CN103012151A - Preparation method of n-butyl benzoate - Google Patents
Preparation method of n-butyl benzoate Download PDFInfo
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- CN103012151A CN103012151A CN2012105847937A CN201210584793A CN103012151A CN 103012151 A CN103012151 A CN 103012151A CN 2012105847937 A CN2012105847937 A CN 2012105847937A CN 201210584793 A CN201210584793 A CN 201210584793A CN 103012151 A CN103012151 A CN 103012151A
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- phenylformic acid
- butyl ester
- positive butyl
- propyl carbinol
- acid
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method of n-butyl benzoate. The preparation method mainly comprises the following steps of: taking benzoic acid as a raw material, enabling the benzoic acid to react with n-butyl alcohol under the existence of a solid acid catalyst to obtain a crude product, then neutralizing the crude product by using solid alkali, and then rectifying and purifying to obtain the finished product, namely the n-butyl benzoate. The preparation method disclosed by the invention is simple, convenient and stable in operation process, little in three-waste pollution and suitable for industrial production.
Description
Technical field
The present invention relates to the manufacture method of Chemicals, particularly the manufacture method of the positive butyl ester of a kind of phenylformic acid.
Background technology
The positive butyl ester of phenylformic acid is the liquid of water white transparency band fruit fragrance, and mainly as solvent and the perfume base of resin, paint etc., purposes is comparatively extensive.
At present, the industrial method for making commonly used of the positive butyl ester of phenylformic acid is take the vitriol oil as catalyzer, carries out esterification by phenylformic acid and propyl carbinol and makes.The drawbacks such as the method exists that the sulfuric acid consumption is large, side reaction is many, seriously corroded, aftertreatment trouble and environmental pollution.People adopt various solid super-strong acids, heteropolyacid and gac solid-carrying heteropolyacid, some Lewis acid or immobilized Lewis acid to obtain very good effect as esterifying catalyst in recent years.Tosic acid (Fujian chemical industry wherein, 2001, (2): 25 ~ 26), iron(ic) chloride (Zhongnan Polytechnic College's journal, 1996,10(2): 94 ~ 97), 12 ferric sulfate hydrate ammoniums (Shenyang Normal College's journal/natural science edition, 2001,19(2): 39 ~ 42), sodium pyrosulfate (Changde college of education journal/natural science edition, 2000,12(4): 63 ~ 64), TiSiW
12O40/TiO
2(chemical engineer, 2001,3 ~ 4) etc. (1): solid acid is the good catalyst of the positive butyl ester of synthesizing benzoic acids, compared with mineral acids such as sulfuric acid, is easy to keeping, transportation and uses, security is large, economy is easy to get, and is little to equipment corrosion, and environmental pollution is low, be to catalyze and synthesize the industrial developing direction of the positive butyl ester of phenylformic acid, be worth deeply inquiring into and screening.
In the actual industrial applied research, when discovery prepares the positive butyl ester of phenylformic acid with the method in the above-mentioned document, have following deficiency on its Technology:
1, since in the reacting rear material the complete benzoic acid content of unreacted affect the acid number of finished product after the rectifying, so the method that document adopts the rear organic layer of reaction to wash through water, dilute sodium carbonate solution and water respectively removes the complete phenylformic acid of unreacted, and can produce so a large amount of waste water, and the propyl carbinol in the organic layer also can be washed in the waste water, causes propyl carbinol consumption increase and wastewater treatment difficulty.According to the production practical situation, 1 ton of finished product of every production can produce 4 tons of waste water, and COD value of waste water is brought immense pressure to environmental protection about 40,000.
2, reflux water-dividing reaction in the disposable input reactor of propyl carbinol causes the early stage speed of response too fast, and quantity of reflux is excessive; Late phase reaction heats up difficult, and the reaction times prolongs.The amount of the propyl carbinol that uses in the document is greatly more than amount required on the reaction theory, excessive propyl carbinol has improved reactant concn, play simultaneously solvent and take the water that reaction generates out of, therefore reaction speed in early stage is very fast, quantity of reflux is very large, when suitability for industrialized production, there is like this potential safety hazard, the security incidents such as punching material occur easily.And when the decline of reaction later stage concentration of benzoic acid causes speed of response to descend, still have a large amount of propyl carbinols in the reaction system, cause the intensification difficulty can't improve speed of response, thereby the reaction times is prolonged.Drop in addition too much propyl carbinol and can reduce plant factor, increase energy consumption, and the consumption of etherification reaction increase propyl carbinol occurs easily.
Summary of the invention
The purpose of this invention is to provide that a kind of simple process is stable, three-waste pollution is few, energy consumption is low, be easy to the manufacture method of the positive butyl ester of phenylformic acid of suitability for industrialized production.
