CN101735049A - Method and equipment for producing C4-C6 diacid low-carbon alcohol ester - Google Patents
Method and equipment for producing C4-C6 diacid low-carbon alcohol ester Download PDFInfo
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- CN101735049A CN101735049A CN200910248528A CN200910248528A CN101735049A CN 101735049 A CN101735049 A CN 101735049A CN 200910248528 A CN200910248528 A CN 200910248528A CN 200910248528 A CN200910248528 A CN 200910248528A CN 101735049 A CN101735049 A CN 101735049A
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Abstract
The invention belongs to the chemical field, in particular to method and equipment for producing C1-C2 low-carbon alcohol ester of C4-C6 diacid. The method is characterized by comprising the following steps of: adding a catalytic agent, C4-C6 diacid and C1-C2 alcohol to a dispensing kettle, stirring and heating to enable the solid diacid to be dissolved; and then continuously delivering feed liquid to an esterification reactor to carry out esterification reaction under the conditions of a certain pressure, a certain reaction temperature and the like; continuously delivering an obtained esterification reaction mixture to a flash evaporator for flash evaporation; separating out unreacted alcohol and generated water from the upper part of the flash evaporator; discharging the product ester and unreacted raw material acid from the lower part of the flash evaporator; and then rectifying to obtain the C1-C2 alcohol ester of the C4-C6 diacid. The invention has the characteristics of low energy consumption and continuous esterification production, and aims to solve the problems existing in the aspects of long time, high energy consumption and the like in the esterification reaction for traditionally producing the C1-C2 low-carbon alcohol ester.
Description
One, technical field
The invention belongs to chemical field, particularly relate to a kind of production C
4～C
6The C of diprotic acid
1～C
2The production method of ester of low-carbon alcohol and equipment.
Two, background technology
C
4～C
6The diprotic acid ester of low-carbon alcohol comprises: the mixed dibasic acid (nylon acid) by Succinic Acid or pentanedioic acid or hexanodioic acid or Succinic Acid, pentanedioic acid and hexanodioic acid are formed, carry out the synthetic corresponding diprotic acid ester of low-carbon alcohol of esterification with methyl alcohol or ethanol respectively.Wherein, the dibasic acid dimethyl ester of being produced by nylon acid abbreviates DBE as, and this type of dibasic acid dimethyl ester is extensively as solvent, clean-out system etc.This type of dibasic acid dimethyl ester (DBE) has five big characteristics as solvent: the first, and colourless, light perfume (or spice), low toxicity, low cost, environmental protection; The second, the normal temperature volatilization is slow, and volatilization is fast down for high temperature, is specially adapted to the coatings industry solvent; The 3rd, the solubilized various kinds of resin, also can with most of immiscible organic solvents; The 4th, can improve levelling property, gloss, snappiness and the sticking power of coating, increase the pigment opacifying power, reduce pin hole and tangerine peel, eliminate white mist; The 5th, biodegradable, can burn the fuel value height neatly.Because C
4～C
6Dibasic acid dimethyl ester has These characteristics and is widely used, as is used for car paint, color steel sheet coating, can lacquer, enameled wire coating and appliance finishes high boiling solvent.Dimethyl adipate and Methyl glutarate by hexanodioic acid, pentanedioic acid production then are good cold-resistant plasticizers, can give goods good low-temperature pliability, also are simultaneously the intermediates of synthetic corresponding dibasic alcohol.Dimethyl succinate can be used for synthetic photostabilizer, high-grade paint, sterilant, medicine intermediate.And C
4～C
6The diprotic acid diethyl ester all is organic synthesis, medicine synthetic intermediate.
At present, China is producing C
4～C
6The processing method of dibasic acid dimethyl ester mainly contains three: a kind ofly be low pressure esterification process patent CN 1225919A representative, in dosing plant, under 0.3～1.0MPa pressure; A kind of be patent CN 1327975A representative, normal pressure esterification method in dosing plant; Article three, be CN 100537511CA proposes, the continuous esterification method in tower reactor.The advantage of first kind of working method is: can react under higher temperature (boiling point that is higher than used alcohols) when the esters product of synthetic lower boiling alcohols, thereby raising esterification reaction rate, shorten reaction time of esterification, but have long, defective such as process cost is higher, production cost is bigger than normal overhead time.The major advantage of second kind of working method is simple to operate, and esterification reaction rate is low, reaction time of esterification long, the methyl alcohol loss is bigger but exist, thereby makes production cost higher.The advantage of the third method is: in tower reactor, make Dimethyl Adipate Catalyzed realize operate continuously by pre-esterification, esterification under the solid acid catalysis.
