CN108863722A - A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process - Google Patents
A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process Download PDFInfo
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Abstract
The present invention provides a kind of techniques of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone, hydration method pimelinketone device by-product mink cell focus is sent into and is just divided in the middle part of tower, the group for just dividing the isolated boiling point of the tower reactor of tower to be greater than phenol is distributed into intermediate species tower, and the light component for just dividing the isolated phenol of the tower top of tower and boiling point to be less than phenol is sent into the middle part of azeotropy rectification column；The tower top of azeotropy rectification column obtains the mixture of cyclohexanone and cyclohexanol, is sent into the middle part of cyclohexanone tower, the isolated phenol of tower reactor and azeotropic dosage form at maximum azeotrope object, be sent into the middle part of phenol recovery column；The isolated cyclohexanone extraction of cyclohexanone column overhead；The isolated cyclohexanol of tower reactor is produced as product.The present invention carries out comprehensive reutilization to mink cell focus, respectively obtains cyclohexanone, cyclohexanol, phenol and two polyketone products, while by-product chemical industry light oil and residual oil, improves the utilization rate of by-product mink cell focus, reduce device operating cost, reduce environmental pollution.
Description
Technical field
The invention belongs to chemical separating fields, generate more particularly, to during a kind of integrated treatment hydration method preparing cyclohexanone
Mink cell focus technique.
Background technique
Adipic acid, caprolactam production route based on cyclohexene hydration method are the mainstream works in current industrialized production
Skill.In cyclohexanone refining step, the satisfactory cyclohexanone of purity and cyclohexanol are obtained for separation, part lightweight can be generated
Oil and mink cell focus.Wherein, light oil mainly contains pentane, n-hexane, methyl cyclopentane, methyl cyclopentene, benzene, cyclohexene, ring
Hexane, hexahydrotoluene, cyclohexanol and cyclohexanone etc., wherein the content of benzene, hexamethylene, cyclohexanone and cyclohexanol is higher, can be with
It is recycled by simple rectifying.Currently, the case study that light oil recycles is more, such as from pimelinketone device waste liquid
Middle recycling cyclohexanol obtains cyclohexanol of the mass concentration greater than 90% using washing, drying, dehydrogenation and purification four towers separation and produces
Product.The method of pimelinketone device waste oil recycling comprehensive utilization, separates and recovers waste oil using single tower.This method divides waste oil
From for light oil, alcohol ketone product and heavy oil three parts, wherein light oil and alcohol ketone product send to the corresponding workshop section of original device and are divided again
From.And mink cell focus mainly contain cyclohexanone, cyclohexanol, phenol, 1- cyclohexenyl hexamethylene alkene, hexamethylene ether, 2- cyclohexylidene base cyclohexanone,
2- (1- cyclohexenyl group) cyclohexanone and 4- cyclohexylphenol etc., due to complicated components and molecular weight it is larger cause separation and recovery compare
Difficulty, more at present to carry out burning processing in the device, Some Enterprises are sold as by-product fuel oil, and price is lower, and its
It containing poisonous and harmful substance, causes secondary harm more, pollutes environment, be narrowly not allow direct marketing.
The hydration method pimelinketone device production capacity that the country has gone into operation at present is about 2,240,000 tons/year, and by-product mink cell focus is about 6
Ten thousand tons/year, as adipic acid, caprolactam Market Situation are become better and better, it is contemplated that following country's hydration method pimelinketone device production capacity
It will increase year by year, the mink cell focus scale of by-product will also increase.Therefore, as being efficiently used, economic benefit can be generated,
It can be reduced environmental pollution.
