CN106946699A - A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid - Google Patents
A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid Download PDFInfo
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- CN106946699A CN106946699A CN201710321581.2A CN201710321581A CN106946699A CN 106946699 A CN106946699 A CN 106946699A CN 201710321581 A CN201710321581 A CN 201710321581A CN 106946699 A CN106946699 A CN 106946699A
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- acid
- catalyst
- tributyrin
- polyvinyl chloride
- butyric acid
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it the described method comprises the following steps：(a) glycerine, butyric acid and water entrainer are pre-mixed, preheated, subsequently into esterification is carried out in the reaction column filled with catalyst, esterification reaction temperature is controlled between 120 160 DEG C, the 25h of reaction time 18；The catalyst is the catalyst of macropore polyvinyl chloride resin carried heteropoly acid；The heteropoly acid is at least one in phosphotungstic acid, silico-tungstic acid；(b) using vacuum distillation removing butyric acid after esterification terminates, then organic base is used to be used as acid binding agent to adsorb remaining butyric acid；(c) decoloration and deodorization and then using activated carbon is carried out, refines, obtains tributyrin finished product.Through the above way, not only catalytic activity is high, the good, reusing of selectivity is good and environment-friendly for the inventive method, greatly improves production efficiency, reduces the discharge of the three wastes.
Description
Technical field
The present invention relates to chemical products preparation field, and in particular to a kind of preparation method of tributyrin.
Background technology
Tributyrin, No. CAS is 60-01-5, and molecular formula is C15H26O6, and colourless oil liquid has bitter taste, Ying Mi
Shady place preservation is encapsulated in, to determine the substrate of lipase (Esterase) and lipase (Lipase), plasticizer, spices.
Short chain fatty acids can provide energy for colon, be the energy source of enterocyte preference, and easily be absorbed in enteric cavity.
Wherein, butyric acid is the main energy sources of Colon mucosa cell, accounts for the 70% of short chain fatty acids oxygen consumption institute production capacity amount, is
Animal provides up to 30% maintenance energy.Butyric acid has strong cream, the unhappy smell as cheese, in feed manufacturing mistake
Cheng Zhonghui brings many inconvenience to operating personnel.Glycerol monobutyralte is the product after butyric acid and glycerine esterification, can be added as feed
Plus agent, the problem of butyric acid is difficult to addition for oily liquids can be solved, the butyric acid shortcoming that the smell is awful can be overcome again.Butyric acid glycerine
Ester include only son's acid glyceride, two glycerol monobutyraltes and tributyrin, into animal body in be decomposed into after butyric acid and glycerine
Absorbed and utilized；But for the quantity that three provides butyric acid, tributyrin is best.
The method that some synthesis tributyrins are inquired during literature search, it is mostly direct using acetic acid and glycerine
The method of esterification, except needing acetic acid excessive outer by a relatively large margin, (Liu Qun etc., sulphur zirconium is catalyzed the catalyst that also use costly
Synthesize the kinetics of triacetyl glycerine【J】, process engineering journal, 2009 (1)：43-46).Chinese invention patent application
A kind of method for preparing tributyrin is disclosed in CN104045556A, including：Using organic base as acid binding agent, make glycerine and
Butyl chloride is reacted, and obtains the mixture containing tributyrin.Wherein, the glycerine, butyl chloride, three kinds of materials of organic base
Mol ratio be 1：(3-3.3)：3.3.Methods described, which is still further comprised, extracts the mixture containing tributyrin with water,
Organic phase is collected, and by the solvent under reduced pressure evaporative removal in organic phase, obtains tributyrin.But in the patented technology, instead
It should be carried out in organic solvents, chloroform, subsequent treatment needs to remove the organic solvent in organic phase, increases intractability,
And preparation process is not environmentally.
A kind of green of high content feed tributyrin is disclosed in the A of Chinese patent application CN 105801413
Synthetic method, this method is using glycerine and butyric acid as raw material, using solid super acid catalyst, with nitrogen as protective agent and band
Aqua, tributyrin is obtained by rectifying and vacuum distillation.
The content of the invention：
With reference to the content in above-mentioned background technology, the purpose of present specification is：There is provided a kind of miscellaneous using polyvinyl chloride resin load
The method of the catalyst preparation tributyrin of polyacid, this method is not only with catalytic activity is high, selectivity is good, recycling
Property is good and environment-friendly, greatly improves production efficiency, reduces the discharge of the three wastes.