In sum, adopt the production technique of patent CN 1225919A or CN 1327975A representative, be periodical operation, have that equipment efficiency of usage is lower, non-productive operation expense height, throughput are low, be unfavorable for automatic production.The operate continuously that patent CN 1005375 11CA adopt then the operant response time long, only pre-esterification reactor just needs 4h, also need carry out continuous esterification more then, simultaneously need be in the continuous esterification tower loading catalyst, the periodic replacement catalyzer, the catalyst system therefor amount is bigger.
Three, summary of the invention:
Goal of the invention: the invention provides a kind of C
4～C
6The production method of diprotic acid ester of low-carbon alcohol and equipment, it has the characteristics of less energy-consumption, continuous esterification production, and its purpose is to overcome traditional mode of production C
1～C
2The problem that aspects such as lifetime length, energy consumption height exist in the esterification of ester of low-carbon alcohol.
Technical scheme: the present invention is achieved through the following technical solutions:
A kind of C
4～C
6The production method of diprotic acid ester of low-carbon alcohol is characterized in that:
This method may further comprise the steps:
(1) in the batching still, adds esterifying catalyst, C
4～C
6Diprotic acid and C
1～C
2Alcohol; Under normal pressure, agitation condition, heating makes solid binary acid dissolving, and catalyst levels is 0.5%～2% of a diprotic acid quality, C
1～C
2Alcohol and C
4～C
6The mol ratio of diprotic acid is 2～6: 1;
(2) after batching finishes, the feed liquid of step (1) is sent in the basin, sent in the esterifier continuously through volume pump from the feed liquid in the basin and react, pressure is 0.8～1.5MPa, temperature of reaction is 120 ℃～140 ℃, and the esterification residence time is 10min～40min; Reaction mass enters the flasher flash distillation from esterifier, system pressure 0.05～0.1MPa, and 100 ℃～130 ℃ of temperature, the water of unreacted pure and mild generation is discharged from flasher top, through after the condenser condenses, enters pure recovery system; Product ester, unreacted raw material acid are discharged from the flasher bottom, enter product diester separation system, and the unreacting material acid of telling is back to continuously in the batching still and recycles;
(3) aqueous alcohol that step (2) is obtained under the normal pressure by separate to purify qualified after, be transported to the raw alcohol basin and recycle; The reaction mass that obtains can obtain purity by the method for rectification under vacuum and reach diprotic acid ester of low-carbon alcohol more than 99%, and the rectifying residuum is unreacted raw material acid or monoesters, is delivered to the batching still and continues batching and carry out esterification.
The C of step (1)
4～C
6Diprotic acid is the mixture of one of Succinic Acid, pentanedioic acid, hexanodioic acid or their arbitrary proportions; The C of step (1)
1～C
2Alcohols is methyl alcohol or ethanol; The used catalyzer of esterification of step (1) is a p-methyl benzenesulfonic acid.
The batching condition of step (1) is: normal pressure, stirring, Heating temperature are 40 ℃～80 ℃.
A kind of aforesaid production C
4～C
6The equipment that the diprotic acid ester of low-carbon alcohol is used is characterized in that: the batching still that agitator is installed is connected with the feed liquid basin by pipeline, and the feed liquid basin is connected with the continuous esterification device by pipeline; The continuous esterification device is connected with flasher by valve; The flasher outlet at bottom is connected with product diprotic acid ester of low-carbon alcohol recovery system by pipeline; The flasher top exit is connected with condenser by pipeline, and condenser is connected with pure recovery system by pipeline.
Described continuous esterification device is the horizontal tubular reactor device, and length-to-diameter ratio is (10～15) * 10
3: 1.
Described flasher is vertical, and aspect ratio is 5～10: 1.
