CN108358808A - A method of dimethylacetylamide in recycling pimelinketone device waste oil - Google Patents
A method of dimethylacetylamide in recycling pimelinketone device waste oil Download PDFInfo
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- CN108358808A CN108358808A CN201810167861.7A CN201810167861A CN108358808A CN 108358808 A CN108358808 A CN 108358808A CN 201810167861 A CN201810167861 A CN 201810167861A CN 108358808 A CN108358808 A CN 108358808A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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Abstract
The present invention provides a kind of methods of dimethylacetylamide in recycling pimelinketone device waste oil, include using the mixture of water or water and ethyl alcohol as entrainer, the method being combined using azeotropic distillation and rectification under vacuum, by in pimelinketone device waste oil hexamethylene and dimethylacetylamide separation, obtain mass concentration >=99.9wt% dimethylacetamide amine product the step of.The method of dimethylacetylamide in recycling pimelinketone device waste oil of the present invention, technological operation is simple, and separation accuracy is high, the recycling of dimethylacetylamide can not only be improved, also the light component based on cyclohexanol can be recycled and be used for reproduction, while reducing waste oil discharge capacity, reduce environmental pollution.
Description
Technical field
The invention belongs to chemical technology fields, more particularly, to dimethylacetylamide in a kind of recycling pimelinketone device waste oil
Method.
Background technology
Dimethylacetylamide is a kind of widely used raw material of industry, is commonly applied to PETROLEUM PROCESSING and organic synthesis industry
In.As a kind of polar solvent of aprotic, dimethylacetylamide is the fine solvent of many organic synthesis.Currently,
Domestic pimelinketone device is frequently with dimethylacetylamide as extractant, separating-purifying cyclohexene raw material.In Cyclohexanone Production mistake
Cheng Zhong, it may occur that a variety of side reactions cause to contain plurality of impurities in extractant, purify cyclohexene by separation of extractive distillation and follow
While loopback extractant, partial extraction agent can be caused to enter in waste oil and caused damages.
Cyclohexanol is the main component in cyclohexanone production apparatus waste oil, and boiling point is 161 DEG C.And dimethylacetylamide
Boiling point is 166 DEG C, and the two polarity is similar, and belongs to nearly boiling-point mixture, and isolated high-purity is difficult to using conventional distillation
Dimethylacetamide amine product.
Azeotropic distillation is the common method of separating polar phase Sihe nearly boiling point object system.Wherein, the screening of entrainer is azeotropic
The key of distillation process is related to the complexity of azeotropic distillation process, while being also to improve azeotropic distillation production capacity and drop
The fundamental way of low energy consumption.
Invention content
In view of this, the present invention is directed to propose it is a kind of recycling pimelinketone device waste oil in dimethylacetylamide method, with
It overcomes the deficiencies of existing technologies, is first detached cyclohexanol with dimethylacetylamide using azeotropic distillation technique, recycle decompression essence
It evaporates to obtain the dimethylacetamide amine product of high-purity, can not only reduce the operating cost of pimelinketone device, while reducing waste oil
Pollution to environment, with good economic efficiency and environmental benefit.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A method of dimethylacetylamide in recycling pimelinketone device waste oil, includes the mixture with water or water and ethyl alcohol
For entrainer, the method being combined using azeotropic distillation and rectification under vacuum, by the hexamethylene and diformazan in pimelinketone device waste oil
The step of yl acetamide detaches, the dimethylacetamide amine product of acquisition mass concentration >=99.9wt%.
Preferably, when entrainer is water, include the following steps：
(1) azeotropic distillation will be sent into containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component
Tower carries out azeotropic distillation using water as entrainer；
(2) water phase that the azeotropic distillation tower top material is isolated by oil water separator returns to azeotropy rectification column cycle and makes
With oil phase material sends pimelinketone device back to；The recombination dispensing of azeotropy rectification column tower reactor is to weight-removing column through the isolated matter of rectification under vacuum
Measure concentration >=99.9wt% dimethylacetylamides.
