CN1049425C - Preparation of tricetate glyceride - Google Patents
Preparation of tricetate glyceride Download PDFInfo
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- CN1049425C CN1049425C CN96102341A CN96102341A CN1049425C CN 1049425 C CN1049425 C CN 1049425C CN 96102341 A CN96102341 A CN 96102341A CN 96102341 A CN96102341 A CN 96102341A CN 1049425 C CN1049425 C CN 1049425C
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- acetic acid
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- acetate
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- trichloropropane
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Abstract
The present invention discloses a method for preparing triacetyl glycerine. Trichloropropane and sodium acetate which are used as raw materials react in a medium containing aqueous acetic acid or glacial acetic acid so as to prepare triacetyl glycerine. 1, 2-dichloro-3-propanol acetate and 1-chloro-2, 3-propanediol diacetate which are intermediate products are returned into a reaction system, and thus, 1, 2-dichloro-3-propanol acetate and 1-chloro-2, 3-propanediol diacetate continue reacting with the sodium acetate so as to prepare triacetyl glycerine. Trichloropropane and acetic acid are used as light components (mixture) to be recovered. According to the compounding requirement, acetic acid (or trichloropropane) is added to the mixture. The energy consumption and the material breakage because trichloropropane and acetic acid are singly recovered can be avoided, and acetic acid as a reaction medium can be circularly used for a long time. The reaction is carried out in a titanium (or composite titanium) reaction kettle or a glass lining reaction kettle, and the corrosion of reaction materials to reaction equipment is greatly reduced.
Description
The present invention relates to a kind of method for preparing glycerine triacetate, particularly relating to a kind of is raw material with trichloropropane and sodium-acetate, is the method that reaction medium prepares glycerine triacetate with water-containing acetic acid or Glacial acetic acid.
Glycerine triacetate is a kind of good solvent and softening agent, can be used for food, spices and printing and dyeing industry.Because the intermiscibility of its Dichlorodiphenyl Acetate Mierocrystalline cellulose, Nitrocellulose, ethyl cellulose is good, thereby be specially adapted to do the jelling agent of cigarette filter Cellulose diacetate.As everyone knows, be raw material with glycerine and acetic acid, be the classical way of preparation glycerine triacetate.But this method produces a large amount of water in building-up process, causes the glycerine triacetate yield to reduce, and is raw material with glycerine, because market shortages causes product cost higher.Deutsches Reichs-Patent DE3,545,583 to disclose a kind of be the method for the synthetic glycerine triacetate of raw material with trichloropropane and sodium-acetate.This method requires the water content of reaction system must be below 0.5%, otherwise the yield of glycerine triacetate sharply reduces, and in fact, in actually operating, this condition is difficult to reach, even if can, also to expend sizable energy, thereby reduce this method feasibility economically.Secondly, this method requires must be with Glacial acetic acid as reaction medium, because the Glacial acetic acid water in the absorbing environmental very easily, thereby must manage to stop contacting of Glacial acetic acid and air, this also gives accumulating and uses Glacial acetic acid to bring inconvenience.
The objective of the invention is to overcome the weak point that exists in the prior art, a kind of novel method for preparing glycerine triacetate is provided, prepare glycerine triacetate with method of the present invention, can improve the yield of glycerine triacetate, reduce production costs, and make the by-product of epoxy chloropropane device be able to reasonable utilization.
In order to achieve the above object, the technical solution used in the present invention is summarized as follows:
The trichloropropane, sodium-acetate, acetic acid (be not limited only to Glacial acetic acid, but to use Glacial acetic acid for well) and the aceticanhydride that in titanium material (or titanium composite material) reactor (or glassed steel reaction vessels), add metering, sealed reactor.After reacting certain hour at a certain temperature, reactant is emitted in the reactive system cooling, centrifugation goes out the by product sodium-chlor of reaction, then with mother liquor rectifying so that reclaim acetic acid, trichloropropane, 1,2-two chloro-3-propanol acetate ester and 1-chloro-2, ammediol two acetic acid vinegar (this mixture is called light constituent) carry out rectifying to the heavy constituent that are stored in the tower still, get final product the product glycerine triacetate.The light constituent mixture is analyzed, and required to replenish an amount of trichloropropane, acetic acid and aceticanhydride, this mixture can be recycled with reference to the reaction batching.
