CN101434539B - Preparation of benzyl acetate - Google Patents
Preparation of benzyl acetate Download PDFInfo
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- CN101434539B CN101434539B CN2008102368775A CN200810236877A CN101434539B CN 101434539 B CN101434539 B CN 101434539B CN 2008102368775 A CN2008102368775 A CN 2008102368775A CN 200810236877 A CN200810236877 A CN 200810236877A CN 101434539 B CN101434539 B CN 101434539B
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- dibenzyl ether
- jasmal
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Abstract
The invention discloses a method for producing jasmal, which mainly adopts dibenzyl ether which is a high boiling waste produced by benzoic alcohol, as a raw material. The dibenzyl ether reacts with acetic anhydride in the presence of solid acid catalysts to obtain a crude product, and then the crude product is refined and purified to obtain an end product. The technology has simple operation process, stability, high efficiency, less pollution of the three wastes and applicability to the industrialized production.
Description
Technical field
The present invention relates to the manufacture method of Chemicals, particularly a kind of method for preparing jasmal.
Background technology
Jasmal is a kind of sophisticated, consumption spices widely, is mainly used in the essence and soap compound of preparation jasmine fragrance; It still is a kind of widely used meticulous organic chemical industry's product in addition, as the solvent of resin, dyestuff, grease, printing ink etc.
At present, the preparation of jasmal is mainly by following three kinds of methods preparation: 1. be that raw material is synthesized into vinegar ester sodium in the presence of phase-transfer catalyst with the Benzyl Chloride.2. be that raw material gets with acetic acid reaction under strong ester (as sulfuric acid) catalysis with benzylalcohol.3. be that raw material gets with the aceticanhydride reaction under super acidic catalyst catalysis with the dibenzyl ether.
In above-mentioned method, preceding two kinds of methods are studied at most, and open source literature is more, and its technology is also ripe, use more generally in suitability for industrialized production, and present production firm both domestic and external adopts preceding two kinds of explained hereafter jasmals.The employing dibenzyl ether is that the method research of raw material synthetic benzyl acetate is inchoate in recent years.
Dibenzyl ether is the main by product in the benzylalcohol production (Benzyl Chloride hydrolysis method), and its amount reaches 13% (mass ratio) of benzylalcohol ultimate capacity, and it has occupied quite a few in the benzylalcohol production cost; Dibenzyl ether is except a small amount of part is used as solvent at present, and major part also is underutilized.Report super acids SO in disclosed document (chemical engineer, [2005] 3,60～63)
4 2-/ TiO
2Make catalyzer, dibenzyl ether and aceticanhydride are in 150 ℃～160 ℃ reactions down of temperature, and its yield reaches as high as 83.7%.
Its major technique key point of technology in above-mentioned document announcement is super acids titanium catalyst (SO
4 2-/ TiO
2) preparation and recycling.The preparation technology of super acids titanium catalyst comprises: from TiCL
4Hydrolysis, ammoniacal liquor neutralization and ageing, washing, filtration drying obtain H
4TiO
4, use H again
2SO
4Solution soaking, filtration drying, activation (550 ℃ of following roasting 3h in retort furnace) and obtain SO
4 2-/ TiO
2The height of the catalytic activity of catalyzer directly has influence on the yield of product, so calcination activation is the controlled step of most critical in the operation of preparation catalyzer.
In the actual industrial applied research, find to use SO
4 2-/ TiO
2During the Preparation of Catalyst jasmal, have following difficult point on its Technology:
1. the preparation devices needed of catalyst themselves is many, even also more than the equipment of producing ethyl ester benzyl ester, and cost of equipment is bigger.
2. the operation steps of Preparation of Catalyst is many, and uncertain factor is also many in the production process, and quality is wayward.
3. because of the catalystic material titanium metal is relatively more expensive,, keep stable and the active effect behind the catalyst regeneration is difficult so need recycle and reuse.
4. the most difficult is after industrial scale is produced, and (is difficult at present obtain as the required relevant device of calcination activation operation in 50～100kg) the Preparation of Catalyst in batches.
Above-mentioned some greatly to have limited with the dibenzyl ether be the industrial application of raw material synthetic benzyl acetate operational path.
Summary of the invention
The purpose of this invention is to provide that a kind of operating process is more easy, stable, three-waste pollution is few, efficient is high, being suitable for the dibenzyl ether is the manufacture method of primary industry production jasmal.
