CN1958552A - Method for producing aromatic carboxylic acid - Google Patents
Method for producing aromatic carboxylic acid Download PDFInfo
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- CN1958552A CN1958552A CN 200610015365 CN200610015365A CN1958552A CN 1958552 A CN1958552 A CN 1958552A CN 200610015365 CN200610015365 CN 200610015365 CN 200610015365 A CN200610015365 A CN 200610015365A CN 1958552 A CN1958552 A CN 1958552A
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Abstract
This invention discloses a method for producing aromatic carboxylic acids. Based on the present MPC process of aromatic carboxylic acids production by aromatic hydrocarbons oxidation, the method introduces a small amount of transition metal or Zr, Ce, Mo, Cr or W (preferential Zr) into conventional Co-Mn-Br catalyst system, and utilizes air as the oxidant to oxidize aromatic hydrocarbons into aromatic carboxylic acids. After the improvement of the catalyst system, the oxidation rate is increased by 10-30%, and the impurity content is decreased by 10-50%. The oxidized mother liquor can be recycled, and has the same reaction effect as fresh mother liquor. After washed with acetic acid, the introduced metal component has few residues, and does not influence the following hydrogenation process. The method solves the problem of low production capacity of the present MPC process caused by low reaction rate induced by low reaction temperature and pressure.
Description
Technical field
The present invention relates to a kind of arene oxidizing production aromatic carboxylic acid's method, particularly relate to based on Mitsui oiling (MPC) technology arene oxidizing and produce improving one's methods of aromatic carboxylic acid's catalyst system.
Background technology
Highly purified aromatic carboxylic acid is used to produce polyester, and polyester is widely used in synthon, film etc.Aromatic carboxylic acid's production method of world industry widespread use at present is under acetic acid (HAc) solvent, cobalt-manganese-bromide catalizer system, prepares corresponding aromatic carboxylic acid with air (molecular oxygen) oxidation aromatic hydrocarbons.What have this technology mainly is AMOCO, DUPONT, Mitsui oiling (MPC), companies such as the Hua Cheng of Mitsubishi, EAST-MAN.The main difference of oxidation technology is that the form of oxidation reactor is different with the oxidizing process condition, and the oxidation technology contrast of AMOCO, DUPONT, Mitsui oiling (MPC) three companies sees Table 1
The comparison of table 1 oxidation technology processing condition
| Project | Technology | ||
| AMOCO | DUPONT | MPC | |
| Oxidation reaction condition | 191 ℃ of pressure 1.26MPa of temperature gas-liquid phase blistering reaction | 201 ℃ of pressure 1.5MPa of temperature gas-liquid phase blistering reaction | 185～191 ℃ of pressure 0.98～1.18MPa of temperature gas-liquid phase blistering reaction |
| Oxidation reactor | 1 enterprising shaft turbine formula of vertical tank φ 5.7m * 8.9m and oar formula stir, and secondary stirs, the second gear rotating speed | 1 special agitator of vertical tank φ 5.51m * 64m enterprising axle Gas Foil | 1 vertical tank top connects a moisture content separator, advances an anchor formula under the φ 5.60m * 12.5m of top and stirs |
| Catalyzer | Solvent ratio HAc/PX=3 (m/m) cobalt manganese is than Co/Mn=0.5 (n/n) Br/ (Co+Mn)=0.5 (n/n) | Solvent ratio HAc/PX=4.5 cobalt manganese is than Co/Mn=0.5 Br/ (Co+Mn)=2.77 | Solvent ratio HAc/PX=5～6 cobalt manganese are than Co/Mn=2 cobalt consumption 500ppm Br/ (Co+Mn)=0.8～1.0 |
| The residence time/min | 51 | 40 | 55～65 |
| Have or not secondary oxidation | Have | Have | Do not have |
The catalyst system of AMOCO company oxidizing reaction adopts low Co/Mn ratio; The Co/Mn of the catalyst system of the oxidizing process of DUPONT company is lower than also, and reaction pressure, temperature are slightly high; The catalyst system of Mitsui oiling company oxidizing reaction adopts higher Co/Mn ratio, and the separate unit oxidation reactor, and comparatively gentle oxidizing process condition and comprehensive solvent recovering system are the maximum feature of its patented technology.
