CN103467237A - Method for preparing aromatic hydrocarbons by catalytic decarboxylation of terephthalic acid residues - Google Patents
Method for preparing aromatic hydrocarbons by catalytic decarboxylation of terephthalic acid residues Download PDFInfo
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- CN103467237A CN103467237A CN2013104198661A CN201310419866A CN103467237A CN 103467237 A CN103467237 A CN 103467237A CN 2013104198661 A CN2013104198661 A CN 2013104198661A CN 201310419866 A CN201310419866 A CN 201310419866A CN 103467237 A CN103467237 A CN 103467237A
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- terephthalic acid
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Abstract
The invention discloses a method for preparing aromatic hydrocarbons by catalytic decarboxylation of terephthalic acid residues. The method comprises the following steps of: drying, crushing and high-temperature gasifying terephthalic acid residues, carrying out decarboxylation reaction onto terephthalic acid residues under the action of a decarboxylation catalyst at 450 DEG C-550 DEG C and 0-2Mpa, wherein the high-temperature gasifying temperature is at least 350 DEG C; cooling a product obtained by the decarboxylation reaction to 200 DEG C-240 DEG C, carrying out solid-liquid separation, further cooling the separated gas to 20 DEG C-80 DEG C, and carrying out gas-liquid separation to obtain a gas and aromatic hydrocarbon mixed liquor; and rectifying the obtained aromatic hydrocarbon mixed liquor to respectively obtain benzene and the aromatic hydrocarbon mixed liquor except the benzene. Environmental protection and economic benefits are taken into consideration in the method, so that a novel direction is disclosed for comprehensive utilization of PTA (Pure Terephthalic Acid) residues. Besides, the method can be used for obtaining such aromatic hydrocarbons with a low boiling point as benzene and toluene, has high economic benefits, and is energy-saving and environment-friendly.
Description
Technical field
The present invention relates to the process field of terephthalic acid residue, be specifically related to a kind of method that terephthalic acid residue catalytic decarboxylation prepares aromatic hydrocarbons.
Background technology
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 terephthalic acid industry brings serious " three wastes " pollution problem, especially serious with the discharge of terephthalic acid residue.Contain a large amount of organic acids in terephthalic acid 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.Terephthalic acid residue is the difficult problem of environmental protection always, needs effective means badly and is processed.
To the recycling of chemical fibre industry terephthalic acid residue, domestic have many people to do research work at present.The Chinese patent literature that is CN1126730C as publication number discloses a kind of separating and purifying method of terephthaldehyde's acid waste products, sulfuric acid by 75%~98% becomes nitration mixture for 1:1~9:1 joins respectively in acid tank by volume with 50%~95% nitric acid after stirring, then terephthaldehyde's acid waste products of solid is added in this nitration mixture; The slurry that above process is generated filters with filtering net under negative pressure, and filter cake is sent into washing pool after concentrating; The isolated filter cake of above process is washed with de-salted water in washing pool, generate the terephthalic acid solid wet cake and deliver to moisture eliminator; Dry 20~40 minutes, obtain the terephthalic acid solid finished product.
The Chinese patent literature that publication number is CN1012954B discloses a kind of separation method of terephthalic acid residue, acid out principle according to improvement Heng Geerfa, at first oxidation residua is washed to processing, then carry out selective reaction under high temperature, salt of weak acid existence condition, terephthalic acid is separated with m-phthalic acid, carry out extracting with solvent again, mixed cell acid is separated with terephthalic acid, m-phthalic acid respectively.
Above-mentioned separation method is the difference of utilizing aromatic acid physics and chemistry character, by unit operations such as extraction, fractionation and centrifugings, one or more components is wherein separated.Because the diprotic acid isomer is chemical and physical properties is extremely similar, cause the separating technology complexity, cost is higher, generate a large amount of waste water in sepn process, and product purity is difficult to reach industrial requirements.
There are the problems referred to above in Separation and Recovery based on the PTA residue, someone puts forward the comprehensive utilization to the PTA residue, as disclosing, the publication number Chinese patent literature that is CN1508067A a kind ofly with oxidized dregs of terephthalic acid, prepares active carbon method, by calcification, oxidation residua is made to the oxidation residua calcium salt, again the oxidation residua calcium salt is carried out to carbonization under isolated air or oxygen debt atmosphere, obtain a periporate shaped activated carbon 1, remove soluble metallic salt (being mainly calcium carbonate) with pickling again, drying, obtain final powdered carbon product.
