CN104817457A - Method for preparation of methyl benzoate from recovered benzoic acid oxidized high boiling product - Google Patents
Method for preparation of methyl benzoate from recovered benzoic acid oxidized high boiling product Download PDFInfo
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- CN104817457A CN104817457A CN201510105382.9A CN201510105382A CN104817457A CN 104817457 A CN104817457 A CN 104817457A CN 201510105382 A CN201510105382 A CN 201510105382A CN 104817457 A CN104817457 A CN 104817457A
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- methyl benzoate
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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Abstract
The invention discloses a method for preparation of methyl benzoate from a recovered benzoic acid oxidized high boiling product. The method includes the following steps in order: 1) taking a certain amount of the recovered benzoic acid oxidized high boiling product and adding it into a reaction vessel, adding dilute sodium hydroxide into the reaction vessel, performing liquid separation treatment, and collecting the lower layer aqueous phase alkali hydrolysis solution; 2) adding concentrated sulfuric acid dropwise into the alkali hydrolysis solution to conduct acidification treatment, dissolving out a lot of yellow solids from the system, monitoring the pH value of the to-be-reacted object in real time to be less than or equal to 4, stopping adding concentrated sulfuric acid, and conducting filtering to obtain a benzoic acid crude product; 3) adding enough methanol and concentrated sulfuric acid into the benzoic acid crude product, conducting stirring till complete reaction; 4) subjecting the reactant to distillation separation to remove methanol, and carrying out alkali washing and water washing on the organic phase obtained by liquid separation treatment so as to obtain a methyl benzoate crude product; and 5) conducting rectification purification on the methyl benzoate crude product to obtain methyl benzoate. The method can realize separation and conversion utilization of all the components in the high boiling product by means of simple chemical conversion, the technological operation is simple, the reaction process is stable, and the purification cost is low.
Description
Technical field
The invention belongs to technical field of fine, specifically refer to a kind of method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate.
Background technology
Methyl benzoate is a kind of conventional aromatic carboxylic acid esters's essence and flavoring agent, has the strong fragrance of a flower and fruital fragrance.Adjustable strawberries, raspberry, cherry, pineapple, sweet wine, XIANGJIALANDOU and nuts flavor essence, also can be used in food and daily chemical essence formula.At present, industrial production methyl benzoate main method adopts phenylformic acid and methyl alcohol to carry out esterification preparation under sulfuric acid catalysis.
Phenylformic acid oxidation high boiling material is that in phenylformic acid production technique, rectifying continues the high boiling component steamed after boiling off phenylformic acid, high boiling mixture complicated components, main component is peruscabin, a small amount of phenylformic acid and other a small amount of high-boiling-point impurity, and phenylformic acid is oxidized high boiling material after purifying mainly for the production of peruscabin.At present, the conventional method of purification of peruscabin mainly contains high-temperature pressure-reduction rectification method and low temperature crystallization method of purification two kinds of techniques.But, containing a small amount of phenylformic acid (3 ~ 6% in the peruscabin crude product of gained, mass ratio), under its high temperature, the physico-chemical property of distillation and ambient temperature curing crystallization makes phenylformic acid after two kinds of purifying techniques, all easily have part to remain in peruscabin, finally affects purification efficiency and cost.Therefore, in industrial production, peruscabin crude product first carries out purification more usually after alkaline hydrolysis technique removing phenylformic acid.Alkaline hydrolysis process can produce a large amount of phenylformic acid oxidation high boiling material alkali solution liquid, and the main component of alkali solution liquid is the high mixture that boils of Sodium Benzoate and a small amount of solubility, and in sorrel, COD is greater than 200000.The recovery of alkali solution liquid or degraded, due to the many factors such as technology and economic benefit, can not find suitable terms of settlement, become a difficult point in phenylformic acid oxidation high boiling material recovery process.
Summary of the invention
For realizing the efficient recovery recycling to recovery of benzoic acid oxidation high boiling material, the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate of the present invention, each component separating and effective trans-utilization in high boiling material is realized after simple chemical conversion, technological operation is simple, reaction process is stablized, and purifying is with low cost.
