CN102627561B - Preparation process for plasticizer-tributyl citrate - Google Patents
Preparation process for plasticizer-tributyl citrate Download PDFInfo
- Publication number
- CN102627561B CN102627561B CN201210090021.8A CN201210090021A CN102627561B CN 102627561 B CN102627561 B CN 102627561B CN 201210090021 A CN201210090021 A CN 201210090021A CN 102627561 B CN102627561 B CN 102627561B
- Authority
- CN
- China
- Prior art keywords
- dealcoholysis
- water
- described step
- adds
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of fine chemical synthesis, and particularly relates to a synthesis process for tributyl citrate. The synthesis process comprises the steps as follows: (1) mixing citric acid monohydrate with n-butyl alcohol, then adding p-toluenesulfonic acid and active carbon, and adding nitrogen for performing esterification reaction to obtain an esterified substance; (2) dealcoholizing the esterified substance for the first time until the flash point is not less than 162 DEG C; (3) dissolving and recovering the p-toluenesulfonic acid in the esterified substance after dealcoholization by water, and adding the separated water phase into the preparation step (1) of next batch for recycling; (4) adding an alkali solution into an oil phase for neutralizing, removing the water phase, and washing the oil phase to be neutral by water; (5) adding the active carbon into the esterified substance after washing, and dealcoholizing again until the flash point is not less than 180 DEG C so as to obtain raw ester; and (6) filtering the raw ester to obtain the tributyl citrate as the industrial product. According to the synthesis process, the esterification reaction conversion rate reaches up to above 99.0%, the yield of the tributyl citrate can reach above 98%, and the unit consumption and the cost are reduced; and the catalyst, namely the p-toluenesulfonic acid has a good catalytic effect, the recovery rate reaches above 75% after the esterification reaction is ended, the p-toluenesulfonic acid can be repeatedly used as the catalyst, the pollution discharge is reduced, and the COD (Chemical Oxygen Demand) and BOD (Biochemical Oxygen Demand) in wastewater are reduced.
Description
Technical field
The invention belongs to the synthetic field of fine chemistry industry, be specifically related to a kind of synthesis technique of tributyl citrate.
Background technology
Tributyl citrate is environmental protection softening agent, is widely used in the industries such as food and medical apparatus packing, makeup, daily necessities, substitutes gradually the phthalate that tradition is used, and becomes the primary plasticizer of plastic industry.The production method of tradition tributyl citrate is take the vitriol oil as catalyzer, has the side reactions such as oxidation, refining difficulty, the shortcomings such as equipment corrosion is serious, environmental pollution.Some factories' employing tosic acid are catalyzer in recent years, have good catalytic effect, but catalyst levels are larger, and price is more expensive, not yet finds the method for recycling use, and production cost is higher.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method that can easy recovery tosic acid be reused for next batch and produces tributyl citrate and be used as catalyzer is provided, present method provides the way that a kind of lemon acid monoester, dibasic acid esters reclaim simultaneously, reduce neutralization loss, improve product yield, reduce cost, reduced organism discharge, alleviated pollution.
One, the chemical reaction of institute of the present invention foundation is as follows:
Two, the solution of the present invention mainly comprises the following steps:
(1), Citric acid monohydrate Food grade and propyl carbinol are mixed, then add tosic acid and gac, pass into nitrogen and control under 125 ~ 135 ℃ of temperature, still pressure≤0.015Mpa and react, acid number≤2.3mgKOH/g is esterification terminal, obtains carboxylate; Mol ratio 1:3.5 ~ 4.5 of described Citric acid monohydrate Food grade and propyl carbinol, described tosic acid weight is 0.021 ~ 0.037 times of 1.7 ~ 3.0%(of Citric acid monohydrate Food grade weight molar weight of being Citric acid monohydrate Food grade);
(2), carboxylate dealcoholysis is first arrived to flash-point >=162 ℃;
(3), reclaim the tosic acid in carboxylate after dealcoholysis by the water dissolution of 1.6 ~ 2.0 times of catalyst weights, isolated water adds recycled in the production stage (1) of next batch;
(4), in oil phase, add alkali lye to neutralize PH=7.0 ~ 7.5, remove water, oil phase is washed to neutrality;
(5), by washing after carboxylate add gac and again dealcoholysis to flash-point >=180 ℃, obtain thick ester;
(6), thick ester obtains industrial goods tributyl citrate after filtration.
In order further to improve technique effect of the present invention, such scheme also comprises following improvement:
In step (1), propyl carbinol adds at twice, adds 70 ~ 80% of total alcohol amount before intensification, adds remaining propyl carbinol while being warmed up to 125-130 ℃, and the reaction time of esterification of described 125-135 ℃ is 7-8 hour.