Summary of the invention
In view of this, the present invention is directed to propose a kind of mink cell focus generated during integrated treatment hydration method preparing cyclohexanone
Technique, will be not yet received in such a way that rectification under vacuum, atmospheric distillation and azeotropic distillation combine the mink cell focus of recycling into
Row comprehensive reutilization respectively obtains cyclohexanone, cyclohexanol, phenol and two polyketone products, while by-product chemical industry light oil and residual oil,
The utilization rate for improving by-product mink cell focus reduces device operating cost, reduces environmental pollution.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process, includes the following steps：
Hydration method pimelinketone device by-product mink cell focus is sent into just to divide and carries out pre-separation in the middle part of tower, the tower reactor of tower is just divided to separate
The component that boiling point is greater than phenol is obtained, is just divided tower tower reactor to be pumped into intermediate species tower, the isolated phenol of tower top and boiling point are small
In the light component of phenol, after just being divided tower condenser and just dividing tower backflash, by just dividing tower reflux to be pumped into azeotropy rectification column
Portion；
Azeotropy rectification column, as entrainer, is passed through, tower top obtains cyclohexanone using acetophenone from the top of azeotropy rectification column
It is flowed back and is pumped by azeotropy rectification column after azeotropy rectification column condenser and azeotropy rectification column backflash with the mixture of cyclohexanol
Enter in the middle part of cyclohexanone tower, the isolated phenol of tower reactor and azeotropic dosage form at maximum azeotrope object, pumped through azeotropy rectification column tower reactor
Enter in the middle part of phenol recovery column；
The cyclohexanone of the isolated purity >=99.9wt% of cyclohexanone column overhead, through cyclohexanone tower condenser and cyclohexanone tower
After backflash, produced as product by cyclohexanone tower reflux pump；The cyclohexanol of the isolated purity >=99.5wt% of tower reactor, as
Product is pumped by cyclohexanone tower tower reactor and is produced；
The phenol of the isolated purity >=99.9wt% of phenol recovery column overhead is returned through phenol recovery column condenser and phenol
After receiving tower backflash, produced as product by phenol recovery column reflux pump；Tower reactor obtains the entrainer containing a small amount of phenol, by phenol
Recovery tower tower reactor pump is back to azeotropy rectification column top, recycles as entrainer；
The isolated boiling point of intermediate species column overhead is less than resonance isomers 2- (1- cyclohexenyl group) cyclohexanone and 2- hexamethylene
The component for pitching pentylcyclohexanone (2- (1- cyclohexenyl group) cyclohexanone and 2- cyclohexylidene base are hereafter referred to collectively as two polyketone), through intermediate species
After tower condenser and intermediate species tower backflash, produced as chemical industry light oil by intermediate species tower reflux pump；Tower reactor is isolated
Two polyketone and boiling point are higher than the component of two polyketone, are pumped into two polyketone knockout towers by intermediate species tower tower reactor；
Two polyketone of the isolated purity >=99wt% of the tower top of two polyketone knockout towers, through two polyketone knockout tower condensers and
After two polyketone knockout tower backflashes, the synthesis material as o-phenyl phenol is produced by two polyketone knockout tower reflux pumps, tower reactor point
It is pumped and is produced by two polyketone knockout tower tower reactors as residual oil from obtained heavy constituent.
Further, entrainer be acetophenone and benzoic acid binary mixture, wherein benzoic acid content be 0~
15wt%.
Further, the mass flow ratio of entrainer and phenol in mink cell focus is 2:1~4:1.
Further, the reflux ratio of tower is just divided to be set as 8~12, tower top temperature is set as 130-150 DEG C, and bottom temperature is set
It is set to 195-215 DEG C, pressure is -0.07~-0.09MPaG, number of theoretical plate >=40.
Further, the reflux ratio of azeotropy rectification column is set as 2~6, and tower top temperature is set as 50-70 DEG C, bottom temperature
It is set as 90-110 DEG C, pressure is -0.09~-0.099MPaG, number of theoretical plate >=40.
Further, the reflux ratio of cyclohexanone tower is set as 3~7, and tower top temperature is set as 60-80 DEG C, and bottom temperature is set
It is set to 80-100 DEG C, pressure is -0.09~-0.099MPaG, number of theoretical plate >=25.
