CN109772391A - A kind of catalyst preparing phthalic anhydride by benzene oxidatoin - Google Patents

Abstract

The present invention discloses a kind of catalyst that phthalic anhydride is prepared by benzene oxidatoin, particularly relates to the catalyst for preparing phthalic anhydride through gas-solid phase catalytic oxidation reaction using benzene as raw material.The catalyst is using containing V, Mo, Ti, and P, Na, the salt or oxide of Ni is that presoma is configured to solution or suspension, and through drying, activation, emulsifying, spraying is prepared.The present invention solves the problem of existing catalyst induction period is long, and active matter is easy to fall off, and catalyst raw material availability is low, and the working environment of workers is poor, and environmental pollution is serious.

Description

A kind of catalyst preparing phthalic anhydride by benzene oxidatoin

Technical field

The invention belongs to the preparation of hydrocarbon oxidation catalyst and applications, particularly relate to a kind of by the adjacent benzene two of benzene oxidatoin preparation The catalyst of formic anhydride.

Background technique

Phthalic anhydride is important Organic Chemicals, is the third-largest acid that consumption figure is only second to aceticanhydride and phthalic anhydride Acid anhydride is mainly used for diene synthesis, pharmacy, pesticide, dyestuff intermediate and prepares polyester resin, alkyd resin, maleic acid etc., application Field is extensive, and the market demand is huge.

Phthalic anhydride producer, the country mainly produces phthalic anhydride by raw material of benzene at present, and phthalic anhydride is urged Agent producer is all made of pyrolytic coating method and prepares catalyst.Patent " the high load capacity high yield benzene gas phase invented such as Yao Shaohua et al. Aoxidizing the catalyst of maleic anhydride processed, " (Authorization Notice No.: CN101284242B), the spraying temperature mentioned are 270 ± 15 DEG C, catalyst raw material availability is only 70% or so, and there are about 30% to lose.A kind of patent of invention " suitable fourth of Chen Yaping et al. " (Authorization Notice No. CN102850307B), what is used is still pyrolytic coating to the production method of enedioic acid acid anhydride, and spraying temperature is 200-300 DEG C, raw material availability is 83% or so.A kind of patent " benzene oxidatoin phthalic anhydride catalysis of Liu Xianguo invention " (open notification number: CN103816931A), the spraying temperature of the catalyst is 210 DEG C, and the raw material availability of the catalyst is about for agent It can be seen that the catalyst significant loss prepared using pyrolytic coating method is tight from the patent of the above industrializeding catalyst for 66%. Weight, increases environmental pollution, and catalyst activity component is easy to fall off, and it is longer to be catalyzed economic induction period, the working environment of workers compared with It is severe.

Summary of the invention

The purpose of the present invention is to provide a kind of catalyst that phthalic anhydride is prepared by benzene oxidatoin.

The present invention is to provide a kind of catalyst that phthalic anhydride is prepared by benzene oxidatoin, are technically characterized in that and urge Agent is by containing V, Mo, P, Ti, Ni, the hexa-atomic metal composite oxide composition of Na, according to the member in claim specification 1 Element, atomic ratio V₁Mo_0.1-1.0Ti_0.2-5.0P_0.01-0.5Na_0.002-0.5Ni_0.002-_0.5, preferably V₁Mo_0.2-0.5Ti_{0.3- 2.0}P_0.03-0.3Na_0.04-0.3Ni_0.005-0.2.The precursor salt or oxide of each element are dissolved, dry, activation, emulsifying, spray Painting is prepared.

Gaseous oxidation of the catalyst provided using the invention for benzene prepares phthalic anhydride, is remarkably improved catalysis Agent raw material availability shortens catalyst induction period, improves active component adhesion-tight degree, improves the working environment of workers, reduces ring Border pollution, and the yield of phthalic anhydride can be improved.

Specific embodiment

Embodiment 1

Catalyst preparation

In water by 144.0g dissolving oxalic acid, then under heating stirring 99.20g ammonium sulfate is added until ammonium sulfate is completely molten Solve, add 60.00g ammonium molybdate, 3.80g ammonium dihydrogen phosphate, 1.76g Nickelous nitrate hexahydrate, 6.19g sodium nitrate, heating until It is completely dissolved.Obtained slurries are subjected to mist projection granulating in spray dryer, catalyst granules using cyclone separator into Row is collected, and dryer inlet temperature is 150 ± 5 DEG C, spray gun pressure 0.2Mpa.By the catalyst granules being collected into fluidized bed It is activated in activation furnace, activates temperature program are as follows: 6h is kept the temperature to 450 DEG C and at such a temperature with the rate of 2 DEG C/min, then Naturally it is down to room temperature.By after activation catalyst activity object and 30g titanium dioxide be added in 500ml deionized water, and be added 35 grams of white glue carry out dispersion and emulsion using Homogenizing pump, and homogeneous revolution speed is 1000rpm, and the emulsifying time is that 15min will be emulsified Catalyst medicine slurry afterwards is sprayed on 760g carrier, and spraying temperature is 120 ± 10 DEG C.The weight of finally obtained catalyst A is 913.2g, active component content 16.8%, the utilization rate of catalyst raw material are about 98%.

Evaluating catalyst

The catalyst of above-mentioned preparation is taken, slowly in the reaction tube that internal diameter is 21mm, filling height is 315cm. molten Salt bath inlet temperature is 350-360 DEG C, air speed 2000-2500h^-1, benzene concentration is in 50-60g/Nm³Under the conditions of continuously evaluated Test, evaluation time is that 960h. evaluation result is benzene conversion ratio 98.5-99.5%, phthalic anhydride weight yield 90- 92%.