The water of step (4) neutralizes PH 1 ~ 2 with the sulfuric acid that mass concentration is 70 ~ 90%, and point oil-yielding stratum (citric acid mono—n—butylester and two butyl ester) adds recycled in next batch production stage (1).
In step (1) and step (5), gac is wood activated charcoal, and its add-on is 0.2% of Citric acid monohydrate Food grade and butanols gross weight.In dealcoholysis first in step (2) and step (5), the control parameter of dealcoholysis is again: liquidus temperature≤120 ℃, pressure≤-0.095Mpa.Step (3) solvent temperature is 80-90 ℃, and in order to improve dealcoholysis effect, in the dealcoholysis of step (5), in the time that liquidus temperature reaches 100 ℃, logical steam stripped 0.5-1 hour, then leads to N
2to flash-point (opening)>=180 ℃; The alkali lye of step (4) is 6 ~ 8% sodium hydroxide or sodium carbonate solution, and neutral temperature is 70-75 ℃; The filtration temperature of described step (6) is 80 ~ 90 ℃.
Compared with prior art, the present invention has the following advantages:
(1) this technique esterification transformation efficiency is high, can be up to more than 99.0%, and tributyl citrate yield can reach more than 98%, has reduced unit consumption, has reduced cost.
(2) the catalyzer Catalyzed by p-Toluenesulfonic Acid of this technique is effective, and after esterification completes, available short-cut method reclaims, and the rate of recovery reaches more than 75%, can repeat to do catalyzer and use, and reduces blowdown, reduces COD, BOD in waste water.
(3) in this technique, citric acid mono—n—butylester and two butyl ester are recyclable, and resterification becomes tributyl citrate again, reduces supplies consumption, not only economy but also environmental protection.
(4) this technique, directly take reactant propyl carbinol as band aqua, has been avoided the use of poisonous toluene, cyclohexane, heptane etc.
(5) simple, the esterification mild condition of technique of the present invention, reaction times are short.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Being equipped with in 5 m3 enamel stills of three layers of paddle stirrer, temperature indicator, esterification column, condenser, water trap, dropping into 1600kg butanols for the 1st time (adds after front batch of all recovery alcohol foldings 100%, add again fresh butanols to 1600kg, account for total charging capacity 70%), open stirring, add tosic acid 25kg, gac 8kg, speed adds Citric acid monohydrate Food grade 1450kg, logical N
2(esterification and dealcoholysis stage be logical N from start to finish
2, about 2m3 per hour).Chuck leads to steam, while making material steadily be warmed up to 125-130 ℃, slowly adds the fresh butanols of 700kg the 2nd time, control esterification temperature 125-135 ℃, still pressure≤0.015Mpa, surveys an acid number every 30min, in the time of acid number≤2.3mgKOH/g, be esterification terminal, the reaction times is about 7-8 hour.In esterifying kettle, carry out the 1st dealcoholysis, control dealcoholysis temperature≤120 ℃, pressure≤-0.095Mpa, dealcoholysis time 1-2h, flash-point (opening) >=162 ℃.In the time of 80 ~ 90 ℃ of ester temperature, with the tosic acid in 50kg dissolved in purified water carboxylate, isolate water.At ester temperature 70-75 ℃, can be chosen as sodium hydroxide or sodium carbonate solution with the soda ash liquid 800kg(of mass concentration 8%) neutralization is to PH=7.5, then stir 30min, then repetition measurement PH=7.5, leave standstill 30min, separate water alkali lye.The oil phase pure water 800kg of 65-70 ℃, when acid number≤0.5mgKOH/g is arrived in washing, separates water lotion.Add again gac 8kg, carry out vacuum dealcoholysis at dealcoholysis still, pressure≤-0.095Mpa, material temperature≤120 ℃.In the time of temperature rise to 100 ℃, logical steam (vapour pressure≤0.04Mpa) continuously, stripping 0.5-1h, until after seldom liquid steams, more logical N
2about 0.5h, obtains thick ester 2460kg(Citric acid monohydrate Food grade transformation efficiency 99%) in the time of 80-90 ℃ of thick ester temperature, carry out filter press and obtain finished product 2435kg(yield 98%), acid number 0.05mgKOH/g, 180 ℃ of flash-points, No. 30, look number (Pt-Co).
Embodiment 2
Except the input amount adjustment of each raw material, remaining reaction parameter is identical with embodiment 1, and experimental data is as follows in detail:
.
Embodiment 3
Except the input amount adjustment of each raw material, remaining reaction parameter is identical with embodiment 1, and experimental data is as follows in detail:
。
Embodiment 4
Except the input amount adjustment of each raw material, remaining reaction parameter is identical with embodiment 3, and experimental data is as follows in detail:
Embodiment 5
Except the input amount adjustment of each raw material, remaining reaction parameter is identical with embodiment 3, and experimental data is as follows in detail:
Embodiment 6
In embodiment 1-5, tosic acid yield is all more than 75%, therefore the first batch of tosic acid of applying mechanically derive from the tosic acid 27kg(rate of recovery 75% that embodiment 3 reclaims in the present embodiment) and new tosic acid 9kg, the tosic acid of each batch is all applied mechanically the tosic acid (rate of recovery is all more than 75%) that last consignment of reclaims later, and supplementary new tosic acid, guarantee that tosic acid total amount is 36 kg, other reaction parameter of all batches is consistent with embodiment 3, and the result of experiment of many batches of circulating is successively as follows:
Visible by above experiment, repeatedly the circulate product that recovery obtains and the product that adopts new tosic acid to reach completely of tosic acid there is no significant difference, no matter yield or technical target of the product is all consistent.
Embodiment 7
To in embodiment 3 alkali lye, neutralize PH 1 ~ 2 with the rear water separating with the sulfuric acid that mass concentration is 70 ~ 90%, separate a small amount of oil reservoir, it is mainly citric acid mono—n—butylester and two butyl ester, then cover is used in the esterification of first batch of the present embodiment, the recovery oil reservoir of each batch all overlaps in the esterification of using next batch later, keep other reaction parameter of all batches consistent with embodiment 3, the result of experiment of many batches of circulating is successively as follows:
Visible by above experiment, the recycling of citric acid mono—n—butylester and two butyl esters, in the situation that technical target of the product remains unchanged substantially, and product yield improves to some extent.
Above embodiment contributes to the technician in field of the present invention further to understand the present invention, but does not limit the present invention in any way.
Claims (4)
1. the production technique of plasticizer tirbutyl citrate, is characterized in that, comprises the following steps:
(1) Citric acid monohydrate Food grade and propyl carbinol are mixed, then add tosic acid and gac, pass into nitrogen and be controlled under 125 ~ 135 ℃ of temperature, still pressure≤0.015Mpa and react, acid number≤2.3mgKOH/g is esterification terminal, obtains carboxylate; Mol ratio 1:3.5 ~ 4.5 of described Citric acid monohydrate Food grade and propyl carbinol, described tosic acid weight is 1.7 ~ 3.0% of Citric acid monohydrate Food grade weight;
(2), carboxylate dealcoholysis is first arrived to flash-point >=162 ℃;
(3), reclaim the tosic acid in carboxylate after dealcoholysis by the water dissolution of 1.6 ~ 2.0 times of catalyst weights, isolated water adds recycled in the production stage (1) of next batch;
(4), in oil phase, add alkali lye to neutralize PH=7.0 ~ 7.5, remove water, oil phase is washed to neutrality; Water neutralizes PH 1 ~ 2 with the sulfuric acid that mass concentration is 70 ~ 90%, and a point oil-yielding stratum adds recycled in next batch production stage (1);
(5), by washing after carboxylate add gac and again dealcoholysis to flash-point >=180 ℃, obtain thick ester;
(6), thick ester obtains industrial goods tributyl citrate after filtration;
In described step (1), propyl carbinol adds at twice, adds 70 ~ 80% of total alcohol amount before intensification, adds remaining propyl carbinol while being warmed up to 125-130 ℃, and the reaction time of esterification of described 125-135 ℃ is 7-8 hour;
Described step (3) solvent temperature is 80-90 ℃; The alkali lye of described step (4) is 6 ~ 8% sodium hydroxide or sodium carbonate solution, and neutral temperature is 70-75 ℃; The filtration temperature of described step (6) is 80 ~ 90 ℃.
2. the production technique of plasticizer tirbutyl citrate according to claim 1, is characterized in that, in described step (1) and step (5), gac is wood activated charcoal, and its add-on is 0.2% of Citric acid monohydrate Food grade and butanols gross weight.
3. the production technique of plasticizer tirbutyl citrate according to claim 1, is characterized in that, in the dealcoholysis first in described step (2) and step (5), the control parameter of dealcoholysis is again: liquidus temperature≤120 ℃, pressure≤-0.095Mpa.
4. the production technique of plasticizer tirbutyl citrate according to claim 3, is characterized in that, in the dealcoholysis of described step (5), in the time that liquidus temperature reaches 100 ℃, logical steam stripped 0.5-1 hour, then leads to N
2to flash-point (opening)>=180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210090021.8A CN102627561B (en) | 2012-03-30 | 2012-03-30 | Preparation process for plasticizer-tributyl citrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210090021.8A CN102627561B (en) | 2012-03-30 | 2012-03-30 | Preparation process for plasticizer-tributyl citrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102627561A CN102627561A (en) | 2012-08-08 |
| CN102627561B true CN102627561B (en) | 2014-05-14 |
Family
ID=46585989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210090021.8A Expired - Fee Related CN102627561B (en) | 2012-03-30 | 2012-03-30 | Preparation process for plasticizer-tributyl citrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102627561B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030560A (en) * | 2013-01-16 | 2013-04-10 | 江南大学 | Catalyzing and decoloring integrated method for synthesizing environment-friendly plasticizer triethylhexyl (2-propylheptyl) citrate |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10133743C1 (en) * | 2001-07-11 | 2003-03-27 | Dhw Deutsche Hydrierwerke Gmbh | Process for the preparation of citric acid esters |
| CN101353305A (en) * | 2007-07-24 | 2009-01-28 | 中山联成化学工业有限公司 | Synthetic method of environment-friendly type high-purity acetyl tributyl citrate (ATBC) |
| CN101402571A (en) * | 2008-11-06 | 2009-04-08 | 河南庆安化工高科技股份有限公司 | Process for producing acet-tributyl citrate |
| CN101712617A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Preparation method of tirbutyl citrate |
-
2012
- 2012-03-30 CN CN201210090021.8A patent/CN102627561B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10133743C1 (en) * | 2001-07-11 | 2003-03-27 | Dhw Deutsche Hydrierwerke Gmbh | Process for the preparation of citric acid esters |
| CN101353305A (en) * | 2007-07-24 | 2009-01-28 | 中山联成化学工业有限公司 | Synthetic method of environment-friendly type high-purity acetyl tributyl citrate (ATBC) |
| CN101712617A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Preparation method of tirbutyl citrate |
| CN101402571A (en) * | 2008-11-06 | 2009-04-08 | 河南庆安化工高科技股份有限公司 | Process for producing acet-tributyl citrate |
Non-Patent Citations (4)
| Title |
|---|
| 柠檬酸三丁酯的合成研究;罗炜等;《南京师范大学报自然科学版》;20100320;第33卷(第1期);第59-62页 * |
| 活性炭固载对甲苯磺酸催化合成柠檬酸三丁酯;黄红生等;《塑料助剂》;20040620(第3期);第10-12页 * |
| 罗炜等.柠檬酸三丁酯的合成研究.《南京师范大学报自然科学版》.2010,第33卷(第1期),第59-62页. |
| 黄红生等.活性炭固载对甲苯磺酸催化合成柠檬酸三丁酯.《塑料助剂》.2004,(第3期),第10-12页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102627561A (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RO120539B1 (en) | Process for preparing ester plasticizers | |
| US5510514A (en) | Process for the production of alkyl (meth)acrylates by direct esterification | |
| JP2009502812A (en) | Process for producing carboxylic acid alkyl ester | |
| CN102850155A (en) | Preparation method of methacrylate products | |
| CN102993078A (en) | Method for purifying N-methyl pyrrolidone | |
| CN102627561B (en) | Preparation process for plasticizer-tributyl citrate | |
| CN113024376A (en) | Production process of hexadecanediester | |
| CN101045682A (en) | Method for retrieving organic acid, ester from cyclic ethane oxidation liquid | |
| CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
| CN105452230B (en) | For manufacturing the method for epoxy monomer and epoxides | |
| CN1193009A (en) | Process for making adipic acid and dibasic acid | |
| CN103848739A (en) | Production method of high-purity dimethyl fumarate | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN103922930B (en) | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst | |
| CN110885287B (en) | Synthetic method for synthesizing isooctyl salicylate from sodium salicylate | |
| CN102731299B (en) | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system | |
| CN104276937A (en) | Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct | |
| CN105384629B (en) | A kind of energy-conserving and environment-protective production technology of the different monooctyl ester of lactic acid | |
| CN1317255C (en) | Method for synthesizing high-recovery and high-optical purity L-butyl lactate | |
| CN1418877A (en) | Process for extracting vitamin E from plant-oil debrominated distillate | |
| CN114149308B (en) | Method for preparing beta-anisole | |
| CN101412739B (en) | Production process of beta-glucose pentaacetate | |
| CN107459462A (en) | A kind of fast synthesis method of Di-2-ethylhexyl terephthalate | |
| CN105749967A (en) | Method for preparing tributyl citrate in presence of bamboo-charcoal-based solid sulfonic acid catalyst | |
| CN109534996A (en) | A kind of technique that Butyl acetylpropanoate is produced as raw material using cellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20190330 |