CN1295999A - Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation - Google Patents
Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation Download PDFInfo
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- CN1295999A CN1295999A CN 99122527 CN99122527A CN1295999A CN 1295999 A CN1295999 A CN 1295999A CN 99122527 CN99122527 CN 99122527 CN 99122527 A CN99122527 A CN 99122527A CN 1295999 A CN1295999 A CN 1295999A
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- benzoic anhydride
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Abstract
A method for producing monochlorophenylanhydride uses monochloroortho-xylene as raw material, and includes the following steps: making oxidation of liquid phase air to produce monochlorophthalic acid, heating to remove solvent and water to produce crude monochlorophenylanhydride through reduced pressure distillation, and can obtain high-yield and high-purity 4-chlorophenylanhydride and 3-chlorophenylanhydride. The above-mentioned monochloroortho-xylene is 3-chloroortho-xylene or 4-chloroortho-xylene or mixture of both of them. Said invention is high in yield, high in purity, low in corrosion to equipment and slight in air pollution.
Description
The invention belongs to from the monochloro o-Xylol and produce high yield, high purity monochloro method, belong to liquid phase air catalyzed oxidation field in the chemical industry for phthalic anhydride through liquid phase air oxidation.Monochloro is meant 3-chloro-benzoic anhydride or 4-chloro-benzoic anhydride or both mixtures for phthalic anhydride.
At present, monochloro has for the method for making of phthalic anhydride: the clorox chlorination process of phthalic anhydride, phthalic anhydride gas phase chloro method and monochloro-o-dimethyl benzene vapour phase oxidation process etc.SU1004328 and spy open clear 55-20705 and have reported phthalic anhydride through clorox chlorination process manufacturing 4-chloro-benzoic anhydride.But it is low that the main drawback of this method is a yield, and impurity is many in the crude product, thereby be difficult to refining and operational path is long and serious etc. to equipment corrosion.U.S.P2400565 has introduced the phthalic anhydride steam and chlorine together passes through the catalyst bed that heats, and the preparation monochloro is for phthalic anhydride.Although operational path is shorter, complicated mixed reaction product and lower yield still make this method can not carry out suitability for industrialized production.Ger Offen2336875 has disclosed air catalytic gas phase oxidation monochloro-o-dimethyl benzene production of steam monochloro for phthalic anhydride.Although it is shorter that this method has technical process, product purity higher (reaching 84.9% in the crude product) can be carried out the advantage of suitability for industrialized production, but still it is on the low side to exist yield, and weight yield only reaches 90%, to the seriously corroded of equipment, the shortcoming that is difficult to expand the scale of production.
At the deficiency of above-mentioned preparation monochloro for the phthalic anhydride method, the invention provides the method for a kind of yield height, purity height,, manufacture order chloro-benzoic anhydride that atmospheric pollution light little to equipment corrosion, thick monochloro is for phthalic anhydride weight yield 〉=107%, pass through into after acid anhydride and the rectifying separation, the purity of 3-chloro-benzoic anhydride and 4-chloro-benzoic anhydride all 〉=99%, ultimate yield is 〉=105%.
The present invention is raw material with the monochloro-o-dimethyl benzene, generates monochloro for phthalic acid through liquid phase air oxidation, and heating desolventizing and water generate thick monochloro for phthalic anhydride, obtain high yield and highly purified 4-chloro-benzoic anhydride and 3-chloro-benzoic anhydride through rectification under vacuum.Monochloro-o-dimethyl benzene is meant 3-chloro-o-xylene or 4-chloro-o-xylene or both miscellanys.
Concrete grammar:
Monochloro-o-dimethyl benzene is at pressure 0.5-3.0MPa, temperature is under the condition between 150-300 ℃, be used in solvability is good in the solvent cobalt salt, manganese salt and brominated organic compound as catalyzer, the acetic acid that with purity is 80-100% is solvent, and adding inhibiter and neutralizing agent, carry out liquid phase air oxidation and generate monochloro, further heat desolventizing and water and form monochloro for phthalic anhydride for phthalic acid; Obtain 4-chloro-benzoic anhydride and 3-chloro-benzoic anhydride through rectification under vacuum again.Rectification under vacuum pressure is 2.0 * 10
-5-2.0 * 10
-3MPa, the required stage number of rectifying is the 10-100 piece.Catalyzer is meant the compound that can be dissolved in the acetic acid, specifically is Cobaltous diacetate, manganese acetate and tetrabromoethane, and its atomic ratio is Co: Mn: Br=1: 0.1-2.0: 1-10, the total concn scope of catalyzer is the 1-50 grams per liter.Inhibiter, neutralizing agent are meant sodium-acetate, Sodium Benzoate, yellow soda ash, volatile salt, and the total concn scope is the 1.0-8.0 mg/litre.Slightly more than 107%, the desolventizing of thick product and dehydration are to utilize the method that heats to finish to monochloro for the weight yield of adjacent dibenzoic acid, and its temperature of reaction is 150-250 ℃.
The monochloro that the present invention produces for phthalic anhydride yield height, purity height, little to equipment corrosion, atmospheric pollution is light.
Provide most preferred embodiment of the present invention below:
Embodiment 1:
With 400 gram monochloro-o-dimethyl benzenes, wherein the ratio of 3-chloro-o-xylene and 4-chloro-o-xylene is 47: 53 and Cobaltous diacetate 10 grams, manganese acetate 0.51 gram, tetrabromoethane 15 grams, yellow soda ash 4 grams, Sodium Benzoate 2 grams, acetic acid 2000 grams, add in the oxidizing tower behind the mixed dissolution, bubbling air is pressurized to 2.0MPa, be heated to 200 ℃, bubbling air carries out oxidation, and air flow quantity is 500 milliliters/hour, 90 minutes reaction times, after oxidation finishes, emit product, weight is 2350 grams, wherein contains monochloro for phthalic acid 469 grams, weight yield is 117.3%, and the ratio of 3-chlorophthalic acid and 4-chlorophthalic acid is 51.49%.
