CN1023864C - Process for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure - Google Patents
Process for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure Download PDFInfo
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- CN1023864C CN1023864C CN 88104172 CN88104172A CN1023864C CN 1023864 C CN1023864 C CN 1023864C CN 88104172 CN88104172 CN 88104172 CN 88104172 A CN88104172 A CN 88104172A CN 1023864 C CN1023864 C CN 1023864C
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Abstract
The present invention relates to a method for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure. Co2 (CO) 8 is used as a catalyst, NaOH, methanol and water are used as reaction media, CO or industrial exhaust gas enriching CO is used as raw gas, the reaction pressure is normal pressure, the Co2 (CO) 8 is chloridized to recover cobalt, and the end-point of hydrolysis distillation is controlled at the temperature of 90 DEG C. When the method of the present invention is used for producing the phenylacetic acid, the yield ratio is from 85% to 95%, the purity degree is higher than 98%, and the melting point is from 75 DEG C to 77 DEG C. Compared with the prior art, the present invention has the advantages of simple and reasonable technology, convenient operation and low cost.
Description
The present invention relates to a kind of method of preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure, it comprises following several steps: synthetic benzene acetate under catalyst action, and methyl alcohol is reclaimed in distillation, and catalyst cobalt is reclaimed in chemical precipitation, and acidification reaction liquid gets toluylic acid.
The method of synthesize phenylacetic acid sees reach tens of kinds of document, but industrialized several is only arranged, and exists some problems to some extent, and for this reason, since the sixties, people have developed the method for halohydrocarbon oxo process toluylic acid.
At USP3, a kind of method of benzyl chloride oxo process preparing phenylacetic acid is disclosed in 928,429, this method is with Co
2(CO)
8Make catalyzer, NaOH makes neutralizing agent, methyl alcohol is solvent, through oxonation, the reaction solution acidification, extracted with diethyl ether toluylic acid and methyl phenylacetate, distillation extraction liquid are removed ether and are got 65% toluylic acid and 35% methyl phenylacetate, by distillation toluylic acid and methyl phenylacetate are separated again, handle methyl phenylacetate and get toluylic acid.This method reaction conditions gentleness, the product yield height, weak point is: first, at least need to separate through reaction, acidifying, extraction, distillation extraction liquid, again five or six steps (also not comprising recovery) such as acid and ester to methanol solution and ether, whole process is more numerous and diverse, production cycle is long, the cost height; The second, the extraction agent ether is volatile, and is inflammable and explosive, and pungency is strong, and consumption is big; The 3rd, do not report catalyzer and solvent and recoverying and utilizing method.
A kind of method of synthesizing phenylacetic acid by low pressure carbonylation is also disclosed in CN85100362, its purpose is to improve the method for the clear 48-8094 report of Japan's special permission communique, step is: under the composite catalyst effect that is made of cobalt salt, Ferro Manganese and Sulfothiorine, in methanol solution, with NaOH is neutralizing agent, and the synthesize phenylacetic acid sodium salt is through distillating recovering solvent methyl alcohol, add the soda ash precipitate cobalt behind the acidification reaction liquid, acidifying gets toluylic acid.Weak point is, the first, and the entire operation process is still more complicated, and the pH value of reaction solution is had relatively high expectations, otherwise influences the recovery of reaction yield and cobalt; Second, what use is composite catalyst, so the ratio that must very carefully allocate catalyzer, in addition,, reclaims in yellow soda ash though precipitating the cobalt more than 90%,, simultaneously also with iron, manganese precipitation, when reusing, also want separation of cobalt, fundamentally, do not solve the recovery problem of cobalt well; The 3rd, do not report the methyl phenylacetate problem how processing reaction generates.
The method that the objective of the invention is to avoid above-mentioned weak point of the prior art and simple, reasonable, feasible, the economic preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure of a kind of technology is provided, method of the present invention will obtain toluylic acid with the least possible step and starting material, help realizing suitability for industrialized production.
