CN103467224B - A kind of Aromatic carboxylic acid decarboxylastion - Google Patents

A kind of Aromatic carboxylic acid decarboxylastion Download PDF

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CN103467224B
CN103467224B CN201310419887.3A CN201310419887A CN103467224B CN 103467224 B CN103467224 B CN 103467224B CN 201310419887 A CN201310419887 A CN 201310419887A CN 103467224 B CN103467224 B CN 103467224B
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carboxylic acid
aromatic carboxylic
reaction
catalyst
gas
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CN103467224A (en
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蒋斌波
庄岩
陈楠
廖祖维
王靖岱
阳永荣
黄正梁
蒋云涛
严丽霞
陆飞鹏
冯翔
杨遥
季来军
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Zhejiang University ZJU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a kind of Aromatic carboxylic acid decarboxylastion, aromatic carboxylic acid is passed in reactor, under temperature of reaction 300 DEG C ~ 600 DEG C, pressure 0 ~ 2Mpa and the effect of solid decarboxylation catalyst, carry out heterogeneous decarboxylic reaction; Described aromatic carboxylic acid has following structural formula: wherein, radicals R 1~ R 5for COOH, H, halogen or C 1~ C 5alkyl, described radicals R 1~ R 5identical or different.Present method is applied widely, does not have particular requirement to the structure of aromatic carboxylic acid, and has that solvent load is few, the reaction times is short, reactive behavior is high and catalyzer easily produces with reaction the advantage expecting to be separated, to reclaim and to regenerate; Present method can realize operate continuously, and obtained aromatic substance yield is high, steady quality.Present method may be used for treatment PTA residue, realizes the high value added utilization of PTA residue.

