CN1439636A - Production of metaphenyltrimethyl anhydride from metatrimethylbenzene by solid bed gas phase oxidation - Google Patents

Production of metaphenyltrimethyl anhydride from metatrimethylbenzene by solid bed gas phase oxidation Download PDF

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CN1439636A
CN1439636A CN 03111257 CN03111257A CN1439636A CN 1439636 A CN1439636 A CN 1439636A CN 03111257 CN03111257 CN 03111257 CN 03111257 A CN03111257 A CN 03111257A CN 1439636 A CN1439636 A CN 1439636A
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unsym
trimethyl benzene
trimellitic anhydride
phase oxidation
gas phase
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CN100364984C (en
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王德成
赵继芳
王文彬
徐虹
刘培
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HEILONGJIANG PROVINCIAL PETROLEUM CHEMISTRY INST
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HEILONGJIANG PROVINCIAL PETROLEUM CHEMISTRY INST
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Abstract

A process for preparing metaphenuyl triformic acid anhydride from metatritoluene by fixed-bed gas oxidizing incldues such steps as proportionally mixing metatritoluene, water vapor and air, feeding the mixture in tubular reactor containing V-Ti fixed-bed catalyst, and oxidizing at 350-450 deg.C, 1000-10000 L/L.h of space speed and 10-100 g/L.h of catalyst load. Its advantages are low corrosion to equipment and simple process.