Because the reaction conditions of MPC technology is relatively gentleer, has reduced side reaction, the consumption of p-Xylol (PX) and HAc remains on the advanced level, and equipment manufacturing cost and power consumption reduction.But reducing temperature of reaction and reaction pressure reduces speed of reaction, the residence time of reactant prolongs, and has limited the raising of its throughput, simultaneously higher solvent ratio and the catalyst concn of MPC process using, especially the concentration height of precious metal cobalt increases production cost.
The present invention mainly on MPC technology basis, improves aromatic hydrocarbon oxide catalyst system, to overcome its weak point.
The various countries research worker is doing many work aspect the improvement aromatic hydrocarbon oxidation catalyst system.The patent US5112922 of AMOCO company is in the process of p xylene oxidation system terephthalic acid (TA), with Hf (HfBr for example
4) make activator, when guaranteeing the TA yield, greatly reduce the Co-Mn-Br catalyst levels, reduce impurity, when the Co-Mn-Br consumption was identical, owing to add Hf (massfraction is 30ppm in the mother liquor), by product can reduce by 23.6% (massfraction) to carboxyl benzaldehyde (4-CBA) growing amount, and Hf activatory Co-Mn-Br system can reduce the generation of methyl bromide in the TA manufacturing processed, thereby reduces the loss of catalyst component and the corrosion of equipment.This patent is the improvement at AMOCO process catalyst system, and AMOCO process catalyst system adopts low Co/Mn ratio, has secondary oxidation, has listed in table 1 with the concrete difference of MPC technology.
Patent US 5453538 reports, in catalyzer, add a certain amount of cerium thing, the cerium add-on is n (Ce)/n (Co)=0.005～1.0, and the consumption that can reduce bromide is to n (Br)/n (Co+Mn)=0.1～0.45, thereby has reduced the generation of equipment corrosion and methyl bromide.
Patent US6565754 has introduced the 3rd metal component Hf in the Co-Mn-Br catalyst system or Zr improves catalytic activity, and the consumption of Hf or Zr is greater than 250ppm.Because the consumption of Hf or Zr is big, hydrolysis can take place in Hf salt or Zr salt in follow-up TA unifining process, forms gluey oxide precipitation and is covering in the hydrogenation catalyst surface, and hydrogenation catalyst is poisoned.Patent has adopted behind the PX oxidation reactor increases adsorption bed, solves hydrogenation catalyst poisoning problem with the method for adsorbing most of Hf or Zr oxide compound.The addition of this patented technology Zr is bigger, greater than 250ppm, therefore has the active problem of follow-up hydrogenation process catalyst that influences.
WO 00/37406 has reported that the intermediate product of oxygen-rich oxide alkylaromatic hydrocarbon or its partial oxidation prepares aromatic carboxylic acid's method, patent adds transition metal or lanthanide series metal to improve catalytic performance in common Co-Mn-Br catalyzer, comprise Ce, Zr, Hf, Fe, Cr and Mo salt, preferred Ce, oxidation uses the volume content of oxygen in the gas greater than 50%.Oxygen enrichment technology rate of oxidation height, but explosion hazard is big, industrial application as yet.And this patent is based on low Co/Mn than being that Co/Mn is the improvement of 0.5 or 1.0 catalyst system, and is different with MPC process catalyst system.
Present most catalyst system improves research to carry out at AMOCO technology, and few to the improved research of catalyst system under the Mitsui MPC processing condition.Because the reaction conditions of MPC technology is relatively gentleer, has reduced side reaction, the consumption of PX and HAc remains on the advanced level, and equipment manufacturing cost and power consumption reduction.But reduce temperature of reaction and reaction pressure speed of reaction is reduced, the residence time of reactant prolongs, and has limited the raising of its throughput.The present invention improves the Co-Mn-Br catalyst system with regard to the MPC processing condition, in common Co-Mn-Br catalyzer, added particularly zirconium of a spot of transition metal or lanthanide series metal, oxidizing reaction rate improves 10～30%, when terephthalic acid (TA) was produced in the PX oxidation, impurity reduced by 50% to the content of carboxyl benzaldehyde (4-CBA) among the thick TA.
