CN102964252A - Technology for preparing propyl gallate by utilizing mixed catalyst - Google Patents
Technology for preparing propyl gallate by utilizing mixed catalyst Download PDFInfo
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- CN102964252A CN102964252A CN2012104913448A CN201210491344A CN102964252A CN 102964252 A CN102964252 A CN 102964252A CN 2012104913448 A CN2012104913448 A CN 2012104913448A CN 201210491344 A CN201210491344 A CN 201210491344A CN 102964252 A CN102964252 A CN 102964252A
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Abstract
The invention relates to a technology for preparing propyl gallate by utilizing a mixed catalyst. The technology comprises the following steps of: putting gallic acid, n-propanol, the mixed catalyst and cyclohexane into a reaction kettle, performing heating and esterification in the reaction kettle, enabling a generated mixture of water, the n-propanol and the cyclohexane to enter a rectifying tower which is directly connected with the reaction kettle for separation, controlling the reflux ratio R at 1-4, keeping the temperature at the top of the tower at 81-84 DEG C, returning the n-propanol and the cyclohexane which are distilled out into the reaction kettle for reacting continuously, enabling the water to enter a water segregator connected with the lower part of the rectifying tower, performing esterification reaction for 8-14h, then filtering reaction materials and cooling to obtain coarse crystals; and dissolving the obtained coarse crystals, filtering, washing with water, recrystallizing and drying to obtain the propyl gallate. The preparation technology disclosed by the invention has the advantages of simplicity and convenience and low requirements for equipment and technical conditions, and has the effects of reducing production cost, reducing the discharge of three wastes and realizing high quality and high yield.
Description
Technical field
The invention belongs to the fine chemical product field of Organic chemical products, relate to a kind of novel preparation process of Tenox PG.
Background technology
Tenox PG claims again 3,4,5-nipasol.English name: Propyl Gallate, molecular formula: C
10H
12O
5, molecular weight: 212.20, white crystalline powder is soluble in hot water, ethanol, propylene glycol, glycerine, is insoluble in cold water.146 ~ 150 ℃ of fusing points, resistance to elevated temperatures is poor.Water absorbability is arranged, and illumination can promote it to decompose, and can generate coloured mixture to metal ion.
Tenox PG is made antioxidant to being widely used in the food and feeds such as food oils, food oils, fried food product, biscuit, instant noodles, instant rice, canned nut, dried fish product and pickle cured meat product at home and abroad, can directly use or with using after the dissolution with solvents, optimum quantum of utilization 0.01 ~ 0.02g/kg, maximum usage quantity 0.1g/kg.Also can be used as in the inhibitor of pharmacy, makeup, resisting ultraviolet radiation.
Lower alcohol ester synthesis as gallic acid, classical method is take sulfuric acid or tosic acid as catalyzer, makes gallic acid and corresponding lower alcohol carry out esterification, uses excessive alcohol reflux, the water that generates in the reaction process adopts water-retaining agent or azeotropic aqua to get rid of.
Gallic acid and n-propyl alcohol can carry out esterification, produce Tenox PG.
Because the vitriol oil has strong oxidizing property, gallic acid is the adjacent diphenol structure of tool again, easier oxidation, and by product is many, goes back severe corrosion equipment.And mixed catalyst is not had a strong oxidizing property, can reduce the generation of side reaction and can lower product colourity, can also recycle, and reduces raw materials cost.
Summary of the invention
Purpose of the present invention aims to provide a kind of simple process, and equipment and technical qualification are less demanding, can reduce production costs again, reduces three waste discharge, and can obtain the preparation technology of the Tenox PG of good quality and high output effect.
A kind of technique of utilizing mixed catalyst to prepare Tenox PG: gallic acid, n-propyl alcohol, mixed catalyst and hexanaphthene are dropped in the reactor, esterification heats up in reactor, the water that generates with separate in n-propyl alcohol, hexanaphthene vapour mixture enter the rectifying tower that directly links to each other with reactor, n-propyl alcohol, the hexanaphthene that distills out from rectifying tower returns and continues reaction in the reactor, and water then enters in the water trap that the rectifying tower bottom is connected with; After the esterification, excessive n-propyl alcohol and hexanaphthene are distilled away, reaction mass filtration, cooling are obtained coarse-grain; Gained coarse-grain dissolution filter, washing, recrystallization, dry getting final product;
Described mixed catalyst comprises any in following three kinds: (1) sulfuric acid, tosic acid and gac; (2) phosphoric acid, tosic acid and gac; (3) phosphoric acid and gac;
Weight proportion is sulfuric acid in the described mixed catalyst: tosic acid: gac=4-12: 6-17: 1; Phosphoric acid: tosic acid: gac=1-5: 5-15: 1-3; Phosphoric acid: gac=4-12: 1;
Described mixed catalyst consumption is 6 – 15% of gallic acid weight.
Described mixed catalyst is preferably phosphoric acid, tosic acid and gac, and the weight proportion between the three is preferably=1-5: 7-9: 1-1.5.
Described mixed catalyst consumption is preferably 9% of gallic acid weight.