Description

The method of Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride
Technical field: the manufacture method that the present invention relates to a kind of trimellitic anhydride.
Background technology: trimellitic anhydride (Trimellitic anhydride), be called for short inclined to one side acid anhydride, be a kind of important chemical material, be widely used in production industries such as high temperature plasticizer, vibrin, polyester epoxy powder coating, insullac, water soluble alkyd resin, lubricating oil, printing ink, tackiness agent.At present in the world trimellitic anhydride to produce be the unsym-trimethyl benzene liquid-phase oxidation technology of representative based on the U.S. and Japan mainly, account for about 70% of ultimate production in the world.This technology is to be raw material with the unsym-trimethyl benzene, in acetic aid medium, is catalyzer with Co-Mn-Br, under about 2Mpa pressure, makes trimellitic anhydride with atmospheric oxidation.This operational path yield height, but long flow path require harshness to aspects such as equipment anticorrosion, automatic controls, and the counter investment volume is big, production maintenance cost height.Domestic existing liquid-phase oxidation production equipment overlaps more, about 1.5 ten thousand tons of general design throughput.Because domestic prior art is not perfect, equipment corrosion is serious, and its working rate only has about 30%, can't satisfy the domestic trimellitic anhydride market requirement.Domestic Dalian University of Technology, Anshan chemical industry once carried out the research of unsym-trimethyl benzene gaseous oxidation system trimellitic anhydride, adopt the V-Ti-P-O System Catalyst, its thick acid anhydride weight yield reaches as high as 55.6%.
Summary of the invention:, the invention provides a kind of method of Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride for solving the problem that the existing equipment corrosion of present employing liquid-phase oxidation technology production trimellitic anhydride is serious, yield is low.Method of the present invention is: unsym-trimethyl benzene, water vapor and air mixed are sent into be equipped with in the tubular reactor that vanadium-titanium is a fixed bed catalyst, make unsym-trimethyl benzene be oxidized to trimellitic anhydride: reaction conditions is: water vapour and unsym-trimethyl benzene input material volume ratio are 1: 5～40, catalyst loading is 10～100g/Lh, air speed is 1000～10000L/Lh, and temperature of reaction is 350～450 ℃.The internal diameter of the tubular reactor that above-mentioned reaction is used is 20～30mm, and the best is 25mm.The reaction gas of carrying the trimellitic anhydride steam secretly is cooled in trap, and trimellitic anhydride is separated out with the crystalloid solid, and is collected in trap.Tail gas is by emptying behind the water absorption bottle.Trap to constant weight, weighs solids crude product volume with minusing through air blow drying.The water absorption bottle is measured its thick acid anhydride content with alkali titration.Both sums are the thick acid anhydride amount of reaction gained.Optimum reaction condition is: water vapor and unsym-trimethyl benzene input material volume ratio be preferably 1: 10～and 30; Catalyst loading is preferably 20～50g/Lh; Air speed is preferably 200～5000L/Lh; Temperature of reaction is preferably 360～420 ℃.The present invention uses the spherical or ring-type catalyzer of coating type.Carrier is inert SiC, α-Al 2O 3Or acid-proof ceramics, be processed into the ring-type of the spherical of φ 4-6mm or internal diameter 4mm, external diameter 6mm, long 6mm.Catalyst activity component is with V 2O 5And TiO 2Be main, also contain P in addition 2O 5And Na 2O, K 2O, Rb 2O, Cs 2O wherein one or more.Useful as catalysts prepares the material of active constituent and is made of A:NH A, B, C, D 4VO 3Or V 2O 5B:TiCl 4Or TiO 2C:NH 4H 2PO 4: one or more in the alkali-metal nitrate of D:Na, K, Rb or Cs, vitriol or the carbonate.The weight ratio of catalyst activity material is: V 2O 5: TiO 2: P 2O 5: X 2O=5～25: 75～95: 0.1～4.5: 0.01～0.5, X is wherein one or more of Na, K, Rb, Cs in the formula.The concrete preparation method of catalyzer is, at first oxalic acid is dissolved in the distilled water, adds NH then 4VO 3Or V 2O 5Heating for dissolving; Use a small amount of dissolved in distilled water NH again 4H 2PO 4And an alkali metal salt, add above-mentioned NH 4VO 3Or V 2O 5In the solution; Under 50～60 ℃ of temperature, stirred 30 minutes, use water cooling then, slowly in this solution, drip TiCl 4Perhaps with anatase titanium dioxide TiO 2Add suitable quantity of water and grind this solution of back adding; Fully stir and make active constituent pulpous state liquid; Put into carrier in being provided with the rotary drum of indirect heating, above-mentioned pulpous state liquid is sprayed on the carrier equably, quantity for spray is 10～15% of a vehicle weight, will spray good catalyzer then and promptly make catalyzer in roasting 6-8 hour in 550 ℃ of hot blasts.Used an alkali metal salt is K 2CO 3, Cs 2SO 4, RbNO 3, Na 2CO 3Wherein one or more, the present invention can make thick acid anhydride weight yield reach more than 100%, reaches as high as 107%.The method of system trimellitic anhydride of the present invention is low to equipment corrosion, and technical process is simple, and is easy to form suitability for industrialized production.Gaseous oxidation technological process of the present invention is simple, and atmospheric operation does not have corrosion, has the unrivaled superiority of liquid phase oxidation technique.
Embodiment one: with NH 4VO 3, CsNO 3, NH 4H 2PO 4And TiCl 4Being raw material, is carrier with the SiC ball of φ 4-6mm, and making the active constituent weight ratio is V 2O 5: TiO 2: P 2O 5: Cs 2O=8.60: 86.42: 2.83: 0.15 catalyzer.Get 50ml and pack in the internal diameter 25mm glass reaction tube, 400 ℃ of temperature of reaction, water vapor: unsym-trimethyl benzene=20, catalyst loading 35g/Lh, under the air speed 3000L/Lh operational condition, thick trimellitic anhydride weight yield is 98.7%.
Embodiment two: with NH 4VO 3, RbNO 3, K 2CO 3, NH 4H 2PO 4And TiCl 4Be raw material, with α-Al of internal diameter 4mm, external diameter 6mm, long 6mm 2O 3Ring is carrier, and making the active constituent weight ratio is V 2O 5: TiO 2: P 2O 5: Rb 2O: K 2O=10.56: 86.71: 2.50: 0.12: 0.11 catalyzer.Getting 50ml packs in the internal diameter 25mm glass reaction tube, 395 ℃ of temperature of reaction, water vapor: unsym-trimethyl benzene=25, catalyst loading 34.5g//Lh, under the air speed 3500L/Lh operational condition, the thick trimellitic anhydride weight yield of unsym-trimethyl benzene is 107% relatively, and the thick trimellitic anhydride purity that is obtained by trap is 96.8%.
Embodiment three: with NH 4VO 3, TiO 2(anatase titanium dioxide), NH 4H 2PO 4, RbNO 3And K 2CO 3Being raw material, is V to make the active constituent weight ratio at embodiment two same carriers 2O 5: TiO 2: P 2O 5: Rb 2O: K 2O=8.55: 86.70: 2.55: 0.10: 0.10 oxide catalyst.Get 50ml and pack in the internal diameter 25mm glass reaction tube, 405 ℃ of temperature of reaction, water vapor: unsym-trimethyl benzene=22, catalyst loading 35g/Lh, under the air speed 3500L/Lh operational condition, thick trimellitic anhydride weight yield is 98.9%.

Claims (6)