For achieving the above object, the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate of the present invention, its special character is, it comprises the following steps successively:
1) get a certain amount of recovery of benzoic acid oxidation high boiling material and add reaction vessel, in reaction vessel, add thin liquid alkali to reaction system pH >=9, reaction 20 ~ 50min, separatory process, collects lower floor's aqueous phase alkali solution liquid; The main component of alkali solution liquid is that Sodium Benzoate and height boil organic impurity;
2) in alkali solution liquid, drip vitriol oil acidification, in system, separate out a large amount of yellow solids, pH value≤4 of Real-Time Monitoring question response thing, stop adding the vitriol oil, continue stirring 0.5 ~ 1.5h, filter to obtain phenylformic acid crude product;
3) in phenylformic acid crude product, add enough methyl alcohol and the vitriol oil, be stirred to abundant reaction;
4) by reactant fractionation by distillation removing methyl alcohol under 80 ~ 90 DEG C of conditions, the organic phase obtained after separatory process, then obtain methyl benzoate crude product through alkali cleaning, washing;
5) methyl benzoate crude product is at 120 ~ 130 DEG C, namely obtains methyl benzoate under 0.008 ~ 0.015bar condition after rectification and purification.
Preferably, step 1) in, described sig water be weight percentage concentration be 10 ~ 20% sodium hydroxide or potassium hydroxide solution.
Again preferably, step 2) in, described vitriol oil consumption is 3 ~ 5% of phenylformic acid oxidation high boiling material quality.
Again further, step 3) in, described vitriol oil consumption is 3 ~ 5% of phenylformic acid oxidation high boiling material quality.
Further, step 3) in, add methyl alcohol amount be 1ml ︰ 0.5 ~ 1.5g with the ratio of phenylformic acid crude product amount.
The present invention utilizes recovery of benzoic acid to be oxidized high boiling material to prepare the technological principle of the method for methyl benzoate and advantage is:
The present invention is oxidized high boiling material for raw material with phenylformic acid, transform phenylformic acid through Basic fluxing raction and be separated this benzyl formate of removing, obtain phenylformic acid crude product after the alkali solution liquid enriching sulfuric acid acidation process of reclaiming, phenylformic acid crude product main component is phenylformic acid and a small amount of high boiling mixture be wrapped in phenylformic acid and sodium sulfate.Then by not purified for phenylformic acid crude product directly and methyl alcohol carry out esterification and be produced into the relatively low methyl benzoate of boiling point, be easy to be separated under rectifying condition with the high boiling point organic compound impurity in crude product; The salt that methyl benzoate crude product wraps up in alkali cleaning, water washing process separate benzoic acid crude product again, then methyl benzoate and boiling point difference is larger with it high-boiling-point impurity in the thick product of rectifying separation, obtain high-quality methyl benzoate.
The boiling point that present invention utilizes impurity in phenylformic acid crude product differs larger with methyl benzoate and realizes separation and purification.Solubility high-boiling-point impurity complicated components in alkali solution liquid, boiling point concentrates between 250 DEG C to 350 DEG C mostly, is generate in toluene oxidation technique a series of high boiling point by-products produced.And benzoic boiling point is 249 DEG C, the impurity boiling point of the phenylformic acid crude product generated with alkali solution liquid acidifying differs less, not easily realizes being separated completely.Meanwhile, because benzoic price is lower, direct recovery of benzoic acid is more unfavorable in Financial cost.Consider technique and Financial cost two aspect factor, phenylformic acid crude product directly reacts with methyl alcohol without separation and generates the methyl benzoate that boiling point is 199 DEG C by the present invention, differs more than 50 DEG C, be easy to be separated completely through rectifying realization with the impurity in crude product.Meanwhile, the methyl benzoate that rectifying obtains is best in quality, and existing market price is benzoic 2 times.In addition, in the alkali solution liquid acidified waste water after this art breading, organic content and COD value all significantly decline, and greatly reduce cost of sewage disposal, and environmental protection contribution is great; Reduce benzoic cost recovery in alkali solution liquid simultaneously, be converted into considerable cost after methyl benzoate product, turn waste into wealth, remarkable in economical benefits.The catalyzer vitriol oil recoverable used in the esterification of phenylformic acid crude product, in acidifying lower batch of phenylformic acid oxidation high boiling material alkali solution liquid, reduces the usage quantity of the vitriol oil, obtains the treatment process of strongly-acid sulfuric acid water after also eliminating phenylformic acid esterification.Therefore, the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate all realizes larger advantage in process operability, Financial cost, environmental emission reduction three, has fabulous using value.And present invention process operating process is stable, reliable, efficiency is high, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes recovery of benzoic acid oxidation high boiling material to prepare the process flow diagram of the method for methyl benzoate.
Embodiment
Below in conjunction with the drawings and specific embodiments, the method that the present invention utilizes recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate is described in further detail.
