CN102924255A - Method for preparing 9-fluorenone through liquid-phase oxidation - Google Patents
Method for preparing 9-fluorenone through liquid-phase oxidation Download PDFInfo
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- CN102924255A CN102924255A CN2012104427651A CN201210442765A CN102924255A CN 102924255 A CN102924255 A CN 102924255A CN 2012104427651 A CN2012104427651 A CN 2012104427651A CN 201210442765 A CN201210442765 A CN 201210442765A CN 102924255 A CN102924255 A CN 102924255A
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Abstract
The invention relates to a method for preparing 9-fluorenone through liquid-phase oxidation. The method takes industrial fluorine as the raw material, N,N-dimethylpropyleneurea (DMPU) as solvent, and sodium hydroxide aqueous solution as the catalytic agent. The method comprises the steps of heating the mixture of the fluorine and the solvent to perform dissolution through a constant-temperature magnetic stirrer, adding the catalytic agent, pouring the mixture into a bubbling type reactor, heating the mixture to 40-80 DEG C, introducing oxygen to the bottom of the reactor, and performing oxidizing reaction for 3-6 hours, wherein the flow rate of the oxygen is 10-20L/ (min.kg of the raw material fluorine). The method adopts the DMPU solvent with low toxicity, so that the safety is high. The solvent and the catalytic agent can be recycled, so that cost is reduced, waste discharge during production is reduced, and pollution to the environment is reduced. By means of the method, the reaction temperature is low, the reaction process is easy to control, one-time investment is enough, and large-scale popularization and production of the 9-fluorenone can be achieved.
Description
Technical field
The present invention relates to the 9-Fluorenone preparation method, be specifically related to the method that a kind of liquid-phase oxidation prepares 9-Fluorenone.
Background technology
9-Fluorenone, the another name Fluorenone is yellow oblique square crystal body under the normal temperature, 84 ℃ of fusing points, 342 ℃ of boiling points, molecular formula C13H8O, structural formula is
Fluorenone is the raw material of important fine chemicals, is widely used at aspects such as dyestuff, medicine, agricultural chemicals.
At present, the method for fluorenes liquid-phase oxidation 9-Fluorenone processed, domestic and international existing major technique is as follows:
The abundant hall of University Of Shanxi bear in 1989 waits has delivered take potassium hydroxide as catalyzer atmospheric oxidation 9-Fluorenone processed.Adopting process is to add industrial fluorenes (content 90%) and potassium hydroxide in the dimethyl sulfoxide (DMSO), and heating makes fluorenes dissolve rear oxidation fully, separates thick Fluorenone, and through recrystallizing and refining, getting purity is 99.1%, and productive rate is more than 92.5%.
The Hu Xin of Anshan University of Science and Technology etc. have reported the method for fluorenes liquid-phase oxidation Fluorenone processed in 2002.It is take pyridine, fluorenes and potassium hydroxide as raw material, under more excellent reaction conditions: 40 ℃ of temperature of reaction, the mass ratio of catalyzer and fluorenes are 0.4, and air flow quantity is 1000ml/min, and the Fluorenone productive rate reaches 98%, and purity is greater than 99%.
Patent CN100667346 has introduced oxygen and has made oxygenant, and fluorenes and dimethyl sulfoxide solvent and sodium hydroxide catalyst make Fluorenone.Patent CN100422128 has invented air and has done under the oxygenant condition, the method for a kind of liquid phase oxidation reaction of fluorenes and tetrahydrofuran solvent and potassium hydroxide catalyst.
Soviet Union's Moscow chemical institute report in 1989 utilizes 3-chlorobenzene and a small amount of lipid acid to be solvent, uses the Co-Mn-Br catalyzer, and at 0.5～1.0MPa, 110-150 ℃ of lower reaction obtained preferably result.
Osaka, Japan gas department of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, utilizes air to be oxygenant, adds phase-transfer catalyst in alkali hydroxide soln, is respectively 86% and 92% at 4～5 hours Fluorenone yields of 40～50 ℃ of reactions.
In sum, although there are at present a lot of fluorenes liquid-phase oxidations to prepare the method for Fluorenone, also do not use the extremely low DMPU of toxicity to do the method for solvent.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, cost is low, safety and environmental protection, and a kind of liquid-phase oxidation of good product quality prepares the method for 9-Fluorenone.
Particular content of the present invention is as follows:
Take industrial fluorenes as raw material, N, N-dimethyl propylene thiazolinyl urea (DMPU) is solvent, aqueous sodium hydroxide solution is catalyzer, mixture with fluorenes and solvent, through the constant temperature blender with magnetic force heating for dissolving, add catalyzer, then with in its impouring bubbling style reactor, be heated to 40～80 ℃, pass into oxygen to reactor bottom, oxygen flow 10～20L/(min.kg raw material fluorenes), oxidation time is 3～6 hours;
The adding mass ratio of described DMPU is DMPU: industrial fluorenes=(2～6): 1;
The adding mass ratio of described catalyzer is catalyzer: industrial fluorenes=(0.05～0.08): 1;
More than be mass ratio.