The Chinese patent literature that and for example publication number is CN1508167A discloses a kind of method of utilizing the diprotic acid waste residues such as terephthalic acid to prepare unsaturated polyester resin, adopt the industrial residue containing diprotic acid containing terephthalic acid, phthalic acid etc., particularly terylene industrial is produced the waste residue of terephthalic acid, replace or partly replace diprotic acid, particularly Tetra hydro Phthalic anhydride, butene dioic acid production unsaturated polyester.The catalyzer that a kind of unsaturated dibasic acid of this invention development reacts with dibasic alcohol ester is tin protoxide, or tin salt or other stannous compound, the significant quantity that its addition is catalyzer.
Summary of the invention
The invention provides a kind of method that terephthalic acid residue catalytic decarboxylation prepares aromatic hydrocarbons, for the comprehensive utilization of PTA residue has proposed a new direction, the method can obtain the low boiling point arenes such as benzene, toluene, and economic benefit is high, energy-conserving and environment-protective.
A kind of terephthalic acid residue catalytic decarboxylation prepares the method for aromatic hydrocarbons, comprises the following steps:
1) after terephthalic acid residue drying, pulverizing, high-temperature gasification, under the effect of 450 ℃~550 ℃ and 0~2MPa, decarboxylation catalyst, carry out decarboxylic reaction, described high-temperature gasification temperature is at least 350 ℃;
2) product decarboxylic reaction obtained is cooled to 200 ℃~240 ℃, and through gas solid separation, the gas that separation is obtained further is cooled to 20 ℃~80 ℃, then, through gas-liquid separation, obtains gas and aromatic hydrocarbons mixed solution;
3) aromatic hydrocarbons mixed solution step 2) obtained, through rectification process, obtains respectively benzene and the aromatic hydrocarbons mixed solution except benzene.
Benzoic liter temperature (100 ℃) is lower, with other binary aromatic acids, very big-difference is arranged, by distilling the phenylformic acid of rear refining recyclable higher degree.
As preferably, when in described terephthalic acid residue, benzoic content surpasses 5wt.%, terephthalic acid residue at first through distillation, heating and gasifying, obtain thick phenylformic acid product again after condensation, and described heating and gasifying temperature is 260 ℃~270 ℃; Remain not residue after gasifying again by step 1)~3) carry out.The distillation of described terephthalic acid residue is processed and is carried out in batch fractionating tower.
As preferably, the inorganic salt that contain cobalt and manganese in the high-temperature gasification resistates in step 1), dissolve, filter through acid, the sodium bicarbonate precipitation, then obtain cobalt-manganese catalyst through separating dried recovered.
As preferably, in step 1), 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 acid can generate carboxylate compound at the ZnO chemical absorption of surface, and carboxylate salt further decomposes generation aromatic hydrocarbons.
Decarboxylic reaction, under above-mentioned decarboxylation catalyst effect, occurs and generates the aromatic hydrocarbons such as benzene, toluene, biphenyl and phenylformic acid in terephthalic acid residue under hot conditions.
As preferably, in step 1), the reactant quality air speed of decarboxylic reaction is 0.1/h~2/h, more preferably 0.1/h~0.6/h.To pass into appropriate rare gas element in decarboxylic reaction, regulate the duration of contact of terephthalic acid residue and decarboxylation catalyst, prevent from causing because of overstand the formation of carbon deposit.Under the identical residence time, weight hourly space velocity is higher, and the aromatic acid transformation efficiency is lower.When mass space velocity is 2/h, the PTA residue still can keep the transformation efficiency more than 60%.
Mainly comprise benzene, toluene, carbonic acid gas, phenylformic acid and biphenyl etc. in the reaction product that the decarboxylic reaction of step 1) makes, in process of cooling, phenylformic acid and unreacted benzene diprotic acid are first separated from gas; The residual gas component, through further being cooled to 20 ℃~80 ℃, is separated carbonic acid gas and aromatic hydrocarbons with gas-liquid separator.
Step 2) solid gone out through gas solid separation in obtains thick phenylformic acid product again after distillation, heating and gasifying, condensation, and described heating and gasifying temperature is 260 ℃~270 ℃; Remain not residue after gasifying again by step 1)~3) carry out, further improved the utilization ratio of terephthalic acid residue.
In step 1), terephthalic acid residue carries out high-temperature gasification through high temperature gasifier, through the decarboxylic reaction device, carries out decarboxylic reaction; Step 2) carry out coolingly in through Heat Exchanger in Circulating Water System, through gas-solid separator, carry out gas solid separation.As preferably, the gasifier related in the technique of terephthalic acid residue catalytic decarboxylation aromatic hydrocarbons processed, batch fractionating tower, decarboxylic reaction device, interchanger, gas-solid separator all arrange stand-by unit, be convenient to the solid residue in each device of periodic cleaning, avoid solid matter to stop up process unit or pipeline, so that decarboxylation technique can normally be moved continuously.