Summary of the invention
The objective of the invention is in arene oxidizing production aromatic carboxylic acid's process, improve oxidizing reaction rate by catalyst system is improved, reduce side reaction, produce long, the limited shortcoming of throughput of aromatic carboxylic acid's technological reaction thing residence time thereby overcome present MPC aromatic hydrocarbon oxidation.
Compare with the arene oxidizing technology of AMOCO company and DUPONT company, the MPC catalyst system adopts higher Co/Mn ratio, separate unit oxidation reactor, reaction conditions is relatively gentleer, reduced side reaction, the consumption of PX and HAc remains on the advanced level, and equipment manufacturing cost and power consumption reduction.But reduce temperature of reaction and reaction pressure speed of reaction is reduced, the residence time of reactant prolongs, and has limited the raising of its throughput.
In order to overcome the above-mentioned limitation of MPC technology, the present invention improves existing Co-Mn-Br catalyst system, has promptly introduced in catalyst system after a spot of transition metal or the lanthanide series metal, particularly Zr, the arene oxidizing speed of reaction obviously improves, and foreign matter content obviously reduces.The present invention proposes following technical scheme:
In common cobalt-manganese-bromide catalizer system, introduce a spot of transition metal or lanthanide series metal, with the air is the intermediate product of oxygenant oxidation alkyl aromatic compound and their partial oxidations, the preparation aromatic carboxylic acid, catalyzer improves the rear oxidation speed of reaction and improves 10%-30%, and foreign matter content reduces by 10%～50%.
The improvement of catalyst system is based on that present MPC arene oxidizing system aromatic carboxylic acid's processing condition carry out, be 185～191 ℃ of temperature, pressure 0.98～1.18MPa, solvent quality is than HAc/PX=5～6, cobalt manganese mol ratio Co/Mn=2, Br/ (Co+Mn)=0.8～1.0 (mol ratio).
Used transition metal or lanthanide series metal selected among zirconium, cerium, molybdenum, chromium and tungsten, the preferable alloy zirconium.
Zirconium is introduced with the form of its acetate, halogen or nitrate, is 10-1000ppm in the add-on of zirconium metal zirconium, preferred 40～160ppm.
Described alkyl aromatic compound can be p-Xylol, m-xylene, o-Xylol.
When catalyst system of the present invention was used for PX oxidation production terephthalic acid (TA), impurity reduced by 50% to the content of carboxyl benzaldehyde (4-CBA) among the thick TA.
Described oxidation products is after the acetic acid washing, and the residual quantity of zirconium does not influence the purification operations of postorder less than 5ppm.
Oxidizing reaction Recycling Mother Solution in the described preparation process is used, and can reach the reaction effect identical with fresh mother liquor.
Produce aromatic carboxylic acid's technology compares with present MPC arene oxidizing, aromatic carboxylic acid preparation method's provided by the present invention beneficial effect is: do not changing existing installation, do not increase under the situation of facility investment, by introducing a small amount of the 3rd metal component, improve catalytic efficiency, shorten the reaction times, speed of reaction improves 10%～30%, has improved plant capacity; Foreign matter content reduces by 10%～50%, and particularly during PX oxidation system terephthalic acid, impurity has alleviated the load of follow-up hydrogenation operation, thereby helped prolonging on-stream time the content reduction by 50% of carboxyl benzaldehyde (4-CBA), reduces production costs.
Description of drawings
Accompanying drawing 1 is present method process flow sheet, the industrial continuous bubbling tower reactor basically identical of the structure of continuous bubbling tower reactor and MPC technology.The operation process is as follows: the reaction evaluating device through suppress leak test gentle closely knit test qualified after, a certain amount of initial action raw material PX, solvent acetic acid and catalyzer are passed through volume pump 8 and 9, join in the bubbling column reactor 12 through preheater 11, and with circulating heat conduction oil heat temperature raising.Feed small amount of N by mass flowmeter 5b control in the temperature-rise period
2Stir, carry out supercharging to reactor simultaneously.
