CN101891610A - Continuous esterification production method for mixed dibasic acid dimethyl ester - Google Patents
Continuous esterification production method for mixed dibasic acid dimethyl ester Download PDFInfo
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Abstract
The invention discloses a continuous esterification production method for mixed dibasic acid dimethyl ester. The method comprises the following steps of: (1) pre-esterifying, namely, mixing dibasic acid and methanol in a mole ratio of 1:2-3 and performing pre-esterification at the normal temperature and normal pressure to obtain a pre-esterified material; (2) pre-heating the methanol, namely, pressurizing and pre-heating the methanol to form overheated methanol gas with the temperature of between 145 and 155 DEG C; and (3) continuously esterifying, namely, adding the pre-esterified material into a continuous esterification reactor, of which the middle part is provided with a catalyst reaction bed, from the top, adding the overheated methanol gas into the continuous esterification reactor from the bottom, performing a reverse flow reaction on the ascending methanol gas and the descending pre-esterified material on the catalyst reaction bed, and continuously discharging the mixed dibasic acid dimethyl ester which is generated by the esterification from the bottom of the esterification reactor.
Description
Technical field
The present invention relates to the esterification synthesis technical field, relate in particular to a kind of continuous esterification production method of mixed dibasic acid dimethyl ester.
Background technology
Mixed dibasic acid dimethyl ester (MDBE) is by a kind of high boiling solvent, is to be formed with methanol esterification by the byproduct di-carboxylic acid (mixed dibasic acid of C4, C5, C6) that the production hexanodioic acid brings.The MDBE solvent has the boiling point height, distillate evenly, the smell gentleness, low and the biodegradable characteristics of energy of toxicity, has superpower dissolving power, the title that menstruum universale is arranged, it and urethane resin, acrylic resin, vibrin, the consistency of Resins, epoxy is superior, can extensively replace ketone (as pimelinketone, isophorone etc.), ethers is (as ethylene glycol monobutyl ether, propylene glycol monomethyl ether etc.), the ester class is (as ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate etc.) wait each kind solvent, be widely used in coil coating, coatings for tin plate printing, car paint, wood lacquer, printing ink, the synthetic industry of jet ink and resin etc.
The production technique that high boiling solvent MDBE is traditional is to adopt sulfuric acid to make catalyzer, adopt the intermittent type esterification process, in the presence of catalyzer, mixed dibasic acid and methyl alcohol are in reaction kettle of the esterification internal heating back flow reaction, esterification finishes, make finished product through neutralization, washing, distillation, unreacted methanol reclaims rectification and purification.
But traditional batch production technology has following shortcoming:
1, intermittently esterification energy consumption height, product yield is low, quality is unstable, foreign matter content in the product of different batches and acid number instability;
2, intermittent esterification reaction is not thorough, and product yield is low;
3, nitration mixture causes generating a large amount of high molecular polymers at the esterifying kettle overstand, causes product yield to reduce, and occluding device cleans frequently, has increased cost of labor;
4, the high molecular polymer of reaction generation can't be handled, and causes serious pollution problem;
5, methyl alcohol runs off manyly in reaction process, consumes high;
6, batch production yields poorly, and is unfavorable for large-scale production.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiency that prior art exists, provide that a kind of product purity height, steady quality, production energy consumption are low, the continuous esterification production method of the simple mixed dibasic acid dimethyl ester of technological operation.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of continuous esterification production method of mixed dibasic acid dimethyl ester may further comprise the steps:
(1) pre-esterification: mixed dibasic acid and methyl alcohol with 1: 2～3 mixed in molar ratio, are carried out pre-esterification at normal temperatures and pressures, obtain pre-esterification material;
(2) methyl alcohol preheating: methyl alcohol is preheated to 145～155 ℃ overheated methanol gas through pressurization;
(3) continuous esterification: in the middle part is provided with the continuous esterification device of catalyst reaction bed, described pre-esterification material enters from the top of continuous esterification device, described overheated methanol gas enters from the bottom of continuous esterification device, the methanol gas that rises and the pre-esterification material of whereabouts carry out countercurrent reaction on the catalyst reaction bed, the mixed dibasic acid dimethyl ester that esterification generates is discharged continuously from the bottom of described esterifier.
Wherein, described catalyzer is iron trichloride or sodium pyrosulfate, and the add-on of described catalyzer is 5～15wt% of mixed dibasic acid.
Described mixed dibasic acid is the mixed dibasic acid of C4, C5, C6.
140～150 ℃ of the bottom temps of described continuous esterification device, 70～81 ℃ of head temperature.
As a kind of improvement, methyl alcohol is preheating to 130～140 ℃ through pressurization, be heated to 145～155 ℃ overheated methanol gas again through superheated vapour.
As further improvement, after described overheated methanol gas was carried out the adverse current esterification, unreacted methanol gas was discharged from the top of continuous esterification device, and circulation participates in reaction after purifying.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention adopts continuous esterification production method, and pre-esterification material enters from the top of continuous esterification device, overheated methanol gas enters from the bottom of continuous esterification device, on the catalyst reaction bed, carry out countercurrent reaction, so two kinds of material full contacts, esterification is complete, the feed stock conversion height, the product purity height, and shortened the reaction times, improved production efficiency.