Advantage and effect:, can solve existing C well by the enforcement of technical solution of the present invention
4～C
6The problem that reaction time of esterification is long, energy consumption is high, catalyst levels is big that exists in dibasic acid dimethyl ester and the diethyl ester production process.Major advantage of the present invention and effect have:
(1) reaction time of esterification is short, cuts down the consumption of energy and manufacturing cost;
(2) catalyst levels is low, reduces three waste discharge;
(3) under identical diester output, the low-carbon alcohol consumption reduces nearly 10%.
The present invention is with C
4～C
6Diprotic acid and C
1～C
2Monohydroxy-alcohol is a raw material, produces C through processes such as batching, continuous esterification, flash distillation, separation
4～C
6Diprotic acid two C
1～C
2A kind of method of alcohol ester.Present method not only has advantages such as technical process is short, catalyst levels is few, the reaction times is short, and C
1～C
2Low, the C of alcohol consumption
4～C
6Diprotic acid two C
1～C
2The alcohol ester total recovery reaches 95%, and in the production chemical product, has reduced the sewage discharge in the process, has reduced environmental pollution.
Four, description of drawings:
Fig. 1 C of the present invention
4～C
6Diprotic acid and C
1～C
2Monohydroxy-alcohol continuous esterification schematic flow sheet.
Five, embodiment:
The present invention is a kind of with C
4～C
6Diprotic acid and C
1～C
2Low-carbon alcohol is raw material production C
4～C
6The method of dibasic acid dimethyl ester or diethyl ester product, this method may further comprise the steps: (1) adds catalyzer, C in the batching still
4～C
6Diprotic acid and C
1～C
2Alcohol; Under normal pressure, agitation condition, heating makes solid binary acid dissolving, and temperature is 40 ℃～80 ℃, and catalyst levels is 0.5%～2% of a diprotic acid quality, C
1～C
2Alcohol is 2～6 with the mol ratio of diprotic acid; In the operating process, C
1～C
2Alcohol steam is got back in the batching still through condensation; (2) after batching finishes, the feed liquid of step (1) is sent in the basin, sent into esterifier from the feed liquid in the basin continuously through volume pump and react, pressure is 0.8～1.5MPa (gauge pressure), temperature of reaction is 120 ℃～140 ℃, and the esterification residence time is 10min～40min; Reaction mass enters flasher from esterifier, and the water of unreacted pure and mild generation is told from flasher top, through after the condenser condenses, enters pure recovery system; Product ester, unreacted raw material acid are discharged from the flasher bottom, enter product diprotic acid diester separation system, and the unreacting material acid of telling is back to the batching district continuously and recycles; (3) aqueous alcohol that step (2) is obtained under the normal pressure by separate to purify qualified after, be delivered to the raw alcohol basin and recycle; The reaction mass that obtains can obtain purity by the method for rectification under vacuum and reach diprotic acid diester more than 99%, and the rectifying residuum is unreacted raw material acid or monoesters, is delivered to the batching still and continues batching and carry out esterification.
Described C
4～C
6Diprotic acid is the mixture of one of Succinic Acid, pentanedioic acid, hexanodioic acid or their any two or three arbitrary proportions; Low-carbon alcohol is C
1～C
2Alcohol promptly is methyl alcohol and ethanol; The esterification catalyzer is a p-methyl benzenesulfonic acid.
Described batching condition is: normal pressure, stirring, temperature are 40 ℃～80 ℃.
Described esterification is operate continuously, C
1～C
2Alcohol and C
4～C
6The mol ratio of diprotic acid is 2～6, the esterifying catalyst consumption is 0.5%～2% of a diprotic acid quality, the esterification operational condition: pressure is 0.8～1.5MPa (gauge pressure), and temperature of reaction is 120 ℃～140 ℃, and the esterification mean residence time is 10min～40min.
Described flash conditions is: 100 ℃～130 ℃ of system pressure 0.05～0.1MPa, temperature.
