.5H2O changes in reaction atmosphere and generates VOPO4Phase；VOHPO prepared by this method4·0.5H2O presoma crystallite dimension is less, and in activation process, the volatile water that decrystallizes, is directly translated into (VO)2P2O7Phase.
(VO)2P2O7Crystalline phase is considered as the chief active phase of vanadium-phosphor oxide catalyst, presoma VOHPO in activation process4·5H2O is to (VO)2P2O7The phase in version of crystalline phase was carried out under mother crystal shape in basic holding, and this phase in version is referred to as Topotactic and changes (local structured's transformation).The activity of vanadium-phosphor oxide catalyst and this (VO)2P2O7The octahedral structure of crystal is closely related.Therefore, size of microcrystal is distributed greater concentration of nanometer VOHPO4·0.5H2(VO) obtained after O crystal is activated2P2O7The octahedral structure of crystalline phase is more regular, the active center distribution of gained catalyst is evenly, make to prepare catalyst structure more stable, the stability of catalysis activity and catalyst is higher, meanwhile, homodisperse active center beneficially normal butane is converted into maleic anhydride, reduces the trend generating by-product COx.
2, the ebullating bed reactor mode in the present invention makes the contact area between reactant liquor and granular solids material increase, and promotes the carrying out of mass-and heat-transfer, substantially increases production intensity；Meanwhile, reaction mass is in the kinestate of rolling, can keep homogeneous temperature, it is to avoid hot-spot.
3, compared with conventional drying methods, boiled bed drying method air-flow and intergranular contact surface are very big, have higher volumetric heat transfer coefficient, and granule can reach to be thoroughly mixed in ebullated bed, and mass-and heat-transfer efficiency is the highest, and dry materials efficiency is the highest.
4, in the inventive method, the activation process of catalyst is carried out in fluidized bed reactor.Catalyst precursor can be fully contacted with by the activated gas of gas distribution grid, and carries out sufficient Mass and heat transfer between thermal current.Compared with Conventional activation methods, the contact surface stirring between state, and air-flow that catalyst granules is in " boiling-like " is very big, thus catalyst activation process tends to perfect, and gained catalyst activity is preferable.
5, the granule of flowing in the inventive method, is readily incorporated into or takes out and will not affect the carrying out of reaction, can make preparation process serialization.
6, the synthesis of catalyst precursor in the present invention, dry, roasting and activation process are all carried out in same fluidized bed reactor, simplify flow process, improve reaction efficiency, shorten the response time, the most simple to operate, process control is steady, is suitable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the fluidized bed reactor structural representation used by the present invention.
Wherein, 1, charging aperture, 2, charging aperture (gas access), 3, discharge port, 4, gas outlet's (capable of circulation), 5, fluid distribution plate.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the vanadium-phosphor oxide catalyst of embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in further detail.Following example are not limiting the scope of the invention, and those skilled in the art combines description of the invention and can do suitable extension in full, and these extensions should be all the protection domain of technical solution of the present invention.
Agents useful for same in embodiment and comparative example, isobutanol (Tianjin recovery fine chemistry industry institute, analytical pure, content ＞ 99.0%), benzyl alcohol (Tianjin recovery fine chemistry industry institute, analytical pure, content ＞ 99.0%), vanadic anhydride (Tianjin good fortune chemical reagent factory in morning, analytical pure, content ＞ 99.0%), phosphoric acid (Shenyang Big Dipper chemical reagent factory, analytical pure, content ＞ 99.0%).The grain size of vanadium-phosphor oxide catalyst of the present invention and Grain size distribution are to use laser particle analyzer to measure.Attrition of catalyst uses Rotating Cutter instrument to be measured, and intensity uses detector for strength of particles to be measured.
The concrete preparation process of vanadium-phosphor oxide catalyst of the present invention is as follows:
In the fluidized bed reactor shown in Fig. 1, charge door 1 add vanadic anhydride and auxiliary agent, isobutanol, benzyl alcohol mixed liquor, isobutanol and benzyl alcohol volume ratio 1:1～100:1；Then fluid is blasted in reactor by charging aperture 2, make reactant liquor and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 85～110 DEG C, keeping response time 2～4 hours；Being passed through strong phosphoric acid (concentration 85%～100%) in reactor by charge door 1 again, phosphorus and vanadium mol ratio are 0.85～1.35, continue to keep " boiling-like " to react 4～6 hours, and reaction terminates.
