CN104961637A - System and method for synthesis of tri-n-butyl citrate through continuous esterification - Google Patents
System and method for synthesis of tri-n-butyl citrate through continuous esterification Download PDFInfo
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- CN104961637A CN104961637A CN201510302549.0A CN201510302549A CN104961637A CN 104961637 A CN104961637 A CN 104961637A CN 201510302549 A CN201510302549 A CN 201510302549A CN 104961637 A CN104961637 A CN 104961637A
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention provides a method for synthesis of tri-n-butyl citrate (TBC) through continuous esterification. The method comprises the following steps: adding a mixture of citric acid, n-butanol and a catalyst into a reaction system at a uniform speed, wherein the reaction system is composed of a plurality of esterification reaction vessels in series connection, the mixture is added into a first esterification vessel, reaction temperature successively rises from 112-160 DEG C, and a semi-finished product containing butanol in a certain proportion is discharged from a last esterification vessel; allowing the semi-finished product to enter an evaporator to remove residual butanol so as to obtain crude ester liquid; and carrying out conventional post-treatment with a plasticizer so as to obtain a TBC finished product. According to the invention, the continuous esterification is more applicable to automatic operation and large-scale production; land occupation is small, and investment is low; reaction is thorough, and the utilization rate of the raw materials is high; safety production and stable product quality are guaranteed; and comprehensive utilization is realized, energy is saved, and discharge of waste water, waste gas and waste industrial residues is reduced.
Description
Technical field
The present invention relates to a kind of continuous production technology of tri-n-butyl citrate, produce tri-n-butyl citrate by the method for continuous esterification, belong to chemosynthesis field of engineering technology.
Background technology
ATBC (ATBC) and tri-n-butyl citrate (TBC) good because having with high molecular polymer consistency, advantages such as plasticizing efficiency is high, nontoxic, weather resisteant is strong, readily biodegradable and extensively concerned, become the genotoxicities such as alternative phthalate large, suspicious carcinogenic and not readily biodegradable and excellent substitute to the large petrochemical industry class softening agent of environmental influence, especially the application of toy for children, food product pack and medical material aspect is the most general.
The first step chemical reaction of synthesis ATBC is that citric acid and propyl carbinol reaction generate TBC.Traditional TBC production technique is generally synthesize through esterification under catalyst action with citric acid and positive butyl ester, adopts batch production process.The shortcoming of this technique is mainly:
1. table of equipment cover is many, and floor space is large, and floor area of building is also many, and by the restriction of chemical engineering design regulation, the output in single workshop is restricted, and is difficult to the single production equipment (workshop) realizing more than 2.5 ten thousand tons/year scales.
2. be difficult to realize Automated condtrol, the amount of labour used is large, and labor strength is large and Working environment is poor.
3. production link and reference mark many, rely on Artificial Control easily to produce misoperation, safety in production difficulty is large, and easily causes the waste of raw material and the energy, and the stability of quality product is difficult to ensure simultaneously.
4. investment is on the high side, and production cost is higher, the market competitiveness that reduces product.
Produce TBC based on interrupter method and there is many deficiencies and defect, the object of this invention is to provide the production technique of a set of serialization, overcome and solve interrupter method and produce Problems existing, and can realize building large-scale production line.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of production realizing serialization, overcome and solve interrupter method and produce Problems existing, and continuous esterification synthesizing citric acid tri-n-butyl system and the synthetic method thereof of building large-scale production line can be realized.
For realizing the object of the invention, provide following technical scheme: a kind of continuous esterification synthesizing citric acid tri-n-butyl system, it is characterized in that comprising dissolution kettle, esterifying kettle, dehydration tower, condenser, water-and-oil separator, dissolution kettle is set at least one, dissolution kettle connects 3 ~ 6 esterifying kettles be connected in series in turn, esterifying kettle all connects dehydration tower, the outlet of dehydration tower top connects condenser, condenser connects water-and-oil separator, water-and-oil separator connects the nearly upper end of dehydration tower, connects first esterifying kettle bottom dehydration tower.
As preferably, dissolution kettle is arranged side by side two.
As preferably, esterifying kettle is 4 or 5.