The feed ratio of described gallic acid and n-propyl alcohol is: weight g: volume ml=1: 4-5; Esterification reaction temperature is controlled at 91 ℃ of 80 –; Reaction time of esterification is 8-14 hour.
The feed ratio of described gallic acid and n-propyl alcohol is preferably: weight g: volume ml=1: 4.35; The temperature of esterification is preferably controlled 85-89 ℃; Reaction time of esterification is preferably 10-12 hour.
The add-on volume of hexanaphthene is 1/10 of n-propyl alcohol.
Control rectifying tower reflux ratio R=1-4 in the above-mentioned technique, tower top temperature is controlled at 84 ℃ of 81 –; Described rectifying tower has 8-20 theoretical tray; Control water trap liquid level is no more than 1/3 of water trap height.
Described mixed catalyst directly cover is used the next batch esterification process, and catalyst attrition is partly done to replenish and got final product.
Can obtain highly purified Tenox PG after the technological process gained coarse-grain simple process of the present invention.And the esterification technique that the present invention adopts, after esterification finished, n-propyl alcohol was reclaimed in the aqueous solution rectifying in the water trap, and discard residual night, and the discharging of n-propyl alcohol and spillage are very slight, require lower to environmental protection treatment.
Mixed catalyst used in the present invention, has good catalytic performance, and do not have strong oxidizing property (because not containing the vitriol oil or the vitriol oil is to a certain degree diluted in the mixed catalyst), therefore the colourity of gained coarse-grain after washing is very good (because mixed catalyst is not had a strong oxidizing property, and gac has decolorization in the mixed catalyst), can remove rear step bleaching process from.Mixed catalyst has good complex ability simultaneously, except katalysis is arranged, can also effectively remove metal ion in the material.Therefore the present invention has simple process, and equipment and technical qualification are less demanding, but have simultaneously the advantages such as three wastes discharge amount is little, and industrial application value is higher.The catalyzer that the present invention reclaims can not done any processing, and directly cover is used the next batch esterification process, and the catalyst attrition part only need be done a small amount of replenishing and get final product, and catalyst levels is little, and production cost is low, and has reduced the quantity discharged of the three wastes.
Among the embodiment finished product after testing, colourity＜70f, fusing point: 147.5-148.5 degree centigrade, content (HPLC):＞99%.
The Tenox PG productive rate reaches 96.0%.
There is opening for feed rectifying tower of the present invention middle and lower part, link to each other with reaction kettle of the esterification by pipeline, the bottom of the rectifying tower water trap of ining succession, the top links to each other with condenser, the bottom of condenser links to each other with an end of reflux splitter simultaneously, a shunting of reflux splitter flows to the top of rectifying tower, and another shunting flows to reaction kettle of the esterification.On the reaction kettle of the esterification with feeding-in solid body mouth and electric mixing device.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1:
The liquid starting material that is contained in head tank enters high-order test tank by transferpump, enters reactor, and solid material is then directly added by the charging opening of reactor.Get a water gallic acid 100 grams in the present embodiment, 400 milliliters of n-propyl alcohols, mixed catalyst 15 grams, this mixed catalyst adopts phosphoric acid, tosic acid and gac formulated, and the weight proportion that adopts between the three is 1: 15: 1.After in material drops into reactor, the esterification that heats up, esterification temperature remains on 85 ℃, and esterification is evaporated comprises the steam of water and n-propyl alcohol, hexanaphthene component, in rectifying tower, separate, control reflux ratio R=1-4 makes tower top temperature remain on 81 ℃, overhead vapours through condenser condenses by reflux splitter, a part flows back to rectifying tower, another part flows into reaction kettle of the esterification to be continued to recycle, and moisture is enriched in the water trap after rectifying tower separates.After the esterification 14 hours, reclaim excessive n-propyl alcohol and hexanaphthene (fractionation by distillation) by rectifying tower, reaction mass filters, cooling, crystallization, filtration, and catalyzer can be for subsequent use for next manufacturing processed esterification, and the catalyst attrition part is replenished by optimizing consumption.Wash crystallization gets the Tenox PG crude product.Gained coarse-grain dissolution filter, washing, recrystallization, the centrifuge dehydration final vacuum is dry that finished product 103.7 restrains.
Embodiment 2-9
Reactions steps is with embodiment 1, and following table is for adopting under the conditions such as different ratios of raw materials, mixed catalytic agent content and reaction times the amount of gained Tenox PG product.Mixed catalyst all adopts phosphoric acid, tosic acid and gac formulated, and three's proportioning is 1: 15: 1 among the embodiment 2-3, among the embodiment 4-6 between the three proportioning be 1: 8: 2, three's proportioning is 1: 5: 2 among the embodiment 7-9.
Embodiment 10-13
Reactions steps is with embodiment 1, mixed catalyst all adopts sulfuric acid, tosic acid and gac formulated, three's proportioning is 12: 17: 1 among the embodiment 10, among the embodiment 11 between the three proportioning be 4: 6: 1, three's proportioning is 4: 4: 1 among the embodiment 12-13.
Embodiment 14-18
Reactions steps is with embodiment 1, and mixed catalyst all adopts phosphoric acid and gac formulated, and both proportionings were respectively 6: 1,8: 1,4: 1,10: 1,7: 1 among the embodiment 14-18.
