CN102976912B - Method for preparing acetophenone - Google Patents
Method for preparing acetophenone Download PDFInfo
- Publication number
- CN102976912B CN102976912B CN201110263493.4A CN201110263493A CN102976912B CN 102976912 B CN102976912 B CN 102976912B CN 201110263493 A CN201110263493 A CN 201110263493A CN 102976912 B CN102976912 B CN 102976912B
- Authority
- CN
- China
- Prior art keywords
- sec
- butylbenzene
- phenyl ketone
- methyl phenyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing acetophenone, and belongs to the field of organic chemical technology. Specifically, the acetophenone is prepared via oxidation of sec-butylbenzene by using molecular oxygen-containing gas under conditions of a certain temperature and a pressure and the existence of an alkaline buffer. Compared with existing methods, the method has the advantages of low cost of raw materials, simple process, no catalysts, no corrosive waste generated during the reaction, and little harm to the environment.
Description
Technical field:
The preparation method who the present invention relates to a kind of methyl phenyl ketone, belongs to field of chemical technology.
Background technology:
Methyl phenyl ketone is a kind of important organic synthesis intermediate, is widely used in manufacturing spices, the raw material of medicine and other organic syntheses, and the while also can be used as the solvent of ether of cellulose, cellulose ester and resin, and the softening agent of plastics etc., has broad application prospects.
Traditional methyl phenyl ketone synthetic method has multiple, and the most frequently used is generally to utilize friedel-crafts acylation method and ethylbenzene oxidation method.Friedel-crafts acylation method is by benzene and Acetyl Chloride 98Min., diacetyl oxide or acetic acidreaction, to be produced under stoichiometric Catalyzed by Anhydrous Aluminium Chloride.This synthetic method has produced a large amount of murders by poisoning, and corrosive waste liquid is large to catalyst levels, recycling difficulty, and product separation difficulty.Ethylbenzene oxidation method is the main method of current industrial use, the method is to take metal complexes as catalyzer, under homogeneous phase high temperature, be oxidized Preparation of ethylbenzene methyl phenyl ketone, as: in JP07196573, disclose the catalyzed oxidation ethylbenzene (135 ℃ of left and right) under oxygen effect with cycloalkyl carboxylic acid cobalt or Cobaltous diacetate and prepared methyl phenyl ketone, conversion of ethylbenzene is low, and methyl phenyl ketone yield is also very low.In addition, utilize photochemical reaction also can prepare methyl phenyl ketone, rare H2O2 or the organo-peroxide of using under photocatalyst effect of ethylbenzene or Alpha-Methyl benzene second is oxygenant, by rayed, can obtain methyl phenyl ketone, and catalyzer mainly contains HTS, contains Cr molecular sieve, metal complexes etc.These class methods are high to catalyzer and reaction unit requirement, and cost is higher.
The preparation method of the methyl phenyl ketone of announcing is up to now all that to take benzene or ethylbenzene be raw material, there is not yet to take sec-butylbenzene and prepare the report of methyl phenyl ketone as raw material.
Summary of the invention:
The object of the present invention is to provide a kind of raw materials cost cheap, without catalyzer, technique is simple, does not have waste caustics to produce, the method for preparing methyl phenyl ketone little to the harm of environment in reaction process.
The technical solution used in the present invention is as follows:
A preparation method for methyl phenyl ketone, mass content is the sec-butylbenzene of 97～100% (they being purity) and the gas of molecule-containing keto, there is oxidizing reaction in heating.
The gas of described molecule-containing keto be pure oxygen, airborne one or both.Sec-butylbenzene reacts according to mol ratio with molecular oxygen at 1: 1.
During described oxidizing reaction, add ealkaline buffer.Described ealkaline buffer comprises one or both in sodium hydroxide, sodium carbonate.
It is 0.1%～0.5% that described ealkaline buffer adds mass percent; In reaction process, add water, consumption is as the criterion can dissolve ealkaline buffer.
Described oxidizing reaction is carried out under 120 ℃～210 ℃ and pressure 0.1～2MPa condition; Oxidation time 3～9 hours.
Described oxidizing reaction need to stir so that oxygen can with the abundant contact reacts of sec-butylbenzene.
After above-mentioned reaction completes, by reaction product rectifying, obtain methyl phenyl ketone.