For realizing the object of the invention, providing a kind of synthetic method of continuous esterification synthesizing citric acid tri-n-butyl system, comprising the following steps:
A. citric acid, propyl carbinol and catalyzer mixed dissolution in mixed dissolution still, the mol ratio of citric acid and propyl carbinol is generally with 1: 4 ~ 7, and catalyzer adds in right amount by need of production;
B. at the uniform velocity add to first esterifying kettle the mixed solution that upper step configures, open steam heating simultaneously.Mixed solution progressively overflow enters the esterifying kettle of series connection in turn;
C. many esterifying kettles share an esterification dehydration tower, tower top is furnished with corresponding condenser and water-and-oil separator, the water that reaction generates and butanols azeotropic are discharged to tower top continuous continuous print after condensation by water-and-oil separator bottom, and upper strata butanols still passes back into the water that the continuous extractive reaction of tower top generates;
D. the butanol concentration of each still is regulated to control the temperature of reaction of each still in a rational interval, each still temperature raises successively, the transformation efficiency of citric acid also improves successively, from last still discharge acid content≤1%(with citrometer), butanol content 25 ~ 30% esterification work in-process;
The esterification work in-process of e. discharging obtain the thick finished product of TBC after continuous dealcoholysis, first esterifying kettle got back to by the alcohol deviate from or dissolution kettle uses, and thick finished product obtains TBC finished product through the process for refining (as neutralization, washing, drying, filtration etc.) that plasticizer production is conventional.
Described catalyzer comprises various conventional strongly acidic catalyst (as sulfuric acid, tosic acid etc.), non-acidic catalyst, many kinds of solids super acids etc., and comprising their compound or the catalyzer with gac solid-carrying type, its consumption needs appropriate interpolation by its catalytic activity and production technique.
As preferably, the mol ratio of citric acid and propyl carbinol is 1:4 ~ 4.5.
As preferably, in multiple esterifying kettles of described series connection, temperature of reaction promotes successively by 112 DEG C, is up to 160 DEG C.
As preferably, temperature of reaction is 118 DEG C ~ 155 DEG C.
Beneficial effect of the present invention: compared with interrupter method production technique, advantage of the present invention following (for 50,000 tons/year):
The production equipment of 1.5 ten thousand tons/year, this technique batching and esterification workshop section floor space are about 150m
2, floor area of building 270m
2, and interrupter method needs the auxiliary facility such as reaction kettle of the esterification 12 cover and corresponding 12 cover esterification dehydration towers, condenser, water-and-oil separator, floor space 450m
2, floor area of building 1200m
2.As added each follow-up workshop section and producing ATBC.The gross building area of continuous processing 50,000 tons/year of devices is at 1600m
2left and right, can be used as set of device (workshop) and builds.And interrupter method 50,000 tons/year of needs floor area of building are more than 4000m
2.Build fire safety rules according to chemical industry, two workshops will be divided into and build, and greatly increase land area and floor area of building.
2. in continuous processing, citric acid feed intake and filter station need workman's execute-in-place, add upper control and other staff, per tour employment 9 ~ 10 people.And interrupter method reaches same output, about per tour employment 40 people.
3. in continuous processing except feeding intake and filter station needs workman's execute-in-place, other whole practicable DCS distribute control, optimum data is obtained through optimizing, organizational standardization is produced, improve raw material availability, stabilized product quality, energy efficient, minimizing three waste discharge, have the unrivaled advantage of interrupter method.
4. continuous processing is suitable for large-scale device construction, less investment, and operation cost is low, enhances the market competitiveness of product.
Accompanying drawing explanation
Fig. 1 is present system schematic diagram.
Embodiment
Embodiment 1: a kind of continuous esterification synthesizing citric acid tri-n-butyl system, comprise dissolution kettle 1, esterifying kettle 2, dehydration tower 3, condenser 4, water-and-oil separator 5, dissolution kettle 1 is set to two, dissolution kettle 1 connects 4 esterifying kettles be connected in series in turn 2, and esterifying kettle 2 all connects dehydration tower 3, and the outlet of dehydration tower 3 top connects condenser 4, condenser 4 connects water-and-oil separator 5, water-and-oil separator 5 connects the nearly upper end of dehydration tower 3, and connect first esterifying kettle 2 bottom dehydration tower 3, operation sequence comprises the following steps:
A. citric acid, propyl carbinol and catalyzer mixed dissolution in mixed dissolution still 1, the mol ratio of citric acid and propyl carbinol is generally with 1: 4, and catalyzer adds in right amount by need of production;
B. at the uniform velocity add to first esterifying kettle the mixed solution that upper step configures, open steam heating simultaneously.Mixed solution progressively overflow enters the esterifying kettle 2 of series connection in turn; In multiple esterifying kettles of described series connection, temperature of reaction promotes successively by 112 DEG C, is up to 160 DEG C.
