CN102010330B - Method for preparing high-content glycerol triacetate - Google Patents
Method for preparing high-content glycerol triacetate Download PDFInfo
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- CN102010330B CN102010330B CN 201010559603 CN201010559603A CN102010330B CN 102010330 B CN102010330 B CN 102010330B CN 201010559603 CN201010559603 CN 201010559603 CN 201010559603 A CN201010559603 A CN 201010559603A CN 102010330 B CN102010330 B CN 102010330B
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- glycerol triacetate
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- glycerine
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 26
- 235000013773 glyceryl triacetate Nutrition 0.000 title claims abstract description 16
- 229960002622 triacetin Drugs 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 210000002268 wool Anatomy 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 230000005587 bubbling Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing high-content glycerol triacetate. The method is a continuous refining process, and comprises the following steps of: performing catalytic esterification, acylation, deacidification and neutralization on glycerol and glacial acetic acid to prepare a crude glycerol triacetate product; and performing decolourization by using activated carbon and separating starting fractions under the condition of the temperature of between 110 and 125 DEG C, the vacuum degree of less than or equal to 300Pa and nitrogen bubbling, cooling in a reactor to less than 60 DEG C, and performing circulating filtration to prepare the glycerol triacetate with the content of over 99.7 percent. Meanwhile, the glycerol triacetate prepared by the method has the chromaticity of less than No.15 and the acid value of less than or equal to 0.007 percent. The method greatly improves the content of the glycerol triacetate and the quality and the stability of the glycerol triacetate.
Description
Technical field
The invention belongs to the separating-purifying field of Chemicals, relate to a kind of method that adopts the continuous treating method to make high-content glycerol triacetate.
Background technology
Glycerine triacetate claims again vanay.English name Glycerol Triacetate, molecular formula C
9H
14O
6, molecular weight 21821 is the no color or smell oily liquids, nontoxic nonirritant.Glycerine triacetate dissolves in alcohol, ether, benzene, chloroform and Viscotrol C, but is insoluble to Semen Lini oil.Can dissolve soluble cotton, acrylic resin, polyvinyl acetate (PVA) etc.Glycerine triacetate has good pectisation and physiology inertia, is widely used as cigarette filter cellulose acetate plasticising solidifying agent, foodstuff additive, makeup fixative and lubricated matrix etc.Glycerine triacetate is widely used in tobacco, food, metallurgy industry as a kind of softening agent of safety non-toxic.
Traditional glycerol triacetate synthesis method is that the liquid acid such as the employing vitriol oil or tosic acid are made catalyst glycerine and the Glacial acetic acid esterification makes.The enterprise that produces at present glycerine triacetate makes the glycerine triacetate finished product usually in two steps.The first step is that glycerine and Glacial acetic acid carry out esterification under acidic conditions, with constantly the water that reaction generates being divided to walk by rectifier unit with aqua, reaction is carried out to positive dirction, does not obtain the product intermediate until there is moisture to go out the rear band aqua is told.Second step is that the glycerine reaction complete unreacted falls product intermediate aceticanhydride acidylate, namely obtains finished product through aftertreatment.Through the glycerine triacetate that this technique makes, one can reach 99% content, but has the shortcomings such as smell is large, acidity higher (between the 0.05-1%).
Refining report is also arranged in the prior art document, place again an airtight container such as the glycerine triacetate that will make in the aforementioned technique, under relatively high vacuum tightness, be heated to 120-140 ℃, constantly vacuumize, pass in case of necessity a small amount of water vapour, N
2Or CO
2, can remove most of acetic acid and smell, thereby thereby obtaining the glycerine triacetate that acidity is lower, smell is lighter reaches the purpose that promotes glycerine triacetate, but still do not reach the quality requirements of content more than 99.5%.
The more external method that the glycerine triacetate of having reported the low acidity of preparation and light smell in patents is also arranged is such as U.S. Patent number 3108133 disclosed methods; German Patent 156804 disclosed methods; German Patent 2900023 disclosed methods.
The above method has certain limitation, or method steps is numerous and diverse, or technique is wayward, or the processing cost height is not easy to large-scale industrial production.The product moisture of producing is higher, makes easily product carry out backward reaction, generates Glacial acetic acid, and the product acid number is improved, and affects quality product.
Thick finished product is made with extra care, can be removed impurity, reduce moisture content, make the acid number qualified of product and improve the unpleasant odor of product, continuous treating promotes the purpose that refining yield reaches improving product content.
