CN103467224A - Aromatic carboxylic acid decarboxylastion method - Google Patents
Aromatic carboxylic acid decarboxylastion method Download PDFInfo
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- CN103467224A CN103467224A CN2013104198873A CN201310419887A CN103467224A CN 103467224 A CN103467224 A CN 103467224A CN 2013104198873 A CN2013104198873 A CN 2013104198873A CN 201310419887 A CN201310419887 A CN 201310419887A CN 103467224 A CN103467224 A CN 103467224A
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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
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- 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
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Abstract
本发明公开了一种芳族羧酸脱羧方法，将芳族羧酸通入反应器中，在反应温度300℃～600℃、压力0～2Mpa及固体脱羧催化剂作用下，进行多相脱羧反应；所述芳族羧酸具有以下结构式：，其中，基团R1～R5为COOH、H、卤素或C1～C5的烷基，所述的基团R1～R5相同或者不同。本方法适用范围广，对芳族羧酸的结构没有特殊要求，并具有溶剂用量少、反应时间短、反应活性高且催化剂易与反应产料分离、回收和再生的优点；本方法可以实现连续操作，制得的芳族化合物收率高、质量稳定。本方法可以用于处理PTA残渣，实现PTA残渣的高附加值利用。The invention discloses a method for decarboxylation of aromatic carboxylic acid. The aromatic carboxylic acid is passed into a reactor, and the heterogeneous decarboxylation reaction is carried out under the action of a reaction temperature of 300°C-600°C, a pressure of 0-2Mpa and a solid decarboxylation catalyst; The aromatic carboxylic acid has the following structural formula: , wherein, the groups R 1 -R 5 are COOH, H, halogen or C 1 -C 5 alkyl, and the groups R 1 -R 5 are the same or different. The method has a wide range of applications, has no special requirements on the structure of the aromatic carboxylic acid, and has the advantages of less solvent consumption, short reaction time, high reactivity, and easy separation, recovery and regeneration of the catalyst from the reaction product; the method can realize With continuous operation, the yield of aromatic compounds is high and the quality is stable. The method can be used to treat PTA residues, and realize high value-added utilization of PTA residues.
Description
Technical field
The present invention relates to the field that the aromatic carboxylic acid prepares aromatic substance, relate in particular to a kind of aromatic carboxylic acid decarboxylation method used.
Background technology
Decarboxylic reaction is widely used in the fields such as chemical industry, biology, medicine, food, by decarboxylic reaction, can make discarded carboxylated compound obtain the high added value utilization, is conducive to resource and reclaims and environment protection.At present, aromatic carboxylic acid's decarboxylation mainly occurs in homogeneous system, by comprehensive actions such as light, electricity, organic amine, heavy metallic salts, realizes removing of single or multiple carboxyls.
The Chinese patent literature that is CN1138023A as publication number discloses a kind of method that is prepared aromatic substance by aromatic carboxylic acid's decarboxylation, particularly fluoridizes that the aromatic carboxylic acid sloughs part or carboxyl makes the method for fluorinated aromatic hydrocarbon.Aromatic carboxylic acid soluble in water mixes with the water-insoluble amine that is inertia under reaction conditions, then pH be 3～9 and temperature be under 70～210 ℃, in the water-insoluble solvent, with longer for some time of decarboxylation catalyst contact reacts, reacted mixture is purified and is 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.
The Chinese patent literature that publication number is CN101225016A discloses the method that pentafluorobenzoic acid catalyst-free decarboxylating in a kind of high temperature liquid water prepares penta fluoro benzene.Add deionized water and pentafluorobenzoic acid in autoclave, deionized water and pentafluorobenzoic acid mass ratio are 2: 1～8: 1, are warming up to 150～250 ℃ of decarboxylation 5～45min; Decarboxylate is cooling, and filtered and recycled is reacted residual pentafluorobenzoic acid, and the standing rear liquid of filtrate-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 to be only applicable to the aromatic acid that contains a plurality of halogens, range of application is narrow.
In above-mentioned patent documentation, disclosed decarboxylic reaction is to carry out in homogeneous system, needs to use a large amount of solvents, and reaction end rear catalyst is difficult to separate, reclaims and regeneration.
Purified terephthalic (purified terephthalic acid, 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.Contain a large amount of organic acids in the PTA residue, also have phenylformic acid, phthalic acid, m-phthalic acid, p-methylbenzoic acid except terephthalic acid, to carboxyl benzaldehyde and cobalt-manganese catalyst and other mechanical impuritys etc.At present, the processing of PTA residue mainly is divided into to burning, Separation and Recovery and three kinds of modes of comprehensive utilization, 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 decarboxylation method used, present method is applied widely, structure to the aromatic carboxylic acid does not have particular requirement, and has advantages of that solvent load is few, the reaction times is short, reactive behavior is high and catalyzer easily produces and expects separate, reclaim and regenerate with reaction; Present method can realize operate continuously, and the aromatic substance yield made is high, steady quality; Present method can, for the treatment of the PTA residue, realize the high value added utilization of PTA residue.