After treating that temperature rises to temperature of reaction, regulate back pressure maintaining valve 23 and make the pressure of system reach the working pressure that reaction is stipulated, then with N
2Switch to air, the beginning initiation reaction.Air is compressed to certain pressure by compressor 2, through entering reactor by the bottom of reaction tower except that mist of oil jar 3, surge tank 4 under mass flowmeter 5a control.Carry out with reaction, the gas, liquid load obviously increases in the tower, and temperature sharply rises, and reaction heat is shifted out in a large amount of solvent evaporations.By condenser 17 condensations, gas-liquid separator 18 carries out gas-liquid separation to rising steam after the cat head rectifying section tentatively divides water in the tower.Phlegma is collected in the storage tank 19, is back in the tower in trim the top of column pump 21 control lower sections, and the part extraction dewaters.The most of emptying of tail gas, part enters tail oxygen concentration detector and CO after further purifying
2Analyser.Reaction is pressed given flow continuous supplementation liquid material with volume pump after causing certain hour, and reaction is carried out continuously.The liquid-solid phase material of reaction by tower at the bottom of the automatically controlled valve liquid level of regulating tower, enter continuously in the flash distillation still 13.Be collected in after the acetic acid condensation of flash distillation in the storage tank 15 and recycle.Slurry separates, the filtrate cycle utilization.
Regular bottom thief hole from reaction tower carries out sampling analysis in the reaction process.CO in the temperature of each point, pressure, flow, liquid level and tail oxygen concentration and the tail gas in the entire reaction course
2Content etc. show that in real time the whole record acquisitions input of monitor data computer can be observed CO in temperature, pressure, flow and tail oxygen concentration and the tail gas in the operating process at any time
2Content curve over time.Temperature of reaction, pressure, liquid level, flow are controlled automatically by the computer tandem.
1 nitrogen steel cylinder among the figure, 2 air compressor, 3 air de-oiling jars, 4 air cushioning jars, 5 mass flow measuring devices, the 6PX storage tank, the 7AcOH storage tank, the 8PX pump, the 9AcOH pump, pressure maintaining valve before 10,11 preheaters, 12 reactors, 13 flash tanks, 14 reacting slurry storage tanks, 15 flash distillation acetic acid tanks, 16 flash distillation acetic acid condensers, 17 overhead condensation vapour devices, 18 gas-liquid separators, 19 overhead condensation liquid storage tanks, 20 cat head liquid effluent storage tanks, 21 trim the top of column pumps, 22 exhaust purifiers, 23 back pressure maintaining valves, 24 exhaust flow meters, 25 oxygen analysers, 26CO
2Analyser, 27 computer control and measuring system
Specific embodiment
Embodiment 1
Reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.0MPa, catalyzer consists of Co 501ppm (0.0085mol/L), Co/Mn=2: 1 (mol/mol), Br 815ppm (0.0102mol/L), Zr 39ppm, Br/ (Co+Mn)=0.8 (mol/mol), liquid feeding are the mixing solutions of p-Xylol (PX), acetic acid (92% aqueous acetic acid) and catalyzer, and wherein the mass ratio of acetic acid and PX is 5: 1.Experimental result is listed in the table 2.
Embodiment 2-4
Other reaction conditions is with embodiment 1, and just the add-on of Zr is respectively 78ppm, 116ppm, 155ppm, and experimental result is listed in the table 2.
The comparative example 1
With reference to the operational condition of MPC technology full scale plant, determine the reference of long run test.Concrete reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.0MPa, and catalyzer is formed: Co 501ppm (0.0085mol/L), Mn233ppm (0.0043mol/L), Co/Mn=2: 1 (mol/mol), Br 815ppm (0.0102mol/L), Br/ (Co+Mn)=0.8 (mol/mol).Liquid feeding is the mixing solutions of p-Xylol (PX), acetic acid (92% aqueous acetic acid) and catalyzer, and wherein the mass ratio of acetic acid and PX is 5: 1, and the residence time of liquid material is 60min.Experimental result is listed in the table 2.