Preferably, theoretical tray quantity >=20 of the azeotropy rectification column, preferably 20~30, feed entrance point is the 2nd~5
Block theoretical tray；Weight-removing column theoretical plate quantity >=35, preferably 35~45, feed entrance point is the 18th~25 piece of theoretical plate institute
It states.
Preferably, it is 5~20kPaA that the azeotropy rectification column, which uses vacuumizing, rectifying column operating pressure, and reflux ratio is
10~15, tower top temperature is 40~58 DEG C, 110~130 DEG C of bottom temperature.
Preferably, the weight-removing column use vacuumizing, reflux ratio be 3.0~6.0, rectifying column operating pressure be 5~
20kPaA, tower top temperature are 100~120 DEG C, 140~170 DEG C of bottom temperature.
Preferably, in step (1), the entrainer is 3.0~7.0 with material liquid mass flow ratio；In step (2),
The azeotropic distillation tower top light component is sent into oil water separator after condensation, and after being layered by liquid-liquid, water phase material is back to
The azeotropy rectification column recycles, and oil phase material sends pimelinketone device back to.
Preferably, when entrainer is the mixture of water and ethyl alcohol, include the following steps：
(1) azeotropic distillation will be sent into containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component
Tower carries out azeotropic distillation using second alcohol and water as binary azeotropic agent；
(2) the azeotropic distillation tower top material is sent to entrainer recovery tower, and it is isolated containing few that entrainer recycles column overhead
Measure the alcohol product of water, the isolated product based on hexamethylene alcohol and water of entrainer recovery tower tower reactor, by oil water separator
Satisfactory cyclohexanol product is obtained after separation returns to pimelinketone device；
(3) the water phase product after the entrainer recovery tower overhead product and tower reactor water-oil separating is collected and is returned described
Azeotropy rectification column recycles；Azeotropic distillation tower reactor heavy constituent send to weight-removing column through the isolated mass concentration of rectification under vacuum >=
99.9wt% dimethylacetylamides.
Preferably, azeotropy rectification column number of theoretical plate >=28, number of theoretical plate >=25 of entrainer recovery tower, weight-removing column reason
By plate number >=35；It is further preferred that the theoretical tray quantity of the azeotropy rectification column is 28~36, feedstock position is the
10~18 pieces of theoretical plates, entrainer feed entrance point are the 1st~5 piece of theoretical plate；The weight-removing column theoretical plate quantity is 35~45, into
Material position is set to the 18th~25 piece of theoretical plate；The entrainer recovery tower theoretical plate quantity be 25~35, feed entrance point be the 12nd~
18 pieces of theoretical plates.
Preferably, the entrainer and material liquid mass flow ratio are 1.0~5.0；Water and second in the entrainer
The mass ratio of alcohol is 1.0~10.0；In step (3), water phase product is the water containing a small amount of cyclohexanol.
Preferably, it is 20~40kPaA that the azeotropy rectification column, which uses vacuumizing, rectifying column operating pressure, and reflux ratio is
1~5, tower top temperature is 50~60 DEG C, 115~150 DEG C of bottom temperature；The entrainer recovery tower uses atmospheric operation, reflux
Than being 2.0~8.0, rectifying column operating pressure is 101kPaA, and tower top temperature is 70~85 DEG C, 90~110 DEG C of bottom temperature；Institute
It is 3.0~6.0 to state weight-removing column and use vacuumizing, reflux ratio, and rectifying column operating pressure is 5~20kPaA, tower top temperature 100
~120 DEG C, 140~170 DEG C of bottom temperature；Preferably, azeotropy rectification column operating pressure is 20~30kPaA.