The inventive method equipment used comprises batching still 1, volume pump 2, Heat-transfer Oil Pump 3, continuous esterification device 4, flasher 5, pure recovery system 6, feed liquid basin 7, diprotic acid ester of low-carbon alcohol recovery system 9, condenser 10 and formations such as pipeline and valve body; The batching still 1 that agitator is installed is connected with feed liquid basin 7 opening for feeds by pipeline, and feed liquid basin 7 discharge ports are connected with continuous esterification device 4 charging volume pumps 2 by pipeline; Continuous esterification device 4 discharge ports are connected with flasher 5 inlets by valve; Flasher 5 outlet at bottoms are connected with diprotic acid ester of low-carbon alcohol recovery system 9 by pipeline; Flasher 5 top exits are connected by the inlet mouth of pipeline with condenser 10, and the outlet of condenser 10 is connected with a basin by pipeline, and tank top is installed blow-off valve, and basin is connected with pure recovery system 6.
Wherein, the continuous esterification device is the horizontal tubular reactor device, and length-to-diameter ratio is (10～15) * 10
3Flasher is vertical, and aspect ratio is 5～10.
Below by example the present invention is carried out more detailed description.
Example 1:
Raw materials used is nylon acid and methyl alcohol, and acid/alcohol=1: 3 (mol/mol), catalyst levels are 1% of nylon acid quality.
In batching still 1, add esterifying catalyst tosic acid, nylon acid and methyl alcohol successively, reinforced finishing opened to stir also and is warming up to 60 ℃, treats that material all after the dissolving, goes into feed liquid basin 7 by tubes rows.Liquid material is sent into continuous esterification device 4 by charging volume pump 2 in the feed liquid basin 7.The operation of control continuous esterification, pressure is 1.0MPa (gauge pressure), and temperature of reaction is 130 ℃, and the esterification residence time is 15min, continuous esterification with this understanding.After continuous esterification device 4 reaches the aforesaid operations condition, slowly open the discharge port valve, make reaction mass enter flasher 5 flash distillations continuously.Flasher 5 system pressures are 120 ℃ of 0.08MPa, temperature.The water of unreacted pure and mild generation is told from flasher 5 tops, after condenser 10 condensations, enters pure recovery system 6 and reclaims the methanol loop use; Product ester, unreacted raw material acid are discharged from flasher 5 bottoms, enter product diprotic acid ester of low-carbon alcohol recovery system 9, and the unreacting material acid of telling is back to the batching district continuously and recycles.Experimental result sees Table 1.
Example 2:
Raw materials used is nylon acid and ethanol, and acid/alcohol=1: 4 (mol/mol), esterifying catalyst consumption are 1.5% of nylon acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 75 ℃ by the technological process of nylon acid and ethanol synthetic nylon diethyl phthalate; (2) control continuous esterification working pressure is 1.2MPa (gauge pressure), and temperature of reaction is 130 ℃, and the esterification residence time is 20min; (3) the flasher system pressure is 120 ℃ of 0.07MPa, temperature.Experimental result sees Table 1.
Example 3:
Raw materials used is Succinic Acid and methyl alcohol, and acid/alcohol=1: 3 (mol/mol), esterifying catalyst consumption are 1% of Succinic Acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 65 ℃ by the technological process of Succinic Acid and methyl alcohol synthesis of dimethyl succinate; (2) control continuous esterification working pressure is 0.9MPa (gauge pressure), and temperature of reaction is 120 ℃, and the esterification residence time is 10min; (3) the flasher system pressure is 120 ℃ of 0.09MPa, temperature.Experimental result sees Table 1.
Example 4:
Raw materials used is Succinic Acid and ethanol, and acid/alcohol=1: 4 (mol/mol), esterifying catalyst consumption are 1.5% of Succinic Acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 75 ℃ by the technological process of Succinic Acid and ethanol synthesizing succinic acid diethyl ester; (2) control continuous esterification working pressure is 0.9MPa (gauge pressure), and temperature of reaction is 100 ℃, and the esterification residence time is 10min; (3) the flasher system pressure is 130 ℃ of 0.07MPa, temperature.Experimental result sees Table 1.
Example 5:
Raw materials used is pentanedioic acid and methyl alcohol, and acid/alcohol=1: 3 (mol/mol), esterifying catalyst consumption are 1% of pentanedioic acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 65 ℃ by the technological process of pentanedioic acid and methyl alcohol synthesizing glutaric acid dimethyl ester; (2) control continuous esterification working pressure is 0.9MPa, and temperature of reaction is 120 ℃, and the esterification residence time is 10min; (3) the flasher system pressure is 120 ℃ of 0.09MPa, temperature.Experimental result sees Table 1.