Embodiment 1
The phenylformic acid oxidation high boiling material steamed is continued after boiling off phenylformic acid in certain phenylformic acid manufacturing enterprise phenylformic acid industrial production, its component of preliminary survey is: peruscabin is about 93% (GC), phenylformic acid is about 4% (GC), high-boiling-point impurity is about 3% (GC), utilize this phenylformic acid to be oxidized high boiling material and prepare methyl benzoate, technical process as shown in Figure 1, comprises the following steps:
1) in 10L reaction flask, add this phenylformic acid of 5000g oxidation high boiling material, add the sodium hydroxide solution that 700g massfraction is 15%, be warming up to 80 DEG C of stirrings; Sampling monitoring pH value after reaction half an hour, pH is stabilized in stopped reaction after more than 9, cooling, leaves standstill separatory, collects lower floor's alkali solution liquid and is about 1000g;
2) alkali solution liquid is gone in 2L beaker, in alkali solution liquid, slowly the vitriol oil is dripped under mechanical stirring, the obvious heat release of system is also separated out with a large amount of yellow solid, monitoring aqueous pH values, until pH value stops dripping the vitriol oil below 4, consume vitriol oil 24.5g altogether, after continuing to stir half an hour, be cooled to room temperature, suction filtration, moisture yellow solid phenylformic acid crude product 250g, its main component is phenylformic acid 77% (GC), and height boils organic mixture 20% (GC), a small amount of sodium sulfate and water;
3) be transferred in there-necked flask by yellow solid phenylformic acid crude product, add 250ml methyl alcohol, more slowly drip the 25g vitriol oil, return stirring, gas-chromatography is followed the tracks of phenylformic acid in organic phase and is transformed completely;
4) under normal pressure after 80 ~ 90 DEG C of fractionation by distillation removing methyl alcohol, the organic phase that after reactant cooling, separatory process obtains, then after alkali cleaning, washing methyl benzoate crude product 170g;
5) methyl benzoate crude product is at 121 ~ 125 DEG C, and under 0.01bar condition, rectifying obtains sterling methyl benzoate 122g (99.2%, GC).
In the present embodiment, the thick product rectification yield 72% of methyl benzoate; The strongly-acid aqueous phase that separatory process obtains reclaims for lower batch of alkali solution liquid acidifying.After testing, phenylformic acid crude product and methyl alcohol under the condition of the vitriol oil as catalyzer after back flow reaction phenylformic acid be substantially converted into methyl benzoate, transformation efficiency is greater than 95% (mass ratio), the product content obtained after the thick product rectifying of methyl benzoate is more than 99% (GC), substantially not containing methyl benzoate in rectifying still raffinate (leftover bits and pieces) monitoring (GC), illustrate that methyl benzoate is separated completely with high boiling material.
Embodiment 2
Phenylformic acid oxidation high boiling material is that the height continuing to steam after boiling off phenylformic acid in certain phenylformic acid manufacturing enterprise phenylformic acid industrial production boils component, its component of preliminary survey is: peruscabin about 94% (GC), phenylformic acid is about 4% (GC), high-boiling-point impurity is about 2% (GC), utilize this phenylformic acid oxidation high boiling material to prepare the method for methyl benzoate, comprise the following steps:
1) in 10L reaction flask, add this phenylformic acid of 5000g oxidation high boiling material, add the sodium hydroxide solution that 800g massfraction is 18%, be warming up to 80 DEG C of stirrings; Reaction half an hour after sampling monitoring pH value, be stabilized in stopped reaction after more than 9 until pH, cooling, leave standstill separatory, collect lower floor alkali solution liquid 1000g;
2) alkali solution liquid is gone in 2L beaker, in alkali solution liquid, slowly drip the vitriol oil under mechanical stirring, the obvious heat release of system is also separated out with a large amount of yellow solid, monitoring aqueous pH values, until pH value stops dripping the vitriol oil below 4, consuming vitriol oil amount is altogether 25g, after continuing to stir half an hour, is cooled to room temperature, suction filtration, moisture yellow solid 245g, recording its main component is phenylformic acid 75% (GC), and height boils organic mixture 21%, a small amount of sodium sulfate and water;
3) be transferred in there-necked flask by yellow solid phenylformic acid crude product, add 245ml methyl alcohol, slowly drip the 25g vitriol oil, return stirring, gas-chromatography is followed the tracks of phenylformic acid in organic phase and is transformed completely;
4) under normal pressure at 80 ~ 90 DEG C of distillation for removing methanol, after reactant cooling, the organic phase that obtains of separatory process obtains methyl benzoate crude product 163g after alkali cleaning, washing;
5) methyl benzoate crude product is at 124 ~ 126 DEG C, and under 0.012bar condition, rectifying obtains sterling methyl benzoate 115g (99.5%, GC).
