CN103467289B - A kind of preparation method of glycerine triacetate - Google Patents
A kind of preparation method of glycerine triacetate Download PDFInfo
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- CN103467289B CN103467289B CN201310459297.3A CN201310459297A CN103467289B CN 103467289 B CN103467289 B CN 103467289B CN 201310459297 A CN201310459297 A CN 201310459297A CN 103467289 B CN103467289 B CN 103467289B
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- ionic liquid
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- ritalin
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Abstract
A preparation method for glycerine triacetate, comprises the steps: to be first that the alkali ionic liquid of 2:100 ~ 20:100 mixes with glycerine by mass ratio, is added by mixed solution in reactor and be heated to 120 ~ 160 DEG C; Again ritalin is added in mixed solution and carry out transesterification reaction, generate glycerol mono acetate bulk and methyl alcohol; Control reacting kettle inner pressure is 0.4 ~ 0.6MPa, reacts 6 ~ 8 hours; Then standing sedimentation 2 ~ 4 hours, discharges lower floor's alkaline ionic liquid catalyst layer; Then the mixing vinegar acid glyceride in reactor is cooled to 80 ~ 120 DEG C, stirring adds acetic anhydride, carry out acetylization reaction 1 ~ 2 hour with the glycerol mono acetate bulk in glyceryl ester and two glycerol mono acetate bulks, the mass ratio of acetic anhydride and glycerine is 20:100 ~ 30:100; In 300 ~ 400Pa vacuum tightness, distillation at 120 ~ 130 DEG C, obtain the glycerine triacetate product of purity more than 99.7%.Method contamination-free of the present invention, technique clean environment firendly, temperature of reaction is low, and energy consumption is low, and rate of catalyst loss is low; Catalyzer is reusable, and 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, be with glycerine and acetic acid for raw material, under an acidic catalyst effect, carry out esterification, generate glycerine triacetate.There is following defect in the method: because the method adopts acetic acid to carry out esterification as an acidic catalyst to glycerine, a large amount of waste waters is generated 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, provides a kind of preparation method of glycerine triacetate, overcomes the defect of the reactant contaminate environment that prior art exists.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method providing a kind of glycerine triacetate, is characterized in that, comprises the steps:
S1, mixed with alkali ionic liquid by glycerine, 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, is heated to 120 DEG C ~ 160 DEG C;
S2, ritalin 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, controls 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 DEG C ~ 120 DEG C, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100 ~ 30:100, a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction, and the reaction times is 1 hour ~ 2 hours;
S5, to distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is more than 99.7%;
Described alkali ionic liquid structure formation is A
+b
-, wherein, cation A is phosphines, glyoxaline compound, one of pyridine compounds and their or aminated compounds, and negatively charged ion B is OH
-, AlCl
4 -, ZnCl
3 -one of.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method providing a kind of glycerine triacetate, is characterized in that, comprises the steps:
S1, mixed with alkali ionic liquid by glycerine, 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, is heated to 120 DEG C ~ 160 DEG C;
S2, ritalin 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, controls 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 DEG C ~ 120 DEG C, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100 ~ 30:100, a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction, and the reaction times is 1 hour ~ 2 hours;
S5, to distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is more than 99.7%;
Described alkali ionic liquid is the mixture of first and second; Wherein, described first is structure formation is A
+b
-alkali ionic liquid in the mixture of one or more, described cation A is phosphines, glyoxaline compound, one of pyridine compounds and their or aminated compounds, and described negatively charged ion B is OH
-, AlCl
4 -, ZnCl
3 -one of; Described second is the mixture of one or more in KOH, NaOH, sodium alkoxide, potassium alcoholate.
In the preparation method of glycerine triacetate of the present invention, described step S2 comprises, and the ritalin of discharge and the mixed gas of methyl alcohol are passed into rectifying tower, and carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused.
In the preparation method of glycerine triacetate of the present invention, described step S3 comprises, and is reused in step sl by the alkaline ionic liquid catalyst of discharge.
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, completely eliminates the pollution problem of glycerine triacetate traditional preparation methods, production technique clean environment firendly;
2. adopt alkali ionic liquid as the catalyzer of glycerine and ritalin transesterification reaction, temperature of reaction low (120 DEG C ~ 160 DEG C), avoid the catalyst attrition that pyrolytic decomposition causes, rate of catalyst loss is lower;
3. the separation temperature of alkaline ionic liquid catalyst and glycerine low (120 DEG C ~ 130 DEG C), does not need pyrogenic distillation, reduces energy consumption; Meanwhile, alkaline ionic liquid catalyst is reusable, greatly reduces production cost.
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 one
As shown in Figure 1, preparation method's step of glycerine triacetate of the present invention is as follows:
1, mixed with glycerine by amino acid ion liquid, 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, is heated to 120 DEG C.
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, controls reacting kettle inner pressure at 0.4MPa, reacts 8 hours.
3, after transesterification reaction terminates, by reactant standing sedimentation 2 hours, the amino acid ion liquid catalyst layer of lower floor is discharged.
4, the mixing vinegar acid glyceride on upper strata is cooled to 80 DEG C, stir and add acetic anhydride, the mass ratio of acetic anhydride and glycerine is 40:100, and the glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction, react 2 hours.
5, distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is 99.76%.
In step 2, the ritalin of discharge and the mixed gas of methyl alcohol are passed into 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 cost.
In step 3, the amino acid ion liquid catalyzer of discharge is reused in step 1, reduce production cost.
Embodiment two
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, add in reactor by glycerine and N-R-N-Methylimidazole hydroxide ion mixed liquid, temperature is increased to 160 DEG C.
2, ritalin is pumped into bottom reactor glycerine in reactor and N-R-N-Methylimidazole hydroxide ion mixed liquid and carry out transesterification reaction with glycerine, 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 0.6MPa, the reaction times is 6 hours.
