CN103601638B - Continuous production process and device of benzoic acid - Google Patents
Continuous production process and device of benzoic acid Download PDFInfo
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- CN103601638B CN103601638B CN201310554365.4A CN201310554365A CN103601638B CN 103601638 B CN103601638 B CN 103601638B CN 201310554365 A CN201310554365 A CN 201310554365A CN 103601638 B CN103601638 B CN 103601638B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00911—Sparger-type feeding elements
Abstract
The invention relates to a continuous production process of benzoic acid. The continuous production process comprises the following steps: (1) introducing toluene liquid and a catalyst; (2) introducing air, wherein the air reacts with the toluene liquid in the presence of a catalyst; (3) controlling temperature; and (4) discharging benzoic acid, and meanwhile, feeding through a feed opening of a reaction tower to realize continuous reaction. Devices used in the process include a reaction tower, a cooling device, an oil-water separator and an absorption tower, wherein a gas-liquid distribution stirrer is installed on the bottom of the reaction tower, two tubular heat exchangers are arranged at the middle part of the reaction tower, and a benzoic acid discharge opening in the upper part of the reaction tower is connected to a benzoic acid flash column. The continuous production process of benzoic acid and the device thereof provided by the invention can be used for improving the selectivity of the catalyst to the benzoic acid product, the gas-liquid mixing and heat exchange and realizing continuous production, thereby reducing the energy consumption in the process, continuously producing low-pressure vapor, improving the product quality and yield, decreasing by-products and reducing the production cost.
Description
Technical field
The present invention relates to phenylformic acid field, especially a kind of phenylformic acid continuous production processes and device thereof.
Background technology
Industrial phenylformic acid obtains with atmospheric oxidation toluene under the catalyzer such as cobalt, manganese exists.Because catalyzed reaction is exothermic process and catalyzer is high to temperature requirement, dependency is strong, therefore temperature is higher, and catalyzed reaction is faster, catalyzed reaction is faster, and temperature is higher, forms vicious cycle, therefore too high, the poor selectivity of catalyst activity, can cause that by product increases, poor selectivity.Along with temperature constantly raises, even there will be temperature runaway, cause reaction tower out of control, set off an explosion.Therefore, in order to control temperature and improve the selectivity of process, ensure safety in production, benzoic batch production process just becomes to be the theme.
Batch production process (discontinuous reaction) i.e. charging, discharging and cleaning need to complete under stopped status, though this rhythmic reaction is widely used, but it exists many defects:
1, reaction be to carry out at a certain temperature, so often criticize initial material all need heating, and enter normal oxidising process need cooling, so cause energy consumption large.
2, charging and discharging need to shut down, and lose time, reduce work efficiency.
3, can take part toluene out of when gas is discharged, this toluene is about 160 DEG C, must carry out cooling process.Usually adopt water coolant to cool at present, the water coolant after heat exchange becomes hot water, and because existing reaction is discontinuous reaction, the hot water therefore obtained after heat exchange can not effectively recycle, and causes energy dissipation equally.
4, reaction tower inner air pressure is 0.7Mpa, needs to use air compressor to maintain, and when charging and discharging, compressor is in idling conditions substantially, wastes energy.
5, unit volume output is little.
6, the heating up process in reaction is first preheating to 110 DEG C, passes into part 0.7Mpa air, exotherm to 160 DEG C, and then pass into air reaction, then cool.This reaction process temperature is wayward, and temperature is too high or too lowly all can produce the by products such as a large amount of phenyl aldehyde, phenylcarbinol, peruscabin, and cause unstable product quality, low conversion rate, current transformation efficiency is generally 50-55%.
7, there are catalyzer, peruscabin can how much have some to be deposited in reactor bottom after cooling, need stop cleaning, cause prolongs operating time.
8, employment is many, cost is high.
