CN104803847A - Technology for synthesizing ATBC (acetyl tributyl citrate) under catalysis of composite solid acid - Google Patents

Technology for synthesizing ATBC (acetyl tributyl citrate) under catalysis of composite solid acid Download PDF

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Publication number
CN104803847A
CN104803847A CN201510096243.4A CN201510096243A CN104803847A CN 104803847 A CN104803847 A CN 104803847A CN 201510096243 A CN201510096243 A CN 201510096243A CN 104803847 A CN104803847 A CN 104803847A
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tributyl citrate
composite solid
solid acid
tbc
acetyl tributyl
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CN104803847B (en
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曹立军
周永芳
陈平
周建安
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Jiangsu Raymond New Material Co., Ltd.
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JIANGSU LEMON CHEMICAL INDUSTRY TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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

Abstract

A technology for synthesizing ATBC (acetyl tributyl citrate) under catalysis of composite solid acid comprises steps as follows: citri acid anhydrous and n-butyl alcohol are added to a reactor, a catalyst is added, the mixture reacts for 3-6 hours at the temperature of 120 DEG C-160 DEG C, and TBC (tributyl citrate) is synthesized and dealcoholized; acetic anhydride is added to dealcoholized TBC and reacts for 1-2 hours at the temperature of 60 DEG C-100 DEG C, the catalyst is obtained through filtering after a reaction liquid is cooled, water is added to filtrate, acetic anhydride is hydrolyzed, acetic acid is recovered through deacidification, and an ATBC finished product is prepared through aftertreatment. Defects of a complicated technology, long production period, high product loss, numerous three wastes, environmental pollution and the like of an existing preparation method of ATBC are overcome; the catalyst is simple to prepare and easy to separate and recover and can be recycled without treatment.