In the present embodiment, the thick product rectification yield 70% of methyl benzoate; The strongly-acid aqueous phase that separatory process obtains reclaims for lower batch of alkali solution liquid acidifying.After testing, phenylformic acid crude product and methyl alcohol under the condition of the vitriol oil as catalyzer after back flow reaction phenylformic acid be substantially converted into methyl benzoate, transformation efficiency is greater than 96% (mass ratio), the product content obtained after the thick product rectifying of methyl benzoate is more than 99% (GC), substantially not containing methyl benzoate in rectifying still raffinate (leftover bits and pieces) monitoring (GC), illustrate that methyl benzoate is separated completely with high boiling material.
Embodiment 3
The phenylformic acid oxidation high boiling material steamed is continued after boiling off phenylformic acid in certain phenylformic acid manufacturing enterprise phenylformic acid industrial production, its component of preliminary survey is: peruscabin about 95% (GC), phenylformic acid is about 3% (GC), high-boiling-point impurity is about 2% (GC), utilize this phenylformic acid to be oxidized high boiling material and prepare methyl benzoate, technical process as shown in Figure 1, comprises the following steps:
1) in 10L reaction flask, add this phenylformic acid of 2500g oxidation high boiling material, add the sodium hydroxide solution that 400g massfraction is 15%, be warming up to 80 DEG C of stirrings; Sampling monitoring pH value after reaction half an hour, is stabilized in stopped reaction after more than 9 until pH, cooling, leaves standstill separatory, collect lower floor alkali solution liquid and be about 500g;
2) alkali solution liquid is gone in 2L beaker, in alkali solution liquid, slowly the vitriol oil is dripped under mechanical stirring, the obvious heat release of system is also separated out with a large amount of yellow solid, monitoring aqueous pH values, until pH value stops dripping the vitriol oil below 4, consume vitriol oil 13g altogether, continue to stir half an hour, be cooled to room temperature, suction filtration, moisture yellow solid phenylformic acid crude product 128g, its main component is phenylformic acid 76% (GC), and height boils organic mixture 21% (GC), a small amount of sodium sulfate and water;
3) be transferred in there-necked flask by yellow solid phenylformic acid crude product, add 130ml methyl alcohol, more slowly drip the 13g vitriol oil, return stirring, gas-chromatography is followed the tracks of phenylformic acid in organic phase and is transformed completely;
4), heat up in a steamer steaming separation removing methyl alcohol under normal pressure under 80 ~ 90 DEG C of conditions after, reactant is lowered the temperature, the organic phase that separatory process obtains, then obtains methyl benzoate crude product 71g after alkali cleaning, washing;
5) methyl benzoate crude product is at 121 ~ 125 DEG C, and under 0.01bar condition, rectifying obtains sterling methyl benzoate 52.5g (99.2%, GC).
In the present embodiment, the thick product rectification yield 73.9% of methyl benzoate; The strongly-acid aqueous phase that separatory process obtains reclaims for lower batch of alkali solution liquid acidifying.After testing, phenylformic acid crude product and methyl alcohol under the condition of the vitriol oil as catalyzer after back flow reaction phenylformic acid be substantially converted into methyl benzoate, transformation efficiency is greater than 96% (mass ratio), the product content obtained after the thick product rectifying of methyl benzoate is more than 99% (GC), substantially not containing methyl benzoate in rectifying still raffinate (leftover bits and pieces) monitoring (GC), illustrate that methyl benzoate is separated completely with high boiling material.
Embodiment 4
The phenylformic acid oxidation high boiling material steamed is continued after boiling off phenylformic acid in certain phenylformic acid manufacturing enterprise phenylformic acid industrial production, its component of preliminary survey is: peruscabin 95% (GC), phenylformic acid is 3.5% (GC), high-boiling-point impurity is about 1.5% (GC), utilize this phenylformic acid to be oxidized high boiling material and prepare methyl benzoate, comprise the following steps:
1) in 10L reaction flask, add this phenylformic acid of 2500g oxidation high boiling material, add the sodium hydroxide solution that 450g massfraction is 15%, be warming up to 80 DEG C of stirrings; Sampling monitoring pH value after reaction half an hour, is stabilized in stopped reaction after more than 9 until pH, cooling, leaves standstill separatory, collect lower floor alkali solution liquid and be about 580g;
2) gone to by alkali solution liquid in 2L beaker, slowly drip the vitriol oil under mechanical stirring in alkali solution liquid, the obvious heat release of system is also separated out with a large amount of solid; Monitoring aqueous pH values, until pH value stops dripping the vitriol oil below 4, consume vitriol oil 15g altogether, continue to stir half an hour, be cooled to room temperature, suction filtration, obtain moisture yellow solid phenylformic acid crude product 161g, its main component is phenylformic acid 85% (GC), and height boils organic mixture 13% (GC), a small amount of sodium sulfate and water;
3) be transferred in there-necked flask by yellow solid phenylformic acid crude product, add 161mL methyl alcohol, more slowly drip the 16g vitriol oil, return stirring, gas-chromatography is followed the tracks of phenylformic acid in organic phase and is substantially transformed completely;
4), after normal pressure heats up in a steamer steaming separation removing methyl alcohol under 80 ~ 90 DEG C of conditions, reactant is lowered the temperature, the organic phase that separatory process obtains, then obtains methyl benzoate crude product 85g after alkali cleaning, washing;
5) methyl benzoate crude product is at 121 ~ 125 DEG C, and under 0.01bar condition, rectifying obtains sterling methyl benzoate 66.3g (99.6%, GC).