As preferably, in step 3), the rectifying of aromatic hydrocarbons mixed solution is carried out in rectifying tower, and separation condition is: 100 ℃~150 ℃ of tower reactor temperature, 80 ℃~90 ℃ of tower top temperatures.After separating, can obtain purer benzene from tower top, obtain other aromatic hydrocarbons mixed solution from tower reactor.
As preferably, step 2) product that in, decarboxylic reaction obtains is cooling through interchanger, and after interchanger is completed to heat exchange with heat-eliminating medium, the rectifying tower reactor heating medium as aromatic hydrocarbon is used again, can reduce energy consumption, improves efficiency of energy utilization.
The invention provides a kind of method that terephthalic acid residue catalytic decarboxylation prepares aromatic hydrocarbons, can the terephthalic acid residue decarboxylation be made to aromatic product and recovery of benzoic acid by the method.Compared with prior art, the present invention has following advantage:
The comprehensive utilization that the present invention is terephthalic acid residue has proposed a new direction, realized the high value added utilization of terephthalic acid residue, recoverying and utilizing method with respect to other terephthalic acid residues, the present invention does not need to use a large amount of solvents and acid-alkali washing, can not produce a large amount of waste liquids, safety and environmental protection; Adopt heterogeneous decarboxylic reaction, catalyzer and product easily separate, and have greatly simplified last handling process, have reduced energy consumption and fund input.
The present invention is a kind of method that brand-new terephthalic acid residue is recycled, and by rational Process configuration, can obtain aromatic product and recovery of benzoic acid, has economic benefit and wide application prospect preferably.
The present invention is low to the selectivity of raw material, is applicable to component and the different terephthalic acid residue of content prepared by different production technique, through method of the present invention, all can obtain the low boiling point arenes such as benzene, toluene and biphenyl.Environment protection and economic benefit have been taken into account, the advantage such as the pollution that have that reaction yield is high, side reaction is few, constant product quality, reaction produces is few.
The accompanying drawing explanation
Fig. 1 is the method flow schematic diagram that embodiment 1 terephthalic acid residue catalytic decarboxylation prepares aromatic hydrocarbons;
Fig. 2 is the method flow schematic diagram that embodiment 3 terephthalic acid residue catalytic decarboxylations prepare aromatic hydrocarbons.
Embodiment
Embodiment 1
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% |
1) dry oxidized dregs of terephthalic acid is heated to 260 ℃ of left and right and makes the phenylformic acid gasification, each component concentration of PTA oxidation residua as shown above, obtains thick phenylformic acid product after the product condensation after gasification.Reclaiming in the PTA residue and obtaining phenylformic acid is 26.47wt.%;
2) step 1) obtains not gasification substance or unclassified stores drying and crushing, be delivered to high temperature gasifier in gasification more than 350 ℃ through the feeding-in solid body machine.Resistates in gasifier, mainly containing inorganic salt and ash contents such as cobalt manganese, dissolves with acid, filters, and the sodium bicarbonate precipitation, then separate the dried recovered cobalt-manganese catalyst;
3) by step 2) vapour that obtains passes into filling decarboxylation catalyst (30wt.%ZnO, 5wt.%Cr
2o
3, 65wt.%Al
2o
3) reactor, reactor feed gas is 0.5/h at mass space velocity, under 500 ℃ and normal pressure, carries out decarboxylic reaction.
4) the reacted product of step 3) is cooled to 200 ℃, realizes that after gas-solid separator gas separates with solid.The PTA residue transforms substantially fully, only has a small amount of solid phenylformic acid to isolate.
5) gas that step 4) obtains further is cooled to 30 ℃, by gas-liquid separator, realizes separating of gas and aromatic hydrocarbons.
Only contain a small amount of toluene and biphenyl etc. in aromatic hydrocarbons except benzene, can not make with extra care directly and sell as product.In liquid product, the purity of benzene reaches more than 95%, and the yield of benzene approaches 70%.
Embodiment 2
The oxidized dregs of terephthalic acid of employing and embodiment 1 same composition and content, decarboxylation reaction conditions is: 550 ℃ of temperature, pressure are 2MPa, and other processing condition are constant.
Reclaim and obtain phenylformic acid 26.47wt.% in the PTA residue, the product after decarboxylic reaction is cooled to 200 ℃, realizes that after gas-solid separator gas separates with solid.Remaining PTA residue has 89% conversion, isolates the solid mixture of phenylformic acid and benzene diprotic acid, and wherein phenylformic acid approximately contains 16%.Again the phenylformic acid in solid mixture is reclaimed.
Only contain a small amount of toluene and biphenyl etc. in aromatic hydrocarbons except benzene, the purity of benzene reaches more than 95%, and the yield of benzene approaches 57%.