In addition, current gas and methylbenzene raw material all enter bottom reaction tower, because gas distribution is uneven, cause catalyst selectivity poor, cause the problem such as low conversion rate and by product height to occur equally.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of and can increase work efficiency, products quality guarantee, minimizing energy dissipation, the phenylformic acid continuous production processes improving conversion rate of products and device thereof.
The present invention solves its technical problem and is achieved through the following technical solutions:
A kind of phenylformic acid continuous production processes, is characterized in that: comprise the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal mainly, and wherein the weight percent of metal is: manganese: 1.3-2.3%; Cobalt: 5-7%; Nickel: 0.3-1%;
(2). bottom reaction tower, pass into air, air and toluene liquid react under the effect of catalyzer;
(3). in reaction process, use temperature control heat exchanger to control temperature in reaction tower, temperature range is 160-170 DEG C;
(4). reaction mass after certain hour, completes oxidising process in reaction tower, and phenylformic acid discharging also carries out subsequent disposal, to discharge and carry out subsequent disposal with the gas of toluene through tower top; While continuous discharging, the opening for feed also constantly charging of reaction tower, the serialization of realization response process.
And install one or more gas-liquid distribution agitator bottom described reaction tower, air is discharged through this distribution agitator, while forming micro-bubble, fully can also stir, react with toluene.
And the (3) described temperature control heat exchanger of step is the tubular heat exchangers that two series connection use.
And step (4) described reaction times is 6-7h.
And, the (4) described benzoic subsequent disposal of step is: phenylformic acid enters flashing tower after reaction tower discharging, isolated toluene enters in reaction tower after mixing with the toluene of the charging bottom reaction tower, and the isolated mixture based on phenylformic acid enters subsequent processing.
And, the (4) described reaction tower top of step with the subsequent disposal of the gas of toluene is: enter refrigerating unit, from refrigerating unit, isolated gas-phase product enters absorption tower, the toluene reclaimed is re-used as raw material and is applied, get back to the toluene liquid inlet opening of reaction tower, and directly discharge through the tail gas of absorption tower process; From refrigerating unit, isolated liquid product enters water-and-oil separator, and isolated toluene liquid gets back to the toluene liquid inlet opening of reaction tower, and isolated water-phase product is again through follow-up process.
A kind of phenylformic acid continuous production device, comprise reaction tower, refrigerating unit, water-and-oil separator and absorption tower, the bottom of reaction tower arranges toluene liquid inlet opening and inlet mouth, the pneumatic outlet at reaction tower top connects refrigerating unit, the gaseous phase outlet of this refrigerating unit connects absorption tower, the toluene liquid inlet opening of one of them outlet ligation tower on absorption tower; The liquid-phase outlet of refrigerating unit connects a water-and-oil separator, the toluene liquid inlet opening of one of them outlet ligation tower of this water-and-oil separator, it is characterized in that: the bottom of reaction tower inside is installed one or more gas-liquid be communicated with inlet mouth and to be distributed agitator, the middle part of reaction tower arranges two tubular heat exchangers, and the phenylformic acid discharge port on reaction tower top connects a phenylformic acid flashing tower.
And, described gas-liquid distribution agitator comprises hood-shaped rotating disk and inlet pipe, the cover body of this hood-shaped rotating disk is made one group of pore, hood-shaped rotating disk coaxial rotation is arranged on the upper end of inlet pipe, the sidewall of inlet pipe is made and discharges gas branch pipe more, this goes out gas branch pipe and is all connected with inlet pipe and is positioned at hood-shaped rotating disk inside, the inner side-wall of hood-shaped rotating disk is installed one group of baffle plate, often discharges the corresponding baffle plate of gas branch pipe.
And two described tubular heat exchangers are arranged in series, the general import of this tubular heat exchanger is connected with an interchanger flashing tower with general export, and water at low temperature import installed by this interchanger flashing tower, and the top of this interchanger flashing tower arranges low-pressure steam outlet.
And, the outlet of the toluene gas of described phenylformic acid flashing tower with enter reaction tower toluene liquid starting material pipeline and be connected.