Description

A kind of technique of composite solid acid catalysis synthesizing acetyl tributyl citrate
Technical field
The invention belongs to chemosynthesis and technology field, relate to a kind of synthetic method of softening agent tributyl acetylcitrate (ATBC).
Background technology
Traditional plasticizer phthalic acid ester class may be brought out carcinogenic, and restriction of abroad having made laws uses.Tributyl acetylcitrate (ATBC) is as " green " environment-friendly plasticizer, obtain U.S. food and Drug Administration (FDA) ratifies to use, there is the advantages such as nontoxic, tasteless, anti-mildew, plasticizing effect are good, cold-resistant, fast light, water-fast, volatility is little, be widely used in the fields such as food product pack, medical article, toy for children, become the first-selected product of alternative phthalic ester plasticizer.
Current ATBC domestic market vacancy is huge, the homogeneous system that the traditional method of ATBC synthesis is is catalyzer with the vitriol oil etc., although homogeneous system excellent catalytic effect, but also there is obvious shortcoming: by product is many, equipment corrosion is serious, catalyzer not easily with raw material and product separation, a large amount of alkali lye is needed to neutralize and wash, aftertreatment is complicated, and " three wastes " discharge is large, contaminate environment.First ATBC preparation technology of the prior art is with citric acid and propyl carbinol for raw material, under catalyst action through esterification, dealcoholysis, in and, washing and dehydration, obtained tributyl citrate (TBC) finished product of decolouring; And then obtain ATBC finished product through acetylize, depickling, neutralization, washing, dehydration, decolouring.This complex technical process, production cycle length, product loss are comparatively large, facility investment is large, " three wastes " quantity discharged is large, contaminate environment.
Summary of the invention
The object of the invention is to research and develop a kind of composite solid acid catalyst; by the TBC that synthesizes under this kind of catalyst action without separation and washing; only need dealcoholysis directly can carry out acylation reaction; the technique of synthesizing acetyl tributyl citrate; overcome the complex process existing for preparation method of existing tributyl acetylcitrate, the production cycle be long, product loss large, " three wastes " are many, the shortcoming such as contaminate environment; simple, the easily separated recovery of catalyst preparing, does not need process repeatedly to reuse with regard to capable of circulation.
For realizing the object of the invention, provide following technical scheme: a kind of technique of composite solid acid catalysis synthesizing acetyl tributyl citrate, is characterized in that comprising the following steps:
A. the preparation of tributyl citrate:
Add (anhydrous) citric acid and propyl carbinol in the reactor, and add catalyzer and react 3 ~ 6 hours at 120 DEG C ~ 160 DEG C, synthesis TBC, dealcoholysis;
B. tributyl acetylcitrate preparation
Add aceticanhydride in TBC after dealcoholysis, react 1 ~ 2 hour at 60 DEG C ~ 100 DEG C, reaction solution cooled and filtered goes out catalyzer, and filtrate adds water, hydrolysis aceticanhydride, and depickling recovery of acetic acid, obtains ATBC finished product through aftertreatment;
Described catalyzer is composite solid acid, and composite solid acid preparation process comprises: take chemically pure reagent SnO 2-SiO 2-Al 2o 3mix roasting in retort furnace, temperature 600 DEG C ~ 650 DEG C, 2 ~ 3 hours time, wherein reagent content ratio is: SiO 2: SnO 2for 1:1 ~ 2, preferred 1:1 ~ 1.5; (SnO 2-SiO 2): Al 2o 3for 1:2.5 ~ 4, preferably: 1:2.5 ~ 3.5.
The preferred maturing temperature of catalyzer is 630 DEG C ~ 640 DEG C.
SnO in described catalyzer 2-SiO 2-Al 2o 3reagent content is>=99%.
Described (anhydrous) citric acid and the mol ratio of propyl carbinol are 1:3.5 ~ 7, preferred 1:4.0 ~ 6
The consumption of described catalyzer is 1% ~ 3.0% of theoretical citrate quality, preferably 1.2% ~ 2.0%.
Described TBC only dealcoholysis.
Described acetic anhydride is 1 ~ 2:1 with the mol ratio of (anhydrous) citric acid.
Described aftertreatment comprises neutralization, washing, dehydration, desolventing technology.
Beneficial effect of the present invention: 1. the present invention adopts composite solid acid catalysis synthesizing acetyl tributyl citrate, and catalyzer is easily separated, and equipment corrosion is few, acid catalyst, without the need to carrying out alkali neutralization, is avoided acid catalyst to enter waste water and is brought environmental pollution.
2. solid acid catalyst of the present invention does not need process repeatedly to reuse with regard to capable of circulation, and catalyzer uses SiO 2,add the surface-area of catalyzer, be more conducive to the reaction of material.
3. catalyst preparation process is simple, with low cost, can reuse again, thus significantly reduce product cost.
4. technique of the present invention eliminates refining TBC link in traditional technology, directly can carry out acylation reaction, reduce " three wastes ", reduce costs, improve product yield after TBC dealcoholysis.
5. the inventive method esterification yield high (>=99.0%), good product quality, tributyl acetylcitrate purity >=99.2%, color and luster≤15#.
In sum, the inventive method is easy and simple to handle, " three wastes " less, cost is low, quality product is high, according to the inventive method synthesizing acetyl tributyl citrate, not only economy but also environmental protection, be applicable to industrialization.Reaction conditions is gentle, good product quality.
Embodiment
Embodiment 1:
1) catalyst preparing
Take SnO 2and SiO 2each 500g, Al 2o 3,3kg, the 200g that adds water stirs, and catalyzer is roasting in retort furnace, and 650 DEG C of 2.5 hours times of temperature obtain solid acid catalyst, SnO in catalyzer 2: SiO 2for 1:1, (SnO 2-SiO 2): Al 2o 3for 1:3.
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and the theoretical citrate quality of above-mentioned catalyzer 4.32kg(1.2%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate is prepared in the TBC crude product (35.7kg) obtained to step 1) and is added acetic anhydride 12.1kg(0.12kmol), at 70 DEG C ~ 80 DEG C reaction 0.5h ~ 1.5h, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), acetic anhydride hydrolysis after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 2: with reference to embodiment 1 catalyst preparing parameter constant, changes the optimum configurations in tributyl citrate preparation and tributyl acetylcitrate preparation:
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 37.1kg(0.5kmol) and the theoretical citrate quality of catalyzer 5.76kg(1.6%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
Acetic anhydride 15.3kg(0.15kmol is added) in obtained TBC crude product (35.5kg), 0.5h ~ 1.5h is reacted at 70 DEG C ~ 80 DEG C, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), acetic anhydride hydrolysis after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 3: with reference to embodiment 1 catalyst preparing parameter constant, changes the optimum configurations in tributyl citrate preparation and tributyl acetylcitrate preparation:
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and the theoretical citrate quality of catalyzer 7.2kg((2.0%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
Acetic anhydride 12.1kg(0.12kmol is added) in obtained TBC crude product (35.8kg), 0.5h ~ 1.5h is reacted at 70 DEG C ~ 80 DEG C, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), hydrolysis acetic anhydride after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 4: with reference to embodiment 1 catalyst preparing parameter constant, changes the optimum configurations in tributyl citrate preparation and tributyl acetylcitrate preparation:
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 51.9kg(0.7kmol) and the theoretical citrate quality of catalyzer 7.2kg((2.0%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
Acetic anhydride 9.6kg(0.05kmol is added) in obtained TBC crude product (35.8kg), 0.5h ~ 1.5h is reacted at 70 DEG C ~ 80 DEG C, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), hydrolysis acetic anhydride after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 5:
1) catalyst preparing
Take SnO 2,150g, SiO 2, 100g, Al 2o 3,, 625 g, the 100g that adds water stirs, and catalyzer is roasting in retort furnace, and 650 DEG C of 2.5 hours times of temperature obtain solid acid catalyst, SiO in catalyzer 2: SnO 2for 1:1.5, (SnO 2-SiO 2): Al 2o 3for 1:2.5.
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and the theoretical citrate quality of above-mentioned catalyzer 4.32kg(1.2%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate is prepared in the TBC crude product (35.7kg) obtained to step 1) and is added acetic anhydride 12.1kg(0.12kmol), at 70 DEG C ~ 80 DEG C reaction 0.5h ~ 1.5h, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), acetic anhydride hydrolysis after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 6:
1) catalyst preparing
Take SnO 2,150g, SiO 2, 100g, Al 2o 3,, 875 kg, the 100g that adds water stirs, and catalyzer is roasting in retort furnace, and 650 DEG C of 2.5 hours times of temperature obtain solid acid catalyst, SiO in catalyzer 2: SnO 2for 1:1.5, (SnO 2-SiO 2): Al 2o 3for 1:3.5.
2) tributyl citrate preparation
In the reaction flask being furnished with agitator, thermometer, water trap and prolong, add Citric Acid, usp, Anhydrous Powder 19.2kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and the theoretical citrate quality of above-mentioned catalyzer 4.32kg(1.2%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesis TBC, acid number is surveyed by GB 1668-81, esterification yield >=99.0%, product obtains TBC crude product after dealcoholysis.
3) tributyl acetylcitrate is prepared in the TBC crude product (35.7kg) obtained to step 1) and is added acetic anhydride 12.1kg(0.12kmol), at 70 DEG C ~ 80 DEG C reaction 0.5h ~ 1.5h, synthesis ATBC, then filtering catalyst, filtrate adds water (amount added water equal or slightly larger than the amount required for unreacted acetic anhydride complete hydrolysis), acetic anhydride hydrolysis after recovery of acetic acid, with 5% sodium carbonate alkali lye neutralization once, washing twice, dehydration, decolour, obtain ATBC finished product.Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.
Embodiment 7: with reference to embodiment 6, other parameter step are constant, amendment catalyst preparing parameter:
1) catalyst preparing
Take SnO 2,200g, SiO 2, 100g, Al 2o 3, 1200 kg, the 100g that adds water stirs, and catalyzer is roasting in retort furnace, and 650 DEG C of 2.5 hours times of temperature obtain solid acid catalyst, SiO in catalyzer 2: SnO 2for 1:2, (SnO 2-SiO 2): Al 2o 3for 1:4.
Color and luster≤15# (platinum-cobalt), product purity >=99.2%, acid number≤0.020mgKOH/g, moisture≤0.030%.