With oxidation products 2350 grams, after heating steams acetic acid, being warmed up to 245 ℃ deviates from moisture content and becomes thick acid anhydride, be to reduce pressure on the rectifying tower of 60 blocks of column plates slightly to heat up in a steamer in theoretical stage number, 3-chloro-benzoic anhydride 220 grams and 4-chloro-benzoic anhydride 211 grams have been told, purity is respectively 99.5% and 99.4%, and weight yield (from the raw material meter) is 107.8%.
Claims (10)
1, a kind of method of liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride is characterized in that using cobalt salt, manganese salt, brominated organic compound as catalyzer; Sodium-acetate, Sodium Benzoate, yellow soda ash, volatile salt are as inhibiter, neutralizing agent; Acetic acid is solvent, under pressurization and heating condition, uses the atmospheric oxidation monochloro-o-dimethyl benzene, and after thermal dehydration became acid anhydride, rectifying obtained highly purified 4-chloro-benzoic anhydride and 3-chloro-benzoic anhydride to the monochloro of generation for phthalic acid.
2, the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride according to claim 1 is characterized in that catalyzer is meant the compound that can be dissolved in the acetic acid.
3, as the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride as described in the claim 2, it is characterized in that catalyzer is Cobaltous diacetate, manganese acetate and tetrabromoethane, its atomic ratio is Co: Mn: Br=1: 0.1-2: 1-10.
4, as the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride as described in the claim 3, the total concn scope that it is characterized in that catalyzer is the 1-50 grams per liter.
5, the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride according to claim 1 is characterized in that inhibiter, neutralizing agent are meant the compound that is dissolved in the acetic acid.
6, as the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride as described in the claim 5, it is characterized in that inhibiter, neutralizing agent are sodium-acetate, Sodium Benzoate, yellow soda ash, volatile salt.
7, as the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride as described in the claim 7, the total concn scope that it is characterized in that inhibiter, neutralizing agent is 1.0～8.0 mg/litre.
8, the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride according to claim 1, the purity range that it is characterized in that acetate solvate is 80-100%.
9, the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride according to claim 1 is characterized in that the reaction pressure scope at 0.5-3.0Mpa, and temperature of reaction is between 150-300 ℃.
10, the method for liquid phase air oxidation monochloro-o-dimethyl benzene manufacture order chloro-benzoic anhydride according to claim 1 is characterized in that the desolventizing of thick product and dehydration are to utilize the method for heating to finish, and its temperature of reaction is 150-250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122527A CN1090171C (en) | 1999-11-11 | 1999-11-11 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122527A CN1090171C (en) | 1999-11-11 | 1999-11-11 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
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| CN1295999A true CN1295999A (en) | 2001-05-23 |
| CN1090171C CN1090171C (en) | 2002-09-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99122527A Expired - Fee Related CN1090171C (en) | 1999-11-11 | 1999-11-11 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739484A (en) * | 2013-12-31 | 2014-04-23 | 黄石市利福达医药化工有限公司 | Preparation method of 1,4-naphthalenedicarboxylic acid |
| CN105646419A (en) * | 2016-03-23 | 2016-06-08 | 天津大学 | Method for crystallizing and purifying 3-chlorophthalic anhydride |
| CN108997284A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of chloro-benzoic anhydride is synthesized in continuous flow micro passage reaction |
| CN113735806A (en) * | 2021-08-03 | 2021-12-03 | 哈尔滨工业大学（威海） | Method for preparing chlorophthalic anhydride by solvent-free liquid phase catalytic oxidation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1806139C (en) * | 1991-06-24 | 1993-03-30 | Институт Физической Химии Им.Л.В.Писаржевского Ан@ Украины | Method of 3-chlorophthalic anhydride synthesis and a catalyst for realization of it |
-
1999
- 1999-11-11 CN CN99122527A patent/CN1090171C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739484A (en) * | 2013-12-31 | 2014-04-23 | 黄石市利福达医药化工有限公司 | Preparation method of 1,4-naphthalenedicarboxylic acid |
| CN103739484B (en) * | 2013-12-31 | 2017-11-10 | 黄石市利福达医药化工有限公司 | The preparation method of 1,4-naphthalene dicarboxylic acids |
| CN105646419A (en) * | 2016-03-23 | 2016-06-08 | 天津大学 | Method for crystallizing and purifying 3-chlorophthalic anhydride |
| CN108997284A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of chloro-benzoic anhydride is synthesized in continuous flow micro passage reaction |
| CN108997284B (en) * | 2018-07-16 | 2022-05-03 | 山东冠森高分子材料科技股份有限公司 | Method for synthesizing chlorophthalic anhydride in continuous flow micro-channel reactor |
| CN113735806A (en) * | 2021-08-03 | 2021-12-03 | 哈尔滨工业大学（威海） | Method for preparing chlorophthalic anhydride by solvent-free liquid phase catalytic oxidation |
| CN113735806B (en) * | 2021-08-03 | 2023-07-28 | 哈尔滨工业大学（威海） | Method for preparing chlorophthalic anhydride by solvent-free liquid phase catalytic oxidation |
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| CN1090171C (en) | 2002-09-04 |
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