Compared with the existing technology, a kind of method recycling dimethylacetylamide in pimelinketone device waste oil of the present invention
It has the advantage that：
It is of the present invention it is a kind of recycling pimelinketone device waste oil in dimethylacetylamide method, using azeotropic distillation with
Rectification under vacuum separates and recovers the dimethylacetylamide in pimelinketone device waste oil, can obtain the dimethylacetamide for meeting purity requirement
Amine product, it is simple for process, the dimethylacetylamide in waste oil has not only been recycled, has reduced cost, while reducing to environment
Pollution, can be used in industrial production.
The method of dimethylacetylamide in a kind of recycling pimelinketone device waste oil of the present invention, for pimelinketone device
The nearly boiling point object system of main component cyclohexanol and dimethylacetylamide in waste oil, using " water " or " ethyl alcohol+water " as altogether
Agent is boiled, the azeotropic distillation for the object system detaches, and obtains the dimethylacetamide amine product of high-purity, reduces dimethylacetylamide
Loss amount reduces device operating cost, reduces the pollution to environment.
Description of the drawings
Fig. 1 be the present invention using water as entrainer when process flow chart；
Fig. 2 is the present invention using water and ethyl alcohol as process flow chart when binary azeotropic agent.
Reference numeral in Fig. 1：
T1141- azeotropy rectification columns；T1142- weight-removing columns；E1141- azeotropic distillation tower reactor reboilers；E1142- azeotropic distillations
Overhead condenser；E1143- weight-removing column kettle reboilers；E1144- weight-removing columns top condenser；E1145- weight-removing column kettle coolers；
V1141- azeotropic distillation tower top surge tanks；V1142- azeotropic distillation tower top oil water separators；V1143- azeotropic distillation tower tops flow back
Tank；V1144- weight-removing columns top return tank；P1141A/B- azeotropic distillation tower reactors extraction pump；P1142A/B- azeotropic distillation tower tops produce
Pump；P1143A/B- azeotropic distillation tower top reflux pumps；P1144A/B- weight-removing column kettles extraction pump；P1145A/B- weight-removing columns top produces
Pump；VP1141A/B- azeotropy rectification column vacuum pumps；VP1142A/B- weight-removing column vacuum pumps.
Reference numeral in Fig. 2：
T1141- azeotropy rectification columns；T1142- entrainer recovery towers；T1143- weight-removing columns；E1141- azeotropic distillations tower reactor is again
Boil device；E1142- azeotropic distillation tower top condensers；E1143- entrainers recycle tower reactor reboiler；E1144- entrainers recycle tower reactor
Cooler；E1145- entrainers recycle overhead condenser；E1146- weight-removing column kettle reboilers；E1147- weight-removing column kettle products cool down
Device；E1148- weight-removing columns top condenser；V1141- azeotropic distillation tower top surge tanks；V1142- entrainers recycle tower buffer tank；
V1143- entrainers recycle tower reactor oil water separator；V1144- azeotropic distillation tower top return tanks；V1145- weight-removing columns top return tank；
P1141A/B- azeotropic distillation tower reactors extraction pump；P1142A/B- azeotropic distillation tower tops extraction pump；P1143A/B- entrainer recovery towers
Kettle extraction pump；P1144A/B- entrainers recycle overhead extraction pump；P1145A/B- azeotropic distillation tower reactor reflux pumps；P1146A/B-
Weight-removing column kettle extraction pump；P1147A/B- weight-removing columns top extraction pump；VP1141A/B- azeotropy rectification column vacuum pumps；VP1142A/B-
Weight-removing column vacuum pump.
Specific implementation mode
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.
All Digital IDs, such as pH, temperature, time, concentration, including range are all approximations.It is to be understood that although
Term " about " is all added before always not describing all Digital IDs explicitly.While it will also be understood that, although always not clear
Narration, reagent described herein is only example, and equivalent is known in the art.
With reference to embodiment and attached drawing, the present invention will be described in detail.
Operating pressure of the present invention is absolute pressure.