To achieve the above object, technical scheme disclosed by the invention is：One kind utilizes polyvinyl chloride resin carried heteropoly acid catalyst
The method for preparing tributyrin, the described method comprises the following steps：
(a) glycerine, butyric acid and water entrainer are pre-mixed, preheated, subsequently into entering in the reaction column filled with catalyst
Row esterification, esterification reaction temperature is controlled between 120-160 DEG C, reaction time 18-25h；The catalyst is macropore PVC
The catalyst of resin-carried heteropoly acid；The heteropoly acid is at least one in phosphotungstic acid, silico-tungstic acid；
(b) using vacuum distillation removing butyric acid after esterification terminates, then it is remaining as acid binding agent absorption using organic base
Butyric acid；
(c) decoloration and deodorization and then using activated carbon is carried out, refines, obtains tributyrin finished product.
It is preferred that, the amount ratio of the glycerine and butyric acid is glycerine：Butyric acid=(90-92)：(420-460).
It is preferred that, the water entrainer uses n-propyl acetate.
It is preferred that, organic base is at least one in calcium stearate, zinc stearate, molecular sieve in the step (b).
It is preferred that, the preparation of step (a) catalyst is：Loaded using macropore polyvinyl chloride resin by precipitation adsorption method miscellaneous
Filter solvents after polyacid, absorption, are then dried in vacuo and are made.
Heretofore described molecular sieve is the silicate or alumino-silicate of crystalline state, by silicon-oxy tetrahedron or alumina on four sides
Body is connected and formed by oxygen bridge key.
Technical scheme disclosed in present specification is replaced by using green, efficient resin-carried heteropolyacid catalyst
Thiosulfuric acid and phosphoric acid prepare tributyrin.This method not only has high, the selective good, reusing of catalytic activity good,
And it is environment-friendly, production efficiency is greatly improved, the discharge of the three wastes is reduced.
The beneficial effects of the invention are as follows：The advantage of the method for the present invention for preparing tributyrin is：Utilize height
Molecule loaded mesoporous catalyst replaces sulfuric acid and phosphoric acid, reduces the discharge of the three wastes in production process, realizes green production；
Catalytic activity is high；Production efficiency is improved；Conversion ratio >=96% in esterification.
Embodiment
Presently preferred embodiments of the present invention is described in detail with reference to embodiment, so that advantages and features of the invention
It can be easier to be readily appreciated by one skilled in the art, apparent clearly be defined so as to be made to protection scope of the present invention.
Embodiment disclosed by the invention includes：
Embodiment 1：A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it is described
Method is as follows：Glycerine, butyric acid and water entrainer are pre-mixed, preheated, is carried out subsequently into the reaction column filled with catalyst
Esterification, esterification reaction temperature is controlled between 140-150 DEG C, reaction time 18-20h；Used catalyst is macropore PVC trees
The catalyst of fat load phosphotungstic acid；Esterification removes butyric acid after terminating using vacuum distillation, and the butyric acid of removing is returned into reaction
Device is circulated utilization；Remaining butyric acid is adsorbed as acid binding agent using zinc stearate again, to deviate from butyric acid stink；
Then decoloration and deodorization is carried out using activated carbon, refines, obtain tributyrin finished product, content is more than or equal to
98.5%.
Catalyst in the present embodiment is the mistake after absorption by precipitation adsorption method carried heteropoly acid using macropore polyvinyl chloride resin
Solvent is filtered, is then dried in vacuo and is made.
Embodiment 2：A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it is described
Method is as follows：Glycerine, butyric acid and water entrainer are pre-mixed, preheated, is carried out subsequently into the reaction column filled with catalyst
Esterification, esterification reaction temperature is controlled in 145 DEG C, reaction time 22h；Used catalyst is macropore polyvinyl chloride resin load silicon tungsten
The catalyst of acid；Esterification removes butyric acid after terminating using vacuum distillation, and the butyric acid of removing is returned into reactor and is circulated
Utilize；Remaining butyric acid is adsorbed as acid binding agent using calcium stearate again, to deviate from butyric acid stink；Then taken off using activated carbon
Color is deodorized, and is refined, and obtains tributyrin finished product, and content is more than or equal to 98.5%.
Catalyst in the present embodiment is the mistake after absorption by precipitation adsorption method carried heteropoly acid using macropore polyvinyl chloride resin
Solvent is filtered, is then dried in vacuo and is made.
Embodiment 3：A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it is described
Method is as follows：Glycerine, butyric acid and water entrainer are pre-mixed, preheated, is carried out subsequently into the reaction column filled with catalyst
Esterification, esterification reaction temperature is controlled in 135 DEG C, reaction time 24h；Used catalyst is macropore polyvinyl chloride resin load silicon tungsten
The catalyst of acid；Esterification removes butyric acid after terminating using vacuum distillation, and the butyric acid of removing is returned into reactor and is circulated
Utilize；Remaining butyric acid is adsorbed as acid binding agent using molecular sieve again, to deviate from butyric acid stink；Then decolourized using activated carbon
Deodorization, is refined, and obtains tributyrin finished product, and content is more than or equal to 98.5%.
Catalyst in the present embodiment is the mistake after absorption by precipitation adsorption method carried heteropoly acid using macropore polyvinyl chloride resin
Solvent is filtered, is then dried in vacuo and is made.