The invention discloses a kind of aromatic carboxylic acid decarboxylation method used, the aromatic carboxylic acid is passed in reactor, under 300 ℃～600 ℃ of temperature of reaction, 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 the aromatic carboxylic acid can generate carboxylate compound in the catalyst surface chemisorption, and carboxylate salt further decomposes generation aromatic hydrocarbons.While especially on phenyl ring, containing electron-withdrawing group, aromatic carboxylic acid's acidity strengthens, and more easily is adsorbed on catalyst surface and generates corresponding carboxylate compound, and reaction is more easily carried out.
Auxiliary agent can improve dispersiveness, the Cloud Distribution around active ingredient and the heat stable property of catalyzer etc. of active ingredient, is conducive to improve activity and the stability of catalyzer.As preferably, described decarboxylation catalyst also comprises auxiliary agent, is one or more in the oxide compound of Mn, Fe, Co, Mo, Cr, Cu and Ni, 0.1wt.%～10wt.% that the auxiliary agent quality is the decarboxylation catalyst quality.
As preferably, first the aromatic carboxylic acid is dissolved in solvent, then passes in reactor.
Described solvent need meet at high temperature higher stability, and the aromatic carboxylic acid is had to higher solvability, with the aromatic carboxylic acid, side reaction does not occur, and the characteristics of easily separating with target product.Described solvent is one or more in water, pyridine, toluene and dimethylbenzene, and described solvent can be selected from but be not limited to above listed.
As preferably, described aromatic carboxylic acid is contacted 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 from causing because of overstand the formation of carbon deposit.
As preferably, described rare gas element and aromatic carboxylic acid's mol ratio is 1～30.
Applicable rare gas element should not hinder the generation of target product, and described rare gas element can be one or more in nitrogen, helium, methane, carbon monoxide, hydrogen, water vapour, and described rare gas element can be selected from but be not limited to above listed.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: 450 ℃～550 ℃ of temperature, pressure 0.1～0.8Mpa, weight hourly space velocity 0.2h
-1～10h
-1.Decarboxylic reaction is affected by the factors such as temperature, pressure, air speed mainly.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, the more high decarboxylic reaction that more is conducive to of temperature.The pyrolysis temperature of different aromatic carboxylic acid salt is mostly more than 400 ℃, and temperature of reaction is too high can increase energy consumption, so temperature is controlled in rational scope.Because described decarboxylic reaction product is mainly aromatic hydrocarbons and carbonic acid gas, the system pressure increase is unfavorable for that decarboxylic reaction carries out to positive dirction, and, along with the increase of pressure, aromatic carboxylic acid's transformation efficiency has a declining tendency.Under the identical residence time, weight hourly space velocity is higher, and aromatic carboxylic acid's transformation efficiency is lower.
The mixture that product after decarboxylic reaction is multiple aromatic substance, the present invention, in order to obtain high-purity single product, can further distill or rectifying, and this step is carried out in as nitrogen at rare gas element equally.
Compared with prior art, the present invention has following advantage:
Carry out decarboxylic reaction after aromatic carboxylic acid's gasification under high temperature and the effect of solid decarboxylation catalyst, do not need to use a large amount of solvents, the residence time is extremely short below 2s, and catalytic activity is high, can realize continuous operation.Present method is carried out in heterogeneous system, and reaction product easily and catalyst separating, has obviously been simplified post-processing step.
The present invention is applied widely, can be raw material containing the aromatic carboxylic acid of different substituents.The advantages such as present method is applied to PTA residue catalytic decarboxylation can preparing aromatic hydrocarbon, has taken into account environment protection and economic benefit, and the pollution that have that reaction yield is high, side reaction is few, constant product quality, reaction produces is few, realize the high value added utilization of PTA residue.
Embodiment
Following examples are intended to describe in detail according to the present invention for the method for aromatic carboxylic acid's decarboxylation, rather than are limited in the scope of following embodiment.
Embodiment 1
Decarboxylation catalyst is placed in to internal diameter to be 2.0cm, highly to be the electric heating tube of 1m.Electric heating tube is three sections temperature controls, upper two sections gasifications for the aromatic carboxylic acid, and the 3rd section for catalyst filling.The catalyst bed part of this pipe is approximately filled the 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 the catalyst layer center.Decarboxylation catalyst is Zn-Fe-Al(30wt.%ZnO, 4wt.%Fe
2o
3, 66wt.%Al
2o
3).