Further, the reflux ratio of phenol recovery column is set as 8~12, and tower top temperature is set as 260-280 DEG C, tower reactor temperature
Degree is set as 290-310 DEG C, and pressure is 0.5~0.7MPaG, number of theoretical plate >=50.
Further, the reflux ratio of intermediate species tower is set as 12~18, and tower top temperature is set as 235-255 DEG C, tower reactor
Temperature setting is 260-280 DEG C, and pressure is normal pressure, number of theoretical plate >=40.
Further, the reflux ratio of two polyketone knockout towers is set as 2~6, and tower top temperature is set as 260-280 DEG C, tower reactor
Temperature setting is 280-300 DEG C, and pressure is normal pressure, number of theoretical plate >=20.
Compared with the existing technology, the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone of the present invention
Technique has the advantage that：
The technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone of the present invention, using decompression essence
It evaporates, the separating technology that atmospheric distillation, azeotropic distillation combine, the mink cell focus generated during hydration method production cyclohexanone is carried out
Separating-purifying, reaches the product requirement of national high-class product, isolated cyclohexanone, cyclohexanol, phenol and two polyketone product
Mass concentration is respectively greater than 99.9wt%, 99.9wt%, 99.9wt% and 99wt%, wherein phenol is phynol method production hexamethylene
The important source material of ketone, condensation product of two polyketone as cyclohexanone are the important source materials for producing o-phenyl phenol；
For the high feature of mink cell focus boiling point, operation temperature and separating difficulty are reduced using rectification under vacuum, for phenol and
The binary azeotropic of cyclohexanone forms, and selects organic solvent to be separated as entrainer, makees entrainer instead of traditional water, keep away
The reluctant problem of phenol wastewater is exempted from；
The efficient utilization to hydration method pimelinketone device by-product mink cell focus is realized, device operating cost is reduced, is reduced
Pollution to environment.
Detailed description of the invention
Fig. 1 is the process flow chart for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process.
Description of symbols：
T-101- just divides tower；T-102- azeotropy rectification column；T-103- cyclohexanone tower；T-104- phenol recovery column；T-105-
Intermediate species tower；Bis- polyketone knockout tower of T-106-；V-101- just divides tower backflash；V-102- azeotropy rectification column backflash；V-
103- cyclohexanone tower backflash；V-104- phenol recovery column backflash；V-105- intermediate species tower backflash；Bis- polyketone of V-106-
Knockout tower backflash；E-101- just divides tower reboiler；E-102- just divides tower condenser；E-103- azeotropic distillation tower reboiler；E-
104- azeotropy rectification column condenser；E-105- cyclohexanone tower reboiler；E-106- cyclohexanone tower condenser；E-107- phenol recovery
Tower reboiler；E-108- phenol recovery column condenser；E-109- intermediate species tower reboiler；The condensation of E-110- intermediate species tower
Device；Bis- polyketone knockout tower reboiler of E-111-；Bis- polyketone knockout tower condenser of E-112-；P-101- just divides tower tower reactor to pump；P-
102- just divides tower reflux pump；P-103- azeotropy rectification column tower reactor pump；P-104- azeotropy rectification column reflux pump；P-105- cyclohexanone tower
Tower reactor pump；P-106- cyclohexanone tower reflux pump；P-107- phenol recovery column tower reactor pump；P-108- phenol recovery column reflux pump；P-
109- intermediate species tower tower reactor pump；P-110- intermediate species tower reflux pump；Bis- polyketone knockout tower tower reactor of P-111- pump；P-112- bis-
Polyketone knockout tower reflux pump.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to examples and drawings 1, the present invention will be described in detail.