Question response finishes, and after the reaction solution that takes out from reactor bottom is cooled to room temperature, filters, and the recovery part catalyzer carries out atmospheric distillation with filtrate in rectifying tower, reclaim solvent, and tower reactor is thick Fluorenone.With dry behind the thick Fluorenone washing suction filtration, then use ethyl alcohol recrystallization, obtain the high purity Fluorenone, more than the Fluorenone purity to 99.5%.
By above-mentioned technical scheme as can be known, the present invention adopts bubbling style reactor to prepare 9-Fluorenone because gas duct stretches into reactor bottom, thereby realize the abundant contact of gas-liquid two-phase, improved the utilization ratio of gas.Do not use air to make oxygenant, because airborne carbonic acid gas composition is easy and the reaction of catalyzer sodium hydroxide generates yellow soda ash, thereby make catalyst failure.Select oxygen not only can avoid this problem among the present invention, and the reaction times is shortened greatly.
The requirement of selective solvent is large to the solubleness of fluorenes, and is little to the solubleness of catalyzer, do not react with catalyzer, can reclaim catalyzer, and separates with Fluorenone easily again, is convenient to recycle.The solvent that adopts in the technology at present has dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), pyridine etc., and comparatively speaking, this example adopts DMPU to make solvent, toxicity is extremely low, and is insignificant to harm, also reduced the pollution to environment, with solvent phase ratio commonly used, security is stronger.
The catalyzer that the present invention uses is sodium hydroxide, and is cheap, and can recycling, the production cost decrease of product.
Recrystallization is to utilize solvent to being purified the different solubility of material and impurity, can make and be purified material and from supersaturated solution, separate out, and allow impurity all or major part still stay in the solution, if the solubleness in solvent is minimum, then be made into to be filtered behind the saturated solution and remove, thereby reach the purification purpose.During with recrystallization method refining crude Fluorenone, its key is to select suitable recrystallization solvent.Selected solvent must satisfy can make Fluorenone dissolve in a large number under comparatively high temps, the solubleness of Fluorenone is then very little at low temperatures, it is little that the major impurity solubility with temperature is changed, and the loss of Fluorenone when being beneficial to reduce recrystallization improves the purity of product.In this experiment, we select dehydrated alcohol as the solvent of recrystallization, and the dehydrated alcohol wide material sources are cheap, and have good decolorizing effect.
The present invention adopts the extremely low DMPU solvent of toxicity, and security is stronger, and solvent and catalyzer can recycle, and make cost, and has reduced the discharge of wastewater in the production process, has reduced the pollution to environment.Temperature of reaction of the present invention is low, and reaction process is controlled easily, one-time investment, can large-scale promotion produce 9-Fluorenone.
Description of drawings
Fig. 1: process flow diagram of the present invention.Compare with the equipment that prior art is used, this equipment has simple, maneuverable advantage.
1. oxygen bottle 2. reducing valve 3. strainers 4. gas mass flow controllers 5. check valves 6. reactors 7. ball valves 8. condensers 9. back pressure valves 10. scrubbing bottles
Embodiment
Embodiment 1
Adopt technique as shown in Figure 1, take by weighing respectively industrial fluorenes 10g, DMPU20g and sodium hydroxide 0.5g, it is 30% solution that sodium hydroxide is configured to massfraction, mixture with fluorenes and solvent, through the constant temperature blender with magnetic force heating for dissolving, add catalyzer, then with in its impouring bubbling style reactor 6, open agitator, pass into oxygen by 0.1L/min simultaneously, Oxygen Flow is through oxygen bottle 1, reducing valve 2, strainer 3, gas mass flow controller 4, check valve 5 enters reactor, 80 ℃ of lower reactions 3 hours, the solvent of evaporation flows back to reactor after by condenser 8 condensations, and unreacted Oxygen Flow is through filter 3, back pressure valve 9, scrubbing bottle 10 is discharged in the environment.Reaction finishes, and product takes out by ball valve 7, through cooling off, filtering, reclaims catalyzer.Filtrate is carried out atmospheric distillation in rectifying tower, the recovered overhead solvent, tower reactor is thick Fluorenone.With dry behind the thick Fluorenone washing suction filtration, then carry out recrystallization with dehydrated alcohol, obtain Fluorenone, Fluorenone purity to 99.5%.
Adopt technique as shown in Figure 1, take by weighing respectively industrial fluorenes 10g, DMPU60g and sodium hydroxide 0.8g, it is 0.15% solution that sodium hydroxide is configured to massfraction, mixture with fluorenes and solvent, through the constant temperature blender with magnetic force heating for dissolving, add catalyzer, then with in its impouring bubbling style reactor 6, open agitator, pass into oxygen by 0.1L/min simultaneously, Oxygen Flow is through oxygen bottle 1, reducing valve 2, strainer 3, gas mass flow controller 4, check valve 5 enters reactor, 60 ℃ of lower reactions 4 hours, the solvent of evaporation flows back to reactor after by condenser 8 condensations, and unreacted Oxygen Flow is through filter 3, back pressure valve 9, scrubbing bottle 10 is discharged in the environment.Reaction finishes, and product takes out by ball valve 7, through cooling off, filtering, reclaims catalyzer.Filtrate is carried out atmospheric distillation in rectifying tower, the recovered overhead solvent, tower reactor is thick Fluorenone.With dry behind the thick Fluorenone washing suction filtration, then carry out recrystallization with dehydrated alcohol, obtain Fluorenone, Fluorenone purity to 99.7%.