Purpose of the present invention can reach by following measure:
The present invention selects Co for use when synthetic benzene acetate
2(CO)
8Be catalyzer, NaOH makes neutralizing agent and is made into reaction solvent with water and methyl alcohol, and unstripped gas CO can also be an industrial tail gas, and reaction pressure is a normal pressure, and the pH value of reaction solution is controlled at 7.1～14, and preferably 9～14, back usefulness oxygenant oxidation Co is finished in reaction
2(CO)
8, precipitation reclaims cobalt, distillation is reclaimed methyl alcohol and is also made the methyl phenylacetate hydrolysis, the terminal temperature that methyl alcohol is reclaimed in distillation is controlled at 90 ℃, treat that methyl alcohol steams after, get the crude benzol acetic acid product with hydrochloric acid or sulfuric acid acidation residue mother liquor, centrifugation gets technical grade product.
Said process can be expressed as follows with chemical formula:
Purpose of the present invention can also reach by following measure:
When synthetic benzene acetate, the aqueous solution that at first in reactor, adds alkali, the concentration of alkali lye is 20～40%, be preferably 30 ± 5%, alkali lye can be selected oxyhydroxide, oxide compound or the carbonate preparation of basic metal or alkaline-earth metal for use, but preferably alkali-metal oxyhydroxide, and this alkali is preferably cheap and easy to get, NaOH for example, Na
2CO
3, mol ratio is excessive is advisable the consumption of alkali by reacting.Then, in suitable temperature with under stirring, the mixed solution that adds alcohol is made reaction medium, pure optional methyl alcohol or ethanol, water accounts for 5～60%(weight in alcohol-water mixture), be preferably in 20～45%(weight) between.The add-on of catalyzer is with Co
2(CO)
8And the mol ratio between the halogen benzyl was advisable in 1: 30～1: 100, be preferably in 1: 43～and between 1: 86.At last, add halogen benzyl and CO simultaneously under constantly stirring, the halogen benzyl can be selected bromo benzyl or benzyl chloride, preferably benzyl chloride.CO can select pure CO or industrial tail gas for use, when CO selects industrial tail gas for use, the purity of CO obviously has tangible influence to reaction, therefore the content of CO preferably is not less than 85%(weight in the tail gas), when the content of CO unstripped gas is lower than 80%, preferably make the content of CO raise O in the industrial tail gas through gas processing
2, oxious components such as sulphur and arsenic, the most handy ordinary method is handled, and can improve reaction yield like this and reduce catalyst consumption.Usually the industrial tail gas of selecting for use has: phosphorus production tail gas, cuprammonium are produced (high furnace exhaust gas) again, and silicon carbide is produced tail gas etc., and generally between 85～98%, content of harmful gas such as oxygen preferably are no more than 0.1% to the CO content of these industrial tail gas, CO
2Content is no more than 5%, for example: phosphorus production tail gas CO85～97%, CO
22～5%, O
20.1～0.5%, CO90～99% is produced in cuprammonium regeneration, silicon carbide is produced tail gas CO90～97%.In whole oxonation process, the temperature of reaction system should remain on 45～65 ℃, is preferably in 45～60 ℃, and keeps the full atmosphere of carbon monoxide, and the pressure of reaction system is normal pressure, and obviously pressure boost does not have detrimentally affect to reaction.
Above-mentioned reaction can be finished in 3～6 hours.Question response finishes back (CO no longer absorbs), adds oxygenant precipitated catalyst Co to reaction solution
2(CO)
8The oxygenant that adds is air or oxygen, and obviously bubbling air more economically, conveniently, rationally.Along with air or oxygen constantly feed reaction solution, the color of reaction solution becomes tawny by the white powder look, shows, catalyzer has become cobalt oxide and cobaltous hydroxide by cobalt-carbonyl, after filtration, calcination, the rate of recovery of cobalt is more than 90%, the CO that obtains
2O
3Can directly make Co
2(CO)
8
Filtrate (reaction solution) heating, distillation method reclaims solvent methanol or ethanol, methyl esters hydrolysis in still-process, terminal temperature is controlled at 90 ℃.The pH value of filtrate (reaction solution) is controlled at 7.1～14, and preferably 9～14.Help the hydrolysis of ester like this.The rate of recovery of methyl alcohol is more than 80%.
