CN101088981B - Aromatic carboxylic acid producing process - Google Patents
Aromatic carboxylic acid producing process Download PDFInfo
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- CN101088981B CN101088981B CN200710022808XA CN200710022808A CN101088981B CN 101088981 B CN101088981 B CN 101088981B CN 200710022808X A CN200710022808X A CN 200710022808XA CN 200710022808 A CN200710022808 A CN 200710022808A CN 101088981 B CN101088981 B CN 101088981B
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Abstract
The aromatic carboxylic acid producing process includes the following steps: dissolving Co, Mn and Br as catalyst in C1-C6 fatty carboxylic acid in an oxidation reactor and adding guanidine compound(s) to form a catalyst system; and oxidizing aromatic compound, which is benzene compound, naphthalene compound or other alkyl arene with substituent alkyl radical or oxidized alkyl radical, with gas with oxygen. The process has mild oxidation reaction condition, high selectivity, high reaction speed and less side reactions.
Description
Technical field
The present invention relates to a kind of production method of aromatic carboxylic acid, specifically, the present invention relates to contain the oxygen-containing gas of carbonic acid gas, and add guanidine compound by use, in conjunction with traditional cobalt, manganese, bromine catalyst, adopt liquid-phase oxidation to produce the method for high quality aromatic carboxylic acid.
Background technology
Produce the especially method of terephthalic acid (PTA) of aromatic carboxylic acid at present, what widely use is MC type technology, promptly uses cobalt, manganese, bromine to be catalyzer, and adopting the aliphatic carboxylic acid of C1～C6 is the liquid phase air oxidation method of solvent.By oxidizable aromatic compound and their intermediate product, produce as terephthalic acid, m-phthalic acid, naphthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid.Wherein the industrial scale maximum is terephthalic acid.
Since this production technique occurred, its Technology, catalyst system constantly obtained further investigation, explored and how to improve reaction efficiency, reduced reaction times and side reaction, enhanced productivity.Wherein improve the catalytic process of reaction, improving selectivity of catalyst is one of main direction of studying that improves product competitiveness.
Discover that the efficient that improves catalyzer can make speed of response accelerate, reduce the reaction times, reduce side reaction and take place, reduce cost, improve output, it means a great.These researchs are generally adopted and add the third metal ion in the raw catalyst systems, in original catalyst system, add hafnium, lanthanum, zirconium ion form such as mentioning in the U.S. Pat 5112992, purpose is to improve efficiency, but catalyzer costs an arm and a leg and is difficult to realize in industry; Also have to add alkali-metal research, as method as described in the PCT patent WO/96/41791, nickel is joined in cobalt, manganese, the bromine catalyst system, but need two or more bromides simultaneously, method is very complicated, is difficult to realize.
Also emerged many new technologies at process aspect, being equipped with TA with pure oxygen or oxygen-rich oxide legal system is exactly wherein a part of achievement.This method is a kind of method of having improved on the basis that produces TA with atmospheric oxidation, and the purpose of this method is to reduce the formation of by products such as 4-CBA in the process of producing TA, improves the TA optical property, reduce the material consumption and the energy consumption of reaction simultaneously.The used oxygenant of this method is pure oxygen or oxygen rich gas (oxygen content is no less than the oxygen-containing gas of 50vol%, and all the other are rare gas element).This method is under the situation identical with catalyzer with above-mentioned air oxidation process solvent for use, directly obtains highly purified terephthalic acid (CN1160707 CN1114643A US5596129US5523474) from oxidation reactor.Improved the oxygen concentration of liquid phase when adopting pure oxygen or oxygen enrichment to replace air to carry out the aromatic oxidation reaction greatly, the concentration of PX descends to some extent comparatively speaking, this has just stoped the formation of reaction intermediate, and enlarged the throughput of reactor, reduced energy expenditure, quality is much improved, but the high cost of safety and renewal and renovation of equipment is a stubborn problem always.
But ripple limited-liability company (CN1160038A) is also with the CO in the reaction end gas of discharging
2Be recycled to reactor head after the separation, reduce the oxygen concn in the tail gas, to reach security purpose.U.S. Pat 5693856 is also illustrated and is used CO
2Improve thorny blast problem.But studies show that CO
2Beyond thought effect is but arranged.