Adopt technique as shown in Figure 1, take by weighing respectively industrial fluorenes 10g, DMPU40g and sodium hydroxide 0.6g, it is 30% solution that sodium hydroxide is configured to massfraction, mixture with fluorenes and solvent, through the constant temperature blender with magnetic force heating for dissolving, add catalyzer, then with in its impouring bubbling style reactor 6, open agitator, pass into oxygen by 0.2L/min simultaneously, Oxygen Flow is through oxygen bottle 1, reducing valve 2, strainer 3, gas mass flow controller 4, check valve 5 enters reactor, 40 ℃ of lower reactions 6 hours, the solvent of evaporation flows back to reactor after by condenser 8 condensations, and unreacted Oxygen Flow is through filter 3, back pressure valve 9, scrubbing bottle 10 is discharged in the environment.Reaction finishes, and product takes out by ball valve 7, through cooling off, filtering, reclaims catalyzer.Filtrate is carried out atmospheric distillation in rectifying tower, the recovered overhead solvent, tower reactor is thick Fluorenone.With dry behind the thick Fluorenone washing suction filtration, then carry out recrystallization with dehydrated alcohol, obtain Fluorenone, Fluorenone purity to 99.5%.
Product quality indicator of the present invention and processing parameter are compared as follows table 1,2.
Table 1 9-Fluorenone product quality indicator relatively
Table 2 processing parameter relatively
The result of table 1, table 2 can find out: (1) owing to adopt ethanol as recrystallization solvent, the product purity of 9-Fluorenone and refining yield are apparently higher than the other side; (2) owing to adopt bubbling style reactor, the Fluorenone yield obviously improves; (3) technological process of this synthetic 9-Fluorenone is simple, and is safe and reliable.
A kind of liquid-phase oxidation that the present invention proposes prepares the method for 9-Fluorenone, be described by preferred embodiment, person skilled obviously can be within not breaking away from content of the present invention, spirit and scope to structure as herein described with technological method is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and the content.
Claims (3)
1. a liquid-phase oxidation prepares the method for 9-Fluorenone, it is characterized in that: take industrial fluorenes as raw material, and N, N-dimethyl propylene thiazolinyl urea is solvent, alkali metal hydroxide aqueous solution is catalyzer, with the mixture of fluorenes and solvent, through the constant temperature blender with magnetic force heating for dissolving, add catalyzer, then with in its impouring bubbling style reactor, be heated to 40～80 ℃, pass into oxygen to reactor bottom, oxygen flow 10～20L/(min.kg raw material fluorenes), oxidation time is 3～6 hours;
N, N-dimethyl propylene thiazolinyl urea: industrial fluorenes mass ratio is 2～6:1;
Catalyzer: industrial fluorenes mass ratio is 0.05～0.08:1.
2. the method for claim 1 after it is characterized in that being cooled to room temperature from the reaction solution that reactor bottom takes out, is filtered the recovery part catalyzer.
3. the method for claim 1 is characterized in that filtrate is carried out atmospheric distillation in rectifying tower, reclaims solvent, and tower reactor is thick Fluorenone; With dry behind the thick Fluorenone washing suction filtration, then use ethyl alcohol recrystallization.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131435A1 (en) * | 2014-03-03 | 2015-09-11 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone from fluorene |
| CN107253905A (en) * | 2017-05-11 | 2017-10-17 | 张照明 | A kind of method that the Fluorenone of high-purity 9 is prepared with Industrial fluorene |
| CN107469737A (en) * | 2017-09-26 | 2017-12-15 | 贾海亮 | A kind of charging device of 9 Fluorenone production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754867A (en) * | 2004-09-28 | 2006-04-05 | 上海焦化有限公司 | Method for oxidizing fluorene to 9-fluorenone |
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
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- 2012-11-07 CN CN2012104427651A patent/CN102924255A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754867A (en) * | 2004-09-28 | 2006-04-05 | 上海焦化有限公司 | Method for oxidizing fluorene to 9-fluorenone |
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
Non-Patent Citations (1)
| Title |
|---|
| 周建荣: "芴氧化制9-芴酮", 《上海化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131435A1 (en) * | 2014-03-03 | 2015-09-11 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone from fluorene |
| JP2016523227A (en) * | 2014-03-03 | 2016-08-08 | 宝舜科技股▲フン▼有限公司 | Method for producing 9-fluorenone from fluorene |
| CN107253905A (en) * | 2017-05-11 | 2017-10-17 | 张照明 | A kind of method that the Fluorenone of high-purity 9 is prepared with Industrial fluorene |
| CN107469737A (en) * | 2017-09-26 | 2017-12-15 | 贾海亮 | A kind of charging device of 9 Fluorenone production |
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Application publication date: 20130213 |