CN103467289A - Method for preparing glycerol triacetate - Google Patents
Method for preparing glycerol triacetate Download PDFInfo
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- CN103467289A CN103467289A CN2013104592973A CN201310459297A CN103467289A CN 103467289 A CN103467289 A CN 103467289A CN 2013104592973 A CN2013104592973 A CN 2013104592973A CN 201310459297 A CN201310459297 A CN 201310459297A CN 103467289 A CN103467289 A CN 103467289A
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- glycerine
- ionic liquid
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- ritalin
- methyl alcohol
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Abstract
A method for preparing the glycerol triacetate comprises the following steps of mixing basic ionic liquid and glycerin, adding the mixed liquid in a reaction kettle and heating the mixed liquid to 120-160DEG C, wherein the weight ratio of the basic ionic liquid and the glycerin is 2:100-20:100; adding methyl acetate in the mixed liquid to carry out transesterification, and generating acetoglyceride and methyl alcohol; controlling the pressure inside the reaction kettle to be 0.4-0.6MPa, and carrying out reaction for 6-8 hours; carrying out still standing and sedimentation for 2-4 hours, and discharging the lower basic ionic liquid catalyst layer; cooling the mixed acetoglyceride in the reaction kettle to 80-120DEG C, adding acetic anhydride with stirring to carry out acetylation action with acetate glyceride and diacetate glyceride in the acetoglyceride for 1-2 hours, wherein the weight ratio of the acetic anhydride and the glycerin is 20:100-30:100; carrying out distillation at 300-400Pa vacuum degree under 120-130DEG C to obtain glycerol triacetate products with purity higher than 99.7%. The method for preparing the glycerol triacetate is free from pollutants, clean and environmentally friendly in technology, low in reaction temperature and energy consumption and low in catalyst loss rate; the catalyst can be used repeatedly, and thus production cost is low.
Description
Technical field
The present invention relates to a kind of preparation method of glycerine triacetate.
Background technology
Glycerine triacetate is a kind of good solvent and softening agent, is widely used in food, spices, printing and dyeing and tobacco industry.Tradition prepares the method for glycerine triacetate, is that to take glycerine and acetic acid be raw material, carries out esterification under an acidic catalyst effect, generates glycerine triacetate.There is following defect in the method: because the method adopts acetic acid, as an acidic catalyst, glycerine is carried out to esterification, generate a large amount of waste waters in its reactant, bring the enormous pressure of wastewater treatment to manufacturing enterprise, and usually become the severe contamination source of contaminate environment.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of preparation method of glycerine triacetate is provided, and overcomes the defect of the reactant contaminate environment of prior art existence.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of glycerine triacetate is provided, it is characterized in that, comprise the steps:
S1, glycerine is mixed with alkali ionic liquid, the mass ratio of alkali ionic liquid and glycerine is 2:100～20:100; Glycerine and alkali ionic liquid mixed solution are added in reactor, be heated to 120 ℃～160 ℃;
S2, ritalin is added in glycerine and alkali ionic liquid mixed solution and carries out transesterification reaction, generate glycerol mono acetate bulk and methyl alcohol; The mixed gas of discharge section ritalin and methyl alcohol, control reacting kettle inner pressure between 0.4MPa～0.6MPa, 6 hours～8 hours reaction times;
S3, by reactant standing sedimentation 2 hours～4 hours, discharge the alkaline ionic liquid catalyst layer of lower floor;
S4, the mixing vinegar acid glyceride stayed in reactor is cooled to 80 ℃～120 ℃, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100～30:100, a glycerol mono acetate bulk and two glycerol mono acetate bulks in acetic anhydride and glyceryl ester carry out acetylization reaction, and the reaction times is 1 hour～2 hours;
S5, under 300Pa～400Pa vacuum tightness, distilled, collect the overhead product of 120 ℃～130 ℃, obtaining purity is the glycerine triacetate product more than 99.7%.
In the preparation method of glycerine triacetate of the present invention, the structure formation of described alkali ionic liquid is A
+b
-, wherein, cation A is one of phosphines, glyoxaline compound, pyridine compounds and their or aminated compounds, negatively charged ion B is OH
-, AlCl
4 -, ZnCl
7 -one of.
In the preparation method of glycerine triacetate of the present invention, the mixture that described alkali ionic liquid is first and second; Wherein, described first is that structure formation is A
+b
-alkali ionic liquid in one or more mixture, described cation A is one of phosphines, glyoxaline compound, pyridine compounds and their or aminated compounds, described negatively charged ion B is OH
-, AlCl
4 -, ZnCl
7 -one of; Described second is one or more the mixture in KOH, NaOH, sodium alkoxide, potassium alcoholate.
In the preparation method of glycerine triacetate of the present invention, described step S2 comprises, the mixed gas of the ritalin of discharge and methyl alcohol is passed into to rectifying tower, carries out methyl alcohol and ritalin separating-purifying, and the ritalin after purification is reused.
In the preparation method of glycerine triacetate of the present invention, described step S3 comprises, the alkaline ionic liquid catalyst of discharge is reused in step S1.