1, the method for Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride is characterized in that unsym-trimethyl benzene, water vapor and air mixed sent into and is equipped with in the tubular reactor that vanadium-titanium is a fixed bed catalyst, makes unsym-trimethyl benzene be oxidized to trimellitic anhydride; Reaction conditions is: water vapour and unsym-trimethyl benzene input material volume ratio are 1: 5～40, and catalyst loading is 10～100g/Lh, and air speed is 1000～10000L/Lh, and temperature of reaction is 350～450 ℃.
2, the method for Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride according to claim 1 is characterized in that using the spherical or ring-type catalyzer of coating type, and the carrier of catalyzer is inert SiC, α-Al 2O 3Or acid-proof ceramics.
3, the method for Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride according to claim 1 and 2 is characterized in that the weight ratio of activity of such catalysts material is: V 2O 5: TiO 2: P 2O 5: X 2O=5～25: 75～95: 0.1～4.5: 0.01～0.5, X is wherein one or more of Na, K, Rb, Cs in the formula.
4,, it is characterized in that forming A:NH by A, B, C, D as the material of Preparation of Catalyst active constituent according to the method for claim 1 or 3 described Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride 4VO 3Or V 2O 5B:TiCl 4Or TiO 2C:NH 4H 2PO 4In the alkali-metal nitrate of D:Na, K, Rb or Cs, vitriol or the carbonate one or more.
5, the method for Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride according to claim 1 and 2 is characterized in that the concrete preparation method of catalyzer is, at first oxalic acid is dissolved in the distilled water, adds NH then 4VO 3Or V 2O 5Heating for dissolving; Use a small amount of dissolved in distilled water NH again 4H 2PO 4And an alkali metal salt, add above-mentioned NH 4VO 3Or V 2O 5In the solution; Under 50～60 ℃ of temperature, stirred 30 minutes, use water cooling then, slowly in this solution, drip TiCl 4Perhaps with anatase titanium dioxide TiO 2Add suitable quantity of water and grind this solution of back adding, fully stir and make active constituent pulpous state liquid; Put into carrier in being provided with the rotary drum of indirect heating, above-mentioned pulpous state liquid is sprayed on the carrier equably, quantity for spray is 10～15% of a vehicle weight, will spray good catalyzer then and promptly make catalyzer in roasting 6-8 hour in 550 ℃ of hot blasts.
6, the method for Fixed Bed Gas Phase oxidation unsym-trimethyl benzene system trimellitic anhydride according to claim 4 is characterized in that used an alkali metal salt is K 2CO 3, Cs 2SO 4, RbNO 3, Na 2CO 3Wherein one or more.
CNB031112579A 2003-03-21 2003-03-21 Production of metaphenyltrimethyl anhydride from metatrimethylbenzene by solid bed gas phase oxidation Expired - Fee Related CN100364984C (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
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CN105498817A (en) * 2015-12-31 2016-04-20 江苏正丹化学工业股份有限公司 Catalyst for production of trimellitic anhydride and preparation method and application of catalyst
CN109647469A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 It is used to prepare the catalyst of inclined acid anhydride
CN109647470A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 Catalyst for the preparation of inclined acid anhydride
CN109647463A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 Catalyst for pseudocumene oxidation reaction
CN110560112A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for preparing trimellitic anhydride
CN110560115A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing trimellitic anhydride
CN110560113A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for pseudocumene catalytic oxidation
CN110560114A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for improving yield of trimellitic anhydride
CN110560110A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene
CN110560111A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride from pseudocumene
CN110560116A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for oxidation of pseudocumene to prepare meta-anhydride
CN110560109A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for producing trimellitic anhydride

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JPH04208279A (en) * 1990-11-30 1992-07-29 Honsyu Kagaku Kogyo Kk Production of bistrimellitic anhydride bisphenol ester
CN1131223C (en) * 2002-06-28 2003-12-17 丹阳市联大化工有限公司 Process for production of trimellitic anhydride by continuous oxidizing process

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498817A (en) * 2015-12-31 2016-04-20 江苏正丹化学工业股份有限公司 Catalyst for production of trimellitic anhydride and preparation method and application of catalyst
CN105498817B (en) * 2015-12-31 2018-03-13 江苏正丹化学工业股份有限公司 A kind of catalyst for trimellitic anhydride production and its production and use
CN109647469A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 It is used to prepare the catalyst of inclined acid anhydride
CN109647470A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 Catalyst for the preparation of inclined acid anhydride
CN109647463A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 Catalyst for pseudocumene oxidation reaction
CN109647470B (en) * 2017-10-12 2020-10-30 中国石油化工股份有限公司 Catalyst for preparing partial anhydride
CN109647469B (en) * 2017-10-12 2020-10-16 中国石油化工股份有限公司 Catalyst for preparing partial anhydride
CN109647463B (en) * 2017-10-12 2020-10-16 中国石油化工股份有限公司 Catalyst for oxidation reaction of unsym-trimethyl benzene
CN110560109A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for producing trimellitic anhydride
CN110560112A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for preparing trimellitic anhydride
CN110560111A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride from pseudocumene
CN110560116A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for oxidation of pseudocumene to prepare meta-anhydride
CN110560114A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for improving yield of trimellitic anhydride
CN110560113A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for pseudocumene catalytic oxidation
CN110560115A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing trimellitic anhydride
CN110560110A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene
CN110560109B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for producing trimellitic anhydride
CN110560116B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for oxidation of pseudocumene to prepare meta-anhydride
CN110560113B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for pseudocumene catalytic oxidation
CN110560112B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for preparing trimellitic anhydride
CN110560115B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing trimellitic anhydride
CN110560111B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride from pseudocumene
CN110560110B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene
CN110560114B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for improving yield of trimellitic anhydride

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