Korea S Samsung General Chemicals Co., Ltd is using in pure oxygen and the technical study of oxygen-rich oxide aromatic hydrocarbon, by add CO in reactant oxygenant (pure oxygen or oxygen rich gas)
2(US6194607 CN99815798), has improved the selectivity and the activity of producing the aromatic ring yl fatty acid catalyst to gas, particularly, find that simultaneously the reaction times shortens temperature of reaction decline to the preparation process of terephthalic acid and m-phthalic acid, it is gentle that condition becomes, and side reaction reduces.In original catalytic reaction system, this method is by collaborative one or more basic metal, alkaline-earth metal, transition metal or lanthanide series metal, the CO of adding
2The oxygenizement that helps show more highlightedly, patent application person claims, only produces a spot of 4-CBA among the PTA that so obtains.Because this technological reaction speed is fast, the PTA quality height of generation, thus saved production cost effectively.But the problem of metal residual is not settled properly.
In a word, prepare the problem that TA all has aspects such as energy consumption, safety, product purity, renewal and renovation of equipment with air, oxygen-rich oxide PX; In catalyzer, introduce the synergistic effect that the 3rd metal ion component can promote catalyst system, improve oxidizing reaction rate, improve quality product.But what have costs an arm and a leg, and what have has certain residual subsequent handling that influences at solid phase prod, has therefore influenced The Application of Technology.
Summary of the invention
At the problems referred to above, the production method that the purpose of this invention is to provide a kind of new aromatic carboxylic acid: the form that this scheme adopts carbonic acid gas and guanidine compound to be used in combination in the cobalt-manganese-bromide catalizer system, discover and to improve speed of reaction more significantly, increase the selectivity of oxidizing reaction, reduce side reaction, can reduce simultaneously the use of bromine, weaken the corrodibility of reaction system, reduce the corrosion of equipment.
The invention provides following scheme to finish the invention task: a kind of production method of aromatic carboxylic acid, step is as follows:
In an oxidation reactor that is added with certain pressure and certain temperature, use cobalt, manganese, bromine to be catalyzer, this catalyzer is dissolved in the lipid acid solvent of 1～6 carbon, simultaneously one or more guanidine compound component is added in this catalyst system;
The aliphatic carboxylic acid that adopts C1～C6 is that solvent, employing contain oxygen molecule gas aromatics and their intermediate product are carried out oxidizing reaction; ,
Obtain aromatic acid product;
Described aromatics and their intermediate product are meant to have one or more substituted alkyls, or have the alkylaromatic hydrocarbon of benzene, naphthalene or the class quasi-aromatic compound of the functional group of oxidation of alkyl.
Wherein said guanidine compound is single guanidine radicals, biguanides base, polyguanidine base guanidine compound or the corresponding salt of guanidine compound;
Described oxygen-containing molecules gas can be air or oxygen-rich air;
Described aromatic acid product comprises: terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid, 4,4 '-diphenyl dicarboxylic acid and phenylformic acid.
The present invention has following prioritization scheme:
1, the oxygen-containing gas that uses of the present invention can be the gaseous mixture of pure oxygen and carbon dioxide gas mixture or oxygen and rare gas element (as nitrogen) and carbonic acid gas.Wherein the amount of carbonic acid gas should be 1～50% (volume) of gas, or more preferably 1～30% (volume), most preferably 1～15% (volume).Add the method for carbonic acid gas, can be metered into reactor separately, also can mix the back with oxygen-containing gas and add reactor, can add continuously or intermittently.
2, catalyzer is dissolved in the lipid acid solvent of 1～6 carbon, wherein can comprise the water of 0～20% (wt).
3, described alkyl aromatics is selected from p-Xylol, m-xylene, o-Xylol, 1, sym-trimethylbenzene, 1, pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene;
4, described oxidation intermediary product is for being selected from tolyl acid, m-methyl benzoic acid, o-toluic acid, p-tolyl aldehyde, 2-carboxyl benzaldehyde, a tolyl aldehyde, o-methyl-benzene formaldehyde, 3-carboxyl benzaldehyde, 4-carboxyl benzaldehyde;
5, wherein the bromine source is taken from hydrogen bromide, Potassium Bromide, tetrabromoethane; Manganese source and cobalt source are taken from the acetate that contains manganese and cobalt that can be dissolved in solvent, or the acetate tetrahydrate;
6, wherein catalyzer is respectively Co (OAc)
24H
2O, Mn (OAc)
24H
2O, hydrogen bromide, guanidine acetate.
7, the present invention is cobalt-manganese-bromo-guanidine catalyst system.The mol ratio of Co/Mn is 0.1～20 in the catalyst system, preferred 0.5～10.The mol ratio of Br/ (Co+Mn) is 0.1～10, preferred 0.5～5.The concentration of cobalt is 50～5000ppm of weight of solvent, preferred 100～1000ppm.The bromine source can be a bromine-containing compound, as hydrogen bromide, Potassium Bromide, tetrabromoethane etc.; Manganese and cobalt source are for being dissolved in the compound that contains manganese and cobalt of solvent.More preferably, be respectively Co (OAc) as cobalt, manganese, bromine source
24H
2O, Mn (OAc)
24H
2O and hydrogen bromide.