The 40.0g terephthalic acid is dissolved in to the solution that is configured to 0.08g/ml in the 250ml pyridine and is placed in container for storing liquid.Speed by terephthaldehyde's acid solution with 1ml/min pumps in reaction tubes, and nitrogen flow is 600ml/min, and three sections temperature of reaction tubes all are made as 500 ℃, 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 the aromatic hydrocarbons 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 carbon deposit situation of TG analysis of catalyst.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 the 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% |
| The alkali insolubles | 1.01% |
| Ash content | 0.74% |
Composition, consumption and the filling method of embodiment 2 decarboxylation catalysts are identical with embodiment 1.
30.0g PTA oxidation residua is dissolved in the 250ml pyridine, removes by filter insolubles, filtrate is placed in to container for storing liquid.Each component concentration of PTA oxidation residua as shown above.Speed by PTA oxidation residua solution with 1ml/min pumps in reaction tubes, and nitrogen flow is 600ml/min, and three sections temperature of reaction tubes all are made as 550 ℃, and the reaction times is 1h, and the 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 is with embodiment 1, the analytical results of product: benzene: 37.36wt.%, and toluene: 0.61wt.%, biphenyl: 0.72wt.%, benzophenone: 0.29wt.%, carbonic acid gas: 48.23wt.%, other: 3.67wt.%, charcoal: 9.12wt.%.
Hence one can see that, and the present invention can be applicable to reclaim the organic acid resource in the PTA residue, and decarboxylation is produced aromatic substance and taken into account environment protection and economic benefit.
Embodiment 3
Embodiment 3 decarboxylation catalyst consumptions and filling method are identical with embodiment 1.Catalyst component is 60wt.%ZnO, 5wt.%CuO, 35wt.%Al
2o
3.
By 2,3 of 15g, 4,5-tetrafluorobenzoic aid is dissolved in the 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 three sections temperature of reaction tubes all are made as 450 ℃.2,3,4,5-tetrafluorobenzoic aid changes into 1,2,3,4-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 of collecting, isolate organic phase, uses dried over mgso, filters, and obtains 10.7g1, and 2,3,4-tetra fluoro benzene crude product.
Claims (8)
1. an aromatic carboxylic acid is decarboxylation method used, it is characterized in that, the aromatic carboxylic acid is passed in reactor, under 300 ℃～600 ℃ of temperature of reaction, pressure 0～2Mpa and the effect of solid decarboxylation catalyst, carries 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.
2. aromatic carboxylic acid according to claim 1 is decarboxylation method used, it is characterized in that, 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.
3. aromatic carboxylic acid according to claim 2 is decarboxylation method used, it is characterized in that, described decarboxylation catalyst also comprises auxiliary agent, is one or more in the oxide compound of Mn, Fe, Co, Mo, Cr, Cu, Ni, 0.1wt.%～10wt.% that the auxiliary agent quality is the decarboxylation catalyst quality.
4. aromatic carboxylic acid according to claim 1 and 2 is decarboxylation method used, it is characterized in that, first the aromatic carboxylic acid is dissolved in solvent, then passes in reactor, and described solvent is one or more in water, pyridine, toluene, dimethylbenzene.
5. aromatic carboxylic acid according to claim 4 is decarboxylation method used, it is characterized in that, described aromatic carboxylic acid is contacted under the condition of protection of inert gas with decarboxylation catalyst, and described rare gas element and aromatic carboxylic acid's mol ratio is 1～30.
6. aromatic carboxylic acid according to claim 5 is decarboxylation method used, it is characterized in that, described rare gas element is one or more in nitrogen, helium, methane, carbon monoxide, hydrogen, water vapour.
7. aromatic carboxylic acid according to claim 1 and 2 is decarboxylation method used, it is characterized in that, the reactant weight hourly space velocity of described decarboxylic reaction is 0.01h
-1～20h
-1.
8. aromatic carboxylic acid according to claim 7 is decarboxylation method used, it is characterized in that, described decarboxylation reaction conditions is: 450 ℃～550 ℃ of temperature, pressure 0.1～0.8Mpa, weight hourly space velocity 0.2h
-1～10h
-1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610011A (en) * | 2015-01-08 | 2015-05-13 | 华东理工大学 | A kind of preparation method of phenylheptadecane |
Citations (2)
| 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 |
-
2013
- 2013-09-13 CN CN201310419887.3A patent/CN103467224B/en active Active
Patent Citations (2)
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610011A (en) * | 2015-01-08 | 2015-05-13 | 华东理工大学 | A kind of preparation method of phenylheptadecane |
| CN104610011B (en) * | 2015-01-08 | 2016-08-24 | 华东理工大学 | A kind of margaric preparation method of phenyl |
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| Publication number | Publication date |
|---|---|
| CN103467224B (en) | 2015-11-11 |
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