Implement the preparation method of glycerine triacetate of the present invention, compared with the prior art, its beneficial effect is:
1. production process produces without waste water, has thoroughly eliminated glycerine triacetate tradition preparation method's pollution problem, the production technique clean environment firendly;
2. adopt the catalyzer of alkali ionic liquid as glycerine and ritalin transesterification reaction, temperature of reaction low (120 ℃～160 ℃), the catalyst attrition of avoiding pyrolytic decomposition to cause, rate of catalyst loss is lower;
3. the separation temperature of alkaline ionic liquid catalyst and glycerine low (120 ℃～130 ℃), do not need pyrogenic distillation, reduced energy consumption; Simultaneously, alkaline ionic liquid catalyst is reusable, greatly reduces production costs.
The accompanying drawing explanation
Fig. 1 is the schema of a kind of embodiment of preparation method of glycerine triacetate of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment mono-
As shown in Figure 1, preparation method's step of glycerine triacetate of the present invention is as follows:
1, amino acid ion liquid is mixed with glycerine, the mass ratio of amino acid ion liquid and glycerine is 20:100; Glycerine and amino acid ion liquid mixed solution are added in reactor, be heated to 120 ℃.
2, ritalin is added in glycerine and amino acid ion liquid mixed solution and carry out transesterification reaction with glycerine, generate glycerol mono acetate bulk and methyl alcohol; The mixed gas of discharge section ritalin and methyl alcohol, control reacting kettle inner pressure at 0.4MPa, reacts 8 hours.
3,, after transesterification reaction finishes, by reactant standing sedimentation 2 hours, discharge the amino acid ion liquid catalyst layer of lower floor.
4, the mixing vinegar acid glyceride on upper strata is cooled to 80 ℃, it is 40:100 that stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine, and a glycerol mono acetate bulk and two glycerol mono acetate bulks in acetic anhydride and glyceryl ester carry out acetylization reaction, react 2 hours.
5, distilled under 300Pa～400Pa vacuum tightness, collected the overhead product of 120 ℃～130 ℃, the glycerine triacetate product that to obtain purity be 99.76%.
In step 2, the mixed gas of the ritalin of discharge and methyl alcohol is passed into to rectifying tower, carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused, and improves the utilization ratio of ritalin, reduces production costs.
In step 3, the amino acid ion liquid catalyzer of discharge is reused in step 1, reduce production costs.
Embodiment bis-
1, N-R-N-Methylimidazole hydroxide ion liquid is mixed with glycerine, the mass ratio of N-R-N-Methylimidazole hydroxide ion liquid and glycerine is 10:100, glycerine and N-R-N-Methylimidazole hydroxide ion mixed liquid are added in reactor, and temperature is increased to 160 ℃.
2, ritalin from pumping into glycerine in reactor and N-R-N-Methylimidazole hydroxide ion mixed liquid, reactor bottom is carried out to transesterification reaction with glycerine, generation glycerol mono acetate bulk and methyl alcohol; Open the vent valve on reactor top, the mixed gas of the unreacted ritalin of discharge section and methyl alcohol, control reacting kettle inner pressure at 0.6MPa, and the reaction times is 6 hours.
3,, after transesterification reaction finishes, by reactant standing sedimentation 4 hours, discharge the N-R-N-Methylimidazole hydroxide ion liquid catalyst layer of lower floor.
4, the mixing vinegar acid glyceride on upper strata is cooled to 120 ℃; stirring adds acetic anhydride; the mass ratio of acetic anhydride and glycerine is 30:100; a glycerol mono acetate bulk and two glycerol mono acetate bulks in acetic anhydride and glyceryl ester carry out acetylization reaction; further improve the transformation efficiency of glycerine triacetate, the reaction times is 1 hour.
5, distilled under 300Pa～400Pa vacuum tightness, collected the overhead product of 120 ℃～130 ℃, the glycerine triacetate product that to obtain purity be 99.70%.
In above-mentioned steps 2, the mixed gas of discharge is directly passed into to rectifying tower, carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused, and improves the utilization ratio of ritalin, reduces production costs.
In above-mentioned steps 3, the N-R-N-Methylimidazole hydroxide ion liquid of discharge is reused in step 1, reduce production costs.
Embodiment tri-
1, by 1-(N, the N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester salt ion liquid mixes with glycerine, by glycerine and 1-(N, the N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester salt ion mixed liquid adds in reactor, is heated to 140 ℃.
2, ritalin is pumped into to glycerine and the 1-(N in reactor, N-dimethyl aminoethyl from the reactor bottom)-2, carry out transesterification reaction with glycerine in 3-methylimidazole trifluoromethyl sulphur ester salt ion mixed liquid, generate glycerol mono acetate bulk and methyl alcohol; Open the vent valve on reactor top, the mixed gas of the unreacted ritalin of discharge section and methyl alcohol, control reacting kettle inner pressure at 0.5MPa, and the reaction times is 6 hours.
3,, after transesterification reaction finishes, by reactant standing sedimentation 2 hours, discharge the 1-(N of lower floor, the N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester salt ion liquid catalyst layer.