C. many esterifying kettles share an esterification dehydration tower 3, tower top is furnished with corresponding condenser and water-and-oil separator, the water that reaction generates and butanols azeotropic are discharged to tower top continuous continuous print after condensation by water-and-oil separator bottom, and upper strata butanols still passes back into the water that the continuous extractive reaction of tower top generates;
D. the butanol concentration of each still is regulated to control the temperature of reaction of each still in a rational interval, each still temperature raises successively, the transformation efficiency of citric acid also improves successively, from last still discharge acid content≤1%(with citrometer), butanol content 25 ~ 30% esterification work in-process;
The esterification work in-process of e. discharging obtain the thick finished product of TBC after continuous dealcoholysis, first esterifying kettle 2 got back to by the alcohol deviate from or dissolution kettle 1 uses, and thick finished product obtains TBC finished product through the process for refining (as neutralization, washing, drying, filtration etc.) that plasticizer production is conventional.
Described catalyzer comprises various conventional strongly acidic catalyst (as sulfuric acid, tosic acid etc.), non-acidic catalyst, many kinds of solids super acids etc., and comprising their compound or the catalyzer with gac solid-carrying type, its consumption needs appropriate interpolation by its catalytic activity and production technique.
Embodiment 2: for 50,000 tons/year of TBC production equipments.
System with reference to embodiment 1:
1. design each esterifying kettle volume and heating-surface area, esterification dehydration tower diameter and packed height (or stage number), condenser size and form, water-and-oil separator specification etc., and consider suitable surplus, build 50,000 tons/year of TBC continuous esterification devices.
2. configure citric acid and propyl carbinol with 1: 4.5(mol ratio) mixing solutions and add appropriate catalyzer, mixed solution (by corresponding acid content) is at the uniform velocity added number one esterifying kettle, and logical steam heating.
3. open butanols pump for subsequent use and add appropriate butanols to number one esterifying kettle, and regulate each esterifying kettle steam consumption, control each still temperature and be followed successively by 112 ~ 120 DEG C, 126 ~ 132 DEG C, 138 ~ 146 DEG C, 152 ~ 160 DEG C, continuously feeding is reacted, and continuous discharge---.
4. detect the half-finished acidity of TBC that last esterifying kettle is discharged, when certain limit, system gets final product normal discharging, the TBC work in-process (wherein butanol content about 20% ~ 28%) obtained, technique (neutralization, washing, dehydration, filtration etc.) conventional in plasticizer production is refining obtains TBC finished product.
5. regulate and optimize each reference mark parameter, determining optimum control scheme and the throughput scope of this device.
Claims (8)
1. a continuous esterification synthesizing citric acid tri-n-butyl system, it is characterized in that comprising dissolution kettle, esterifying kettle, dehydration tower, condenser, water-and-oil separator, dissolution kettle is set at least one, dissolution kettle connects 3 ~ 6 esterifying kettles be connected in series in turn, esterifying kettle all connects dehydration tower, and the outlet of dehydration tower top connects condenser, and condenser connects water-and-oil separator, water-and-oil separator connects the nearly upper end of dehydration tower, connects first esterifying kettle bottom dehydration tower.
2. a kind of continuous esterification synthesizing citric acid tri-n-butyl system according to claim 1, is characterized in that dissolution kettle is arranged side by side two.
3. a kind of continuous esterification synthesizing citric acid tri-n-butyl system according to claim 1, is characterized in that esterifying kettle is 4 or 5.