A method of dimethylacetylamide in recycling pimelinketone device waste oil, includes the mixture with water or water and ethyl alcohol
For entrainer, the method being combined using azeotropic distillation and rectification under vacuum, by the hexamethylene and diformazan in pimelinketone device waste oil
The step of yl acetamide detaches, the dimethylacetamide amine product of acquisition mass concentration >=99.9wt%.
1, when entrainer is water, include the following steps：
(1) azeotropic distillation will be sent into containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component
Tower carries out azeotropic distillation using water as entrainer；
(2) in waste oil cyclohexanol boil together agent water in the form of azeotropic mixture with micro light component from the azeotropy rectification column tower
Top extraction, after oil water separator detaches, aqueous portion is back to azeotropy rectification column recycling, organic based on cyclohexanol
Phase (namely oil phase) is sent to pimelinketone device and is used for reproduction；Dimethylacetylamide and heavy constituent are from the azeotropic distillation in waste oil
Tower tower reactor send to weight-removing column the dimethylacetylamide production through the isolated high-purity of rectification under vacuum (mass concentration >=99.9wt%)
Product.
Entrainer uses water, since cyclohexanol forms azeotropic mixture in water and waste oil so that the azeotropic mixture boiling point of formation is notable
It reduces, is steamed from tower top in the form of azeotropic mixture in distillation process.
The theoretical tray quantity of the azeotropy rectification column is 20~30, and feed entrance point is the 2nd~5 block of theoretical tray；It is described
Weight-removing column theoretical plate quantity is 35~45, and feed entrance point is described in the 18th~25 piece of theoretical plate.
It is 5~20kPaA that the azeotropy rectification column, which uses vacuumizing, rectifying column operating pressure, and reflux ratio is 10~15,
Tower top temperature is 40~58 DEG C, 110~130 DEG C of bottom temperature.With this condition, azeotropic distillation column overhead passes through oil water separator
Cyclohexanol (aqueous wt9.3%) product that mass concentration is 90% can be obtained afterwards and the water that mass concentration is 97.5% (contains hexamethylene
Alcohol wt1.8%).Water after separation is back to the azeotropy rectification column and recycles.
It is 3.0~6.0 that the weight-removing column, which uses vacuumizing, reflux ratio, and rectifying column operating pressure is 5~20kPaA, tower
It is 100~120 DEG C to push up temperature, 140~170 DEG C of bottom temperature.Tower top can be obtained the two of mass concentration 99.9% with this condition
Methyl vinyl amine product.
In step (1), the entrainer is 3.0~7.0 with material liquid mass flow ratio；In step (2), the azeotropic
Rectifying tower top light component is sent into oil water separator after condensation, and after being layered by liquid-liquid, water phase material is back to the azeotropic
Rectifying column recycles, and oil phase material sends pimelinketone device back to.
2, when entrainer is the mixture of water and ethyl alcohol, include the following steps：
(1) azeotropic distillation will be sent into containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component
Tower carries out azeotropic distillation using second alcohol and water as binary azeotropic agent；
(2) in waste oil cyclohexanol boil together agent " ethyl alcohol+water " in the form of azeotropic mixture with micro light component from the azeotropic
Rectifying tower top produces, and send to entrainer recovery tower, and the isolated alcohol product containing a small amount of water of column overhead is recycled from entrainer；Altogether
The isolated product based on hexamethylene alcohol and water of agent recovery tower tower reactor is boiled, is met the requirements after oil water separator detaches
Cyclohexanol product return to pimelinketone device；
(3) the water phase product after the entrainer recovery tower overhead product and tower reactor water-oil separating is collected and is returned described
Azeotropy rectification column recycles；Azeotropic distillation tower reactor heavy constituent send to weight-removing column through the isolated mass concentration of rectification under vacuum >=
99.9wt% dimethylacetylamides.
Entrainer uses " ethyl alcohol+water ", since cyclohexanol forms azeotropic mixture in binary azeotropic agent " ethyl alcohol+water " and waste oil,
So that the azeotropic mixture boiling point formed significantly reduces, steamed from tower top in the form of azeotropic mixture in distillation process.