Embodiment 19-22
Reactions steps is with embodiment 1, and mixed catalyst all adopts phosphoric acid, tosic acid and gac formulated, and three's proportioning is 1: 7: 1.The Tenox PG productive rate reaches 96.0%.
Claims (8)
1. technique of utilizing mixed catalyst to prepare Tenox PG, it is characterized in that, gallic acid, n-propyl alcohol, mixed catalyst and hexanaphthene are dropped in the reactor, esterification heats up in reactor, the water that generates with separate in n-propyl alcohol, hexanaphthene vapour mixture enter the rectifying tower that directly links to each other with reactor, n-propyl alcohol, the hexanaphthene that distills out from rectifying tower returns and continues reaction in the reactor, and water then enters in the water trap that the rectifying tower bottom is connected with; After the esterification, excessive n-propyl alcohol and hexanaphthene are distilled away by rectifying tower, reaction mass filtration, cooling are obtained coarse-grain; Gained coarse-grain dissolution filter, washing, recrystallization, dry getting final product;
Described mixed catalyst comprises any in following three kinds: (1) sulfuric acid, tosic acid and gac; (2) phosphoric acid, tosic acid and gac; (3) phosphoric acid and gac;
Weight proportion is sulfuric acid in the described mixed catalyst: tosic acid: gac=4-12: 6-17: 1; Phosphoric acid: tosic acid: gac=1-5: 5-15: 1-3; Phosphoric acid: gac=4-12: 1;
Described mixed catalyst consumption is 6 – 15% of gallic acid weight.
2. the technique of preparation Tenox PG according to claim 1 is characterized in that, described mixed catalyst is phosphoric acid, tosic acid and gac, and the weight proportion between the three is=1-5: 7-9: 1-1.5.
3. the technique of preparation Tenox PG according to claim 1 is characterized in that, described mixed catalyst consumption is 9% of gallic acid weight.
4. the technique of preparation Tenox PG according to claim 1 is characterized in that, the feed ratio of described gallic acid and n-propyl alcohol is: weight g: volume ml=1: 4-5; Esterification reaction temperature is controlled at 91 ℃ of 80 –; Reaction time of esterification is 8-14 hour.
5. the technique of preparation Tenox PG according to claim 4 is characterized in that, the feed ratio of described gallic acid and n-propyl alcohol is: weight g: volume ml=1: 4.35; 85-89 ℃ of the temperature control of esterification; Reaction time of esterification is 10-12 hour.
6. the technique of preparation Tenox PG according to claim 1 is characterized in that, the add-on volume of hexanaphthene is 1/10 of n-propyl alcohol.
7. the technique of preparation Tenox PG according to claim 1 is characterized in that, control rectifying tower reflux ratio R=1-4, and tower top temperature is controlled at 84 ℃ of 81 –; Described rectifying tower has 8-20 theoretical tray; Control water trap liquid level is no more than 1/3 of water trap height.
8. the technique of preparation Tenox PG according to claim 1 is characterized in that, described mixed catalyst directly cover is used the next batch esterification process, and catalyst attrition is partly done to replenish and got final product.
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| CN2012104913448A CN102964252A (en) | 2012-11-27 | 2012-11-27 | Technology for preparing propyl gallate by utilizing mixed catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456195A (en) * | 2018-10-22 | 2019-03-12 | 浙江华军药业有限公司 | A kind of method of substep catalysis preparation high-purity propyl ester |
| CN111807962A (en) * | 2020-06-17 | 2020-10-23 | 遵义市倍缘化工有限责任公司 | Method for directly producing propyl gallate by using tannic acid |
| CN112745217A (en) * | 2020-12-30 | 2021-05-04 | 湖南先伟实业有限公司 | Propyl gallate preparation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1498683A (en) * | 2002-11-05 | 2004-05-26 | 罗 伟 | Mixed catalyst for preparing methyl ester of 3,4,5-trihydroxybenzoic acid methyl ester |
| CN1498883A (en) * | 2002-11-05 | 2004-05-26 | 罗 伟 | Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester |
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2012
- 2012-11-27 CN CN2012104913448A patent/CN102964252A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498683A (en) * | 2002-11-05 | 2004-05-26 | 罗 伟 | Mixed catalyst for preparing methyl ester of 3,4,5-trihydroxybenzoic acid methyl ester |
| CN1498883A (en) * | 2002-11-05 | 2004-05-26 | 罗 伟 | Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester |
Non-Patent Citations (1)
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| 薄采颖等: "没食子酸酯的合成方法综述", 《现代化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456195A (en) * | 2018-10-22 | 2019-03-12 | 浙江华军药业有限公司 | A kind of method of substep catalysis preparation high-purity propyl ester |
| CN111807962A (en) * | 2020-06-17 | 2020-10-23 | 遵义市倍缘化工有限责任公司 | Method for directly producing propyl gallate by using tannic acid |
| CN112745217A (en) * | 2020-12-30 | 2021-05-04 | 湖南先伟实业有限公司 | Propyl gallate preparation process |
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Application publication date: 20130313 |