Claims (7)

1. a technique for composite solid acid catalysis synthesizing acetyl tributyl citrate, is characterized in that comprising the following steps:
A. the preparation of tributyl citrate:
Add (anhydrous) citric acid and propyl carbinol in the reactor, and add catalyzer and react 3 ~ 6 hours at 120 DEG C ~ 160 DEG C, synthesis TBC, dealcoholysis;
B. tributyl acetylcitrate preparation
Add aceticanhydride in TBC after dealcoholysis, react 1 ~ 2 hour at 60 DEG C ~ 100 DEG C, reaction solution cooled and filtered goes out catalyzer, and filtrate adds water, hydrolysis aceticanhydride, and depickling recovery of acetic acid, obtains ATBC finished product through aftertreatment;
Described catalyzer is composite solid acid, and composite solid acid preparation process comprises: take chemically pure reagent SnO 2-SiO 2-Al 2o 3mix roasting in retort furnace, temperature 600 DEG C ~ 650 DEG C, 2 ~ 3 hours time, wherein reagent content ratio is: SnO 2: SiO 2for 1:1 ~ 2, (SnO 2-SiO 2): Al 2o 3for 1:2.5 ~ 4.
2. the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate according to claim 1, is characterized in that SnO in described catalyzer 2-SiO 2-Al 2o 3reagent content is>=99%.
3. the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate according to claim 1, is characterized in that the mol ratio of described (anhydrous) citric acid and propyl carbinol is 1:3.5 ~ 7.
4. the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate according to claim 1, is characterized in that the consumption of described catalyzer is 1% ~ 3.0% of theoretical citrate quality.
5., according to the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate described in claim 1, it is characterized in that described TBC only dealcoholysis.
6., according to the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate described in claim 1, it is characterized in that described acetic anhydride is 1 ~ 2:1 with the mol ratio of (anhydrous) citric acid.
7. the technique of a kind of composite solid acid catalysis synthesizing acetyl tributyl citrate according to claim 1, is characterized in that described aftertreatment comprises neutralization, washing, dehydration, desolventing technology.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304045A (en) * 2011-07-11 2012-01-04 南京工业大学 Integrated process for synthesizing acetyl tributyl citrate (ATBC) from active carbon solid-carried sulphuric acid catalyst
CN102701975A (en) * 2012-04-11 2012-10-03 江苏雷蒙化工科技有限公司 Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid
CN104086417A (en) * 2014-07-28 2014-10-08 中国石油化工股份有限公司 Esterification method of pentaerythritol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304045A (en) * 2011-07-11 2012-01-04 南京工业大学 Integrated process for synthesizing acetyl tributyl citrate (ATBC) from active carbon solid-carried sulphuric acid catalyst
CN102701975A (en) * 2012-04-11 2012-10-03 江苏雷蒙化工科技有限公司 Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid
CN104086417A (en) * 2014-07-28 2014-10-08 中国石油化工股份有限公司 Esterification method of pentaerythritol

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Inventor after: Zhou Jianan

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