2, the present invention is in the continuous esterification process, unreacted methanol gas is constantly discharged from the top of continuous esterification device and is recycled, the running balance that keeps methyl alcohol in the reaction vessel, and methyl alcohol is constantly taken away the water that esterification generates, help reaction and carry out, improved reaction conversion ratio to the positive reaction direction.
3, the present invention adopts the continuous esterification method to produce because technology continuously and operate steadily, the steady quality homogeneous of product, can not occur interrupter method produce in product foreign matter content and the inconsistent problem of acid number between different batches.
4, methanol gas dynamic flow among the present invention constantly reclaims and purifies, and has improved the utilization ratio of methyl alcohol, the utilization ratio of comparing methyl alcohol with traditional interrupter method improves more than 50%, and the loss of methyl alcohol is few, does not need to be equipped with the methanol rectification recovery system, has reduced facility investment.
5, adopt continuous esterification after because reaction time of esterification shortens, reduced reaction heat-up time, greatly reduce energy consumption and production cost.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
Mixed dibasic acid that employing is obtained from the mother liquor of hexanodioic acid (containing Succinic Acid 20wt%, pentanedioic acid 50wt%, hexanodioic acid 29wt%, impurity 1wt%) and methyl alcohol are raw material, mixed dibasic acid is mixed in pre-esterifying kettle with 1: 2 mol ratio with methyl alcohol, carry out pre-esterification at normal temperatures and pressures, obtain pre-esterification material.
Methyl alcohol is preheating to 135 ℃ with the pressurization of pressurization preheater, is heated to be 150 ℃ overheated methanol gas again with steam heater through superheated vapour.
In the middle part is provided with the continuous esterification tower of fixed-bed reactor of catalyzer iron trichloride, the add-on of described catalyzer iron trichloride is the 10wt% of mixed dibasic acid, pre-esterification material is sent into from the top of continuous esterification tower with magnetic force driving pump, pre-esterification material is loaded with the fixed-bed reactor of iron trichloride from the top process under action of gravity, flow to the continuous esterification tower bottom step by step; The bottom of overheated methanol gas from the continuous esterification tower fed, the methanol gas that rises fully contacts on the catalyst reaction bed with the pre-esterification material of whereabouts carries out countercurrent reaction, 146 ℃ of the bottom temps of continuous esterification tower, 76 ℃ of head temperature, it is up step by step that the methyl alcohol band the water that reacts generation, the contact feed liquid is progressively carried out esterification, the water that reaction generates is in time taken away to the continuous esterification top of tower, the water that excessive methanol and reaction generate recycles after purifying from the top extraction, when the acid number of reaction mass is 10mgKOH/g, esterification finishes, and the mixed dibasic acid dimethyl ester that reacts completely is discharged from tower bottom.
Embodiment 2
Mixed dibasic acid that employing is obtained from the mother liquor of hexanodioic acid (containing Succinic Acid 25%, pentanedioic acid 53%, hexanodioic acid 20%, impurity 2%) and methyl alcohol are raw material, mixed dibasic acid is mixed in pre-esterifying kettle with 1: 2.2 mol ratio with methyl alcohol, carry out pre-esterification at normal temperatures and pressures, obtain pre-esterification material.
Methyl alcohol is preheating to 137 ℃ with the pressurization of pressurization preheater, is heated to be 152 ℃ overheated methanol gas again with steam heater through superheated vapour.
In the middle part is provided with the continuous esterification tower of fixed-bed reactor of catalyst sulfuric acid hydrogen sodium, the add-on of described catalyst sulfuric acid hydrogen sodium is the 8wt% of mixed dibasic acid, pre-esterification material is sent into from the top of continuous esterification tower with magnetic force driving pump, pre-esterification material is loaded with the fixed-bed reactor of sodium pyrosulfate from the top process under action of gravity, flow to the continuous esterification tower bottom step by step; The bottom of overheated methanol gas from the continuous esterification tower fed, the methanol gas that rises fully contacts on the catalyst reaction bed with the pre-esterification material of whereabouts carries out countercurrent reaction, 148 ℃ of the bottom temps of continuous esterification tower, 78 ℃ of head temperature, it is up step by step that the methyl alcohol band the water that reacts generation, the contact feed liquid is progressively carried out esterification, the water that reaction generates is in time taken away to the continuous esterification top of tower, the water that excessive methanol and reaction generate recycles after purifying from the top extraction, when the acid number of reaction mass is 11mgKOH/g, esterification finishes, and the mixed dibasic acid dimethyl ester that reacts completely is discharged from tower bottom.
Embodiment 3
Mixed dibasic acid that employing is obtained from the mother liquor of hexanodioic acid (containing Succinic Acid 15%, pentanedioic acid 38%, hexanodioic acid 45%, impurity 2%) and methyl alcohol are raw material, mixed dibasic acid is mixed in pre-esterifying kettle with 1: 2.5 mol ratio with methyl alcohol, carry out pre-esterification at normal temperatures and pressures, obtain pre-esterification material.
