CN105646226A - Plasticizer tributyl citrate production process - Google Patents
Plasticizer tributyl citrate production process Download PDFInfo
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- CN105646226A CN105646226A CN201410635560.4A CN201410635560A CN105646226A CN 105646226 A CN105646226 A CN 105646226A CN 201410635560 A CN201410635560 A CN 201410635560A CN 105646226 A CN105646226 A CN 105646226A
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Abstract
The present invention discloses a plasticizer tributyl citrate production process, which comprises: (1) mixing citric acid monohydrate and n-butanol, adding p-toluenesulfonic acid and active carbon, introducing nitrogen gas, and carrying out an esterification reaction to obtain an esterified product; (2) carrying out dealcoholization on the esterified product to achieve a flash point of more than or equal to 162 DEG C; (3) dissolving and recovering the p-toluenesulfonic acid in the esterified product after the dealcoholization with water, and adding the separated water phase to the next batch production step (1) so as to be applied; (4) adding an alkali liquid to the oil phase, neutralizing, removing the water phase, and carrying out water washing on the oil phase to achieve a neutral state; (5) adding active carbon to the esterified product being subjected to the water washing, and carrying out dealcoholization again to achieve a flash point of more than or equal to 180 DEG C so as to obtain a crude ester; and (6) filtering the crude ester to obtain the industrial product tributyl citrate. According to the present invention, the conversion rate of the esterification reaction is up to 99.0%, the tributyl citrate yield can achieve more than or equal to 98%, and the unit consumption and the cost are reduced; and the catalyst has the good p-toluenesulfonic acid catalysis effect, the recovery rate after the completion of the esterification achieves more than or equal to 75%, the catalyst can be reused, the sewage emission can be reduced, and the COD and the BOD in the wastewater can be reduced.
Description
Technical field
The invention belongs to technical field of chemical synthesis, it is specifically related to the production technique of a kind of plasticizer tirbutyl citrate.
Background technology
The production technique of plasticizer tirbutyl citrate at least comprises filtration, stirs, takes out the primary processes such as filter, washing. In current plasticizer tirbutyl citrate building-up process method, technical process is not easy to implement, and the tributyl citrate finished product purity of generation is low, reactant per pass conversion is low, production process is complicated, and production efficiency is low and cost height, is not suitable for scale operation.
Summary of the invention
In order to overcome the above-mentioned technical problem that prior art exists, it is an object of the invention to, the production technique of a kind of plasticizer tirbutyl citrate is provided, the present invention not only production process simple, increase work efficiency, and the plasticizer tirbutyl citrate product purity generated is big, it is applicable to suitability for industrialized production.
The production technique of plasticizer tirbutyl citrate provided by the invention, comprises the following steps:
(1) Citric acid monohydrate Food grade and propyl carbinol being mixed, then add tosic acid and gac, lead to nitrogen and control to react under temperature 155 ~ 175 DEG C, still pressure��0.025Mpa, acid number��2.5mgKOH/g is esterification terminal, obtains carboxylate; Mol ratio 1:3.5 ~ 6.5 of described Citric acid monohydrate Food grade and propyl carbinol, described tosic acid weight is the 1.7 ~ 3.0% of Citric acid monohydrate Food grade weight;
(2) by carboxylate dealcoholysis first to flash-point >=162 DEG C;
(3) tosic acid reclaimed after dealcoholysis in carboxylate by the water dissolution of catalyst weight 1.6 ~ 2.0 times, the aqueous phase isolated adds recycled in the production stage (1) of next batch;
(4) adding alkali lye in oil phase and neutralize PH=7.0 ~ 7.5, remove aqueous phase, oil phase carries out being washed to neutrality;
(5) carboxylate after washing is added gac and dealcoholysis is to flash-point >=180 DEG C again, obtain thick ester;
(6) thick ester obtains industrial goods tributyl citrate after filtration.
The production technique of plasticizer tirbutyl citrate provided by the invention, its useful effect is, overcoming prior art, to prepare operation in plasticizer tirbutyl citrate technological process more, the problem that workload is big, it is to increase working efficiency; Improve the per pass conversion of reactant and the product rate of resultant.
Embodiment
Below in conjunction with an embodiment, the production technique of plasticizer tirbutyl citrate provided by the invention is described in detail.