Embodiment 4：A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it is described
Method comprises the following steps：
(a) glycerine, butyric acid and water entrainer are pre-mixed, preheated, subsequently into entering in the reaction column filled with catalyst
Row esterification, esterification reaction temperature is controlled between 120-160 DEG C, reaction time 18-25h；The catalyst is macropore PVC
The catalyst of resin-carried heteropoly acid；The heteropoly acid is at least one in phosphotungstic acid, silico-tungstic acid；
(b) using vacuum distillation removing butyric acid after esterification terminates, then it is remaining as acid binding agent absorption using organic base
Butyric acid；The organic base is at least one in calcium stearate, zinc stearate, molecular sieve；
(c) decoloration and deodorization and then using activated carbon is carried out, refines, obtains tributyrin finished product.
In the present embodiment, the amount ratio of glycerine and butyric acid is glycerine：Butyric acid=(90-92)：(420-460)；Water entrainer is adopted
It is n-propyl acetate.
Catalyst in the present embodiment is the mistake after absorption by precipitation adsorption method carried heteropoly acid using macropore polyvinyl chloride resin
Solvent is filtered, is then dried in vacuo and is made.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (5)
1. a kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid, it is characterised in that described
Method comprises the following steps：
(a) glycerine, butyric acid and water entrainer are pre-mixed, preheated, subsequently into carrying out ester in the reaction column filled with catalyst
Change reaction, esterification reaction temperature is controlled between 120-160 DEG C, reaction time 18-25h；The catalyst is macropore polyvinyl chloride resin
The catalyst of carried heteropoly acid；The heteropoly acid is at least one in phosphotungstic acid, silico-tungstic acid；
(b) using vacuum distillation removing butyric acid after esterification terminates, then organic base is used to be used as acid binding agent to adsorb remaining butyric acid；
(c) decoloration and deodorization and then using activated carbon is carried out, refines, obtains tributyrin finished product.
2. preparation method according to claim 1, it is characterised in that the amount ratio of the glycerine and butyric acid is glycerine：Fourth
Acid=(90-92)：(420-460).
3. preparation method according to claim 2, it is characterised in that the water entrainer uses n-propyl acetate.
4. preparation method according to claim 1, it is characterised in that in the step (b) organic base be calcium stearate, it is hard
At least one in resin acid zinc, molecular sieve.
5. preparation method according to claim 1, it is characterised in that the preparation of step (a) catalyst is：Using big
Hole polyvinyl chloride resin is by precipitation adsorption method carried heteropoly acid, filter solvents after absorption, is then dried in vacuo and is made.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710321581.2A CN106946699A (en) | 2017-05-09 | 2017-05-09 | A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid |
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| CN201710321581.2A CN106946699A (en) | 2017-05-09 | 2017-05-09 | A kind of method of the catalyst preparation tributyrin of utilization polyvinyl chloride resin carried heteropoly acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107373094A (en) * | 2017-07-14 | 2017-11-24 | 浙江汇能生物股份有限公司 | A kind of synthesis of tributyrin and the application in feed |
| CN107673970A (en) * | 2017-11-01 | 2018-02-09 | 泸天化（集团）有限责任公司 | A kind of preparation method of tributyrin |
| CN112321423A (en) * | 2020-12-11 | 2021-02-05 | 河南智盛优品生物科技有限公司 | Synthesis process of tributyrin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801413A (en) * | 2016-05-10 | 2016-07-27 | 上海旭牧联生物科技有限公司 | Green synthesis method for tributyrin for high-content feed |
| CN106518670A (en) * | 2016-09-19 | 2017-03-22 | 湖北神舟化工有限公司 | Method for synthesizing butyrin |
-
2017
- 2017-05-09 CN CN201710321581.2A patent/CN106946699A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801413A (en) * | 2016-05-10 | 2016-07-27 | 上海旭牧联生物科技有限公司 | Green synthesis method for tributyrin for high-content feed |
| CN106518670A (en) * | 2016-09-19 | 2017-03-22 | 湖北神舟化工有限公司 | Method for synthesizing butyrin |
Non-Patent Citations (1)
| Title |
|---|
| 韦卉 等: "大孔聚氯乙烯树脂负载H3PMo12O40杂多酸催化剂的研", 《应用化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107373094A (en) * | 2017-07-14 | 2017-11-24 | 浙江汇能生物股份有限公司 | A kind of synthesis of tributyrin and the application in feed |
| CN107673970A (en) * | 2017-11-01 | 2018-02-09 | 泸天化（集团）有限责任公司 | A kind of preparation method of tributyrin |
| CN112321423A (en) * | 2020-12-11 | 2021-02-05 | 河南智盛优品生物科技有限公司 | Synthesis process of tributyrin |
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