4. a synthetic method for the continuous esterification synthesizing citric acid tri-n-butyl system as described in one of claim 1 ~ 3, comprises the following steps:
Citric acid, propyl carbinol and catalyzer mixed dissolution in mixed dissolution still, the mol ratio of citric acid and propyl carbinol is generally with 1: 4 ~ 7, and catalyzer adds in right amount by need of production;
At the uniform velocity add to first esterifying kettle the mixed solution that upper step configures, open steam heating simultaneously.
5. mixed solution progressively overflow enter the esterifying kettle of series connection in turn;
Multiple esterifying kettle shares an esterification dehydration tower, tower top is furnished with corresponding condenser and water-and-oil separator, the water that reaction generates and butanols azeotropic are discharged to tower top continuous continuous print after condensation by water-and-oil separator bottom, and upper strata butanols still passes back into the water that the continuous extractive reaction of tower top generates;
The butanol concentration of each still is regulated to control the temperature of reaction of each still in a rational interval, each still temperature raises successively, the transformation efficiency of citric acid also improves successively, from last still discharge acid content≤1%(with citrometer), butanol content 25 ~ 30% esterification work in-process;
The esterification work in-process of discharging obtain the thick finished product of TBC after continuous dealcoholysis, and first esterifying kettle got back to by the alcohol deviate from or dissolution kettle uses, and thick finished product obtains TBC finished product through the process for refining that plasticizer production is conventional.
6. the synthetic method of a kind of continuous esterification synthesizing citric acid tri-n-butyl system according to claim 4, is characterized in that the mol ratio of citric acid and propyl carbinol is 1:4 ~ 4.5.
7. the synthetic method of a kind of continuous esterification synthesizing citric acid tri-n-butyl system according to claim 4, is characterized in that in multiple esterifying kettles of described series connection, temperature of reaction promotes successively by 112 DEG C, is up to 160 DEG C.
8. the synthetic method of a kind of continuous esterification synthesizing citric acid tri-n-butyl system according to claim 4, is characterized in that temperature of reaction is 118 DEG C ~ 155 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693514A (en) * | 2016-03-18 | 2016-06-22 | 江苏雷蒙化工科技有限公司 | Continuous production system and production method of polyalcohol low-carbon carboxylate ester |
| CN105693516A (en) * | 2016-03-18 | 2016-06-22 | 江苏雷蒙化工科技有限公司 | System and method for continuously producing triethyl citrate |
| 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 |
| CN112778132A (en) * | 2021-01-27 | 2021-05-11 | 杭一林 | Acylation process device and process method of tri-n-butyl citrate |
| CN114307920A (en) * | 2021-07-30 | 2022-04-12 | 江苏雷蒙新材料有限公司 | Continuous production system and production process of polyol acetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101591244A (en) * | 2009-04-24 | 2009-12-02 | 淄博蓝帆化工有限公司 | The semi-continuous production technology of tributyl acetylcitrate |
| CN101735055A (en) * | 2009-12-07 | 2010-06-16 | 无锡双象化学工业有限公司 | Method for producing plasticizer tirbutyl citrate |
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2015
- 2015-06-05 CN CN201510302549.0A patent/CN104961637A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591244A (en) * | 2009-04-24 | 2009-12-02 | 淄博蓝帆化工有限公司 | The semi-continuous production technology of tributyl acetylcitrate |
| CN101735055A (en) * | 2009-12-07 | 2010-06-16 | 无锡双象化学工业有限公司 | Method for producing plasticizer tirbutyl citrate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693514A (en) * | 2016-03-18 | 2016-06-22 | 江苏雷蒙化工科技有限公司 | Continuous production system and production method of polyalcohol low-carbon carboxylate ester |
| CN105693516A (en) * | 2016-03-18 | 2016-06-22 | 江苏雷蒙化工科技有限公司 | System and method for continuously producing triethyl citrate |
| CN105693514B (en) * | 2016-03-18 | 2018-05-15 | 江苏雷蒙化工科技有限公司 | The continuous production system and its production method of a kind of low-carbon carboxylate of polyalcohol |
| 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 |
| CN112778132A (en) * | 2021-01-27 | 2021-05-11 | 杭一林 | Acylation process device and process method of tri-n-butyl citrate |
| CN114307920A (en) * | 2021-07-30 | 2022-04-12 | 江苏雷蒙新材料有限公司 | Continuous production system and production process of polyol acetate |
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