The molar ratio range of sodium-acetate of the present invention and glyceryl trichloride is 0.8: 1～1.5: 1, is advisable with 1.0: 1～1.4: 1, on this proportioning basis, then causes the transformation efficiency of sodium-acetate to reduce if increase the consumption of sodium-acetate; And reduce the consumption of sodium-acetate, though the transformation efficiency that can guarantee sodium-acetate near 100%, but the efficient of whole synthesizer reduces.The molar ratio range of acetic acid and sodium-acetate is 1.5: 1～4.5: 1, and is comparatively suitable with 1.5: 1～4.0: 1.The water content of complete reaction mixture should be controlled at below 10%, is controlled at below 5% better.The usage quantity of aceticanhydride can determine that every mol water is added aceticanhydride 0.99～1.76mol according to the water content of reaction mixture.Temperature of reaction remains in 160～290 ℃ of scopes, with 190～220 ℃ for well, the reaction times is 2～8 hours, with 3～6 hours for well.Reaction pressure is 0.58～2.0MPa, and is comparatively suitable with 0.58～0.75MPa, and under the lower situation of temperature of reaction, reaction pressure can be regulated by nitrogen.Reaction is isolated byproduct sodium chloride after finishing from reaction mass, filtrate is carried out rectifying, reclaim acetic acid, glyceryl trichloride and a spot of 1-chloro-2, the mixture of ammediol diacetate esters is left and taken synthetic use next time, and rectifying goes out the product glycerine triacetate then.
Characteristics of the present invention are:
1. the by-product trichloropropane that utilizes chloropropane-epoxy chloropropane device has changed the synthetic route of traditional glycerine-acetic acid (aceticanhydride) as raw material, has reduced production cost.
2. by adding an amount of aceticanhydride to remove the water in the reaction system in reaction system, can avoid reducing because of the yield of the too high glycerine triacetate that causes of raw material water content, compare with the Deutsches Reichs-Patent technology, product yield has improved tens percentage points.
3. trichloropropane, acetic acid and intermediate product are reclaimed together conserve energy.
4. the reaction intermediate Returning reacting system reacts again, with the yield of raising glycerine triacetate, and can avoid because of handling the intermediate product pollution on the environment.
5. can avoid reaction mass corrosion to equipment under reaction conditions with titanium (or composite titanium material) system conversion unit.
In order to describe technical characterstic of the present invention better, be described further below in conjunction with embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=1.2: 1 (mol/mol)
Acetic acid: sodium-acetate=3: 1 (mol/mol)
In being furnished with the 1000ml reactor of magnetic agitation, add sodium-acetate 1.8mol, glyceryl trichloride 1.5mol, Glacial acetic acid 5.4mol.Learn that by analysis the water content of this mixture is 0.4%, therefore do not add aceticanhydride, sealed reactor stirs, in the cooling after 3 hours of reaction under 195 ℃ the temperature condition, reaction mixture.Collect acetic acid, glyceryl trichloride and 3-chloro-2, the mixture of ammediol diacetate esters and product glycerine triacetate by rectifying.The sodium-acetate transformation efficiency is 99.3%, and the yield of glycerine triacetate is 76.6% (in sodium-acetate), and purity is 99.2%.
Embodiment 2
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=1.2: 1 (mol/mol)
Acetic acid: sodium-acetate=3: 1 (mol/mol)
Get acetic acid, glyceryl trichloride and the 3-chloro-2 collected among the embodiment 1, the mixture of ammediol diacetate esters adds reactor, adds acetic acid 0.16mol after the calculating, and glyceryl trichloride 0.65mol adds sodium-acetate 1.8mol then to formula ratio.The water content of assaying reaction mixture is 2%, adds aceticanhydride 1.23mol.Reaction conditions is with embodiment 1.Reaction finishes the back and collects acetic acid and glyceryl trichloride 0.85mol and 3-chloro-2, and ammediol diacetate esters 0.04mol collects glycerine triacetate 0.437mol.Reaction result sodium-acetate transformation efficiency is 99.1%, and glycerine triacetate yield (in sodium-acetate) is 77.8%.
Embodiment 3
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=0.8: 1 (mol/mol)
Acetic acid: sodium-acetate=1.5: 1 (mol/mol)
Add Glacial acetic acid 3.0mol, glyceryl trichloride 2.5mol, sodium acetate, anhydrous 2.0mol.Assaying reaction mixture water content is 1.4%, adds aceticanhydride 0.55mol.Temperature of reaction is 210 ℃, and the reaction times is 2.5 hours.Reaction finishes the back and collects glycerine triacetate 0.509mol, and the sodium-acetate transformation efficiency is 99.6%, and glycerine triacetate yield (in sodium-acetate) is 76.3%.
Embodiment 4
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=1.5: 1 (mol/mol)
Acetic acid: sodium-acetate=4.0: 1 (mol/mol)
Get acetic acid, glyceryl trichloride and the 3-chloro-2 collected among the embodiment 2, the mixture of ammediol two/acetic ester adds reactor, adds acetic acid 1.96mol and glyceryl trichloride 0.35mol after the calculating to formula ratio, adds sodium-acetate 1.80mol then.Assaying reaction mixture water content is 0.7%, adds aceticanhydride 0.29mol.210 ℃ of temperature of reaction, 2.5 hours reaction times.Reaction finishes the back and collects glycerine triacetate 0.43mol, and the sodium-acetate transformation efficiency is 99.0%, and glycerine triacetate yield (in sodium-acetate) is 71.7%.