It is below the oxidation equation formula of sec-butylbenzene
Sec-butylbenzene air oxidation reaction process is followed free radical mechanism, unavoidably produces organic acid, and the existence of Determining Micro Acid can impel sec-butylbenzene peroxide breakdown to generate phenol and butanone, and phenol can react by remarkable inhibited oxidation, thereby affects reaction process.For eliminating the negative effect of Determining Micro Acid, the organic acid and the phenol that in system, add a small amount of alkali to produce in can neutralization reaction, be conducive to the carrying out of oxidizing reaction.Ealkaline buffer comprises sodium carbonate or sodium hydroxide.In addition, can introduce water, to help the dissolving of ealkaline buffer.
The gas of molecule-containing keto of the present invention comprises air, pure oxygen and above two kinds of gases gas mixture in any proportion.The gas distributor of gas being introduced to reactor bottom, is distributed in liquid phase with tiny as far as possible bubble, further increases the touch opportunity of molecular oxygen and sec-butylbenzene by high-speed stirring, is conducive to improve oxidizing reaction speed.The oxygen level of controlling in tail gas is less than 5% to guarantee safety.
Raw material sec-butylbenzene of the present invention can obtain by the butylene in benzene and liquefied gas is synthetic, and benzene and liquefied gas are all oil-refining chemical products cheap and easy to get.Along with a large amount of exploitations of Sweet natural gas are used, the liquefied gas of refinery is sold and is impacted, so sec-butylbenzene raw materials enjoy stable sources, cheap in recent years.
Compared with prior art, the invention provides a kind of new way of preparing methyl phenyl ketone, raw materials enjoy stable sources, cheap, technique is simple, easy handling, reaction does not have waste caustics to produce, without catalyzer, little to the harm of environment, the transformation efficiency of sec-butylbenzene reaches 76%, and product methyl phenyl ketone selectivity reaches 82%.
Embodiment
Below in conjunction with embodiment, be intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment 1:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.5 gram of NaOH and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 130 ℃, adjusting pressure regulator valve makes still internal pressure maintain 0.2M Pa, react sampling after 6 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 17.8%, and the selectivity of methyl phenyl ketone is 15.2%.
Embodiment 2:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.5 gram of Na2CO3 and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 130 ℃, adjusting pressure regulator valve makes still internal pressure maintain 1.2MPa, react sampling after 9 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 27.6%, and the selectivity of methyl phenyl ketone is 14.3%.
Embodiment 3:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.5 gram of Na2CO3 and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 180 ℃, adjusting pressure regulator valve makes still internal pressure maintain 1.2MPa, react sampling after 9 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 76.1%, and the selectivity of methyl phenyl ketone is 67.5%.
Embodiment 4:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.1 gram of Na2CO3 and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 160 ℃, adjusting pressure regulator valve makes still internal pressure maintain 0.4MPa, react sampling after 3 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 39.7%, and the selectivity of methyl phenyl ketone is 80.5%.
Embodiment 5:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.3 gram of Na2CO3 and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 160 ℃, adjusting pressure regulator valve makes still internal pressure maintain 1.2MPa, react sampling after 6 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 64.7%, and the selectivity of methyl phenyl ketone is 82.6%.
Embodiment 6:
It is in the autoclave of 500ml that 259 grams of sec-butylbenzenes that is 98.67% by purity add volume, add again 0.1 gram of NaOH and 2ml water, airtight, under the mechanical stirring speed of 700rpm, this mixture is heated to 160 ℃, adjusting pressure regulator valve makes still internal pressure maintain 0.4MPa, react sampling after 6 hours and do GC analysis, the transformation efficiency of sec-butylbenzene is 61.0%, and the selectivity of methyl phenyl ketone is 79.4%.
Claims (4)
1. a preparation method for methyl phenyl ketone, is characterized in that, the sec-butylbenzene that mass content is 97～100% and the gas of molecule-containing keto, and there is oxidizing reaction in heating;
Sec-butylbenzene reacts according to mol ratio 1:1 with molecular oxygen; During oxidizing reaction, add ealkaline buffer, described ealkaline buffer comprises one or both in sodium hydroxide, sodium carbonate; It is 0.1%～0.5% that described ealkaline buffer adds mass percent;
Described oxidizing reaction is carried out under 160 ℃～210 ℃ and pressure 0.4～2M Pa condition; Described oxidation time 3～9 hours.
2. the method for claim 1, is characterized in that, the gas of described molecule-containing keto be pure oxygen, airborne one or both.