Embodiment 1
A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process, includes the following steps：
The legal pimelinketone device by-product mink cell focus 2000kg/h that fetches water, which is sent into, just divides tower T-101, just divides the reflux of tower T-101
Than being 8, tower top temperature is 141 DEG C, and bottom temperature is 205 DEG C, and pressure is -0.08MPaG, number of theoretical plate 40；Just divide tower T-
The isolated boiling point of 101 tower reactor is greater than the component of phenol, and tower tower reactor pump P-101 is just divided to be sent into intermediate species tower T-105, tower
It pushes up isolated phenol and boiling point is less than the light component of phenol, just divided tower condenser E-102 and just divide tower backflash V-101
Afterwards, by just dividing tower reflux pump P-102 to be sent into the middle part of azeotropy rectification column T-102.
Azeotropy rectification column T-102 is using the binary mixture of acetophenone and benzoic acid as entrainer, flow 1600kg/
H, wherein benzoic acid content is 5wt%, is passed through from the top of azeotropy rectification column T-102, the reflux ratio of azeotropy rectification column T-102 is
3, tower top temperature is 62 DEG C, and bottom temperature is 102 DEG C, and pressure is -0.095MPaG, number of theoretical plate 40.Tower top obtains cyclohexanone
With the mixture of cyclohexanol, after azeotropy rectification column condenser E-104 and azeotropy rectification column backflash V-102, by azeotropic distillation
Tower reflux pump P-104 is sent into the middle part of cyclohexanone tower T-103, the isolated phenol of tower reactor and azeotropic dosage form at maximum azeotrope object,
It is sent into the middle part of phenol recovery column T-104 through azeotropy rectification column tower reactor pump P-103.
The reflux ratio of cyclohexanone tower T-103 be 4, tower top temperature be 67 DEG C, bottom temperature be 85 DEG C, pressure be-
0.097MPaG, number of theoretical plate 25.The isolated cyclohexanone of cyclohexanone tower T-103 tower top, through cyclohexanone tower condenser E-106
After cyclohexanone tower backflash V-103, produced as product by cyclohexanone tower reflux pump P-106；The isolated cyclohexanol of tower reactor,
As product by the pump P-105 extraction of cyclohexanone tower tower reactor.
The reflux ratio of phenol recovery column T-104 is 8, and tower top temperature is 262 DEG C, and bottom temperature is 291 DEG C, and pressure is
0.5MPaG, number of theoretical plate 50；The isolated phenol of phenol recovery column T-104 tower top, through phenol recovery column condenser E-108
After phenol recovery column backflash V-104, produced as product by phenol recovery column reflux pump P-108；Tower reactor is obtained containing a small amount of
The entrainer of phenol is back to the top azeotropy rectification column T-102 by phenol recovery column tower reactor pump P-107, recycles as entrainer
It utilizes.
The reflux ratio of intermediate species tower T-105 is 13, and tower top temperature is 243 DEG C, and bottom temperature is 271 DEG C, and pressure is normal
Pressure, number of theoretical plate 40；The intermediate species isolated boiling point of tower T-105 tower top is less than resonance isomers 2- (1- cyclohexenyl group) ring
The group of hexanone and 2- cyclohexylidene base cyclohexanone (2- (1- cyclohexenyl group) cyclohexanone and 2- cyclohexylidene base are hereafter referred to collectively as two polyketone)
Point, after intermediate species tower condenser E-110 and intermediate species tower backflash V-105, as chemical industry light oil by intermediate species tower
Reflux pump P-110 extraction；Isolated two polyketone of tower reactor and boiling point are higher than the component of two polyketone, pump P- by intermediate species tower tower reactor
109 are sent into two polyketone knockout tower T-106.
The reflux ratio of two polyketone knockout tower T-106 is 3, and tower top temperature is 267 DEG C, and bottom temperature is 291 DEG C, and pressure is normal
Pressure, number of theoretical plate 20, isolated two polyketone of tower top of two polyketone knockout tower T-106, through two polyketone knockout tower condenser E-
112 and two after polyketone knockout tower backflash V-106, and the synthesis material as o-phenyl phenol is by two polyketone knockout tower reflux pump P-
112 extraction, the isolated heavy constituent of tower reactor is as residual oil by the pump P-111 extraction of two polyketone knockout tower tower reactors.