After treating that methyl alcohol steams, solution is chilled to room temperature, and with hydrochloric acid or sulfuric acid acidation, endpoint pH is controlled between 1～2, promptly gets crude benzol acetate, and centrifugation gets the technical grade toluylic acid.The concentration range of used acid is preferably in 20～30% 10～40% during acidification.
Produce toluylic acid with method of the present invention, yield is 85～95%, and purity is more than 98%, 75～77 ℃ of fusing points.
Isolate the waste water of toluylic acid, the methyl alcohol of recovery and cobalt, reusable, the yield of toluylic acid there is not obvious influence.
The present invention compares present technology and has following advantage:
1. cobalt, hydrolysis distillation and four steps of acidifying only need be reacted, be reclaimed to whole process of production, and the industrial chemicals that uses is cheap and easy to get, and production technique is simple, and is easy to operate, with short production cycle.
2.CO unstripped gas can use the industrial tail gas that is rich in CO, phosphorus production tail gas for example, and cuprammonium resurgent gases or silicon carbide are produced tail gas, have so both utilized industrial tail gas, have reduced cost again.
3. neutralizing agent NaOH directly is made into reaction medium with methanol solution, and reaction solution only requires it is that alkalescence get final product, and feasible the operation becomes simple and easy to do.
4. air oxidation process is adopted in the recovery of catalyzer cobalt-carbonyl, and it is easy to reclaim technology, does not need to use pharmaceutical chemicals, and is convenient feasible, with low cost.
5. reaction pressure is a normal pressure.
The present invention below will be further described:
Example 1:
Get 205ml methyl alcohol, 60 gram NaOH, 125ml water adds simultaneously and is equipped with in the 1 liter three-necked bottle of condenser and agitator, and under CO atmosphere (purity＞99%), keeping the CO flow velocity is 0.3～0.5 liter/minute, and stirring velocity is＞700 rev/mins, adds Co
2(CO) 86 grams, heating and begins to drip benzyl chloride, and temperature of reaction is controlled at 40～60 ℃, 95 gram benzyl chlorides is dripped completely in 1.5～2 hours, and then reacts 1～2 hour, till carbon monoxide no longer absorbs.After reaction finished, logical oxygen or air leached residue, got the 2.8 gram cobalt rate of recovery 93.3% after the calcination.Methyl alcohol is reclaimed in reaction solution hydrolysis distillation, and distillating carbinol 1～2 hour gets methyl alcohol 134.5 grams, the rate of recovery 83%.The Methanol Recovery postcooling adds 20～40% hcl acidifying processing to room temperature, gets toluylic acid 97 grams, productive rate 95%.
Example 2:
By example 1 described condition and process, change the source of carbon monoxide, utilize and produce the tail gas that yellow phosphorus gave off (tail gas composition CO97.1%, CO
22%, O
20.2%) carries out oxonation, get crude benzol acetate 96 grams, yield 94.1%.
Example 3:
By example 1 described condition and process, solvent methanol is changed into ethanol.Ethanol drops into 205 milliliters, reclaims 190 grams.Get toluylic acid 76 grams, yield 74.5%.
Example 4:
In 500 liter enamel stills, add 41 kilograms of methyl alcohol, 15 kilograms of NaOH, 32 kg of water, 80～130 rev/mins of stirring velocitys feed yellow phosphoric tail gas (CO86.5%, O
20.3%, other gas 13.2%), add 1.5 kilograms of Co again
2(CO)
8, be warming up to 60 ℃ then, begin to drip 24 kilograms of benzyl chlorides, dropwise in 3 hours, and then reacted 2～3 hours, after reaction finished, blowing air was removed residue, the reaction solution distillating carbinol of heating, temperature to 90 ℃ after 2 hours, the distillation stopping acidification gets 20.6 kilograms of crude benzol acetate, yield 79.5%.It is industrial goods more than 98% that centrifugation gets purity.
Example 5:
In the 1000ml three-necked bottle, add 205ml methyl alcohol, 60 gram NaOH, 125ml water stirs, and feeds carbon monoxide gas, and the carbon monoxide source is for producing the tail gas of silicon carbide, and its CO content is 95%, so adds Co
2(CO)
86 grams, all the other operation stepss are identical with example 1, and are last, and treated reaction solution gets toluylic acid 92.8 grams, yield 91.0%.