The scheme that technology of the present invention solves is:
With dibenzyl ether and quantitative aceticanhydride under solid acid catalyst catalysis, react 2～6h down for 120 ℃～160 ℃ in temperature, residual dibenzyl ether component concentration is 0.05%～1.0% (GC in reaction mass, and long-pending %, down with) but the time stopped reaction, the products therefrom crude product carries out negative pressure rectifying again and can obtain the jasmal finished product after isolating catalyzer through pre-treatment earlier; The reaction material ratio of throwing is a dibenzyl ether: aceticanhydride=1: 1.0～1.5 (mol ratio, down together), catalyst consumption are 0.8%～3.0% (mass ratio, down together) of dibenzyl ether input amount.
The preferred value of the ingredient proportion of dibenzyl ether and aceticanhydride is 1: 1.1～1.2 in the above-mentioned technology.
Selected solid acid catalyst is a p-methyl benzenesulfonic acid in the above-mentioned technology.
Product crude product described in the above-mentioned technology is isolated catalyzer through pre-treatment earlier and is meant reaction mass is carried out catalyzer and the high boiling point tar thing of simple vacuum distillation to remove crude product, or with reaction mass by filter, alkali neutralization and washing to be to remove catalyzer in the crude product and aceticanhydride, acetic acid, preferentially selects the isolating method of simple vacuum distillation pre-treatment for use.
The preferred value of catalyst levels is 1.5%～2.5% of a dibenzyl ether amount in the above-mentioned technology.
The preferred value of temperature of reaction is 130 ℃～150 ℃ in the above-mentioned technology
The reaction formula of above-mentioned technology is as follows:
In above-mentioned reaction mass system, used dibenzyl ether can be technical grade (content 〉=98.5%, specification GC), also can be during crude product dibenzyl ether-is produced through purified benzylalcohol high boiling material (content: 90.0%～92.0%, GC).Find to detect from the result of esterification terminal point in our research, at 80.0%～85.5% (GC), gap is little mostly for the product components contents, so the preferred crude product dibenzyl ether that adopts in this bright technology also can be saved comprehensive production cost.
Adopting the solid acid p-methyl benzenesulfonic acid in technology of the present invention is catalyzer, and p-methyl benzenesulfonic acid is a kind of industrial goods cheap and easy to get, and its performance is more stable, and transportation and storage safe are easy to operate, and be also little to the corrosion of production unit.Used p-methyl benzenesulfonic acid is the industrial goods of buying from market in this technology, does not need to be directly used in esterification through any processing, and the transformation efficiency of its dibenzyl ether reaches more than 99%.
In esterification, can accelerate reaction process though increase catalyst consumption, if speed of reaction is too fast, by product is easily produced in the bad control of reaction process on the contrary, yield sharply descends.Catalytic amount is 0.8%～3.0% of a dibenzyl ether amount among the present invention, and preferred value is 1.5～2.5%.
Temperature is the important factor that reaction is carried out smoothly in reaction, and the too low then reaction of temperature of reaction can not normally be carried out; The temperature of reaction height, speed of reaction is fast, yield increases, if but too high then reaction carry out also can generating high boiling material impurity too soon, thereby productive rate descends.Temperature of reaction is controlled at 120 ℃～160 ℃ in the technology of the present invention, and preferable range is 130 ℃～150 ℃.
Crude product material after reaction is good need carry out the catalyzer in the pre-treatment separation of material when rectification and purification becomes commodity, otherwise the height by product that boils can roll up in the rectifying of back, and the final product yield descends significantly.Common processing be with the crude product after the esterification by filtering to isolate catalyzer, with alkali lye neutralization, washing to remove aceticanhydride excessive in the material, acetic acid.Another kind method be with reaction mass by continuous simple distillation to remove catalyzer and high boiling point tar thing.Preceding processing method can produce a certain amount of waste water, and back processing method can produce the solid waste of a certain amount of high-solidification point.Control both difficulty or ease and factors such as production cost from the disposal of three wastes and production operation and take all factors into consideration a kind of pre-treatment separation method behind the optimal process of the present invention-continuously simple vacuum distillation.
According to the resulting jasmal of processing method of the present invention, product purity can reach 99.5% (GC), and its total recovery can reach 82%～85%.
In sum, operational process of craft of the present invention is easy, and stable, three-waste pollution is few, and the efficient height is suitable for suitability for industrialized production.
Embodiment
Further specify technological process of the present invention below in conjunction with embodiment, embodiment is usefulness as an illustration only, and unrestricted protection scope of the present invention.
Embodiment 1
In the there-necked flask of 1000ml, add respectively the 308g dibenzyl ether (industrial crude product, 91.43%, 1.420mol), 176g acetic anhydride (chemical pure, 99.0%, 1.706mol) and 7g (2.27%) solid acid catalyst p-methyl benzenesulfonic acid, be warmed up to 130 ℃～150 ℃, reaction 3～6h; After finishing, reaction gets the about 483g of crude product, sampling analysis, jasmal content 81.10% (GC), aceticanhydride 3.57% (GC), dibenzyl ether 0.09% (GC).