4, the mixing vinegar acid glyceride on upper strata is cooled to 80 ℃～120 ℃; stirring adds acetic anhydride; the mass ratio of acetic anhydride and glycerine is 20:100; a glycerol mono acetate bulk and two glycerol mono acetate bulks in acetic anhydride and glyceryl ester carry out acetylization reaction; further improve the transformation efficiency of glycerine triacetate, the reaction times is 2 hours.
5, distilled the glycerine triacetate product that to obtain purity be 99.82% under 300Pa～400Pa vacuum tightness, 120 ℃～130 ℃ conditions.
In above-mentioned steps 2, the mixed gas of discharge is directly passed into to rectifying tower, carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused, and improves the utilization ratio of ritalin, reduces production costs.
In above-mentioned steps 3, by the 1-(N discharged, N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester salt ion liquid is reused in step 1, reduces production costs.
In the various embodiments described above, the structure formation of alkali ionic liquid is A
+b
-, wherein, cation A is one of phosphines, glyoxaline compound, pyridine compounds and their or aminated compounds, negatively charged ion B is OH
-, AlCl
4 -, ZnCl
7 -one of.
In the various embodiments described above, alkali ionic liquid can adopt the mixture of first and second.Wherein, first is that the said structure form is A
+b
-alkali ionic liquid in one or more mixture, second is one or more the mixture in KOH, NaOH, sodium alkoxide, potassium alcoholate.
Claims (5)
1. the preparation method of a glycerine triacetate, is characterized in that, comprises the steps:
S1, glycerine is mixed with alkali ionic liquid, the mass ratio of alkali ionic liquid and glycerine is 2:100～20:100; Glycerine and alkali ionic liquid mixed solution are added in reactor, be heated to 120 ℃～160 ℃;
S2, ritalin is added in glycerine and alkali ionic liquid mixed solution and carries out transesterification reaction, generate glycerol mono acetate bulk and methyl alcohol; The mixed gas of discharge section ritalin and methyl alcohol, control reacting kettle inner pressure between 0.4MPa～0.6MPa, 6 hours～8 hours reaction times;
S3, by reactant standing sedimentation 2 hours～4 hours, discharge the alkaline ionic liquid catalyst layer of lower floor;
S4, the mixing vinegar acid glyceride stayed in reactor is cooled to 80 ℃～120 ℃, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100～30:100, a glycerol mono acetate bulk and two glycerol mono acetate bulks in acetic anhydride and glyceryl ester carry out acetylization reaction, and the reaction times is 1 hour～2 hours;
S5, under 300Pa～400Pa vacuum tightness, distilled, collect the overhead product of 120 ℃～130 ℃, obtaining purity is the glycerine triacetate product more than 99.7%.
2. the preparation method of glycerine triacetate as claimed in claim 1, is characterized in that, the structure formation of described alkali ionic liquid is A
+b
-, wherein, cation A is one of phosphines, glyoxaline compound, pyridine compounds and their or aminated compounds, negatively charged ion B is OH
-, AlCl
4 -, ZnCl
7 -one of.
3. the preparation method of glycerine triacetate as claimed in claim 1, is characterized in that, the mixture that described alkali ionic liquid is first and second; Wherein, described first is that structure formation is A
+b
-alkali ionic liquid in one or more mixture, described cation A is one of phosphines, glyoxaline compound, pyridine compounds and their or aminated compounds, described negatively charged ion B is OH
-, AlCl
4 -, ZnCl
7 -one of; Described second is one or more the mixture in KOH, NaOH, sodium alkoxide, potassium alcoholate.
4. as the preparation method of the described glycerine triacetate of one of claims 1 to 3, it is characterized in that, described step S2 comprises, the mixed gas of the ritalin of discharge and methyl alcohol is passed into to rectifying tower, carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused.
5. as the preparation method of the described glycerine triacetate of one of claims 1 to 3, it is characterized in that, described step S3 comprises, the alkaline ionic liquid catalyst of discharge is reused in step S1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588646A (en) * | 2016-12-19 | 2017-04-26 | 田璐 | Method for preparing glyceryl triacetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| 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 |
| CN102876466A (en) * | 2012-10-05 | 2013-01-16 | 盐城师范学院 | Method for catalyzing ester exchange reaction with alkaline ionic liquid |
-
2013
- 2013-09-27 CN CN201310459297.3A patent/CN103467289B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| 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 |
| CN102876466A (en) * | 2012-10-05 | 2013-01-16 | 盐城师范学院 | Method for catalyzing ester exchange reaction with alkaline ionic liquid |
Non-Patent Citations (2)
| Title |
|---|
| LI JI,ET AL.,: "Lewis basic ionic liquid as an efficient and facile catalyst for acetylation of alcohols,phenols,and amines under solvent-free conditions", 《MONATSH CHEM》 * |
| 高建荣等: "三醋酸甘油酯合成工艺研究", 《浙江化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588646A (en) * | 2016-12-19 | 2017-04-26 | 田璐 | Method for preparing glyceryl triacetate |
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