Methyl alcohol is preheating to 134 ℃ with the pressurization of pressurization preheater, is heated to be 148 ℃ overheated methanol gas again with steam heater through superheated vapour.
In the middle part is provided with the continuous esterification tower of fixed-bed reactor of catalyzer iron trichloride, the add-on of described catalyzer iron trichloride is the 12wt% of mixed dibasic acid, pre-esterification material is sent into from the top of continuous esterification tower with magnetic force driving pump, pre-esterification material is loaded with the fixed-bed reactor of iron trichloride from the top process under action of gravity, flow to the continuous esterification tower bottom step by step; The bottom of overheated methanol gas from the continuous esterification tower fed, the methanol gas that rises fully contacts on the catalyst reaction bed with the pre-esterification material of whereabouts carries out countercurrent reaction, 144 ℃ of the bottom temps of continuous esterification tower, 74 ℃ of head temperature, it is up step by step that the methyl alcohol band the water that reacts generation, the contact feed liquid is progressively carried out esterification, the water that reaction generates is in time taken away to the continuous esterification top of tower, the water that excessive methanol and reaction generate recycles after purifying from the top extraction, when the acid number of reaction mass is 13mgKOH/g, esterification finishes, and the mixed dibasic acid dimethyl ester that reacts completely is discharged from tower bottom.
Claims (6)
1. the continuous esterification production method of a mixed dibasic acid dimethyl ester is characterized in that may further comprise the steps:
(1) pre-esterification: mixed dibasic acid and methyl alcohol with 1: 2～3 mixed in molar ratio, are carried out pre-esterification at normal temperatures and pressures, obtain pre-esterification material;
(2) methyl alcohol preheating: methyl alcohol is preheated to 145～155 ℃ overheated methanol gas through pressurization;
(3) continuous esterification: in the middle part is provided with the continuous esterification device of catalyst reaction bed, described pre-esterification material enters from the top of continuous esterification device, described overheated methanol gas enters from the bottom of continuous esterification device, the methanol gas that rises and the pre-esterification material of whereabouts carry out countercurrent reaction on the catalyst reaction bed, the mixed dibasic acid dimethyl ester that esterification generates is discharged continuously from the bottom of described esterifier.
2. the continuous esterification production method of mixed dibasic acid dimethyl ester as claimed in claim 1, it is characterized in that: described catalyzer is iron trichloride or sodium pyrosulfate, the add-on of described catalyzer is 5～15wt% of mixed dibasic acid.
3. the continuous esterification production method of mixed dibasic acid dimethyl ester as claimed in claim 1, it is characterized in that: described mixed dibasic acid is the mixed dibasic acid of C4, C5, C6.
4. the continuous esterification production method of mixed dibasic acid dimethyl ester as claimed in claim 1 is characterized in that: 140～150 ℃ of the bottom temps of described continuous esterification device, 70～81 ℃ of head temperature.
5. the continuous esterification production method of mixed dibasic acid dimethyl ester as claimed in claim 1 is characterized in that: methyl alcohol is preheating to 130～140 ℃ through pressurization, is heated to 145～155 ℃ overheated methanol gas again through superheated vapour.
6. as the continuous esterification production method of claim 1,2,3,4 or 5 described mixed dibasic acid dimethyl esters, it is characterized in that: after described overheated methanol gas is carried out the adverse current esterification, unreacted methanol gas is discharged from the top of continuous esterification device, and circulation participates in reaction after purifying.
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Cited By (8)
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| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| 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 |
| CN103508888A (en) * | 2013-09-17 | 2014-01-15 | 北京石油化工学院 | Synthetic method of 2,2-dimethyl dimethylmalonate |
| CN106496031A (en) * | 2016-08-31 | 2017-03-15 | 内蒙古紫光化工有限责任公司 | A kind of method for improving dimethyl malenate yield |
| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN111138286A (en) * | 2018-11-01 | 2020-05-12 | 上海凯赛生物技术股份有限公司 | Method for treating mixture containing long-chain dibasic acid |
| CN111320543A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Method for producing dimethyl adipate from adipic acid |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| 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 |
| CN103508888A (en) * | 2013-09-17 | 2014-01-15 | 北京石油化工学院 | Synthetic method of 2,2-dimethyl dimethylmalonate |
| CN106496031A (en) * | 2016-08-31 | 2017-03-15 | 内蒙古紫光化工有限责任公司 | A kind of method for improving dimethyl malenate yield |
| CN106496031B (en) * | 2016-08-31 | 2019-03-22 | 内蒙古紫光化工有限责任公司 | A method of improving dimethyl malenate yield |
| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN111138286A (en) * | 2018-11-01 | 2020-05-12 | 上海凯赛生物技术股份有限公司 | Method for treating mixture containing long-chain dibasic acid |
| CN111320543A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Method for producing dimethyl adipate from adipic acid |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN112121817B (en) * | 2020-09-22 | 2022-04-26 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
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