3, after transesterification reaction terminates, by reactant standing sedimentation 4 hours, the N-R-N-Methylimidazole hydroxide ion liquid catalyst oxidant layer of lower floor is discharged.
4, the mixing vinegar acid glyceride on upper strata is cooled to 120 DEG C; stirring adds acetic anhydride; the mass ratio of acetic anhydride and glycerine is 30:100; a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction; the transformation efficiency of further raising glycerine triacetate, the reaction times is 1 hour.
5, distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is 99.70%.
In step 2 above, the mixed gas of discharge is directly passed into 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 cost.
In above-mentioned steps 3, the N-R-N-Methylimidazole hydroxide ion liquid of discharge is reused in step 1, reduce production cost.
Embodiment three
1, by 1-(N, N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester ionic liquid mixes with glycerine, by glycerine and 1-(N, N-dimethyl aminoethyl)-2,3-methylimidazole trifluoromethyl sulphur ester ionic liquid mixed solution adds in reactor, is heated to 140 DEG C.
2, ritalin is pumped into bottom reactor the glycerine in reactor and 1-(N, N-dimethyl aminoethyl)-2, carry out transesterification reaction with glycerine in 3-methylimidazole trifluoromethyl sulphur ester ionic liquid mixed solution, 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, the reaction times is 6 hours.
3, after transesterification reaction terminates, by reactant standing sedimentation 2 hours, 1-(N, N-dimethyl aminoethyl)-2, the 3-methylimidazole trifluoromethyl sulphur ester ionic liquid catalyst layer of lower floor is discharged.
4, the mixing vinegar acid glyceride on upper strata is cooled to 80 DEG C ~ 120 DEG C; stirring adds acetic anhydride; the mass ratio of acetic anhydride and glycerine is 20:100; a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction; the transformation efficiency of further raising glycerine triacetate, the reaction times is 2 hours.
5, distill under 300Pa ~ 400Pa vacuum tightness, 120 DEG C ~ 130 DEG C conditions, obtain the glycerine triacetate product that purity is 99.82%.
In step 2 above, the mixed gas of discharge is directly passed into 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 cost.
In above-mentioned steps 3,1-(N, N-dimethyl aminoethyl)-2, the 3-methylimidazole trifluoromethyl sulphur ester ionic liquid of discharging is reused in step 1, reduce production cost.
In the various embodiments described above, the structure formation of alkali ionic liquid is A
+b
-, wherein, cation A is phosphines, glyoxaline compound, one of pyridine compounds and their or aminated compounds, and negatively charged ion B is OH
-, AlCl
4 -, ZnCl
3 -one of.
In the various embodiments described above, alkali ionic liquid can adopt the mixture of first and second.Wherein, first is said structure form is A
+b
-alkali ionic liquid in the mixture of one or more, second is the mixture of one or more in KOH, NaOH, sodium alkoxide, potassium alcoholate.
Claims (4)
1. a preparation method for glycerine triacetate, is characterized in that, comprises the steps:
S1, mixed with alkali ionic liquid by glycerine, 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, is heated to 120 DEG C ~ 160 DEG C;
S2, ritalin 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, controls 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 DEG C ~ 120 DEG C, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100 ~ 30:100, a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction, and the reaction times is 1 hour ~ 2 hours;
S5, to distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is more than 99.7%;
Described alkali ionic liquid structure formation is A
+b
-, wherein, cation A is phosphines, glyoxaline compound, one of pyridine compounds and their or aminated compounds, and negatively charged ion B is OH
-, AlCl
4 -, ZnCl
3 -one of.
2. a preparation method for glycerine triacetate, is characterized in that, comprises the steps:
S1, mixed with alkali ionic liquid by glycerine, 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, is heated to 120 DEG C ~ 160 DEG C;
S2, ritalin 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, controls 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 DEG C ~ 120 DEG C, stirring adds acetic anhydride, the mass ratio of acetic anhydride and glycerine is 20:100 ~ 30:100, a glycerol mono acetate bulk in acetic anhydride and glyceryl ester and two glycerol mono acetate bulks carry out acetylization reaction, and the reaction times is 1 hour ~ 2 hours;
S5, to distill under 300Pa ~ 400Pa vacuum tightness, collect the overhead product of 120 DEG C ~ 130 DEG C, obtain the glycerine triacetate product that purity is more than 99.7%;
Described alkali ionic liquid is the mixture of first and second; Wherein, described first is structure formation is A
+b
-alkali ionic liquid in the mixture of one or more, described cation A is phosphines, glyoxaline compound, one of pyridine compounds and their or aminated compounds, and described negatively charged ion B is OH
-, AlCl
4 -, ZnCl
3 -one of; Described second is the mixture of one or more in KOH, NaOH, sodium alkoxide, potassium alcoholate.
3. the preparation method of glycerine triacetate as claimed in claim 1 or 2, it is characterized in that, described step S2 comprises, and the ritalin of discharge and the mixed gas of methyl alcohol are passed into rectifying tower, carry out methyl alcohol and ritalin separating-purifying, the ritalin after purification is reused.
4. the preparation method of glycerine triacetate as claimed in claim 1 or 2, it is characterized in that, described step S3 comprises, and is reused in step sl by the alkaline ionic liquid catalyst of discharge.
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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 |
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2013
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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 |
|---|
| Lewis basic ionic liquid as an efficient and facile catalyst for acetylation of alcohols,phenols,and amines under solvent-free conditions;Li Ji,et al.,;《Monatsh Chem》;20120816;第2013卷(第144期);第369-374页 * |
| 三醋酸甘油酯合成工艺研究;高建荣等;《浙江化工》;19941231;第25卷(第4期);第17-19页 * |
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