In the present embodiment, the thick product rectification yield 78% of methyl benzoate; The strongly-acid aqueous phase that separatory process obtains reclaims for lower batch of alkali solution liquid acidifying.After testing, phenylformic acid crude product and methyl alcohol under the condition of the vitriol oil as catalyzer after back flow reaction phenylformic acid be substantially converted into methyl benzoate, transformation efficiency is greater than 96% (mass ratio), the product content obtained after the thick product rectifying of methyl benzoate is more than 99% (GC), substantially not containing methyl benzoate in rectifying still raffinate (leftover bits and pieces) monitoring (GC), illustrate that methyl benzoate is separated completely with high boiling material.
Claims (5)
1. utilize recovery of benzoic acid oxidation high boiling material to prepare a method for methyl benzoate, it is characterized in that, it comprises the following steps successively:
1) get a certain amount of recovery of benzoic acid oxidation high boiling material and add reaction vessel, the liquid that adds dilute alkali, to reaction system pH >=9, reacts 20 ~ 50min, separatory process, collects lower floor's alkali solution liquid;
2) in alkali solution liquid, drip the vitriol oil, in system, separate out solid, question response thing pH value≤4, stop adding the vitriol oil, continue stirring 0.5 ~ 1.5h, filter to obtain phenylformic acid crude product;
3) in phenylformic acid crude product, add enough methyl alcohol and the vitriol oil, fully react;
4) by reactant fractionation by distillation removing methyl alcohol under 80 ~ 90 DEG C of conditions, the organic phase obtained after separatory process, then obtain methyl benzoate crude product through alkali cleaning, washing;
5) methyl benzoate crude product is at 120 ~ 130 DEG C, and rectification and purification under 0.008 ~ 0.015bar condition, namely obtains methyl benzoate.
2. the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate according to claim 1, is characterized in that: step 1) in, described sig water selection weight percent concentration is sodium hydroxide or the potassium hydroxide solution of 10 ~ 20%.
3. the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate according to claim 1, is characterized in that: step 2) in, described vitriol oil consumption is 3 ~ 5% of phenylformic acid oxidation high boiling material quality.
4. the method utilizing recovery of benzoic acid oxidation high boiling material to prepare methyl benzoate according to claim 1, is characterized in that: step 3) in, described vitriol oil consumption is 3 ~ 5% of phenylformic acid oxidation high boiling material quality.
5. according to claim 1ly utilize recovery of benzoic acid to be oxidized high boiling material to prepare the method for methyl benzoate, it is characterized in that: step 3) in, add methyl alcohol amount be 1ml ︰ 0.5 ~ 1.5g with the ratio of phenylformic acid crude product amount.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948387A (en) * | 2010-08-30 | 2011-01-19 | 安徽佳先功能助剂股份有限公司 | Preparation technology of methyl benzoate |
| CN102001935A (en) * | 2010-11-29 | 2011-04-06 | 武汉有机实业有限公司 | Refining method of benzoic acid |
| CN104030924A (en) * | 2013-12-03 | 2014-09-10 | 湖北微控生物科技有限公司 | Method for recovering and refining benzyl benzoate |
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- 2015-03-11 CN CN201510105382.9A patent/CN104817457A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948387A (en) * | 2010-08-30 | 2011-01-19 | 安徽佳先功能助剂股份有限公司 | Preparation technology of methyl benzoate |
| CN102001935A (en) * | 2010-11-29 | 2011-04-06 | 武汉有机实业有限公司 | Refining method of benzoic acid |
| CN104030924A (en) * | 2013-12-03 | 2014-09-10 | 湖北微控生物科技有限公司 | Method for recovering and refining benzyl benzoate |
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Application publication date: 20150805 |