Summary of the invention
The present invention proposes the method that a kind of continuous treating makes high-content glycerol triacetate.Method of the present invention can overcome the part weak point that exists in the existing report technology, can reach more than 99.7% with the glycerine triacetate content of method preparation of the present invention, and colourity is less than No. 15, acid number≤0.007%.Promote quality product and stability, reduced production costs, and made the starting fraction of fractionation by distillation in the treating process apply mechanically production batching recycling to the next batch glycerine triacetate, brought necessarily benefit economically, reduced the pollution to environment.
The present invention is achieved by the following technical solutions:
A kind of preparation method of high-content glycerol triacetate, with glycerine, Glacial acetic acid after esterification, acidylate, depickling, neutralization, make the glycerine triacetate crude product, again with the glycerine triacetate crude product at 110-125 ℃, vacuum tightness is not higher than and adopted gac (consumption of gac is the 0.05-0.1% of glycerine triacetate crude product quality) decolouring under the 300Pa condition 2.5-3 hour; With the product behind the activated carbon decolorizing at 115 ℃, vacuum tightness is not higher than under the 300Pa condition to be cooled off behind the separation starting fraction, adopting the aperture is that 1000 purpose wool felt strainers carry out circulating filtration again, and pressure is 0.2MPa during circulating filtration, obtains the glycerine triacetate of high-content.
Adopt nitrogen bubble during described activated carbon decolorizing.
Product purification after in the above-mentioned reaction activated carbon decolorizing being filtered separates starting fraction, carries out circulating filtration after being cooled to below 60 ℃ again.
The glycerine triacetate product content that the inventive method prepares 〉=99.7%, colourity is less than No. 15, acid number≤0.007%.
In preparation process, after the cleaning and filtering system, the feed clarification situation is added gac during according to reflux cycle.Discharge in case of necessity useless carbon, the cleaning and filtering plate of applying mechanically.The starting fraction made from extra care out pumps into after the collection in the deacidification tank in the preparation glycerine triacetate crude product process, enters the next round preparation.
Separate the complete rear cooling of starting fraction.In cooling time, carried out the circulating filtration operation, before the filtration, according to upper batch filtration velocity situation, determines whether to need to check carbon distribution situation in the strainer.If filtration velocity is slower, then opening filter is cleaned out the carbon slag of caking.
Advantage of the present invention and effect are: adopt the remove impurity with active carbon decolouring, need not add the subsidiary material of any costliness, processing cost is lower, only needs control temperature, vacuum tightness and passes into certain nitrogen bubble, and processing step is easily control comparatively simply also; Control under certain temperature and the vacuum degree condition and separate starting fraction, effectively reduce lower-boiling impurity to the impact of product content; Remove the impurity that gac and gac adsorb by circulating filtration again.Method of the present invention, processing efficiency is high, and the glycerine triacetate content of acquisition obviously improves.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Utilize the acid alcohol mechanisms of esterification reaction, esterification adopts distillation technology, glycerine, Glacial acetic acid and acid catalyst, azeotropic aqua are added the reaction kettle for reaction with rectifying tower, condenser and water trap, constantly will react the moisture of producing at cat head and go out, and entrainer is back in the tower.Thick product is delivered in the acidylate still, adds the rear depickling of aceticanhydride reaction, makes the glycerine triacetate crude product;
The glycerine triacetate crude product that measures is dropped in the refining kettle, drop into the gac that soaks with vanay in advance.The consumption of gac is the 0.05-0.1% of glycerine triacetate crude product quality; After the cleaning and filtering system, the feed clarification situation takes the circumstances into consideration to add gac during according to reflux cycle.Open condenser condenses water, drive the heating fuel tap and heat up, pass into simultaneously an amount of nitrogen bubble.Decoloured 2.5-3 hour; When the good temperature of refining kettle reaches 110 ℃, control vacuum tightness≤300pa, when reaching 125 ℃, the still temperature closes the heat-conducting oil heating valve, control 115 ℃, control vacuum tightness≤300pa fractionation, collect starting fraction, pump into after the collection in the deacidification tank in the preparation glycerine triacetate crude product process, enter the next round preparation.Reaction product is opened the chuck cooling water temperature, is cooled to less than or equal to water more than the emptying chuck after 60 ℃.Carry out the circulating filtration operation in the time of cooling; Adopting the aperture is that 1000 purpose wool felt strainers carry out circulating filtration, and pressure is 0.2MPa during circulating filtration.Carbon slag in the strainer should be cleaned out before filtering.Circulating filtration is pressed into finished pot after the feed liquid that obtains clear, namely get the glycerine triacetate after making with extra care; The glycerine triacetate product content for preparing 〉=99.7%, colourity is less than No. 15, acid number≤0.007%.