8, the guanidine compound that uses among the present invention is meant the compound or derivatives thereof that contains group 1.It can be any compound component that comprises guanidine radicals.Comprise single guanidine radicals, biguanides base, polyguanidine base guanidine compound and the corresponding salt of each guanidine compound.More preferably guanidine, biguanides and polymeric biguanide, most preferably guanidine.This compounds must be the compound that may be dissolved in the lipid acid solvent.Spendable guanidine-containing compounds has guanidine acetate, naphthenic acid guanidine, formic acid guanidine, bromination guanidine, chlorination guanidine, guanidine acetate, Guanidinium nitrate and guanidine sulfate, most preferably is guanidine acetate wherein, and the mol ratio of guanidine and cobalt, manganese approximately is 0.1～10 during use, or more preferably 0.1～1.
R
i=H, CH
3Deng (i=1...5)
9, solvent of the present invention can use any C
1～C
6Lipid acid, as formic acid, acetic acid, propionic acid, butanic acid, own butyric acid, valeric acid, caproic acid, trimethylacetic acid etc., the more preferably mixture of acetic acid or acetic acid and water.Preferably, solvent is the acetic acid that contains 1～25% quality water.Quantity of solvent generally is Alkylaromatics or their intermediate product compounds 1～20 times.
10, the temperature of reaction that is suitable for of the present invention should be 100～255 ℃, or more preferably 175～205 ℃.Reaction pressure is determined that by temperature of reaction minimal pressure should make Alkylaromatics or their intermediate products and solvent mainly remain in the liquid phase, and usually reaction pressure is 0～3.5MPa, or more preferably 1.0～2.0MPa.
The present invention produces the improvement technology of aromatic carboxylic acid for liquid phase catalytic oxidation, a kind of aromatic carboxylic acid's of production method is disclosed, wherein Alkylaromatics and their partial oxidation intermediate product are in containing the lipid acid medium of 1～6 carbon atom, add an amount of guanidine compound and use the oxygen unstripped gas that contains that contains a certain amount of carbonic acid gas to carry out oxidation with cobalt one manganese monobromo catalyst system, with common MC type method for oxidation with adopt MC type method for oxidation and add carbonic acid gas and compare, the present invention makes the alkylaromatic hydrocarbon oxidizing reaction be quickened significantly under identical temperature of reaction and transformation efficiency, and speed of response is faster, reaction times reduces; Selectivity better, has obviously reduced the side reaction generation; And can make at reaction conditions than carrying out under the mild conditions used.
To explain the present invention in more detail by the following examples, but these embodiment do not limit the scope of the invention as just illustration.
Embodiment
Embodiment 1
To volume is to add 700 gram reaction mixtures in 1000 milliliters of titanium material autoclaves, and wherein p-Xylol is 8.3%, and acetic acid is 87.7%, and water-content is 4%.Feed nitrogen as protection gas, with reaction solution heat temperature raising to 191 ℃, pressure rises to 1.35MPa when stirring.Reaction mixture consist of the 58g p-Xylol, 611g acetic acid, with four hydration Cobaltous diacetates, four hydration manganese acetates, tetrabromoethane and guanidine acetate as catalyzer.Wherein catalyst concn is respectively the cobalt of 300ppm, the manganese of 450ppm, the bromine of 600ppm and the guanidine (ppm all is benchmark with the mixed solution) of 100ppm.Under 191 ℃ of pressure 1.35MPa of temperature condition, carry out oxidizing reaction, feed the mixed gas (wherein containing 21% oxygen, 4% carbonic acid gas, 75% nitrogen) that contains oxygen and carbon dioxide in the reaction process continuously, constant charge flow rate is 10L/min, tail gas (comprising oxygen, carbon monoxide, carbonic acid gas) concentration adopts online detection and record, when the reaction end gas oxygen concn reaches 21%, no oxygen consumption, reaction end this moment, stop giving gas, and cooling reactor, take out product and separate, analyze in the solid product content carboxyl benzaldehyde (4-CBA) impurity.With experiment condition, reaction times, CO
2, CO generates that the concentration to carboxyl benzaldehyde (4-CBA) is shown in Table 1 in concentration and the solid product.
Embodiment 1 show have a certain amount of guanidine and carbonic acid gas in the presence of, speed of response is significantly increased, burning reaction also obtains obvious suppression.4-CBA concentration will be starkly lower than comparative example 1,2,3 in the TA product.