3. the method for claim 1, is characterized in that, in described reaction process, adds water, and consumption is as the criterion can dissolve ealkaline buffer.
4. the method for claim 1, is characterized in that, during described oxidizing reaction, will stir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110263493.4A CN102976912B (en) | 2011-09-07 | 2011-09-07 | Method for preparing acetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110263493.4A CN102976912B (en) | 2011-09-07 | 2011-09-07 | Method for preparing acetophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102976912A CN102976912A (en) | 2013-03-20 |
| CN102976912B true CN102976912B (en) | 2014-10-01 |
Family
ID=47851319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110263493.4A Active CN102976912B (en) | 2011-09-07 | 2011-09-07 | Method for preparing acetophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102976912B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735699B (en) * | 2021-09-17 | 2024-01-23 | 黑龙江立科新材料有限公司 | Preparation method of acetophenone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62114922A (en) * | 1985-11-13 | 1987-05-26 | 大日本インキ化学工業株式会社 | Production of phenol together with acetone ad methyl ethyl ketone |
| CN1290682A (en) * | 1999-09-30 | 2001-04-11 | 石碳酸化学股份有限公司 | Method for preparing phenol, methyl-ethyl ketones and acetone |
| WO2009082464A1 (en) * | 2007-12-21 | 2009-07-02 | Exxonmobil Research And Engineering Company | Process for producing phenol and methyl ethyl ketone |
-
2011
- 2011-09-07 CN CN201110263493.4A patent/CN102976912B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62114922A (en) * | 1985-11-13 | 1987-05-26 | 大日本インキ化学工業株式会社 | Production of phenol together with acetone ad methyl ethyl ketone |
| CN1290682A (en) * | 1999-09-30 | 2001-04-11 | 石碳酸化学股份有限公司 | Method for preparing phenol, methyl-ethyl ketones and acetone |
| WO2009082464A1 (en) * | 2007-12-21 | 2009-07-02 | Exxonmobil Research And Engineering Company | Process for producing phenol and methyl ethyl ketone |
Non-Patent Citations (2)
| Title |
|---|
| 金姬.间二异丙苯氧化合成间苯二酚.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2010, |
| 间二异丙苯氧化合成间苯二酚;金姬;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100915;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102976912A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MY160862A (en) | Process for producing acetic acid | |
| CN103524345B (en) | Product separation process for preparing methyl acrylate from methyl acetate | |
| JP2020522530A (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN108929221A (en) | A kind of preparation method of n propyl propionate | |
| CN103274883B (en) | A kind of catalyzing ketone compound oxidation prepares the method for lactone | |
| CN102976912B (en) | Method for preparing acetophenone | |
| CN102219662B (en) | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene | |
| CN109574834A (en) | The production method of glyoxylic ester | |
| CN107737611B (en) | Composite catalyst and method for preparing 5-hexenoic acid by using same | |
| CN107827720B (en) | Production method for improving concentration of formaldehyde | |
| Jiaqi et al. | 2, 2, 6, 6-Tetramethylpiperidine-1-Oxyl-Promoted Hydroxylation of Benzene to Phenol over a Vanadium-Based Catalyst Using Molecular Oxygen | |
| CN103951546B (en) | Novel synthetic process of thymol | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN109574843A (en) | The method for producing glyoxylic ester | |
| CN107400038B (en) | Method for preparing cyclohexanone and cyclohexanol by decomposing cyclohexyl hydroperoxide | |
| CN109574844A (en) | The manufacturing method of glyoxylic ester | |
| CN104418782A (en) | Method for preparing hydroperoxide mixture through diisopropylbenzene oxidation | |
| CN104961632A (en) | Method for preparing p-ethyl acetophenone by catalytic oxidation of p-diethylbenzene with supported molecular sieve | |
| CN102649082B (en) | Method for enhancing activity of catalyst for preparing oxalic ester from CO | |
| RU2378253C1 (en) | Method of preparing ethylbenzene hydroperoxide | |
| CN101885682B (en) | Method for directly synthesizing diphenyl carbonate by carbon dioxide and phenol | |
| CN105732361A (en) | An anhydride producing method | |
| CN101817747A (en) | Preparation method of 4-acetoxyl-2-methyl-2-butene-1-aldehyde | |
| CN109553514A (en) | A method of catalysis Sheep's-parsley alcohol dehydrogenase prepares carvol | |
| CN103214402A (en) | Method for directly preparing glycidol from glycerol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |