CN102627561A - Preparation process for plasticizer-tributyl citrate - Google Patents
Preparation process for plasticizer-tributyl citrate Download PDFInfo
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- CN102627561A CN102627561A CN2012100900218A CN201210090021A CN102627561A CN 102627561 A CN102627561 A CN 102627561A CN 2012100900218 A CN2012100900218 A CN 2012100900218A CN 201210090021 A CN201210090021 A CN 201210090021A CN 102627561 A CN102627561 A CN 102627561A
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- dealcoholysis
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- tributyl citrate
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- 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
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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 the environmental protection softening agent, is widely used in industries such as food and medical apparatus packing, makeup, daily necessities, substitutes the phthalate that tradition is used gradually, becomes the primary plasticizer of plastic industry.The working method of tradition tributyl citrate is to be catalyzer with the vitriol oil, has side reactions such as oxidation, refining difficulty, shortcomings such as equipment corrosion is serious, environmental pollution.Some factories' employing tosic acid are catalyzer in recent years, have catalytic effect preferably, but catalyst levels are bigger, and price is more expensive, does not find the method for recycling use as yet, and production cost is higher.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the prior art; Provide a kind of and can be reused for the method that next batch production tributyl citrate is used as catalyzer by easy recovery tosic acid, present method provides the way that a kind of lemon acid monoester, dibasic acid esters reclaim simultaneously, having reduced the neutralization loss; Improved product yield; Reduce cost, reduced the organism discharging, alleviated pollution.
One, the chemical reaction of institute of the present invention foundation is following:
Two, scheme of the present invention mainly may further comprise the steps:
(1), Citric acid monohydrate Food grade and propyl carbinol are mixed, add tosic acid and gac then, feed nitrogen and 125 ~ 135 ℃ of controlled temperature, still pressures≤0.015Mpa reacts down, acid number≤2.3mgKOH/g is the esterification terminal point, obtains carboxylate; The mol ratio 1:3.5 of said Citric acid monohydrate Food grade and propyl carbinol ~ 4.5, described tosic acid weight are 1.7 ~ 3.0% (being 0.021 ~ 0.037 times of molar weight of Citric acid monohydrate Food grade) of Citric acid monohydrate Food grade weight;
(2), with carboxylate dealcoholysis first to flash-point >=162 ℃;
(3), with the tosic acid in the carboxylate after the water dissolution recovery dealcoholysis of 1.6 ~ 2.0 times of catalyst weights, recycled in the production stage (1) of isolated water adding next batch;
(4), in oil phase, add alkali lye PH=7.0 ~ 7.5 that neutralize, remove water, oil phase is washed to neutrality;
(5), the carboxylate after will washing adds gac and dealcoholysis to flash-point >=180 ℃ once more, obtains thick ester;
(6), thick ester is through filtering the industrial goods tributyl citrate.
In order further to improve technique effect of the present invention, such scheme also comprises following improvement:
Propyl carbinol adds at twice in the step (1), adds 70 ~ 80% of total alcohol amount before heating up, and adds remaining propyl carbinol when being warmed up to 125-130 ℃, and said 125-135 ℃ reaction time of esterification is 7-8 hour.
It is 70 ~ 90% the sulfuric acid PH 1 ~ 2 that neutralizes that the water of step (4) uses mass concentration, divides oil-yielding stratum (Hydrocerol A mono and two butyl esters) to add recycled in the next batch production stage (1).
Gac is a wood activated charcoal in step (1) and the step (5), and its add-on is 0.2% of Citric acid monohydrate Food grade and butanols gross weight.In dealcoholysis first in the step (2) and the step (5) once more the controlled variable of dealcoholysis be: liquidus temperature≤120 ℃, pressure≤-0.095Mpa.Step (3) solvent temperature is 80-90 ℃, in order to improve the dealcoholysis effect, when liquidus temperature reaches 100 ℃, logical steam stripped 0.5-1 hour, leads to N then in the dealcoholysis of step (5)
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 said step (6) is 80 ~ 90 ℃.
Compared with prior art, the present invention has the following advantages:
(1) this technology esterification transformation efficiency is high, can be up to more than 99.0%, and the 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 technology is effective, and available short-cut method reclaimed after esterification was accomplished, and the recovery reaches more than 75%, can repeat to do catalyzer and use, and reduces blowdown, reduces COD, BOD in the waste water.
(3) the Hydrocerol A mono is recyclable with two butyl esters in this technology, and resterification becomes tributyl citrate again, reduces supplies consumption, not only economy but also environmental protection.
(4) this technology serves as the band aqua with the reactant propyl carbinol directly, has avoided the use of deleterious toluene, cyclohexane, heptane etc.
(5) simple, the esterification mild condition of technology of the present invention, reaction times are short.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
In the 5 m3 enamel stills that three layers of paddle stirrer, temperature indicator, esterification column, condensing surface, water trap are housed; Drop into for the 1st time the 1600kg butanols (preceding batch all reclaim alcohol folding 100% back and add, and adds fresh butanols again 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(logical from start to finish N of esterification and dealcoholysis stage
2, per hour about 2m3).Chuck leads to steam, when making material steadily be warmed up to 125-130 ℃, slowly adds the fresh butanols of 700kg the 2nd time; 125-135 ℃ of control esterification temperature, still pressure≤0.015Mpa, every at a distance from acid number of 30min survey; When acid number≤2.3mgKOH/g is the esterification terminal point, and 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 ℃.When 80 ~ 90 ℃ of ester temperature,, isolate water with the tosic acid in the 50kg dissolved in purified water carboxylate.70-75 ℃ of ester temperature, with soda ash liquid 800kg (can be chosen as sodium hydroxide or the sodium carbonate solution) PH=7.5 that neutralizes of mass concentration 8%, restir 30min, repetition measurement PH=7.5 leaves standstill 30min again, tells water alkali lye.Oil phase is with 65-70 ℃ pure water 800kg, when washing acid number≤0.5mgKOH/g, tells water lotion.Add gac 8kg again, carry out the vacuum dealcoholysis at the dealcoholysis still, pressure≤-0.095Mpa, material temperature≤120 ℃.When temperature rise to 100 ℃, and logical continuously steam (vapour pressure≤0.04Mpa), stripping 0.5-1h, after seldom liquid steams, logical again N
2About 0.5h, thick ester 2460kg (Citric acid monohydrate Food grade transformation efficiency 99%) carries out filter press and gets finished product 2435kg (yield 98%), acid number 0.05mgKOH/g, 180 ℃ of flash-points, No. 30, look number (Pt-Co) when 80-90 ℃ of thick ester temperature.
Embodiment 2
Except that the input amount adjustment of each raw material; The remaining reaction parameter is identical with embodiment 1, and experimental data is following in detail:
.
Embodiment 3
Except that the input amount adjustment of each raw material, the remaining reaction parameter is identical with embodiment 1, and experimental data is following in detail:
Embodiment 4
Except that the input amount adjustment of each raw material, the remaining reaction parameter is identical with embodiment 3, and experimental data is following in detail:
Embodiment 5
Except that the input amount adjustment of each raw material, the remaining reaction parameter is identical with embodiment 3, and experimental data is following in detail:
Embodiment 6
The tosic acid yield is all more than 75% among the embodiment 1-5; Therefore the first in the present embodiment batch of tosic acid of applying mechanically promptly derives from tosic acid 27kg (recovery 75%) and the new tosic acid 9kg that embodiment 3 reclaims; The tosic acid of each batch is all applied mechanically the tosic acid (recovery is all more than 75%) that last consignment of reclaims later on; And additional new tosic acid; Guarantee that the tosic acid total amount is 36 kg, other reaction parameter of all batches is consistent with embodiment 3, and many batches the result of experiment of circulating successively is following:
Visible through above experiment, tosic acid repeatedly circulates, and the product that obtains is applied mechanically in recovery and the product that adopts new tosic acid to reach fully do not have significant difference, and no matter yield still is a technical target of the product all is consistent.
Embodiment 7
With using mass concentration with the isolating water in back in embodiment 3 alkali lye is 70 ~ 90% the sulfuric acid PH 1 ~ 2 that neutralizes; Tell a small amount of oil reservoir; It is mainly Hydrocerol A mono and two butyl esters, and cover is used in first batch the esterification of present embodiment then, and the recovery oil reservoir of each batch all overlaps in the esterification of using next batch later on; Keep other reaction parameter of all batches consistent with embodiment 3, many batches the result of experiment of circulating successively is following:
Visible through above experiment, the recycling of Hydrocerol A mono and two butyl esters, under the situation that technical target of the product remains unchanged basically, and product yield improves to some extent.
Above embodiment helps 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 (7)
1. the production technique of plasticizer tirbutyl citrate is characterized in that, may further comprise the steps:
(1) Citric acid monohydrate Food grade and propyl carbinol are mixed, add tosic acid and gac then, feed nitrogen and be controlled at 125 ~ 135 ℃ of temperature, still pressure≤0.015Mpa reaction down, acid number≤2.3mgKOH/g is the esterification terminal point, obtains carboxylate; The mol ratio 1:3.5 of said Citric acid monohydrate Food grade and propyl carbinol ~ 4.5, described tosic acid weight is 1.7 ~ 3.0% of Citric acid monohydrate Food grade weight;
(2), with carboxylate dealcoholysis first to flash-point >=162 ℃;
(3), with the tosic acid in the carboxylate after the water dissolution recovery dealcoholysis of 1.6 ~ 2.0 times of catalyst weights, recycled in the production stage (1) of isolated water adding next batch;
(4), in oil phase, add alkali lye PH=7.0 ~ 7.5 that neutralize, remove water, oil phase is washed to neutrality;
(5), the carboxylate after will washing adds gac and dealcoholysis to flash-point >=180 ℃ once more, obtains thick ester;
(6), thick ester is through filtering the industrial goods tributyl citrate.
2. the production technique of plasticizer tirbutyl citrate according to claim 1; It is characterized in that; Propyl carbinol adds at twice in the said step (1); Add 70 ~ 80% of total alcohol amount before heating up, add remaining propyl carbinol when being warmed up to 125-130 ℃, said 125-135 ℃ reaction time of esterification is 7-8 hour.
3. the production technique of plasticizer tirbutyl citrate according to claim 1; It is characterized in that; It is 70 ~ 90% the sulfuric acid PH 1 ~ 2 that neutralizes that the water of said step (4) uses mass concentration, divides oil-yielding stratum to add recycled in the next batch production stage (1).
4. according to the production technique of claim 1,2 or 3 described plasticizer tirbutyl citrates, it is characterized in that gac is a wood activated charcoal in described step (1) and the step (5), its add-on is 0.2% of Citric acid monohydrate Food grade and butanols gross weight.
5. according to the production technique of claim 1,2 or 3 described plasticizer tirbutyl citrates; It is characterized in that; In dealcoholysis first in the said step (2) and the step (5) once more the controlled variable of dealcoholysis be: liquidus temperature≤120 ℃, pressure≤-0.095Mpa.
6. according to the production technique of claim 1,2 or 3 described plasticizer tirbutyl citrates, it is characterized in that said step (3) solvent temperature is 80-90 ℃; The alkali lye of said step (4) is 6 ~ 8% sodium hydroxide or sodium carbonate solution, and neutral temperature is 70-75 ℃; The filtration temperature of said step (6) is 80 ~ 90 ℃.
7. the production technique of plasticizer tirbutyl citrate according to claim 5 is characterized in that, when liquidus temperature reaches 100 ℃, logical steam stripped 0.5-1 hour, leads to N then in the dealcoholysis of said step (5)
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 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210090021.8A CN102627561B (en) | 2012-03-30 | 2012-03-30 | Preparation process for plasticizer-tributyl citrate |
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| CN102627561A true CN102627561A (en) | 2012-08-08 |
| CN102627561B CN102627561B (en) | 2014-05-14 |
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| CN201210090021.8A Expired - Fee Related CN102627561B (en) | 2012-03-30 | 2012-03-30 | Preparation process for plasticizer-tributyl citrate |
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Cited By (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 (2)
| Title |
|---|
| 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》 * |
| 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》 * |
Cited By (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 |
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| CN102627561B (en) | 2014-05-14 |
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Granted publication date: 20140514 Termination date: 20190330 |