Description

A kind of Aromatic carboxylic acid decarboxylastion
Technical field
The present invention relates to the field that aromatic carboxylic acid prepares aromatic substance, particularly relate to a kind of Aromatic carboxylic acid decarboxylastion.
Background technology
Decarboxylic reaction is widely used in the fields such as chemical industry, biology, medicine, food, the carboxylated compound discarded can be made to obtain high added valueization utilize, be conducive to resource reclaim and environment protection by decarboxylic reaction.At present, the decarboxylation of aromatic carboxylic acid mainly occurs in homogeneous system, realizes removing of single or multiple carboxyl by the comprehensive action such as optical, electrical, organic amine, heavy metallic salt.
The method that part or carboxyl obtain fluorinated aromatic hydrocarbon is sloughed as the publication number Chinese patent literature that is CN1138023A discloses a kind of method being prepared aromatic substance by aromatic carboxylic acid's decarboxylation, particularly fluorinated aromatic carboxylic acid.Aromatic carboxylic acid soluble in water mixes with the water-insoluble amine at reaction conditions in inertia, then at pH is 3 ~ 9 and temperature is 70 ~ 210 DEG C, for some time longer with decarboxylation catalyst contact reacts in water-insoluble solvent, reacted mixture is purified obtained target product by extraction, crystallization, drying and other steps.This reaction is carried out in homogeneous system, needs a large amount of strong acid, strong alkali aqueous solution and organic solvent, and speed of response is slow, and the production cycle is long.
Publication number is that the Chinese patent literature of CN101225016A discloses pentafluorobenzoic acid catalyst-free decarboxylating in a kind of high temperature liquid water and prepares the method for penta fluoro benzene.In autoclave, add deionized water and pentafluorobenzoic acid, deionized water and pentafluorobenzoic acid mass ratio are 2: 1 ~ 8: 1, are warming up to 150 ~ 250 DEG C of decarboxylation 5 ~ 45min; Decarboxylate cools, the pentafluorobenzoic acid that filtered and recycled reaction is residual, and after filtrate leaves standstill, liquid-liquid layering obtains organic phase, and organic phase obtains penta fluoro benzene after rectifying, activated carbon decolorizing.Although do not need in this reaction to add catalyzer, the method is only applicable to the aromatic acid containing multiple halogen, and range of application is narrow.
Decarboxylic reaction disclosed in above-mentioned patent documentation carries out in homogeneous system, needs to use a large amount of solvents, and reaction end rear catalyst is difficult to be separated, reclaim and regeneration.
Purified terephthalic (purifiedterephthalicacid, PTA) is the important source material of textile industry and plastics industry, mainly for the production of trevira, coating, film etc.The fast development of PTA industry brings serious " three wastes " pollution problem, especially serious with the discharge of PTA residue.Containing a large amount of organic acids in PTA residue, except terephthalic acid, also have phenylformic acid, phthalic acid, m-phthalic acid, p-methylbenzoic acid, p-carboxybenzaldehyde and cobalt-manganese catalyst and other mechanical impuritys etc.At present, be mainly divided into burning, Separation and Recovery and comprehensive utilization three kinds of modes to the process of PTA residue, comprehensive utilization can realize the high value added utilization of PTA residue.
Summary of the invention
The invention provides a kind of Aromatic carboxylic acid decarboxylastion, present method is applied widely, particular requirement is not had to the structure of aromatic carboxylic acid, and has that solvent load is few, the reaction times is short, reactive behavior is high and catalyzer easily produces with reaction the advantage expecting to be separated, to reclaim and to regenerate; Present method can realize operate continuously, and obtained aromatic substance yield is high, steady quality; Present method may be used for treatment PTA residue, realizes the high value added utilization of PTA residue.
The invention discloses a kind of Aromatic carboxylic acid decarboxylastion, aromatic carboxylic acid is passed in reactor, under temperature of reaction 300 DEG C ~ 600 DEG C, pressure 0 ~ 2Mpa and the effect of solid decarboxylation catalyst, carry out heterogeneous decarboxylic reaction; Described aromatic carboxylic acid has following structural formula:
Wherein, radicals R 1~ R 5for COOH, H, halogen or C 1~ C 5alkyl, described radicals R 1~ R 5identical or different.
As preferably, described radicals R 1~ R 5for H or halogen.
As preferably, described decarboxylation catalyst comprises active ingredient and carrier, and active ingredient is ZnO, and carrier is Al 2o 3, ZnO and Al 2o 3mass ratio be 0.1 ~ 5.ZnO is the conductor oxidate of meta-alkalescence, and lattice energy is lower, and aromatic carboxylic acid can generate carboxylate compound in catalyst surface chemisorption, and carboxylate salt decomposes generation aromatic hydrocarbons further.Especially, when phenyl ring containing electron-withdrawing group, the acidity of aromatic carboxylic acid strengthens, and is more easily adsorbed on catalyst surface and generates corresponding carboxylate compound, then react and more easily carry out.
Auxiliary agent can improve the heat stable property etc. of Cloud Distribution around the dispersiveness of active ingredient, active ingredient and catalyzer, is conducive to the activity and the stability that improve catalyzer.As preferably, described decarboxylation catalyst also comprises auxiliary agent, and be one or more in the oxide compound of Mn, Fe, Co, Mo, Cr, Cu and Ni, auxiliary agent quality is the 0.1wt.% ~ 10wt.% of decarboxylation catalyst quality.
As preferably, first aromatic carboxylic acid is dissolved in solvent, then passes in reactor.
Described solvent need meet at high temperature higher stability, has higher solvability to aromatic carboxylic acid, with aromatic carboxylic acid, side reaction does not occur, and the feature be easily separated with target product.Described solvent is one or more in water, pyridine, toluene and dimethylbenzene, described solvent can be selected from but be not limited to above listed by.
As preferably, described aromatic carboxylic acid contacts under the condition of protection of inert gas with decarboxylation catalyst, uses rare gas element can regulate the duration of contact of aromatic carboxylic acid and decarboxylation catalyst, prevents the formation causing carbon deposit because of overstand.
As preferably, the mol ratio of described rare gas element and aromatic carboxylic acid is 1 ~ 30.
The rare gas element be applicable to should not hinder the generation of target product, described rare gas element can be one or more in nitrogen, helium, methane, carbon monoxide, hydrogen, water vapour, described rare gas element can be selected from but be not limited to above listed by.As preferably, described rare gas element is nitrogen, helium or water vapour.