Adjust temperature of reactor, be maintained at 120～160 DEG C.Continue to blast gas, keep " boiling-like " 6～10 hours, solvent is steamed, obtains catalyst Precursors powder.Subsequently in 200～300 DEG C of temperature ranges, by catalyst Precursors powder roasting 4 ~ 8 hours under " fluidized state ", i.e. obtain the presoma of vanadium-phosphor oxide catalyst.
Heat further in the range of 340～450 DEG C, in reactor, blasted activated gas by charging aperture 2 simultaneously, make catalyst precursor powder keep " boiling-like " to activate 8 ~ 40 hours, obtain vanadium-phosphor oxide catalyst.
Described activated gas can be that (butane volumetric concentration is 0.5%～1.5% for the gaseous mixture of butane/air, preferably 0.8%～1.2%), can also is that (steam volumetric concentration is 25%～75% to air/water steam gaseous mixture, preferably 35%～55%), nitrogen/steam gaseous mixture (steam volumetric concentration is 25%～75%, preferably 35%～55%) etc..
Obtained vanadium-phosphor oxide catalyst can need to be prepared as the shape such as lamellar, spherical, bar shaped according to course of reaction, and the thing of catalyst is mainly Vanadyl pyrophosphate ((VO mutually2)2P2O7) phase.Above-mentioned forming process typically may include that and the vanadium phosphorus catalyst after activated add the graphite powder that mass fraction is 3%～5%, or other shaping assistant (mass fraction is generally 3%～5%), after being sufficiently mixed, use rotary tablet machine, suitably adjust impact dynamics, be squeezed into definite shape.The catalyst that this method is prepared is suitable in fixed bed reactors using.
For the people being proficient in this technology, aforesaid vanadium-phosphor oxide catalyst powder can also use other molding mode to prepare different types of catalyst, and can apply in fixed bed, heat exchange reactor, fluidized-bed reactor or moving-burden bed reactor.Add suitable binding agent than vanadium-phosphor oxide catalyst powder as the aforementioned, lubricant can also use the mode molding of extrusion, is suitable for doing binding agent, the material of lubricant includes starch, calcium stearate, stearic acid or graphite etc.；Or in same fluidized bed reactor, it is directly used as butane oxidation cis-butenedioic anhydride.Similarly, the parent of preformed catalyst can also make catalyst microspheres to use in fluid bed and moving bed.The details of operation of these above-mentioned reactors is grasped by insider.
Prepared vanadium-phosphor oxide catalyst, can carry out performance evaluation: loaded in fixed bed reactors by the vanadium-phosphor oxide catalyst of above-mentioned preparation, be passed through reaction mixture gas and react, carry out activity rating of catalyst test as follows.Reaction condition is as follows: reaction temperature 375～450 DEG C, and pressure is normal pressure～0.5MPa, and normal butane gaseous mixture air speed is 1200～3500h-1, in reaction mixture gas, butane volumetric concentration is 1.0%～1.8%.
Embodiment
1
In the fluidized bed reactor shown in Fig. 1, charge door 1 add vanadic anhydride 30.0g；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 particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 100 ± 2 DEG C, keeping 3 hours response time；Being passed through, by charge door 1, strong phosphoric acid 38.0g that concentration is 85% in reactor again, phosphorus/vanadium mol ratio is 1.0.Continuing to keep " boiling-like " to react 6 hours, reaction terminates.Adjust temperature of reactor, be maintained at 120 ± 2 DEG C.Continue to blast gas, keep " boiling-like " 6 hours, solvent is steamed, obtains catalyst Precursors powder.Subsequently in 240 ± 2 DEG C of temperature ranges, by catalyst Precursors powder roasting 5 hours under " fluidized state ", i.e. obtain the presoma of vanadium-phosphor oxide catalyst.Heat further in the range of 400 ± 2 DEG C, in reactor, blasted the gaseous mixture (butane volumetric concentration is 0.8%) of butane/air simultaneously by charging aperture 2, make catalyst precursor powder keep " boiling-like " to activate 20 hours, obtain vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 90%).Specific surface area is 160m2/ g, grain size is less than 120nm；Its Grain size distribution is as follows by volume: the particle proportion of 30～60nm is 14%, 60～the particle proportion of 90nm is 61%, and 90 ~ 120nm particle proportion is 25%.