Advantage of the present invention and beneficial effect are:
1, this production technique is by adjusting the component of catalyzer and weight percent thereof, make catalyzer relatively gentle and there is higher selectivity, not only can reduce by product, but also can temperature of reaction be controlled, for benzoic continuous production processes provides the foundation.
2, by installing one or more gas-liquid distribution agitator in the bottom of reaction tower, air distribution controlled by gas-liquid distribution agitator and the gas-liquid mixture bottom reaction tower is stirred, reaction bottom reaction tower can be made even, be conducive to keeping catalyzer gentleness stable, that stirs act as the condition that heat exchange provides, thus it is balanced to maintain reaction tower bottom temp, is similarly benzoic continuous production processes and provides the foundation.In addition, this gas-liquid distribution agitator runs and does not need power, energy-conserving and environment-protective.
3, the present invention adopts two tubular heat exchangers of connecting to control the temperature of reaction in reaction tower, ensure that temperature of reaction maintains a stable scope, is similarly benzoic continuous production processes and provides the foundation.
4, because this technique achieves continuous seepage, therefore the reaction times shortens, transformation efficiency improves, by product reduces.
5, continuous seepage can make tubular heat exchanger export continuous print water vapour (133 DEG C, 0.3Mpa), in other explained hereafter of later stage, can play the effect of energy-saving and emission-reduction.
6, adopt this continuous production processes and device the reaction times can be shortened to about 6.4h, thus enhance productivity.In addition, this technique and device also have and can reduce air compressor energy consumption, reduce the plurality of advantages such as cost of labor.
7, the reaction tower of this device connects a phenylformic acid flashing tower, and 40% unconverted toluene gas can be separated by it, and this toluene gas gets back to opening for feed, can improve the inlet temperature of methylbenzene raw material.
8, in the phenylformic acid flashing tower in this device, water-and-oil separator and absorption tower isolate the toluene liquid inlet opening that toluene gas all gets back to reaction tower, the serialization of implementation procedure.
9, the present invention is a kind of phenylformic acid continuous production processes and device thereof, the selectivity of catalyzer para Toluic Acid product, gas-liquid mixed and thermal exchange can be improved owing to adopting this technique and device, realize continuous seepage, while cause this reduces the energy consumption of process, all right continuous seepage low-pressure steam, improves quality product and production capacity, decreases by product, reduces production cost.
Accompanying drawing explanation
Fig. 1 is schematic diagram of the present invention;
Fig. 2 is the front view of distribution agitator;
Fig. 3 is the sectional view of Fig. 2;
Fig. 4 is the schematic top plan view one (removing the upper surface of hood-shaped rotating disk) of Fig. 2;
Fig. 5 is the schematic top plan view two (removing the upper surface of hood-shaped rotating disk) of Fig. 2.
Embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
For ease of understanding benzoic continuous production processes, the device that first para Toluic Acid's continuous seepage is used is described.
A kind of phenylformic acid continuous production device, comprise reaction tower 4, refrigerating unit 2, water-and-oil separator 3 and absorption tower 1, the bottom of reaction tower arranges toluene liquid inlet opening and inlet mouth, the pneumatic outlet at reaction tower top connects refrigerating unit, the gaseous phase outlet of this refrigerating unit connects absorption tower, the toluene liquid inlet opening of one of them outlet ligation tower on absorption tower; The liquid-phase outlet of refrigerating unit connects a water-and-oil separator, the toluene liquid inlet opening of one of them outlet ligation tower of this water-and-oil separator.