As preferably, the reactant weight hourly space velocity of described decarboxylic reaction is 0.01h -1~ 20h -1, further preferably, described decarboxylation reaction conditions is as follows: temperature 450 DEG C ~ 550 DEG C, pressure 0.1 ~ 0.8Mpa, weight hourly space velocity 0.2h -1~ 10h -1.Decarboxylic reaction mainly affects by factors such as temperature, pressure, air speeds.According to aromatic carboxylic acid's decarboxylic reaction course, because aromatic carboxylic acid salt lower thermolysis in atmosphere of inert gases needs just can carry out at a certain temperature, temperature is more high is more conducive to decarboxylic reaction.The pyrolysis temperature of different aromatic carboxylic acid salt is mostly more than 400 DEG C, and temperature of reaction is too high, can increase energy consumption, so temperature controls in rational scope.Because described decarboxylic reaction product is mainly aromatic hydrocarbons and carbonic acid gas, system pressure increase is unfavorable for that decarboxylic reaction carries out to positive dirction, and namely along with the increase of pressure, the transformation efficiency of aromatic carboxylic acid has a declining tendency.Under the identical residence time, weight hourly space velocity is higher, and aromatic carboxylic acid's transformation efficiency is lower.
Product after decarboxylic reaction is the mixture of multiple aromatic substance, and the present invention is in order to obtain high-purity single product, and can further distill or rectifying, this step is carried out equally in rare gas element is as nitrogen.
Compared with prior art, tool of the present invention has the following advantages:
Under high temperature and the effect of solid decarboxylation catalyst, carry out decarboxylic reaction after aromatic carboxylic acid's gasification, do not need to use a large amount of solvent, the residence time is extremely short in below 2s, and catalytic activity is high, can realize continuous print operation.Present method is carried out in heterogeneous system, and reaction product easily and catalyst separating, significantly simplify post-processing step.
The present invention is applied widely, can be raw material containing the aromatic carboxylic acid of different substituents.Present method being applied to PTA residue catalytic decarboxylation can preparing aromatic hydrocarbon, has taken into account environment protection and economic benefit, the advantage such as have that reaction yield is high, side reaction is few, pollution that constant product quality, reaction produce is few, realizes the high value added utilization of PTA residue.
Embodiment
Following examples are intended to describe in detail according to the method for the present invention for aromatic carboxylic acid's decarboxylation, instead of are limited in the scope of following embodiment.
Embodiment 1
Decarboxylation catalyst is placed in internal diameter to be 2.0cm, to be highly the electric heating tube of 1m.Electric heating tube is three sections of temperature controls, upper two sections of gasifications for aromatic carboxylic acid, and the 3rd section for catalyst filling.The catalyst bed section of this pipe about fills 10g catalyzer.This part is included in the middle of two glass bead layer, these two portions respectively lower than with higher than catalyst bed 20cm and 40cm.Described granulated glass sphere diameter is 20 ~ 30 orders.Temperature thermocouple is positioned at catalyst layer center.Decarboxylation catalyst is Zn-Fe-Al(30wt.%ZnO, 4wt.%Fe 2o 3, 66wt.%Al 2o 3).
40.0g terephthalic acid is dissolved in the solution being configured to 0.08g/ml in 250ml pyridine and is placed in container for storing liquid.Pump in reaction tubes by terephthalic acid solution with the speed of 1ml/min, nitrogen flow is 600ml/min, and reaction tubes three sections of temperature are all set to 500 DEG C, and the reaction times is 1h, and terephthalic acid changes into benzene and carbonic acid gas etc.After catalytic bed, reaction product is by circulating water and gas-liquid separator, and tail gas washes with water and emptying.
By the content of aromatic hydrocarbons, the carbon deposit situations of TG analysis of catalyst such as benzene in carbon dioxide content, GC-FID analysis liquid product in the three kinds of above-mentioned reaction product of methods analyst: GC-TCD analysis gas-phase products.The analytical results of product is as follows:
Benzene: 40.59wt.%, biphenyl: 0.69wt.%, benzophenone: 0.09wt.%, carbonic acid gas: 50.99wt.%, other: 0.50wt.%, charcoal: 7.14wt.%.
From the above results, the method for aromatic carboxylic acid's decarboxylation provided by the invention can make aromatic carboxylic acid change into corresponding aromatic substance efficiently.
Embodiment 2
Component Oxidation residua
Terephthalic acid 30.3%
M-phthalic acid 35.4%
Phthalic acid 0.66%
Phenylformic acid 30.5%
P-methylbenzoic acid 1.07%
P-tolyl aldehyde 0.32%
Alkali insolubles 1.01%
Ash content 0.74%
The composition of embodiment 2 decarboxylation catalyst, consumption and filling method are identical with embodiment 1.
30.0gPTA oxidation residua is dissolved in 250ml pyridine, crosses and filter insolubles, filtrate is placed in container for storing liquid.Each component concentration of PTA oxidation residua as shown above.Pump in reaction tubes by PTA oxidation residua solution with the speed of 1ml/min, nitrogen flow is 600ml/min, and reaction tubes three sections of temperature are all set to 550 DEG C, and the reaction times is that 1h, PTA oxidation residua changes into benzene and carbonic acid gas etc.After catalytic bed, reaction product is by circulating water and gas-liquid separator, and tail gas washes with water and emptying.
Analytical procedure with embodiment 1, the analytical results of product: benzene: 37.36wt.%, toluene: 0.61wt.%, biphenyl: 0.72wt.%, benzophenone: 0.29wt.%, carbonic acid gas: 48.23wt.%, other: 3.67wt.%, charcoal: 9.12wt.%.
It can thus be appreciated that the present invention can be applicable to reclaim the organic acid resource in PTA residue, and decarboxylation is produced aromatic substance and taken into account environment protection and economic benefit.
Embodiment 3
Embodiment 3 decarboxylation catalyst consumption and filling method identical with embodiment 1.Catalyst component is 60wt.%ZnO, 5wt.%CuO, 35wt.%Al 2o 3.
By 2 of 15g, 3,4,5-tetrafluorobenzoic aid is dissolved in 35ml deionized water, and the solution be configured to is placed in container for storing liquid, and described solution pumps in reaction tubes with the speed of 0.5ml/min, and nitrogen flow is 200ml/min, and reaction tubes three sections of temperature are all set to 450 DEG C.2,3,4,5-tetrafluorobenzoic aid changes into 1, and 2,3,4-tetra fluoro benzene and carbonic acid gas etc.Reaction product is by circulating water and gas-liquid separator, and tail gas washes with water and emptying.The liquid dichloromethane extraction collected, isolates organic phase, by dried over mgso, filters, obtains 10.7g1,2,3,4-tetra fluoro benzene crude product.