It is the graphite powder of 4% by aforesaid catalyst addition mass fraction, after being sufficiently mixed, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column.After measured, the side pressure strength of catalyst is 26.7N mm-1.Attrition of catalyst is 0.04%/h.
Carried out crushing and sieving, be prepared as catalyst granules.Measure 5mL catalyst granules (5～10 mesh) to be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 375 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.3%, and gas volume air speed is 1750h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 91%(mole), Selectivity of maleic anhydride reaches 64%(mole).
Embodiment
2
In the fluidized bed reactor shown in Fig. 1, charge door 1 add vanadic anhydride 30g, auxiliary agent ferric nitrate 0.3g, auxiliary agent zirconium nitrate 0.5g；Isobutanol, benzyl alcohol mixed liquor 690mL, isobutanol/benzyl alcohol volume ratio 15:1.By N2Blasted in reactor by charging aperture 2, make reactant liquor and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 97 ± 2 DEG C, keeping 4 hours response time；Being passed through, by charge door 1, strong phosphoric acid 35.5g that concentration is 100% in reactor again, phosphorus/vanadium mol ratio is 1.1, continues to keep " boiling-like " to react 5 hours, and reaction terminates.Adjust temperature of reactor, be maintained at 140 ± 2 DEG C.Continue to blast gas, keep " boiling-like " 6 hours, solvent is steamed, obtains catalyst Precursors powder.Subsequently in 250 ± 2 DEG C of temperature ranges, by catalyst Precursors powder roasting 6 hours under " fluidized state ", i.e. obtain the presoma of vanadium-phosphor oxide catalyst.Heat further in the range of 420 ± 2 DEG C, in reactor, blasted the gaseous mixture (butane volumetric concentration is 0.8%) of butane/air simultaneously by charging aperture 2, make catalyst precursor powder keep " boiling-like " to activate 24 hours, obtain vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 93%).Specific surface area is 130m2/ g, grain size is less than 120nm；Its Grain size distribution is as follows by volume: the particle proportion of 30～60nm is 10%, 60～the particle proportion of 90nm is 67%, and 90 ~ 120nm particle proportion is 23%.
It is the graphite powder of 4% by aforesaid catalyst addition mass fraction, after being sufficiently mixed, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column.After measured, the side pressure strength of catalyst is 30.1N mm-1.Attrition of catalyst is 0.03%/h.
Carried out crushing and sieving, be prepared as catalyst granules.Measure 5mL catalyst granules (5～10 mesh) to be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 390 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.5%, and gas space velocity is 3500h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 94%(mole), Selectivity of maleic anhydride reaches 68%(mole).
Embodiment
3
In the fluidized bed reactor shown in Fig. 1, charge door 1 add vanadic anhydride 30.0g；Isobutanol, benzyl alcohol mixed liquor 690mL, isobutanol/benzyl alcohol volume ratio 20:1.Helium is blasted in reactor by charging aperture 2, makes reactant liquor and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 98 ± 2 DEG C, keeping 4 hours response time；Being passed through, by charge door 1, strong phosphoric acid 34.0g that concentration is 95% in reactor again, phosphorus/vanadium mol ratio is 1.0.Continuing to keep " boiling-like " to react 6 hours, reaction terminates.Adjust temperature of reactor, be maintained at 120 ± 2 DEG C.Continue to blast gas, keep " boiling-like " 8 hours, solvent is steamed, obtains catalyst Precursors powder.Subsequently in 240 ± 2 DEG C of temperature ranges, by catalyst Precursors powder roasting 4 hours under " fluidized state ", i.e. obtain the presoma of vanadium-phosphor oxide catalyst.Heat further in the range of 450 ± 2 DEG C, in reactor, blasted the gaseous mixture (butane volumetric concentration is 0.8%) of butane/air simultaneously by charging aperture 2, make catalyst precursor powder keep " boiling-like " to activate 20 hours, obtain vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 91%).Specific surface area is 170m2/ g, grain size is less than 120nm；Its Grain size distribution is as follows by volume: the particle proportion of 30～60nm is 14%, 60～the particle proportion of 90nm is 65%, and 90 ~ 120nm particle proportion is 21%.