Innovative point of the present invention is: the bottom of reaction tower inside is installed one or more gas-liquid be communicated with inlet mouth and to be distributed agitator 5, this gas-liquid distribution agitator comprises hood-shaped rotating disk 10 and inlet pipe 11, the cover body of this hood-shaped rotating disk is made one group of pore 9, this pore built in hood-shaped rotating disk cover body top board and or sidewall on, pore quantity is not limit, and diameter can adjust as required.Hood-shaped rotating disk coaxial rotation is arranged on the upper end of inlet pipe, the sidewall of inlet pipe is made many discharge gas branch pipes 12, as shown in Figure 4 and Figure 5, goes out gas branch pipe shape and do not limit, and this goes out gas branch pipe and is all connected with inlet pipe and is positioned at hood-shaped rotating disk inside.Its concrete syndeton is: inlet pipe is L shape pipe, and the vertical section of this L shape pipe stretches in hood-shaped rotating disk, and the upper end of this vertical section is connected with hood-shaped dial rotation, goes out gas branch pipe and to be installed in vertical section and to be connected with vertical intersegmental part.
The inner side-wall of hood-shaped rotating disk is installed one group of baffle plate 13, often discharge the corresponding baffle plate of gas branch pipe.Angle between baffle plate and hood-shaped rotating disk inner side-wall is 50-70 degree, and the exit angle going out gas branch pipe is also 50-70 degree, and inlet pipe axle center is less than the distance of axle center to baffle plate to the distance going out gas branch pipe outermost edge, baffle plate and go out gas branch pipe and collide during to avoid rotating.The quantity of baffle plate and the row going out gas branch pipe are not limit, and in the present embodiment, circumferentially uniformly on the sidewall of inlet pipe make four discharge gas branch pipes, and circumferentially uniform installation four baffle plates on the inner side-wall of hood-shaped rotating disk, this baffle plate is all vertically arranged.Often discharge between gas branch pipe and respective baffle plate and all form a gas shock region 14, pore is arranged on away from the hood-shaped rotating disk faceshield side wall in this region and or top board.
The middle part of reaction tower arranges two tubular heat exchangers 6, these two tubular heat exchangers are arranged in series, the general import of this tubular heat exchanger is connected with an interchanger flashing tower 7 with general export, and water at low temperature import installed by this interchanger flashing tower, and the top of this interchanger flashing tower arranges low-pressure steam outlet.
The phenylformic acid discharge port on reaction tower top connects a phenylformic acid flashing tower 8, the toluene liquid inlet opening of the toluene gas outlet ligation tower of this phenylformic acid flashing tower.
A kind of phenylformic acid continuous production processes, comprises the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal mainly, and wherein the weight percent of metal is: manganese: 1.3-2.3%; Cobalt: 5-7%; Nickel: 0.3-1%;
(2). bottom reaction tower, pass into air, air and toluene liquid react under the effect of catalyzer.Install one or more gas-liquid distribution agitator bottom reaction tower, air is discharged through this distribution agitator, while forming micro-bubble, fully can also stir, react with toluene;
(3). in reaction process, use temperature control heat exchanger to control temperature in reaction tower, temperature range is 160-170 DEG C, and this temperature control heat exchanger is the tubular heat exchanger that two series connection use;
(4). reaction mass after 6-7h, completes oxidising process in reaction tower, and phenylformic acid discharging also carries out subsequent disposal, to discharge and carry out subsequent disposal with the gas of toluene through tower top; While continuous discharging, the opening for feed also constantly charging of reaction tower, the serialization of realization response process.
Above-mentioned benzoic subsequent processes is: phenylformic acid enters flashing tower after reaction tower discharging, and isolated toluene gas gets back to the toluene liquid inlet opening of reaction tower, and the isolated mixture based on phenylformic acid enters subsequent processing.
Above-mentioned reaction tower top with the subsequent disposal of the gas of toluene is: enter refrigerating unit, from refrigerating unit, isolated gas-phase product enters absorption tower, the toluene reclaimed is re-used as raw material and is applied, get back to the toluene liquid inlet opening of reaction tower, and directly discharge through the tail gas of absorption tower process; From refrigerating unit, isolated liquid product enters water-and-oil separator, and isolated toluene liquid gets back to the toluene liquid inlet opening of reaction tower, and isolated water-phase product is again through follow-up process.