Claims (1)

1. an Aromatic carboxylic acid decarboxylastion, is characterized in that,
Decarboxylation catalyst is placed in internal diameter to be 2.0cm, to be highly the electric heating tube of 1m, electric heating tube is three sections of temperature controls, upper two sections of gasifications for aromatic carboxylic acid, 3rd section for catalyst filling, the catalyst bed section of this pipe about fills 10g catalyzer, this part is included in the middle of two glass bead layer, these two portions respectively lower than with higher than catalyst bed 20cm and 40cm;
Described granulated glass sphere diameter is 20 ~ 30 orders, and temperature thermocouple is positioned at catalyst layer center;
Described decarboxylation catalyst is Zn-Fe-Al, consists of 30wt.%ZnO, 4wt.%Fe 2o 3, 66wt.%Al 2o 3;
40.0g terephthalic acid is dissolved in the solution being configured to 0.08g/ml in 250ml pyridine and is placed in container for storing liquid, terephthalic acid solution is pumped in reaction tubes with the speed of 1ml/min, nitrogen flow is 600ml/min, reaction tubes three sections of temperature are all set to 500 DEG C, reaction times is 1h, and terephthalic acid changes into benzene and carbonic acid gas etc., after catalytic bed, reaction product is by circulating water and gas-liquid separator, and tail gas washes with water and emptying;
By the content of aromatic hydrocarbons, the carbon deposit situations of TG analysis of catalyst such as benzene in carbon dioxide content, GC-FID analysis liquid product in the three kinds of above-mentioned reaction product of methods analyst: GC-TCD analysis gas-phase products; The analytical results of product is as follows:
Benzene: 40.59wt.%, biphenyl: 0.69wt.%, benzophenone: 0.09wt.%, carbonic acid gas: 50.99wt.%, other: 0.50wt.%, charcoal: 7.14wt.%.
CN201310419887.3A 2013-09-13 2013-09-13 A kind of Aromatic carboxylic acid decarboxylastion Active CN103467224B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB735300A (en) * 1952-04-16 1955-08-17 Ici Ltd Improvements in and relating to the production of aromatic hydrocarbons and derivatives thereof
US4266084A (en) * 1979-10-19 1981-05-05 Standard Oil Company (Indiana) Non-catalytic pyrolysis of residues from aromatic carboxylic acid manufacture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB735300A (en) * 1952-04-16 1955-08-17 Ici Ltd Improvements in and relating to the production of aromatic hydrocarbons and derivatives thereof
US4266084A (en) * 1979-10-19 1981-05-05 Standard Oil Company (Indiana) Non-catalytic pyrolysis of residues from aromatic carboxylic acid manufacture

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