Embodiment
The production technique of the plasticizer tirbutyl citrate of the present embodiment, comprises the following steps:
(1) Citric acid monohydrate Food grade and propyl carbinol being mixed, then add tosic acid and gac, lead to nitrogen and control to react under temperature 175 DEG C, still pressure=0.025Mpa, acid number=2.5mgKOH/g is esterification terminal, obtains carboxylate; The mol ratio 1:6.5 of described Citric acid monohydrate Food grade and propyl carbinol, described tosic acid weight is the 1.7% of Citric acid monohydrate Food grade weight;
(2) by carboxylate dealcoholysis first to flash-point=162 DEG C;
(3) tosic acid reclaimed after dealcoholysis in carboxylate by the water dissolution of catalyst weight 2.0 times, the aqueous phase isolated adds recycled in the production stage (1) of next batch;
(4) adding alkali lye in oil phase and neutralize PH=7.5, remove aqueous phase, oil phase carries out being washed to neutrality;
(5) carboxylate after washing is added gac and dealcoholysis is to flash-point=180 DEG C again, obtain thick ester;
(6) thick ester obtains industrial goods tributyl citrate after filtration.
The production technique of plasticizer tirbutyl citrate, it is not necessary to loaded down with trivial details post-reaction treatment, substantially increases product performance, and environmentally friendly pollution-free, and technical process is easy to implement, and production cost is low, synthesis output height, it is achieved that the suitability for industrialized production of product.
Claims (1)
1. the production technique of a plasticizer tirbutyl citrate, it is characterised in that: described method comprises the following steps:
(1) Citric acid monohydrate Food grade and propyl carbinol being mixed, then add tosic acid and gac, lead to nitrogen and control to react under temperature 155 ~ 175 DEG C, still pressure��0.025Mpa, acid number��2.5mgKOH/g is esterification terminal, obtains carboxylate; Mol ratio 1:3.5 ~ 6.5 of described Citric acid monohydrate Food grade and propyl carbinol, described tosic acid weight is the 1.7 ~ 3.0% of Citric acid monohydrate Food grade weight;
(2) by carboxylate dealcoholysis first to flash-point >=162 DEG C;
(3) tosic acid reclaimed after dealcoholysis in carboxylate by the water dissolution of catalyst weight 1.6 ~ 2.0 times, the aqueous phase isolated adds recycled in the production stage (1) of next batch;
(4) adding alkali lye in oil phase and neutralize PH=7.0 ~ 7.5, remove aqueous phase, oil phase carries out being washed to neutrality;
(5) carboxylate after washing is added gac and dealcoholysis is to flash-point >=180 DEG C again, obtain thick ester;
(6) thick ester obtains industrial goods tributyl citrate after filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410635560.4A CN105646226A (en) | 2014-11-13 | 2014-11-13 | Plasticizer tributyl citrate production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410635560.4A CN105646226A (en) | 2014-11-13 | 2014-11-13 | Plasticizer tributyl citrate production process |
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| Publication Number | Publication Date |
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| CN105646226A true CN105646226A (en) | 2016-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410635560.4A Pending CN105646226A (en) | 2014-11-13 | 2014-11-13 | Plasticizer tributyl citrate production process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928054A (en) * | 2016-12-20 | 2017-07-07 | 江苏常州酞青新材料科技有限公司 | A kind of synthesis technique of tributyl citrate plasticizer |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108997114A (en) * | 2018-08-06 | 2018-12-14 | 河北驭驰橡塑科技有限公司 | A kind of production technology of tributyl trimellitate |
| CN111499507A (en) * | 2020-05-25 | 2020-08-07 | 东营市金凤凰化工股份有限公司 | Production process of diethylene glycol monobutyl ether adipate |
| CN112209824A (en) * | 2020-10-20 | 2021-01-12 | 山东朗晖石油化学股份有限公司 | Production method of citric acid mixed ester |
| CN112724016A (en) * | 2020-12-31 | 2021-04-30 | 潍坊加易加生物科技有限公司 | Method for recycling esterification catalyst stannous oxide |
-
2014
- 2014-11-13 CN CN201410635560.4A patent/CN105646226A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928054A (en) * | 2016-12-20 | 2017-07-07 | 江苏常州酞青新材料科技有限公司 | A kind of synthesis technique of tributyl citrate plasticizer |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108892613B (en) * | 2018-07-11 | 2021-02-19 | 广东轻工职业技术学院 | Method for synthesizing tri-n-butyl citrate by using acid modified H-ZMS-5 type molecular sieve |
| CN108997114A (en) * | 2018-08-06 | 2018-12-14 | 河北驭驰橡塑科技有限公司 | A kind of production technology of tributyl trimellitate |
| CN111499507A (en) * | 2020-05-25 | 2020-08-07 | 东营市金凤凰化工股份有限公司 | Production process of diethylene glycol monobutyl ether adipate |
| CN112209824A (en) * | 2020-10-20 | 2021-01-12 | 山东朗晖石油化学股份有限公司 | Production method of citric acid mixed ester |
| CN112724016A (en) * | 2020-12-31 | 2021-04-30 | 潍坊加易加生物科技有限公司 | Method for recycling esterification catalyst stannous oxide |
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Application publication date: 20160608 |