Example 6:
Raw materials used is pentanedioic acid and ethanol, and acid/alcohol=1: 4 (mol/mol), esterifying catalyst consumption are 1.5% of pentanedioic acid quality.
With embodiment 1, difference is as follows: (1) is 75 ℃ in batch temperature by the technological process of pentanedioic acid and ethanol synthesizing glutaric acid diethyl ester; (2) control continuous esterification working pressure is 1.0MPa, and temperature of reaction is 130 ℃, and the esterification residence time is 25min; (3) the flasher system pressure is 120 ℃ of 0.06MPa, temperature.Experimental result sees Table 1.
Example 7:
Raw materials used is hexanodioic acid and methyl alcohol, and acid/alcohol=1: 3 (mol/mol), esterifying catalyst consumption are 1% of hexanodioic acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 65 ℃ by the technological process of hexanodioic acid and methyl alcohol Dimethyl Adipate Catalyzed; (2) control continuous esterification working pressure is 0.9MPa, and temperature of reaction is 125 ℃, and the esterification residence time is 20min; (3) the flasher system pressure is 120 ℃ of 0.09MPa, temperature.Experimental result sees Table 1.
Example 8:
Raw materials used is hexanodioic acid and ethanol, and acid/alcohol=1: 4 (mol/mol), esterifying catalyst consumption are 1.5% of hexanodioic acid quality.
With embodiment 1, difference is as follows: (1) batch temperature is 80 ℃ by the technological process of hexanodioic acid and ethanol Synthesis of diethyl adipate; (2) control continuous esterification working pressure is 1.2MPa, and temperature of reaction is 120 ℃, and the esterification residence time is 25min; (3) the flasher system pressure is 120 ℃ of 0.07MPa, temperature.Experimental result sees Table 1.
Table 1 C
4～C
6Diprotic acid and C
1～C
2Monohydroxy-alcohol continuous esterification experimental result
| The experiment number | Yield (%) | Ester content (%) | Acid number (mgKOH/g) |
| ?1 | ?94 | ?98.9 | ?0.28 |
| ?2 | ?92 | ?98.8 | ?0.29 |
| ?3 | ?96 | ?99.2 | ?0.23 |
| ?4 | ?95 | ?99.3 | ?0.23 |
| ?5 | ?96 | ?99.3 | ?0.25 |
| ?6 | ?96 | ?99.4 | ?0.24 |
| ?7 | ?95 | ?99.2 | ?0.25 |
| ?8 | ?95 | ?99.2 | ?0.24 |
The above-mentioned C that obtains
4～C
6Dibasic acid dimethyl ester or diethyl ester product, its product ester content＞99% (weight), product acid number≤0.3mgKOH/g.
Claims (6)
1. C
4～C
6The production method of diprotic acid ester of low-carbon alcohol is characterized in that:
This method may further comprise the steps:
(1) in the batching still, adds esterifying catalyst, C
4～C
6Diprotic acid and C
1～C
2Alcohol; Under normal pressure, agitation condition, heating makes solid binary acid dissolving, and the esterifying catalyst consumption is 0.5%～2% of a diprotic acid quality, C
1～C
2Alcohol and C
4～C
6The mol ratio of diprotic acid is 2～6: 1;
(2) after batching finishes, the feed liquid of step (1) is sent in the basin, sent in the esterifier continuously through volume pump from the feed liquid in the basin and react, pressure is 0.8～1.5MPa, temperature of reaction is 120 ℃～140 ℃, and the esterification residence time is 10min～40min; Reaction mass enters the flasher flash distillation from esterifier, system pressure 0.05～0.1MPa, and 100 ℃～130 ℃ of temperature, the water of unreacted pure and mild generation is discharged from flasher top, through after the condenser condenses, enters pure recovery system; Product ester, unreacted raw material acid are discharged from the flasher bottom, enter product diester separation system, and the unreacting material acid of telling is back to continuously in the batching still and recycles;
(3) aqueous alcohol that step (2) is obtained under the normal pressure by separate to purify qualified after, be transported to the raw alcohol basin and recycle; The reaction mass that obtains can obtain purity by the method for rectification under vacuum and reach diprotic acid ester of low-carbon alcohol more than 99%, and the rectifying residuum is unreacted raw material acid or monoesters, is delivered to the batching still and continues batching and carry out esterification.