With above-mentioned crude product at N
2Down underpressure distillation (about 1 of stage number) of protection, vacuum tightness be-0.097～-0.098Mpa (down with), begin discharging during from feed liquid temperature rise to 45 ℃, when the material temperature rise is not obvious to about 220 ℃ of dischargings, stop to distill.Receive cut 399.3g altogether, jasmal content 91.24% (GC).The thick ester of gained carries out rectification under vacuum (about 8 of rectifying column stage number), N again
2Protection; Control reflux ratio 1: 1, collects 100 ℃/-cut of 0.99Mpa, about 250 ℃ until interior temperature, common finished product 326.6g, content 99.56% (GC), once through yield 75.87%, total recovery 84.8%.
Embodiment 2
Charging capacity and operation are with embodiment 1, with the 20%Na of reaction gained crude product with about 400ml
2CO
3It is 7 that solution is neutralized to the pH value, tells brine layer, and the thick ester of gained carries out rectification under vacuum, altogether finished product 343.5g, content 99.61% (GC), once through yield 79.86%, total recovery 83.9%.
Claims (6)
1. the manufacture method of a jasmal, it is characterized in that: with dibenzyl ether and quantitative aceticanhydride under the catalysis of solid acid catalyst p-methyl benzenesulfonic acid, react 2～6h down for 120 ℃～160 ℃ in temperature, residual dibenzyl ether component concentration is 0.05%～1.0% (GC in reaction mass, area %) but the time stopped reaction, the products therefrom crude product carries out negative pressure rectifying again and can obtain the jasmal finished product after isolating catalyzer through pre-treatment earlier; The reaction material ratio of throwing is a dibenzyl ether: aceticanhydride=1: 1.0～1.5 (mol ratio), catalyst consumption is 0.8%～3.0% (mass ratio) of dibenzyl ether input amount.
2. by the manufacture method of the described jasmal of claim 1, it is characterized in that: the preferred value of the ingredient proportion of dibenzyl ether and aceticanhydride is 1: 1.1～1.2 in the above-mentioned technology.
3. press the manufacture method of the described jasmal of claim 1, it is characterized in that: product crude product described in the above-mentioned technology is isolated catalyzer through pre-treatment earlier and is meant reaction mass is carried out catalyzer and the high boiling point tar thing of simple vacuum distillation to remove crude product, or with reaction mass by filter, alkali neutralization and washing to be to remove catalyzer in the crude product and aceticanhydride, acetic acid.
4. by the manufacture method of claim 1 or 3 described jasmals, it is characterized in that: the product crude product described in the above-mentioned technology is isolated catalyzer through pre-treatment earlier and is preferentially selected the isolating method of simple vacuum distillation pre-treatment for use.
5. by the manufacture method of the described jasmal of claim 1, it is characterized in that: the preferred value of catalyst levels is 1.5%～2.5% of a dibenzyl ether amount in the above-mentioned technology.
6. by the manufacture method of the described jasmal of claim 1, it is characterized in that: the preferred value of temperature of reaction is 130 ℃～150 ℃ in the above-mentioned technology.
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|---|---|---|---|
| CN2008102368775A CN101434539B (en) | 2008-12-17 | 2008-12-17 | Preparation of benzyl acetate |
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|---|---|---|---|
| CN2008102368775A CN101434539B (en) | 2008-12-17 | 2008-12-17 | Preparation of benzyl acetate |
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| CN101434539B true CN101434539B (en) | 2011-12-28 |
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| CN104003871B (en) * | 2014-05-26 | 2016-04-20 | 武汉有机实业有限公司 | Butyl benzyl phthalate rectifying low-boiling-point substance is utilized to prepare the method for jasmal |
| CN104275195A (en) * | 2014-10-11 | 2015-01-14 | 江苏常州酞青新材料科技有限公司 | Preparation method of benzyl acetate catalyst |
| CN108130188A (en) * | 2018-01-12 | 2018-06-08 | 潜江新亿宏有机化工有限公司 | A kind of process for purification of fragrance benzyl acetate |
| CN113087625B (en) * | 2021-02-20 | 2022-04-01 | 潜江新亿宏有机化工有限公司 | Method for synthesizing benzyl acetate by utilizing combined catalytic system |
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Non-Patent Citations (1)
| Title |
|---|
| 张国华.乙酸苄酯合成工艺的研究.《化学工程师》.2005,(第3期), * |
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