The product of synthetical recovery is through analyzing：The mass concentration of cyclohexanone is 99.9wt%, and cyclohexanol mass concentration is
99.6wt%, the mass concentration of phenol are 99.7wt%, and the mass concentration of two polyketone is 99.2wt%.
Embodiment 2
A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process, includes the following steps：Technique
Process is same as Example 1.
The legal pimelinketone device by-product mink cell focus 3750kg/h that fetches water, which is sent into, just divides tower T-101, just divides the reflux of tower T-101
Than being 10, tower top temperature is 143 DEG C, and bottom temperature is 206 DEG C, and pressure is -0.075MPaG, number of theoretical plate 40；Azeotropic distillation
Tower T-102 using the binary mixture of acetophenone and benzoic acid as entrainer, flow 3000kg/h, wherein benzoic acid content
For 10wt%, the reflux ratio of azeotropy rectification column T-102 is 4.8, and tower top temperature is 61 DEG C, and bottom temperature is 101 DEG C, pressure is-
0.097MPaG, number of theoretical plate 40；The reflux ratio of cyclohexanone tower T-103 is 6, and tower top temperature is 67 DEG C, bottom temperature 85
DEG C, pressure is -0.095MPaG, number of theoretical plate 25；The reflux ratio of phenol recovery column T-104 is 10, and tower top temperature is 271 DEG C,
Bottom temperature is 301 DEG C, pressure 0.6MPaG, number of theoretical plate 50；The reflux ratio of intermediate species tower T-105 is 15, tower top temperature
Degree is 245 DEG C, and bottom temperature is 270 DEG C, and pressure is normal pressure, number of theoretical plate 40；The reflux ratio of two polyketone knockout tower T-106 is
5, tower top temperature is 267 DEG C, and bottom temperature is 291 DEG C, and pressure is normal pressure, number of theoretical plate 30.
The product of synthetical recovery is through analyzing：The mass concentration of cyclohexanone is 99.9wt%, and cyclohexanol mass concentration is
99.9wt%, the mass concentration of phenol are 99.9wt%, and the mass concentration of two polyketone is 99.9wt%.
Embodiment 3
A kind of technique for the mink cell focus that integrated treatment hydration method preparing cyclohexanone generates in the process, includes the following steps：Technique
Process is same as Example 1.
The legal pimelinketone device by-product mink cell focus 4500kg/h that fetches water, which is sent into, just divides tower T-101, just divides the reflux of tower T-101
Than being 10, tower top temperature is 136 DEG C, and bottom temperature is 207 DEG C, and pressure is -0.075MPaG, number of theoretical plate 40；Azeotropic distillation
Tower T-102 using the binary mixture of acetophenone and benzoic acid as entrainer, flow 3600kg/h, wherein benzoic acid content
For 15wt%, the reflux ratio of azeotropy rectification column T-102 is 2, and tower top temperature is 64 DEG C, and bottom temperature is 100 DEG C, pressure is-
0.097MPaG, number of theoretical plate 40；The reflux ratio of cyclohexanone tower T-103 is 3, and tower top temperature is 67 DEG C, bottom temperature 85
DEG C, pressure is -0.095MPaG, number of theoretical plate 25；The reflux ratio of phenol recovery column T-104 is 10, and tower top temperature is 270 DEG C,
Bottom temperature is 301 DEG C, pressure 0.6MPaG, number of theoretical plate 50；The reflux ratio of intermediate species tower T-105 is 15, tower top temperature
Degree is 245 DEG C, and bottom temperature is 269 DEG C, and pressure is normal pressure, number of theoretical plate 40；The reflux ratio of two polyketone knockout tower T-106 is
2, tower top temperature is 267 DEG C, and bottom temperature is 291 DEG C, and pressure is normal pressure, number of theoretical plate 20.