Embodiment 2
Carry out the oxidizing reaction of p-Xylol with the mode identical with embodiment 1, the concentration that is the guanidine that added is changed into 200ppm.The result who sums up at table 1 shows that compare with embodiment 1,4, and compare with each simultaneous test, the reaction times obviously shortens, and promptly speed of response obviously increases, and COX obviously reduces, i.e. side reaction obviously reduces.
Embodiment 3,
Carry out the oxidizing reaction of p-Xylol with the mode identical with embodiment 1, the concentration that is the guanidine that added is changed into 800ppm.The result who sums up at table 1 shows that compare with embodiment 2, the reaction times shortens to some extent, and promptly speed of response increases to some extent, and COX reduces, i.e. side reaction reduces.But result difference is not fairly obvious item by item.
Embodiment 4,
Carry out the oxidizing reaction of p-Xylol with the mode identical with embodiment 1, the concentration that is the guanidine that added is changed into 20ppm.The result who sums up at table 1 shows that the reaction times has been compared than big-difference with embodiment 1 with side reaction, but to compare difference little with contrast experiment 1,2, shows that the existence of micro-guanidine is little to the reaction influence.
Embodiment 1-4 shows that when 4% (volume) carbonic acid gas adds in the oxidizing reaction unstripped gas add-on of guanidine increases, and the reaction times obviously shortens, and COX obviously reduces, i.e. side reaction obviously reduces, but the 4-CBA content is little in the solid phase prod.This explanation, the amount that guanidine adds is many more, PX oxidizing reaction speed is fast more, and burning reaction is few more, but surpasses when a certain amount of when the guanidine addition, impact effect to reaction system can become more and more not obvious, as when the add-on concentration of guanidine when 100ppm is increased to 200ppm, the reaction times shortened to 21 minutes by 26 minutes, and when guanidine concentration when 200ppm is increased to 800ppm, reaction times shortened to 20 minutes by 21 minutes, and rangeability is little relatively.When the add-on of guanidine also little to the reaction influence very little the time, as adding 20ppm.Under the reaction conditions of being investigated, the guanidine suitable addition can be determined in 100ppm～200ppm left and right sides proper.
The comparative example 1
Carry out the oxidizing reaction of p-Xylol with the mode identical, just in catalyst system, do not introduce guanidine acetate with embodiment 1.The result compares in table 1, relatively can get with embodiment 1, adds the 100ppm guanidine, and the reaction deadline shortens to 26min by 32min, makes speed of response accelerate 18.8%; Relatively can get with embodiment 2, add the 200ppm guanidine, the reaction deadline shortens to 21min by 32min, and speed of response accelerates 34.4%; Relatively can get with embodiment 3, add the 800ppm guanidine, the reaction times has used 12min can make speed of response accelerate 37.5% less; Relatively can get with embodiment 4, add the 20ppm guanidine, can make speed of response accelerate 3%, and burning reaction also reduce gradually with the adding of guanidine.
The comparative example 2
Carry out the oxidizing reaction of p-Xylol with the mode identical, just in catalyst system, do not introduce guanidine acetate, in oxidizing gas, also do not introduce carbonic acid gas with embodiment 1.Promptly adopt original MC technology.The result compares in table 1, relatively can get with embodiment 1, adds the 100ppm guanidine, and introduces 4% carbonic acid gas, and the reaction deadline shortens to 10min, makes speed of response accelerate 28%; Relatively can get with embodiment 2, add the 200ppm guanidine and introduce 4% carbonic acid gas, the reaction deadline shortens 15min, and speed of response accelerates 42%; Relatively can get with embodiment 3, add the 800ppm guanidine and introduce 4% carbonic acid gas simultaneously, the reaction times has been used 16min less, can make speed of response accelerate 44%; Relatively can get with embodiment 4, add the 20ppm guanidine and introduce 4% carbonic acid gas simultaneously, can make speed of response accelerate 17%, and burning reaction also reduce gradually.
The comparative example 3
Carry out the oxidizing reaction of p-Xylol with the mode identical, just in oxidizing gas, do not introduce carbonic acid gas with embodiment 1.The result compares in table 1, relatively can get with embodiment 1, introduces 4% carbonic acid gas, and the reaction deadline shortens 3min, relatively can get with embodiment 2, and the amount of adding guanidine increases to 200ppm, and introduces 4% carbonic acid gas, and the reaction deadline shortens to 8min; Relatively can get with embodiment 3, add guanidine to 800ppm, and introduce 4% carbonic acid gas, the reaction times has been used 9min less; Relatively can get with embodiment 4, add the 20ppm guanidine, and introduce 4% carbonic acid gas, the reaction times increases 1min, and burning reaction also increases with guanidine and the adding of carbonic acid gas reduces gradually.