Embodiment 1
A kind of phenylformic acid continuous production processes, comprises the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal mainly, and wherein the weight percent of metal is: manganese: 1.3%; Cobalt: 5%; Nickel: 0.3%;
(2). bottom reaction tower, pass into air, air and toluene liquid react under the effect of catalyzer.Install one or more gas-liquid distribution agitator bottom reaction tower, air is discharged through this distribution agitator, while formation micro-bubble, fully can also stir, react with toluene;
(3). in reaction process, use temperature control heat exchanger to control temperature in reaction tower, temperature range is 160-170 DEG C, and this temperature control heat exchanger is the tubular heat exchanger that two series connection use;
(4). reaction mass after 6-7h, completes oxidising process in reaction tower, and phenylformic acid discharging also carries out subsequent disposal, to discharge and carry out subsequent disposal with the gas of toluene through tower top; While continuous discharging, the opening for feed also constantly charging of reaction tower, the serialization of realization response process.
Above-mentioned benzoic subsequent processes is: the product based on phenylformic acid enters and directly enters flashing tower after reaction tower discharging, isolated toluene gas gets back to the toluene liquid inlet opening of reaction tower as raw material, and the isolated mixture based on phenylformic acid enters subsequent processing.
Reaction tower top with the subsequent disposal of the gas of toluene is: enter refrigerating unit, from refrigerating unit, isolated gas-phase product enters absorption tower, the toluene reclaimed is re-used as raw material and is applied, and gets back to the toluene liquid inlet opening of reaction tower, and directly discharges through the tail gas of absorption tower process; From refrigerating unit, isolated liquid product enters water-and-oil separator, and isolated toluene liquid gets back to the toluene liquid inlet opening of reaction tower, and isolated water-phase product is again through follow-up process.
Embodiment 2
A kind of phenylformic acid continuous production processes, comprises the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal mainly, and wherein the weight percent of metal is: manganese: 1.8%; Cobalt: 6%; Nickel: 0.7%;
Step (2)-(4) identical with embodiment 1.
Embodiment 3
A kind of phenylformic acid continuous production processes, comprises the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal mainly, and wherein the weight percent of metal is: manganese: 2.3%; Cobalt: 7%; Nickel: 1%;
Step (2)-(4) identical with embodiment 1.
Claims (8)
1. a phenylformic acid continuous production processes, is characterized in that: comprise the following steps:
(1). bottom reaction tower, pass into toluene liquid and catalyzer, catalyzer is sad metal, and wherein the weight percent of metal is: manganese: 1.3-2.3%; Cobalt: 5-7%; Nickel: 0.3-1%;
(2). bottom reaction tower, pass into air, air and toluene liquid react under the effect of catalyzer;
(3). in reaction process, use temperature control heat exchanger to control temperature in reaction tower, temperature range is 160-170 DEG C;
(4). reaction mass after certain hour, completes oxidising process in reaction tower, and phenylformic acid discharging also carries out subsequent disposal, to discharge and carry out subsequent disposal with the gas of toluene through tower top; While continuous discharging, the opening for feed also constantly charging of reaction tower, the serialization of realization response process;
The production equipment that above-mentioned phenylformic acid continuous production processes uses, comprise reaction tower, refrigerating unit, water-and-oil separator and absorption tower, the bottom of reaction tower arranges toluene liquid inlet opening and inlet mouth, the pneumatic outlet at reaction tower top connects refrigerating unit, the gaseous phase outlet of this refrigerating unit connects absorption tower, the toluene liquid inlet opening of one of them outlet ligation tower on absorption tower; The liquid-phase outlet of refrigerating unit connects a water-and-oil separator, the toluene liquid inlet opening of one of them outlet ligation tower of this water-and-oil separator, the bottom of reaction tower inside is installed one or more gas-liquid be communicated with inlet mouth and to be distributed agitator, the middle part of reaction tower arranges two tubular heat exchangers, and the phenylformic acid discharge port on reaction tower top connects a phenylformic acid flashing tower;
Described gas-liquid distribution agitator comprises hood-shaped rotating disk and inlet pipe, the cover body of this hood-shaped rotating disk is made one group of pore, hood-shaped rotating disk coaxial rotation is arranged on the upper end of inlet pipe, the sidewall of inlet pipe is made and discharges gas branch pipe more, this goes out gas branch pipe and is all connected with inlet pipe and is positioned at hood-shaped rotating disk inside, the inner side-wall of hood-shaped rotating disk is installed one group of baffle plate, often discharge the corresponding baffle plate of gas branch pipe.