Embodiment 3
Component | Rinsing residue |
Terephthalic acid | 76.6% |
M-phthalic acid | 0.01% |
Phthalic acid | 0.01% |
Phenylformic acid | 0.85% |
P-methylbenzoic acid | 20.52% |
P-tolyl aldehyde | 0.46% |
The alkali insolubles | 0.75% |
Ash content | 0.80% |
1), by dry terephthalic acid rinsing residue drying and crushing, each component concentration of PTA oxidation residua as shown above, is delivered to high temperature gasifier in gasification more than 350 ℃ through the feeding-in solid body machine.Resistates in gasifier, mainly containing inorganic salt and ash contents such as cobalt manganese, dissolves with acid, filters, and the sodium bicarbonate precipitation, then separate the dried recovered cobalt-manganese catalyst;
2) vapour step 1) obtained passes into filling decarboxylation catalyst (30wt.%ZnO, 5wt.%Cr
2o
3, 65wt.%Al
2o
3) reactor, reactor feed gas mass space velocity be 0.6/h, carry out decarboxylic reaction under 500 ℃ and normal pressure.
3) step 2) reacted product is cooled to 240 ℃, realizes that after gas-solid separator gas separates with solid.PTA residue transformation efficiency is 95.3%, contains the phenylformic acid of 32wt.% in solid, is back to the process of step 1);
4) gas that step 3) obtains further is cooled to 60 ℃, by gas-liquid separator, realizes separating of gas and aromatic hydrocarbons.Aromatic hydrocarbons further separates by rectifying tower, and tower top can obtain purer benzene, and tower reactor can obtain toluene slightly.Wherein the yield of benzene is 63.4%, and the yield of crude cresylic acid is 83.4%.
Claims (7)
1. a terephthalic acid residue catalytic decarboxylation prepares the method for aromatic hydrocarbons, it is characterized in that, comprises the following steps:
1) after terephthalic acid residue drying, pulverizing, high-temperature gasification, under the effect of 450 ℃~550 ℃ and 0~2MPa, decarboxylation catalyst, carry out decarboxylic reaction, described high-temperature gasification temperature is at least 350 ℃;
2) product decarboxylic reaction obtained is cooled to 200 ℃~240 ℃, and through gas solid separation, the gas that separation is obtained further is cooled to 20 ℃~80 ℃, then, through gas-liquid separation, obtains gas and aromatic hydrocarbons mixed solution;
3) aromatic hydrocarbons mixed solution step 2) obtained, through rectification process, obtains respectively benzene and the aromatic hydrocarbons mixed solution except benzene.
2. terephthalic acid residue catalytic decarboxylation according to claim 1 prepares the method for aromatic hydrocarbons, it is characterized in that, when in described terephthalic acid residue, benzoic content surpasses 5wt.%, terephthalic acid residue at first through distillation, heating and gasifying, obtain thick phenylformic acid product again after condensation, and described heating and gasifying temperature is 260 ℃~270 ℃; Remain not residue after gasifying again by step 1)~3) carry out.
3. terephthalic acid residue catalytic decarboxylation according to claim 1 and 2 prepares the method for aromatic hydrocarbons, it is characterized in that, the inorganic salt that contain cobalt and manganese in the high-temperature gasification resistates in step 1), through acid dissolving, filtration, alkali precipitation, then be dried after separation to cobalt-manganese catalyst.
4. terephthalic acid residue catalytic decarboxylation according to claim 1 and 2 prepares the method for aromatic hydrocarbons, it is characterized in that, in step 1), 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.
5. terephthalic acid residue catalytic decarboxylation according to claim 1 and 2 prepares the method for aromatic hydrocarbons, it is characterized in that, in step 1), the reactant quality air speed of decarboxylic reaction is 0.1/h~2/h.
6. terephthalic acid residue catalytic decarboxylation according to claim 1 and 2 prepares the method for aromatic hydrocarbons, it is characterized in that, step 2) solid gone out through gas solid separation at first through distillation, heating and gasifying, obtain thick phenylformic acid product again after condensation, and described heating and gasifying temperature is 260 ℃~270 ℃; Remain not residue after gasifying again by step 1)~3) carry out.
7. terephthalic acid residue catalytic decarboxylation according to claim 1 and 2 prepares the method for aromatic hydrocarbons, it is characterized in that, in step 3), the rectifying of aromatic hydrocarbons mixed solution is carried out in rectifying tower, and separation condition is: 100 ℃~150 ℃ of tower reactor temperature, 80 ℃~90 ℃ of tower top temperatures.
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CN109694319A (en) * | 2017-10-23 | 2019-04-30 | 杭州双安科技有限公司 | A kind of device and method for handling the solid waste containing organic acid |
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