Embodiment 5
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=1.2: 1 (mol/mol)
Acetic acid: sodium-acetate=4.5: 1
Get acetic acid, glyceryl trichloride and the 3-chloro-2 collected among the embodiment 2, the mixture of ammediol diacetate esters adds reactor, adds acetic acid 2.86mol and glyceryl trichloride 0.65mol after the calculating to formula ratio, adds sodium-acetate 1.80mol then.Assaying reaction mixture water content is 4.7%, therefore adds aceticanhydride 1.83mol.200 ℃ of temperature of reaction, the reaction times is 3.5 hours, and reaction finishes the back and collects glycerine triacetate 0.45mol, and the sodium-acetate transformation efficiency is 99.3%, and glycerine triacetate yield (in sodium-acetate) is 78.2%.
Embodiment 6
Proportioning raw materials:
Sodium-acetate: glyceryl trichloride=1.5: 1 (mol/mol)
Acetic acid: sodium-acetate=2.5: 1 (mol/mol)
Add Glacial acetic acid 4.5mol, glyceryl trichloride 1.2mol, sodium acetate, anhydrous 1.8mol.Assaying reaction mixture water content is 3.1%, adds aceticanhydride 1.0mol.Temperature of reaction is 185 ℃, and the reaction times is 5 hours.Reaction finishes the back and collects glycerine triacetate 0.47mol, and the sodium-acetate transformation efficiency is 99.5%, and glycerine triacetate yield (in sodium-acetate) is 78.1%.
Claims (8)
1, a kind of preparation method of glycerine triacetate, comprise that with trichloropropane and sodium-acetate be raw material, reaction generates glycerine triacetate in water-containing acetic acid or Glacial acetic acid medium, it is characterized in that adding an amount of aceticanhydride in reaction system, is lower than 0.5% with the water content of controlling reaction mixture.
2, method according to claim 1 is characterized in that the water content according to reaction mixture, whenever contains 1mol water and adds aceticanhydride 0.99～1.76mol.
3, method according to claim 1, the batching mol ratio that it is characterized in that sodium-acetate and glyceryl trichloride is 0.8: 1～1.5: 1.
4, according to claim 1 or 3 described methods, the batching mol ratio that it is characterized in that sodium-acetate and glyceryl trichloride is 1.0: 1～1.4: 1.
5, method according to claim 1, the batching mol ratio that it is characterized in that acetic acid and sodium-acetate is 1.5: 1～4.5: 1.
6, method according to claim 1 or 5, the batching mol ratio that it is characterized in that acetic acid and sodium-acetate is 1.5: 1～4.0: 1.
7, method according to claim 1 is characterized in that the reaction times is 2～8 hours.
8,, it is characterized in that the reaction times is 3～6 hours according to claim 1 or 7 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102341A CN1049425C (en) | 1996-07-09 | 1996-07-09 | Preparation of tricetate glyceride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102341A CN1049425C (en) | 1996-07-09 | 1996-07-09 | Preparation of tricetate glyceride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1169979A CN1169979A (en) | 1998-01-14 |
| CN1049425C true CN1049425C (en) | 2000-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96102341A Expired - Fee Related CN1049425C (en) | 1996-07-09 | 1996-07-09 | Preparation of tricetate glyceride |
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| CN (1) | CN1049425C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450897B (en) * | 2007-11-28 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing triacetin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0033929A1 (en) * | 1980-02-08 | 1981-08-19 | Henkel Kommanditgesellschaft auf Aktien | Process for the continuous manufacture of triacetin |
| DE3545583A1 (en) * | 1985-12-21 | 1987-06-25 | Dow Chemical Gmbh | METHOD FOR PRODUCING ORGANIC ESTERS FROM HALOGEN CARBON COMPOUNDS |
| CN1124244A (en) * | 1994-12-06 | 1996-06-12 | 上海申贝办公机械总公司 | Glycerol triacetate |
-
1996
- 1996-07-09 CN CN96102341A patent/CN1049425C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0033929A1 (en) * | 1980-02-08 | 1981-08-19 | Henkel Kommanditgesellschaft auf Aktien | Process for the continuous manufacture of triacetin |
| DE3545583A1 (en) * | 1985-12-21 | 1987-06-25 | Dow Chemical Gmbh | METHOD FOR PRODUCING ORGANIC ESTERS FROM HALOGEN CARBON COMPOUNDS |
| CN1124244A (en) * | 1994-12-06 | 1996-06-12 | 上海申贝办公机械总公司 | Glycerol triacetate |
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| Publication number | Publication date |
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| CN1169979A (en) | 1998-01-14 |
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