2. phenylformic acid continuous production processes according to claim 1, it is characterized in that: install one or more gas-liquid distribution agitator bottom described reaction tower, air is discharged through this distribution agitator, while forming micro-bubble, fully can also stir, react with toluene.
3. phenylformic acid continuous production processes according to claim 1, is characterized in that: the (3) described temperature control heat exchanger of step is the tubular heat exchangers that two series connection use.
4. phenylformic acid continuous production processes according to claim 1, is characterized in that: step (4) described reaction times is 6-7h.
5. phenylformic acid continuous production processes according to claim 1, it is characterized in that: the (4) described benzoic subsequent disposal of step is: phenylformic acid enters flashing tower after reaction tower discharging, isolated toluene enters in reaction tower after mixing with the toluene of the charging bottom reaction tower, and the isolated mixture based on phenylformic acid enters subsequent processing.
6. phenylformic acid continuous production processes according to claim 1, it is characterized in that: the (4) described reaction tower top of step with the subsequent disposal of the gas of toluene is: enter refrigerating unit, from refrigerating unit, isolated gas-phase product enters absorption tower, the toluene reclaimed is re-used as raw material and is applied, get back to the toluene liquid inlet opening of reaction tower, and directly discharge through the tail gas of absorption tower process; From refrigerating unit, isolated liquid product enters water-and-oil separator, and isolated toluene liquid gets back to the toluene liquid inlet opening of reaction tower, and isolated water-phase product is again through follow-up process.
7. phenylformic acid continuous production processes according to claim 1, it is characterized in that: two described tubular heat exchangers are arranged in series, the general import of this tubular heat exchanger is connected with an interchanger flashing tower with general export, water at low temperature import installed by this interchanger flashing tower, and the top of this interchanger flashing tower arranges low-pressure steam outlet.
8. phenylformic acid continuous production processes according to claim 1, is characterized in that: the outlet of the toluene gas of described phenylformic acid flashing tower with enter reaction tower toluene liquid starting material pipeline and be connected.
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| CN104907008B (en) * | 2015-06-04 | 2017-10-27 | 河北科技大学 | A kind of toluene direct oxidation prepares the reaction unit and method of benzoic acid and benzaldehyde |
| CN105503567B (en) * | 2016-01-15 | 2017-12-29 | 湖南弘润化工科技有限公司 | The device and method of continuous production benzoic acid, by-product benzaldehyde |
| CN106977389A (en) * | 2017-04-01 | 2017-07-25 | 来安县万博丰环保科技有限公司 | A kind of benzoic acid continuous production processes and its device |
| CN112552151A (en) * | 2019-09-10 | 2021-03-26 | 南京延长反应技术研究院有限公司 | System and process for enhancing toluene oxidation |
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| CN1305451A (en) * | 1998-04-21 | 2001-07-25 | 联合碳化化学品及塑料技术公司 | Preparation of organic acids |
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| CN203653465U (en) * | 2013-11-08 | 2014-06-18 | 天津东大化工集团有限公司 | Continuous production device for benzoic acid |
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Effective date of registration: 20161017 Address after: Tianjin City, Tanggu Binhai New Area 300455 Kaiweilu No. 728 Patentee after: Tianjin Dongda Chemical Co., Ltd Address before: Tianjin City, Tanggu Binhai New Area 300455 Kaiweilu No. 728 Patentee before: Tianjin Dongda Chemical Co., Ltd Patentee before: Tianjin University of Science & Technology |