2. a kind of C according to claim 1
4～C
6The production method of diprotic acid ester of low-carbon alcohol is characterized in that: the C of step (1)
4～C
6Diprotic acid is the mixture of one of Succinic Acid, pentanedioic acid, hexanodioic acid or their arbitrary proportions; The C of step (1)
1～C
2Alcohols is methyl alcohol or ethanol; The used catalyzer of esterification of step (1) is a p-methyl benzenesulfonic acid.
3. according to the described a kind of C of claim 1
4～C
6Diprotic acid ester of low-carbon alcohol production method is characterized in that: the batching condition of step (1) is: normal pressure, stirring, Heating temperature are 40 ℃～80 ℃.
4. production C as claimed in claim 1
4～C
6The equipment that the diprotic acid ester of low-carbon alcohol is used is characterized in that: the batching still (1) that agitator is installed is connected with feed liquid basin (7) by pipeline, and the feed liquid basin is connected with continuous esterification device (4) by pipeline; Continuous esterification device (4) is connected with flasher (5) by valve; Flasher (5) outlet at bottom is connected with product diprotic acid ester of low-carbon alcohol recovery system (9) by pipeline; Flasher (5) top exit is connected with condenser (10) by pipeline, and condenser (10) is connected with pure recovery system (6) by pipeline.
5. a kind of production C according to claim 4
4～C
6The equipment that the diprotic acid ester of low-carbon alcohol is used is characterized in that: described continuous esterification device is the horizontal tubular reactor device, and length-to-diameter ratio is (10～15) * 10
3: 1.
6. a kind of production C according to claim 4
4～C
6The equipment that the diprotic acid ester of low-carbon alcohol is used is characterized in that: described flasher is vertical, and aspect ratio is 5～10: 1.
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| CN102432460A (en) * | 2011-10-12 | 2012-05-02 | 潍坊市元利化工有限公司 | Method for purifying diacid dimethyl esters by plate distillation separation |
| CN102850542A (en) * | 2012-08-31 | 2013-01-02 | 上海焦耳蜡业有限公司 | Method of preparing synthetic wax by using recovered mixed dibasic acid |
| CN103012128A (en) * | 2012-12-27 | 2013-04-03 | 浙江建业化工股份有限公司 | Method for producing cold-resistant plasticizer through industrial byproduct nylon acid |
| CN103539665A (en) * | 2012-07-10 | 2014-01-29 | 中国科学院大连化学物理研究所 | Succinic acid diester preparation method |
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| CN103539665A (en) * | 2012-07-10 | 2014-01-29 | 中国科学院大连化学物理研究所 | Succinic acid diester preparation method |
| CN103539665B (en) * | 2012-07-10 | 2016-05-25 | 中国科学院大连化学物理研究所 | A kind of method of preparing succinate |
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| US10047035B2 (en) | 2013-05-08 | 2018-08-14 | Basf Se | Process for continuously preparing di-C1-3-alkyl succinates |
| US9738588B2 (en) | 2013-05-08 | 2017-08-22 | Basf Se | Process for continuously preparing di-C1-3-alkyl succinates |
| CN106674008A (en) * | 2016-12-27 | 2017-05-17 | 南京科技职业学院 | Method for preparing tributyl citrate by using tubular reactor |
| CN106674008B (en) * | 2016-12-27 | 2019-04-23 | 南京科技职业学院 | A kind of tubular reactor preparation tributyl citrate method |
| CN110292894A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate |
| CN110698342A (en) * | 2019-10-29 | 2020-01-17 | 虎皇新材料科技集团有限公司 | High-boiling-point solvent and preparation method thereof |
| CN115443263A (en) * | 2020-04-22 | 2022-12-06 | 帝斯曼知识产权资产管理有限公司 | Process for acylating alpha, omega-alkanediols |
| CN113845426A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Method and device for preparing ester compound |
| CN113845426B (en) * | 2020-06-28 | 2024-01-26 | 中国石油化工股份有限公司 | Method and device for preparing ester compound |
| CN112299993A (en) * | 2020-10-30 | 2021-02-02 | 河北金谷再生资源开发有限公司 | Device and method for producing tributyrin |
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