Thick finished product is carried out continuous treating, can remove impurity, reduce moisture content, make the acid number qualified of product and improve the unpleasant odor of product, continuous treating promotes the purpose that refining yield reaches improving product content.
Claims (3)
1. the preparation method of a high-content glycerol triacetate, with glycerine, Glacial acetic acid after esterification, acidylate, depickling, neutralization, make the glycerine triacetate crude product, it is characterized in that again the glycerine triacetate crude product at 110-125 ℃, vacuum tightness is not higher than under the 300Pa condition and adopts gac, the consumption of gac is the 0.05-0.1% of glycerine triacetate crude product quality, decolours after 2.5-3 hour; With the product behind the activated carbon decolorizing at 115 ℃, vacuum tightness is not higher than under the 300Pa condition to be cooled off behind the separation starting fraction, adopting the aperture is that 1000 purpose wool felt strainers carry out circulating filtration again, and pressure is 0.2MPa during circulating filtration, obtains the glycerine triacetate of high-content.
2. the preparation method of high-content glycerol triacetate according to claim 1 is characterized in that, adopts nitrogen bubble during described activated carbon decolorizing.
3. the preparation method of high-content glycerol triacetate according to claim 1 and 2 is characterized in that, described activated carbon decolorizing is all finished in refining kettle with the process of separating starting fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010559603 CN102010330B (en) | 2010-11-26 | 2010-11-26 | Method for preparing high-content glycerol triacetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010559603 CN102010330B (en) | 2010-11-26 | 2010-11-26 | Method for preparing high-content glycerol triacetate |
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| Publication Number | Publication Date |
|---|---|
| CN102010330A CN102010330A (en) | 2011-04-13 |
| CN102010330B true CN102010330B (en) | 2013-03-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010559603 Active CN102010330B (en) | 2010-11-26 | 2010-11-26 | Method for preparing high-content glycerol triacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911978B (en) * | 2018-07-30 | 2020-09-01 | 云南省玉溪市溶剂厂有限公司 | Method for purifying glycerol triacetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104814A1 (en) * | 1982-09-24 | 1984-04-04 | Celanese Corporation | Process of manufacturing diaryl esters of dicarboxylic acids |
| CN101585765A (en) * | 2008-05-21 | 2009-11-25 | 江苏瑞佳化学有限公司 | Method for preparing food grade triacetyl glycerine |
| CN101613275A (en) * | 2009-03-11 | 2009-12-30 | 云南玉溪环腾科工贸有限公司 | Atomizing raw materials is produced the method for glycerine triacetate |
-
2010
- 2010-11-26 CN CN 201010559603 patent/CN102010330B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104814A1 (en) * | 1982-09-24 | 1984-04-04 | Celanese Corporation | Process of manufacturing diaryl esters of dicarboxylic acids |
| CN101585765A (en) * | 2008-05-21 | 2009-11-25 | 江苏瑞佳化学有限公司 | Method for preparing food grade triacetyl glycerine |
| CN101613275A (en) * | 2009-03-11 | 2009-12-30 | 云南玉溪环腾科工贸有限公司 | Atomizing raw materials is produced the method for glycerine triacetate |
Non-Patent Citations (1)
| Title |
|---|
| 胡建等，.三醋酸甘油酯绿色合成工艺.《应用化工》.2008,第37卷(第7期),第787-793页. * |
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| CN102010330A (en) | 2011-04-13 |
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Effective date of registration: 20211221 Address after: 416117 interchange of Changji expressway, Wuxi Town, Luxi County, Xiangxi Tujia and Miao Autonomous Prefecture, Hunan Province (in Wuling Sunshine Biotechnology Co., Ltd.) Patentee after: Hunan Xianwei sunshine Biotechnology Co., Ltd Address before: 410016, No. 4, No. 472, lofty Road, Furong district, Hunan, Changsha Patentee before: HUNAN SHINEWAY ENTERPRISE Co.,Ltd. |
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