The product of synthetical recovery is through analyzing：The mass concentration of cyclohexanone is 99.9wt%, and cyclohexanol mass concentration is
99.7wt%, the mass concentration of phenol are 99.9wt%, and the mass concentration of two polyketone is 99.0wt%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone, it is characterised in that：Including as follows
Step：
Hydration method pimelinketone device by-product mink cell focus is sent into just to divide and carries out pre-separation in the middle part of tower, just divides the tower reactor of tower isolated
The group that boiling point is greater than phenol is distributed into intermediate species tower, and the isolated phenol of the tower top of tower and boiling point is just divided to be less than light group of phenol
It is distributed into the middle part of azeotropy rectification column；
Azeotropy rectification column top is passed through entrainer, and tower top obtains the mixture of cyclohexanone and cyclohexanol, is sent into the middle part of cyclohexanone tower,
The isolated phenol of tower reactor and azeotropic dosage form at maximum azeotrope object, be sent into the middle part of phenol recovery column；
The isolated cyclohexanone extraction of cyclohexanone column overhead；The isolated cyclohexanol of tower reactor is produced as product；
The isolated phenol of phenol recovery column overhead is produced as product；Tower reactor obtains being back to containing the entrainer of a small amount of phenol
Azeotropy rectification column top, recycles as entrainer；
The isolated boiling point of intermediate species column overhead is less than resonance isomers 2- (1- cyclohexenyl group) cyclohexanone and 2- cyclohexylidene base
The component of cyclohexanone (2- (1- cyclohexenyl group) cyclohexanone and 2- cyclohexylidene base are hereafter referred to collectively as two polyketone), is adopted as chemical industry light oil
Out；Isolated two polyketone of tower reactor and boiling point are higher than the component of two polyketone, are sent into two polyketone knockout towers；
Isolated two polyketone of the tower top of two polyketone knockout towers, the synthesis material as o-phenyl phenol produce, and tower reactor separates
The heavy constituent arrived is produced as residual oil.
2. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：Entrainer is the binary mixture of acetophenone and benzoic acid, and wherein benzoic acid content is 0~15wt%.
3. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 2, special
Sign is：The mass flow ratio of phenol is 2 in entrainer and mink cell focus:1~4:1.
4. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：Just the reflux ratio of tower is divided to be set as 8~12, tower top temperature is set as 130-150 DEG C, and bottom temperature is set as 195-
215 DEG C, pressure is -0.07~-0.09MPaG, number of theoretical plate >=40.
5. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：The reflux ratio of azeotropy rectification column is set as 2~6, and tower top temperature is set as 50-70 DEG C, and bottom temperature is set as 90-
110 DEG C, pressure is -0.09~-0.099MPaG, number of theoretical plate >=40.
6. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：The reflux ratio of cyclohexanone tower is set as 3~7, and tower top temperature is set as 60-80 DEG C, and bottom temperature is set as 80-100
DEG C, pressure is -0.09~-0.099MPaG, number of theoretical plate >=25.
7. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：The reflux ratio of phenol recovery column is set as 8~12, and tower top temperature is set as 260-280 DEG C, and bottom temperature is set as
290-310 DEG C, pressure is 0.5~0.7MPaG, number of theoretical plate >=50.
8. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：The reflux ratio of intermediate species tower is set as 12~18, and tower top temperature is set as 235-255 DEG C, and bottom temperature is set as
260-280 DEG C, pressure is normal pressure, number of theoretical plate >=40.
9. the technique of the mink cell focus generated during integrated treatment hydration method preparing cyclohexanone according to claim 1, special
Sign is：The reflux ratio of two polyketone knockout towers is set as 2~6, and tower top temperature is set as 260-280 DEG C, and bottom temperature is set as
280-300 DEG C, pressure is normal pressure, number of theoretical plate >=20.
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| CN112010736A (en) * | 2020-09-27 | 2020-12-01 | 重庆华峰化工有限公司 | Separation and recovery process of cyclohexanol process raw material |
| CN113943217A (en) * | 2021-08-31 | 2022-01-18 | 唐山旭阳化工有限公司 | Method for recovering dipolyketone in cyclohexane oxidation by-product X oil |
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