The different zirconium addition of table 2 PX oxidizing reaction result
| Catalyzer | The residence time/min | Speed of reaction | Solid product TA content wt% | Solid product contains 4CBAwt% | ||||
| Co/Mn(mol) | Co/ppm | Br/ppm | Zr/ppm | Improve % | ||||
| Embodiment 1 | 2 | 501 | 815 | 39.00 | 57.0 | 5.26 | 94.15 | 4.17 |
| Embodiment 2 | 2 | 501 | 815 | 78.00 | 55.0 | 9.09 | 96.40 | 3.41 |
| Embodiment 3 | 2 | 501 | 815 | 116.00 | 52.0 | 15.38 | 95.60 | 3.69 |
| Embodiment 4 | 2 | 501 | 815 | 155.00 | 50.0 | 20.00 | 92.36 | 3.57 |
| Comparing embodiment 1 | 2 | 501 | 815 | 0.00 | 60.0 | - | 92.23 | 4.15 |
Embodiment 5
Reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.0MPa, catalyzer is formed Co 501ppm (0.0085mol/L), Co/Mn=2: 1 (mol/mol), Zr 116ppm, Br 713ppm (0.0089mol/L), liquid feeding are the mixing solutions of p-Xylol (PX), acetic acid (92% aqueous acetic acid) and catalyzer, wherein the mass ratio of acetic acid and PX is 5: 1, and experimental result is listed in the table 3.
Embodiment 6-8
Other reaction conditions is with embodiment 5, and the add-on that only changes Br is respectively 815ppm, 917ppm, 1019ppm, and experimental result is listed in the table 3.
The different bromine concentration PX of table 3 oxidizing reaction result
| Catalyzer | Solid product TA content wt% | Solid product contains 4CBAwt% | ||||
| Co/Mn(mol) | Co/ppm | Br/ppm | Zr/ppm | |||
| Embodiment 5 | 2 | 501 | 713 | 116.00 | 94.96 | 4.08 |
| Embodiment 6 | 2 | 501 | 815 | 116.00 | 95.60 | 3.69 |
| Embodiment 7 | 2 | 501 | 917 | 116.00 | 97.55 | 1.97 |
| Embodiment 8 | 2 | 501 | 1019 | 116.00 | 95.68 | 1.72 |
| Comparing embodiment 1 | 2 | 501 | 815 | 0.00 | 92.23 | 4.15 |
Embodiment 9
Reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.0MPa, catalyzer is formed Co501ppm (0.0085mol/L), Co/Mn=2: 1 (mol/mol), Zr105ppm, Br993ppm (0.0124mol/L), liquid feeding are the mixing solutions of p-Xylol (PX), acetic acid (92% aqueous acetic acid) and catalyzer, wherein the mass ratio of acetic acid and PX is 5: 1, the results are shown in table 4.
Embodiment 10
Reaction conditions has just added circulating mother liquor in the reaction solution with embodiment 9, the results are shown in table 4.
Fresh mother liquor of table 4 and circulating mother liquor PX oxidizing reaction result
| Catalyzer | The residence time/min | Speed of reaction | Solid product TA content wt% | Solid product contains 4CBAwt% | ||||
| Co/Mn(mol) | Co/ppm | Br/ppm | Zr/ppm | Improve % | ||||
| Embodiment 9 | 2 | 501 | 993 | 105.00 | 46.0 | 30.43 | 97.52 | 1.98 |
| Embodiment 10 | 2 | 501 | 990 | 105.00 | 46.5 | 29.03 | 97.28 | 2.03 |
| Comparing embodiment 1 | 2 | 501 | 815 | 0.00 | 60.0 | - | 92.23 | 4.15 |
Embodiment 11
Reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.0MPa, Co497ppm, Co/Mn=2: 1 (mol/mol), Mo120ppm, Br900ppm (0.0112mol/L), liquid feeding are the mixing solutions of m-xylene, acetic acid (92% aqueous acetic acid) and catalyzer, wherein the mass ratio of acetic acid and m-xylene is 5.5: 1, and experimental result is listed in table 5.
Comparing embodiment 2
Except not adding metal M o, Br is that other condition is with embodiment 11 beyond the 803ppm, and experimental result is listed in table 5.