It is the graphite powder of 4% by aforesaid catalyst addition mass fraction, after being sufficiently mixed, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column.After measured, the side pressure strength of catalyst is 29.8N mm-1.Attrition of catalyst is 0.04%/h.
Carried out crushing and sieving, be prepared as catalyst granules.Measure 5mL catalyst granules (5～10 mesh) to be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 400 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.5%, and gas space velocity is 2500h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 90%(mole), Selectivity of maleic anhydride reaches 65%(mole).
Embodiment
4
In the fluidized bed reactor shown in Fig. 1, charge door 1 add vanadic anhydride 30.0g；Isobutanol, benzyl alcohol mixed liquor 600mL, isobutanol/benzyl alcohol volume ratio 15:1.By N2Blasted in reactor by charging aperture 2, make reactant liquor and solid particle keep " boiling-like " tumbling state.Rise high reaction temperature and be maintained at 100 ± 2 DEG C, keeping 4 hours response time；Being passed through, by charge door 1, strong phosphoric acid 32.3g that concentration is 100% in reactor again, phosphorus/vanadium mol ratio is 1.0.Continuing to keep " boiling-like " to react 4 hours, reaction terminates.Adjust temperature of reactor, be maintained at 130 ± 2 DEG C.Continue to blast gas, keep " boiling-like " 8 hours, solvent is steamed, obtains catalyst Precursors powder.Subsequently in 220 ± 2 DEG C of temperature ranges, by catalyst Precursors powder roasting 6 hours under " fluidized state ", i.e. obtain the presoma of vanadium-phosphor oxide catalyst.Heat further in the range of 420 ± 2 DEG C, in reactor, blasted the gaseous mixture (butane volumetric concentration is 0.8%) of butane/air simultaneously by charging aperture 2, make catalyst precursor powder keep " boiling-like " to activate 24 hours, obtain vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 96%).Specific surface area is 210m2/ g, grain size is less than 120nm；Its Grain size distribution is as follows by volume: the particle proportion of 30～60nm is 9%, 60～the particle proportion of 90nm is 74%, and 90 ~ 120nm particle proportion is 17%.
It is the graphite powder of 4% by aforesaid catalyst addition mass fraction, after being sufficiently mixed, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column.After measured, the side pressure strength of catalyst is 30.6N mm-1.Attrition of catalyst is 0.04%/h.
Carried out crushing and sieving, be prepared as catalyst granules.Measure 5mL catalyst granules (5 mesh～10 mesh) to be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 415 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.6%, and gas space velocity is 2750h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 93%(mole), Selectivity of maleic anhydride reaches 69%(mole).
Comparative example
1
In the four-hole boiling flask with agitator, add isobutanol, benzyl alcohol mixed liquor 600mL, isobutanol/benzyl alcohol volume ratio 20:1, vanadic anhydride 30g, stirring heats up, back flow reaction is carried out at reaction temperature 105 ± 2 DEG C, maintaining the reflux for the time 4 hours, add the phosphoric acid 35.5g of concentration 100%, phosphorus/vanadium mol ratio is 1.1, continuing to maintain the reflux for the response time 6 hours, reaction terminates.After reactant liquor is cooled to room temperature, vacuum filtration, filter cake is with after a small amount of isobutanol drip washing three times, filter cake is put in enamel tray natural air drying under room temperature, being dried in 120 DEG C of baking oven 8 hours, finally roasting 5 hours at 260 DEG C in Muffle furnace, obtain the vanadium-phosphor oxide catalyst precursor powder of pitchy.
Vanadium-phosphor oxide catalyst precursor powder obtained above is placed in pipe type calciner, it is passed through the gaseous mixture (butane volumetric concentration is 0.8%) of butane/air, quickly activation temperature is increased to 250 DEG C from room temperature, the most slowly it is warmed up to 400 DEG C and keeps 20 hours, activation process terminates, and i.e. obtains vanadium-phosphor oxide catalyst.Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 88%).Specific surface area is 18m2/ g, grain size is more than 200nm；Its Grain size distribution is as follows by volume: the particle proportion of 180～210nm is 4%, 210～the particle proportion of 250nm is 26%, and ＞ 250 particle proportion is 70%.