Purpose of the present invention is realized by following technical scheme:
The present invention divides water with phenylformic acid and quantitative propyl carbinol reflux under catalysis of solid catalyst, when being elevated to 130 ℃ ~ 140 ℃, the question response temperature drips in addition again the propyl carbinol of equivalent, filtering recovering catalyst after stopped reaction when not having moisture to go out in the water trap, products therefrom are cooled to below 40 ℃.Filtrate is dropped in the quantitative solid alkali and 20min in the time of 60 ℃, benzoic acid content is lower than 0.1%(GC in material, and area % is lower same) after, filtering separation alkali filter residue and obtain the positive butyl ester crude product of phenylformic acid again, its crude product reclaims propyl carbinol by rectifying again can obtain this finished product.
The total consumption of propyl carbinol and benzoic total amount ratio are 1 ~ 1.4:1(mol ratio in the described technique, and be lower same), its preferred value is 1.2 ~ 1.3:1.
Used solid alkali is yellow soda ash in the described technique.
Selected solid catalyst is sodium pyrosulfate in the described technique.
Catalyst levels and benzoic amount ratio are 0.03 ~ 0.3:1(mol ratio in the described technique, and be lower same), its preferred value is 0.05 ~ 0.07:1.
Temperature of reaction is 100 ℃ ~ 160 ℃ in the described technique, and its preferred value is 115 ℃ ~ 150 ℃.
The consumption of solid alkali is the 1.5% ~ 5%(mass ratio that reclaims catalyzer rear filtrate quality in the described technique, and is lower same), its preferred value is 2% ~ 3%.
In the described technique in the solid alkali and the time be 5 min ~ 30min, its preferred value is 15 min ~ 25min.
Isolated alkali filter residue can be used as the raw material of preparation Sodium Benzoate in the described technique.
Beneficial effect of the present invention:
Adopting the solid acid sodium pyrosulfate in technique of the present invention is catalyzer, and it is a kind of industrial goods cheap and easy to get, and performance is more stable, and transportation and storage safe are easy to operate, and be also little to the corrosion of production unit, and can reuse.Used sodium pyrosulfate is the industrial goods of buying from market in this technique, does not need to be directly used in esterification through any processing, and its benzoic transformation efficiency reaches the 99%(mass ratio, and is lower same) more than.
Propyl carbinol is to add at twice reaction system in technique of the present invention, but not disposable and phenylformic acid adding reaction system.Can avoid like this causing the early stage speed of response too fast, quantity of reflux is excessive; Difficult, reaction times prolongation that late phase reaction heats up.Whole reaction can be finished at 1 ~ 1.5h.The consumption of propyl carbinol also greatly reduces simultaneously, has increased plant factor, has reduced the consumption of energy consumption and propyl carbinol.
In technique of the present invention, adopt solid alkali to neutralize, can avoid producing a large amount of waste water.After will neutralizing in the material benzoic content be controlled at 0.1%(GC) the following acid number that can guarantee the finished product that obtains after the rectifying can (annotate: acid number≤0.1mgKOH/g be qualified) up to standard.Very few or the too short then benzoic content of neutralization reaction time of the solid alkali that uses is difficult to be controlled at 0.1%(GC) below.In addition, filter the rear filter residue that obtains and can be used for synthesizing benzoic acids sodium.
Material after having reacted in technique of the present invention does not adopt and reclaims first the again technique that neutralizes of solid alkali of propyl carbinol, the rear recovery propyl carbinol but first solid alkali neutralizes, this is because material has not had solvent after reclaiming propyl carbinol first, reduced like this mutual solubility of material and solid alkali, so that neutralization is bad, rectifying product acid number out is not up to standard.
According to the positive butyl ester of the resulting phenylformic acid of processing method of the present invention, product purity is at 99%(GC) more than, its total recovery is at the 90%(mass ratio, and is lower same) more than.
In sum, operational process of craft of the present invention is more easy to be stable, and three-waste pollution is few, and energy consumption is low, is more suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the positive butyl ester technological process of production of phenylformic acid of the present invention synoptic diagram.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but embodiment should not be construed as limitation of the present invention.
Embodiment 1
In the 1000ml four-hole bottle, add the 450g phenylformic acid, the 170g propyl carbinol, the 25.4g sodium pyrosulfate is loaded onto water trap, reflux condensing tube and thermometer, stirring heating reflux water-dividing.The question response temperature is elevated to 135 ℃ and drips the 170g propyl carbinol again, when temperature rises to when not having moisture to go out in 150 ℃ of water traps, and stopped reaction, the reaction times is 1.5h.Being cooled to suction filtration below 40 ℃ after reaction finishes reclaims catalyzer and gets filtrate 722g, sampling analysis, the positive butyl ester content of phenylformic acid 88.75%(GC), benzoic acid content 0.37%(GC), propyl carbinol content 10.1%(GC).Filtrate adds in the 20g solid alkalis and suction filtration again behind the 20min in 60 ℃, crude product sampling analysis, benzoic acid content (GC) 0.016%.Get the positive butyl ester 610g of finished product phenylformic acid after the rectifying, sampling analysis, content are 99.6%(GC), acid number 0.08(mgKOH/g), total recovery 93%.