Different carbonic acid gas of table 1 and guanidine add-on are to the influence of the oxidizing reaction of p-Xylol
| Embodiment | Temperature of reaction (℃) | Air inlet CO 2Concentration (V%) | Guanidine concentration (ppm) | Product 4-CBA (ppm) | Total reaction time (min) | Tail gas CO 2Concentration (V%) | Tail gas CO concentration (V%) |
| 1? | 191? | 4? | 100? | 2210? | 26? | 6.50? | 0.14? |
| 2? | 191? | 4? | 200? | 1500? | 21? | 6.12? | 0.10? |
| 3? | 191? | 4? | 800? | 1510? | 20? | 6.23? | 0.13? |
| 4? | 191? | 4? | 20? | 2450? | 30? | 6.96? | 0.31? |
| The comparative example 1 | 191? | 4? | 0? | 2520? | 31? | 7.10? | 0.30? |
| The comparative example 2 | 191? | 0? | 0? | 2890? | 36? | 3.86? | 0.45? |
| The comparative example 3 | 191? | 0? | 100? | 2430? | 29? | 3.26? | 0.14? |
Claims (5)
1. the production method of an aromatic carboxylic acid, step is as follows:
In an oxidation reactor that is added with certain pressure and certain temperature, use cobalt, manganese, bromine to be catalyzer, this catalyzer is dissolved in the lipid acid solvent of 1～6 carbon, simultaneously one or more guanidine compound component is added in this catalyst system;
The aliphatic carboxylic acid that adopts C1～C6 is that solvent, employing contain oxygen molecule gas aromatics and its intermediate oxidation product are carried out oxidizing reaction, obtains aromatic acid product;
Described aromatics is selected from p-Xylol, m-xylene, o-Xylol, 1, sym-trimethylbenzene, pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene;
Described guanidine compound is selected from guanidine acetate, naphthenic acid guanidine, formic acid guanidine, bromination guanidine, chlorination guanidine, Guanidinium nitrate and guanidine sulfate;
Also contain carbonic acid gas in the described oxygen-containing gas, be the gaseous mixture of pure oxygen and carbon dioxide gas mixture or oxygen and rare gas element and carbonic acid gas, wherein the volume of carbonic acid gas is 1～50% of a gas gross;
Described temperature of reaction is 100～255 ℃; Reaction pressure is 0～3.5Mpa.
2. according to the production method of the described aromatic carboxylic acid of claim 1, it is characterized in that wherein the bromine source is taken from hydrogen bromide, Potassium Bromide, tetrabromoethane; Manganese source and cobalt source are taken from the acetate that contains manganese and cobalt that can be dissolved in solvent.
3. according to the production method of the described aromatic carboxylic acid of claim 2, it is characterized in that,
The method of adding carbonic acid gas is for being metered into reactor separately, or mixes the back with oxygen-containing gas and add reactor, and the adding mode be continuous or the adding at intermittence;
Described temperature of reaction is 175～205 ℃; Reaction pressure is 1.0～2.0Mpa.
4. according to the production method of the described aromatic carboxylic acid of claim 1, it is characterized in that, is Co (OAc) as cobalt, manganese, bromine, guanidine source respectively
24H
2O, Mn (OAc)
24H
2O, hydrogen bromide and guanidine acetate.
5. according to the production method of the described aromatic carboxylic acid of claim 2, it is characterized in that, in the lipid acid solvent of 1～6 carbon of described catalyst-solvent, include the water of 0～20%wt.
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| CN102219662B (en) * | 2011-04-27 | 2013-04-10 | 武汉万园寺药业有限公司 | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene |
| CN107903165A (en) * | 2017-10-25 | 2018-04-13 | 常州大学 | A kind of method that m-methyl benzoic acid is continuously prepared using tubular reactor |
| CN110642699A (en) * | 2019-10-31 | 2020-01-03 | 江苏正丹化学工业股份有限公司 | Method for producing trimesic acid by low-temperature liquid-phase continuous oxidation of mesitylene |
| CN110746435B (en) * | 2019-10-31 | 2022-04-29 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
| CN113754534B (en) * | 2020-06-02 | 2023-10-31 | 中国石油化工股份有限公司 | Method for purifying crude2,6-naphthalene dicarboxylic acid |
| CN114768477B (en) * | 2022-03-18 | 2023-11-17 | 中国科学技术大学 | Carbon dioxide trapping method |
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