It is the graphite powder of 4% by aforesaid catalyst addition mass fraction, after being sufficiently mixed, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column.After measured, the side pressure strength of catalyst is 6.61N mm-1.Attrition of catalyst is 0.12%/h.
Carried out crushing and sieving, be prepared as catalyst granules.Measure 5mL catalyst granules (5～10 mesh) to be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 400 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.3%, and gas space velocity is 2500h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 66%(mole), Selectivity of maleic anhydride is 34%(mole).
Comparative example
2
The preparation method of catalyst is carried out according to method disclosed in CN101157048A.30 grams of vanadic anhydrides and 240ml dehydrated alcohol and 120ml benzyl alcohol are joined in flask, add 0.81 gram of bismuth nitrate and 1.17ml dimethyl sulfoxide simultaneously, heating reflux reaction 12 hours, add in the phosphoric acid 26.0ml of 85% and the reactant liquor of 1.70 grams of Polyethylene Glycol extremely heat, continue back flow reaction 16 hours, obtain blue solution after completion of the reaction, reactant liquor is cooled to room temperature, much filtrate is washed by 100ml dry isobutanol, this much filtrate is dried 8 hours in 110 DEG C in air atmosphere, i.e. obtains vanadium-phosphor oxide catalyst precursor powder.
Vanadium-phosphor oxide catalyst precursor powder obtained above is added graphite powder and the distilled water that mass fraction is 4%, after mist projection granulating, uses rotary tablet machine, suitably adjust impact dynamics, be squeezed into column, be dried 10 hours at 70 DEG C.Then being placed in pipe type calciner, be passed through the gaseous mixture (butane volumetric concentration is 1.5%) of butane/air, quickly from room temperature, activation temperature be increased to 250 DEG C, be the most slowly warmed up to 400 DEG C and keep 72 hours, activation process terminates.Gained catalyst detects its crystalline phase for (VO through XRD2)2P2O7Phase (volume content is 85%).Specific surface area is 22m2/ g, grain size is less than 200nm；Its Grain size distribution is as follows by volume: the particle proportion of 110～140nm is 18%, 140～the particle proportion of 170nm is 39%, and 170 ~ 200nm particle proportion is 43%.The side pressure strength of catalyst is 6.67N mm-1.Attrition of catalyst is 0.15%/h.
Carry out crushing and sieving by the catalyst cylinder after activation, be prepared as catalyst granules, measure 5mL catalyst granules (5～10 mesh) and be placed in the stainless steel reaction pipe that internal diameter is 10mm.In reaction temperature 400 DEG C, reaction pressure 0.25MPa, reaction gas is the normal butane/air Mixture of butane volumetric concentration 1.5%, and gas space velocity is 2750h-1Reaction condition under carry out catalytic performance test.Through gas chromatographic analysis, n-butane conversion is 71%(mole), Selectivity of maleic anhydride 43%(mole).
Claims (16)
1. the preparation method of a vanadium-phosphor oxide catalyst, it is characterized in that including following content: isobutanol and the mixture of benzyl alcohol, vanadic anhydride and auxiliary agent are joined in fluidized bed reactor by (1), fluid it is passed through in reactor, make material be in " boiling-like " tumbling state, reactor is warming up to reaction temperature and reacts；Then in reactor, it is passed through strong phosphoric acid, keeps " boiling-like ", obtain blue or sky-blue pulpous state reactant liquor；(2) material in step (1) is dried, calcination process, obtain the presoma of vanadium-phosphor oxide catalyst, during this material keep " boiling-like "；(3) being passed through activated gas in reactor, catalyst precursor is carried out activation processing, obtains vanadium-phosphor oxide catalyst, during this, material keeps " boiling-like ".
The most in accordance with the method for claim 1, it is characterised in that: isobutanol described in step (1) and the mixed volume of benzyl alcohol are than for 1:1～100:1.
The most in accordance with the method for claim 1, it is characterised in that: the mixed weight of isobutanol described in step (1) and benzyl alcohol mixture and vanadic anhydride is than for 5:1～25:1.