Embodiment 2

In water by 148.00g dissolving oxalic acid, be added then under heating stirring 101.97g ammonium sulfate until being completely dissolved, 47.43g ammonium molybdate, 4.38g ammonium dihydrogen phosphate, 1.81g Nickelous nitrate hexahydrate, 6.36g sodium nitrate are added, is heated until complete Dissolution.Obtained slurries are subjected to mist projection granulating in spray dryer, catalyst granules is received using cyclone separator Collection, dryer inlet temperature are 120 ± 10 DEG C, spray gun pressure 0.3Mpa；The catalyst granules being collected into is living in fluidized bed Change and activated in furnace, activate temperature program are as follows: keep the temperature 6h to 450 DEG C and at such a temperature with the rate of 2 DEG C/min, then oneself So it is down to room temperature.By after activation catalyst activity object and 33.0g titanium dioxide be added in 500ml deionized water, and be added 35 grams of white glue, are emulsified using Homogenizing pump, and homogeneous revolution speed is 1000rpm, and the dispersion and emulsion time is 15min；It will dispersion cream Catalyst medicine slurry after change is sprayed on 760g carrier, and spraying temperature is 120 ± 10 DEG C.The weight of finally obtained catalyst B For 908.4g, active component content 16.3%, the utilization rate of catalyst raw material is about 98%.

Evaluating catalyst

The catalyst of above-mentioned preparation is taken, slowly in the reaction tube that internal diameter is 21mm, filling height is 315cm. molten Salt bath inlet temperature is 350-360 DEG C, air speed 2000-2500h^-1, benzene concentration is in 50-60g/Nm³Under the conditions of continuously evaluated Test, evaluation time is that 960h. evaluation result is benzene conversion ratio 98.5-99.5%, phthalic anhydride weight yield 90- 93%.

Comparative example 1

Catalyst preparation

In water by 189.1g dissolving oxalic acid, then heat and be added with stirring 130.25g ammonium sulfate until being completely dissolved, 78.78g ammonium molybdate, 4.99g ammonium dihydrogen phosphate, 2.31g Nickelous nitrate hexahydrate, 8.12g sodium nitrate are added, is heated until complete Then dissolution is added 39.39g titanium dioxide and is the emulsified 10min of 1000rpm in homogeneous revolution speed, then catalyst slurry It is sprayed on pyrolytic coating machine in the case where keeping stirring, the weight of carrier is 760.0g, and spraying temperature is 250-290 DEG C, most The weight for obtaining catalyst afterwards is 911.3g, and active component content 16.6%, catalyst raw material availability is about 74%.

Evaluating catalyst

The catalyst of above-mentioned preparation is taken, slowly in the reaction tube that internal diameter is 21mm, filling height is 315cm. molten Salt bath inlet temperature is 350-360 DEG C, air speed 2000-2500h^-1, benzene concentration is in 50-60g/Nm³Under the conditions of continuously evaluated Test, evaluation time are that 960h. evaluation result is benzene conversion ratio 98-99%, and phthalic anhydride weight yield is 88-91%.

Comparative example 2

In water by 203.08g dissolving oxalic acid, it then is heating and is being added with stirring 139.90g ammonium sulfate until completely molten Solve, add 65.07g ammonium molybdate, 6.01g ammonium dihydrogen phosphate, 2.48g Nickelous nitrate hexahydrate, 8.73g sodium nitrate, heating until It is completely dissolved, 45.28g titanium dioxide is then added and is the emulsified 10min of 1000rpm in homogeneous revolution speed, then catalyst Slurries are sprayed on pyrolytic coating machine in the case where keeping stirring, and the weight of carrier is 760.0g, spraying temperature 250-290 DEG C, the weight for finally obtaining catalyst is 909.6g, and active component content 16.4%, catalyst raw material availability is about 72%.

Evaluating catalyst

The catalyst of above-mentioned preparation is taken, slowly in the reaction tube that internal diameter is 21mm, filling height is 315cm. molten Salt bath inlet temperature is 350-360 DEG C, air speed 2000-2500h^-1, benzene concentration is in 50-60g/Nm³Under the conditions of continuously evaluated Test, evaluation time are that 960h. evaluation result is benzene conversion ratio 98-99%, and phthalic anhydride weight yield is 89-91%.

Claims (4)

1. a kind of catalyst for preparing phthalic anhydride by benzene oxidatoin particularly relates to the catalysis of benzene oxidatoin maleic anhydride Agent and preparation method thereof, it is characterised in that using V, Mo, P, Na, Ni is contained, the salt or oxide of Ti is dissolved, dry, activation, Matter emulsification, spraying are prepared.

2. V, Mo, P, Na, what Ni was used is ammonium sulfate, ammonium paramolybdate, nitre respectively according to the element in claim specification 1 Sour sodium, Nickelous nitrate hexahydrate Ti is using titanium dioxide.

3. according to the titanium dioxide in claims 1, it is characterised in that be anatase titanium dioxide, be 5-100m than table²/ g, Preferably 10-50m²/g。

4. according to the drying in claims 1, it is characterised in that the dry dry, heating under reduced pressure using normal heating is done Dry, freeze-drying, spray drying, are preferably spray-dried.