Embodiment 2
Charging capacity and operation are with embodiment 1, and the cooling suction filtration reclaims catalyzer and gets filtrate 724g, sampling analysis, the positive butyl ester content of phenylformic acid 89.29%(GC after the reaction end), benzoic acid content 0.46%(GC), propyl carbinol content 9.55%(GC).Filtrate adds in the 10g solid alkalis and suction filtration again behind the 60min in 60 ℃, crude product sampling analysis, benzoic acid content (GC) 0.17%.Get the positive butyl ester 614g of finished product phenylformic acid after the rectifying, sampling analysis, content are 99.4%(GC), acid number 1.48(mgKOH/g), total recovery 93.4%.
Embodiment 3
Charging capacity and operation are with embodiment 1, and propyl carbinol, clout 670g, sampling analysis, the positive butyl ester content of phenylformic acid 96.42%(GC were reclaimed in the material underpressure distillation after reaction finished), benzoic acid content 0.47%(GC), propyl carbinol content 2.61%(GC).Add in the 20g solid alkalis and suction filtration again behind the 20min in 60 ℃ again, crude product sampling analysis, the positive butyl ester content of phenylformic acid 97%(GC), benzoic acid content 0.33%(GC), propyl carbinol content 2.18%(GC).
Embodiment 4
In the 2000ml four-hole bottle, add the 450g phenylformic acid, the 544g propyl carbinol, the 35.7g sodium pyrosulfate is loaded onto water trap, reflux condensing tube and thermometer, stirring heating reflux water-dividing.When temperature rises to when not having moisture to go out in 150 ℃ of water traps, stopped reaction, the reaction times is 5h.The cooling suction filtration reclaims catalyzer and gets filtrate 892g, sampling analysis, the positive butyl ester content of phenylformic acid 71.11%(GC after the reaction end), benzoic acid content 0.58%(GC), propyl carbinol content 27.64%(GC).
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.If of the present invention these are revised and modification belongs to the scope of claim of the present invention and equivalent technologies thereof, then the present invention also should comprise these changes and modification interior.
If the content that is not described in detail is arranged in this specification sheets, then belong to the known technology of this area professional and technical personnel, repeat no more herein.
Claims (3)
1. the manufacture method of the positive butyl ester of phenylformic acid, it is characterized in that: with phenylformic acid and quantitative propyl carbinol heating reflux reaction under catalysis of solid catalyst, when being elevated to 130 ℃ ~ 140 ℃, the question response temperature drips in addition again the propyl carbinol of equivalent, stopped reaction when not having moisture to go out in the water trap, filtering recovering catalyst after products therefrom is cooled to below 40 ℃, filtrate is dropped in the quantitative solid alkali in the time of 60 ℃ and 20min, benzoic acid content is lower than 0.1%(GC in material, area %) after, filtering separation alkali filter residue and obtain the positive butyl ester crude product of phenylformic acid again, its crude product reclaims propyl carbinol by rectifying again and namely obtains the positive butyl ester finished product of phenylformic acid.
2. the manufacture method of the positive butyl ester of phenylformic acid as claimed in claim 1, it is characterized in that: used solid alkali is yellow soda ash in the described technique.
3. the manufacture method of the positive butyl ester of phenylformic acid as claimed in claim 1 is characterized in that: isolated alkali filter residue is the raw material of preparation Sodium Benzoate in the described technique.
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| CN2012105847937A CN103012151A (en) | 2012-12-28 | 2012-12-28 | Preparation method of n-butyl benzoate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB234458A (en) * | 1924-05-24 | 1926-04-29 | Distilleries Des Deux Sevres | Improvements in the method for the continuous manufacture of esters of the fatty or the aromatic series |
| CN1640866A (en) * | 2004-01-16 | 2005-07-20 | 湖南科技大学 | Method for preparing phthalic acid C4-C5 mixed ester using crude benzoic acid anhydride and alcohol oil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB234458A (en) * | 1924-05-24 | 1926-04-29 | Distilleries Des Deux Sevres | Improvements in the method for the continuous manufacture of esters of the fatty or the aromatic series |
| CN1640866A (en) * | 2004-01-16 | 2005-07-20 | 湖南科技大学 | Method for preparing phthalic acid C4-C5 mixed ester using crude benzoic acid anhydride and alcohol oil |
Non-Patent Citations (2)
| Title |
|---|
| 俞善信等: "硫酸氢钠催化合成苯甲酸正丁酯", 《常德师范学院学报(自然科学版)》, vol. 12, no. 4, 31 December 2000 (2000-12-31) * |
| 杨树等: "硫酸氢钠催化合成苯甲酸正丁酯的研究", 《化学试剂》, vol. 25, no. 3, 31 December 2003 (2003-12-31) * |
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Application publication date: 20130403 |