The most in accordance with the method for claim 1, it is characterised in that: the fluid described in step (1) is N2, one or more in air or noble gas.
The most in accordance with the method for claim 1, it is characterized in that: the fluidized bed reactor described in step (1) is vertical reactor, reactor bottom is provided with the fluid distribution plate of baffle plate, with throttling pore on distribution grid, small aperture is 60 ~ 100 mesh, and the centrage of baffle plate and aperture is at 45 °～90 °.
The most in accordance with the method for claim 1, it is characterised in that: the mass percent concentration of the strong phosphoric acid described in step (1) is 85%～100%, and the addition of strong phosphoric acid is 0.85～1.35 with the molar ratio computing of phosphorus in system Yu vanadium.
The most in accordance with the method for claim 1, it is characterised in that: the reaction temperature described in step (1) is 85～110 DEG C, and the response time is 2～4 hours；Continue after adding strong phosphoric acid to keep " boiling-like " to react 4～6 hours.
The most in accordance with the method for claim 1, it is characterised in that the drying condition described in step (2) is as follows: be dried 6～10 hours at a temperature of 120～160 DEG C.
The most in accordance with the method for claim 1, it is characterised in that the roasting condition described in step (2) is as follows: roasting 4～8 hours at 200～300 DEG C.
The most in accordance with the method for claim 1, it is characterized in that: the combination of one or more in the gaseous mixture that activation gas is the gaseous mixture of nitrogen/air, the gaseous mixture of steam/air or butane/air described in step (3), activation temperature is 340～450 DEG C, and soak time is 8～40 hours.
11. in accordance with the method for claim 1, it is characterized in that: in vanadium-phosphor oxide catalyst preparation process, introducing one or more in Co, Ni, Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr or Ce element, auxiliary element is 0.001:1～0.2:1 with the atomic ratio of v element.
Catalyst prepared by the method described in 12. claim 1 ~ 11 any claim, it is characterised in that: the specific surface area of vanadium-phosphor oxide catalyst is 110～230m2/ g, grain size is less than 120nm, and on the basis of volume, its Grain size distribution is as follows: the particle proportion of 30～60nm is 7%～13%, and the particle proportion of 60～90nm is 47%～80%, and 90 ~ 120nm particle proportion is 13%～40%.
13. according to the catalyst described in claim 12, it is characterised in that: the side pressure strength of described catalyst is 20 ~ 35N mm-1。
14. according to the catalyst described in claim 12, it is characterised in that: described attrition of catalyst is less than 0.05%/h.
15. according to the catalyst described in claim 12, it is characterised in that: in the crystal phase structure of described vanadium-phosphor oxide catalyst, (VO2)2P2O7Volume content be 85%～99%；Phosphorus is 0.85～1.35 with the mol ratio of vanadium.
Catalyst described in 16. claim 12 is applied to preparing cis-anhydride by n-butane oxidation reaction, and reaction condition is: reaction temperature 375～450 DEG C, and pressure is normal pressure～0.5MPa, and normal butane gaseous mixture air speed is 1200～3500h-1, normal butane concentration of volume percent is 1.0%～1.8%.
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| 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 |
| CN112090437A (en) * | 2019-06-18 | 2020-12-18 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst for preparing maleic anhydride by n-butane oxidation and preparation method and application thereof |
| CN112495410A (en) * | 2021-01-19 | 2021-03-16 | 郑州中科新兴产业技术研究院 | Vanadium phosphorus oxygen catalyst, preparation method and application |
| 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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| CN1303741A (en) * | 2000-01-13 | 2001-07-18 | 中国石油化工集团公司 | Preparation method of composite VPO catalyst for preparing cis-butenedioic anhydride by oxidation of n-butane |
| CN1311058A (en) * | 2000-12-29 | 2001-09-05 | 南京大学 | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use |
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| CN1303741A (en) * | 2000-01-13 | 2001-07-18 | 中国石油化工集团公司 | Preparation method of composite VPO catalyst for preparing cis-butenedioic anhydride by oxidation of n-butane |
| CN1311058A (en) * | 2000-12-29 | 2001-09-05 | 南京大学 | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use |
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