Example 6:
According to feeding intake and reaction conditions of example 1, employing cuprammonium resurgent gases is the CO source, and CO content is 98.5%, after reaction finishes, through processing reaction liquid, gets toluylic acid 96.7 grams, and product yield is 94.8%.
Most preferred embodiment is an example 1.
Claims (6)
1, a kind of method of benzyl chloride oxo process toluylic acid comprises:
(1) uses Co
2(CO)
8Make catalyzer, alkali is made neutralizing agent, and CO is a unstripped gas, synthetic benzene acetate;
(2) normal pressure reclaims methyl alcohol;
(3) chemical precipitation method reclaims cobalt;
(4) the reaction solution acidifying is got toluylic acid
It is characterized in that: (1) Na0H, first alcohol and water are reaction medium, and alkali number is excessive for the reaction mol ratio, and water accounts for 5～60% (weight) in the alcohol-water mixture, Co
2(CO)
8And the mol ratio between the halogen benzyl is 1: 30～1: 100, and the industrial tail gas that is not less than 85% (weight) is a unstripped gas, and normal pressure is reaction down, 40～60 ℃ of control reaction temperature, reacting liquid pH value 7.1～14; (2) cobalt is reclaimed in oxidation; (3) hydrolysis distillatory terminal point is controlled at 90 ℃.
2, the method for claim 1, the pH value that it is characterized in that reaction solution is 9～14.
3, the method for claim 1, water accounts for 20～45%(weight in the alcohol-water mixture)
4, the method for claim 1 is characterized in that Co
2(CO)
8And the mol ratio between the halogen benzyl is 1: 43～1: 86.
5, the method for claim 1 is characterized in that the unstripped gas compositing range is as CO during from industrial tail gas:
(1) phosphorus production tail gas, CO85～97%, CO
22～5%, O
20.1～0.5%;
(2) cuprammonium is produced (high furnace exhaust gas) again: CO90～99%
(3) silicon carbide is produced tail gas: CO90～97%
6, the method for claim 1 is characterized in that oxidation Co(CO)
8Reclaiming the used oxygenant of cobalt is air or oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88104172 CN1023864C (en) | 1988-07-05 | 1988-07-05 | Process for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88104172 CN1023864C (en) | 1988-07-05 | 1988-07-05 | Process for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1039241A CN1039241A (en) | 1990-01-31 |
| CN1023864C true CN1023864C (en) | 1994-02-23 |
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ID=4832898
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88104172 Expired - Fee Related CN1023864C (en) | 1988-07-05 | 1988-07-05 | Process for preparing phenylacetic acid by chlorobenzyl carbonylation under normal pressure |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852557B (en) * | 2010-06-12 | 2013-03-13 | 沈阳石蜡化工有限公司 | Decoking method of tubular heater of urea dewaxing device |
| CN103387490B (en) | 2012-05-09 | 2015-08-26 | 中国科学院兰州化学物理研究所 | A kind of method of toluene carboxylation to synthesize phenylacetic acid |
| CN102875361B (en) * | 2012-10-30 | 2016-01-20 | 中蓝连海设计研究院 | The technique that crystallization produces toluylic acid is exempted from by impure phenylacetate solution |
| CN109438215A (en) * | 2018-11-12 | 2019-03-08 | 西南化工研究设计院有限公司 | A kind of method of carbonylation synthesis phenylacetic acid |
| CN111978170A (en) * | 2019-05-24 | 2020-11-24 | 贵州新天鑫化工有限公司 | Green recyclable synthesis method of phenylacetic acid |
| CN113354528A (en) * | 2021-06-07 | 2021-09-07 | 李乾华 | Production method of phenylacetic acid |
| CN113461516A (en) * | 2021-06-30 | 2021-10-01 | 李乾华 | Synthetic method of phenylacetic acid |
| CN114394895B (en) * | 2022-01-21 | 2023-09-15 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
| CN114774973B (en) * | 2022-04-22 | 2024-03-08 | 河北师范大学 | Nanometer flower-like cobalt-molybdenum sulfide supported catalyst and preparation method and application thereof |
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1988
- 1988-07-05 CN CN 88104172 patent/CN1023864C/en not_active Expired - Fee Related
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