Embodiment 12
Reaction conditions is 186～188 ℃ of temperature of reaction, pressure 1.05MPa, Co490ppm, Co/Mn=2: 1 (mol/mol), Mo135ppm, Br930ppm (0.0116mol/L), liquid feeding are the mixing solutions of o-Xylol, acetic acid (92% aqueous acetic acid) and catalyzer, wherein the mass ratio of acetic acid and o-Xylol is 6: 1, and experimental result is listed in table 5.Comparing embodiment 3
Except not adding metal M o, Br is that other condition is with embodiment 11 beyond the 794ppm, and experimental result is listed in table 5.
Table 5 adds the influence of metal M o
| Catalyzer | The residence time/min | Speed of reaction | Purpose product wt% in the solid | Solid product total impurities wt% | ||||
| Co/Mn(mol) | Co/ppm | Br/ppm | Mo/ppm | Improve % | ||||
| Embodiment 11 | 2 | 497 | 900 | 120.00 | 54.0 | 11.85 | 93.83 | 3.34 |
| Embodiment 12 | 2 | 490 | 930 | 135.00 | 51.2 | 19.14 | 93.48 | 3.51 |
| Comparing embodiment 2 | 2 | 497 | 803 | 0.00 | 60.4 | - | 91.59 | 4.95 |
| Comparing embodiment 3 | 2 | 490 | 794 | 0.00 | 61.0 | - | 92.03 | 4.90 |
Embodiment 13
Product to embodiment 9 carries out twice acetic acid making beating filtration, gets filter cake oven dry back survey catalyzer Zr content wherein, and the result shows that the Zr residual quantity is 2.9ppm, can not influence the follow-up hydrogenation refining step.
Claims (8)
1. an aromatic carboxylic acid production method is characterized in that, introduces a spot of transition metal or lanthanide series metal in common cobalt-manganese-bromide catalizer system, is that oxygenant oxidation alkyl aromatic compound prepares the aromatic carboxylic acid with the air; The improvement of catalyst system is based on that present Mitsui oiling arene oxidizing system aromatic carboxylic acid's processing condition carry out, be 185～191 ℃ of temperature, pressure 0.98～1.18MPa, solvent quality is than acetic acid/aromatic hydrocarbons=5～6, cobalt manganese mol ratio Co/Mn=2, Br/ (Co+Mn)=0.8～1.0 mol ratio.
2. according to the described aromatic carboxylic acid's of claim 1 production method, it is characterized in that a kind of in transition metal or lanthanide series metal selected among zirconium, cerium, molybdenum, chromium and the tungsten.
3. according to the described aromatic carboxylic acid's of claim 2 production method, it is characterized in that transition metal or lanthanide series metal are zirconiums.
4. according to the described aromatic carboxylic acid's of claim 3 production method, it is characterized in that zirconium is introduced with the form of its acetate, halogen or nitrate, is 10-1000ppm in the add-on of zirconium metal zirconium, preferred 40～160ppm.
5. according to the described aromatic carboxylic acid's of claim 1 production method, it is characterized in that described alkyl aromatic compound is a kind of in p-Xylol, m-xylene, the o-Xylol.
6. according to the described aromatic carboxylic acid's of claim 1 production method, it is characterized in that when catalyst system was used for dimethylbenzene oxidation production terephthalic acid, impurity reduced by 50% to the content of carboxyl benzaldehyde in the crude terephthalic acid.
7. according to the described aromatic carboxylic acid's of claim 1 production method, it is characterized in that the residual quantity of oxidation reaction product zirconium after the acetic acid washing is less than 5ppm.
8. according to the described aromatic carboxylic acid's of claim 1 production method, it is characterized in that the oxidizing reaction Recycling Mother Solution is used.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924266A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Method for preparing phthalic acid by xylol co-oxidation catalyst system |
| CN107954850A (en) * | 2017-11-02 | 2018-04-24 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN107963964A (en) * | 2017-11-02 | 2018-04-27 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN112645812A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Start-up method for preparing terephthalic acid by liquid-phase oxidation of paraxylene |
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2006
- 2006-08-18 CN CN 200610015365 patent/CN1958552A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924266A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Method for preparing phthalic acid by xylol co-oxidation catalyst system |
| CN107954850A (en) * | 2017-11-02 | 2018-04-24 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN107963964A (en) * | 2017-11-02 | 2018-04-27 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN112645812A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Start-up method for preparing terephthalic acid by liquid-phase oxidation of paraxylene |
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