The theoretical tray quantity of the azeotropy rectification column is 28~36, and feedstock position is the 10th~18 piece of theoretical plate,
Entrainer feed entrance point is the 1st~5 piece of theoretical plate；The weight-removing column theoretical plate quantity be 35~45, feed entrance point be the 18th~
25 pieces of theoretical plates；The entrainer recovery tower theoretical plate quantity is 25~35, and feed entrance point is the 12nd~18 piece of theoretical plate.
The entrainer is 1.0~5.0 with material liquid mass flow ratio；The quality of water and ethyl alcohol in the entrainer
Than being 1.0~10.0；In step (3), water phase product is the water containing a small amount of cyclohexanol.
It is 20~40kPaA that the azeotropy rectification column, which uses vacuumizing, rectifying column operating pressure, and reflux ratio is 1~5, tower
It is 50~60 DEG C to push up temperature, 115~150 DEG C of bottom temperature.The azeotropic distillation tower reactor product dimethylacetamide with this condition
Amine+heavy constituent content >=99.97wt%.
It is 2.0~8.0 that the entrainer recovery tower, which uses atmospheric operation, reflux ratio, and rectifying column operating pressure is
101kPaA, tower top temperature are 70~85 DEG C, 90~110 DEG C of bottom temperature.The entrainer recycling tower top separation with this condition
Ethyl alcohol (93.45wt%) and water (6.54wt%) product are obtained, tower reactor product obtains cyclohexanol after oil water separator detaches
The oil phase product of (aqueous) mass fraction >=91wt%.Entrainer recycling overhead product is detached with tower reactor separation of oil device
Water phase product afterwards returns to the azeotropy rectification column and recycles.
It is 3.0~6.0 that the weight-removing column, which uses vacuumizing, reflux ratio, and rectifying column operating pressure is 5~20kPaA, tower
It is 100~120 DEG C to push up temperature, 140~170 DEG C of bottom temperature；Preferably, azeotropy rectification column operating pressure is 20~30kPaA.
The entrainer recycling tower reactor product is sent into oil water separator after condensation, after being layered by liquid-liquid, aqueous-phase material
Material is the water containing a small amount of cyclohexanol, is back to together with the entrainer recovery tower overhead product (ethyl alcohol and a small amount of water) described total
Rectifying column is boiled to recycle；The oil water separator oil phase material is the cyclohexanol to conform to quality requirements, is pumped up to cyclohexanone
Device.
The middle Yi Shui of the present invention, water+ethyl alcohol are described further respectively as the technique of entrainer, it is specific as follows：
As shown in Figure 1, when using water as entrainer：
The technique of dimethylacetylamide is in azeotropic distillation recycling pimelinketone device waste oil of the present invention:
The tops azeotropy rectification column T1141 are sent into containing the waste oil of dimethylacetylamide and cyclohexanol, entrainer water is by tower
Portion is added, and 5~20KPaA of operating pressure of azeotropy rectification column, azeotrope column tower reactor reboiler E1141 are heated using steam, tower overhead gas
Mutually after the E1142 condensations of azeotropic distillation tower top condenser, into azeotropic distillation tower top surge tank V1141, lime set is through azeotropic distillation
Overhead extraction pumps P1142A/B and is sent into oil water separator V1142, and the water phase isolated enters azeotropic distillation tower top return tank
V1143 sends azeotropy rectification column T1141 back to through azeotropic distillation tower top reflux pump P1143A/B and recycles, and the oil phase isolated is sent
Enter pimelinketone device to be regenerated.The dimethylacetylamide and recombination lease making azeotropy rectification column of azeotropy rectification column T1141 tower reactors
Kettle extraction pump P1141A/B is sent into weight-removing column T1142 and continues to detach.The operating pressure of weight-removing column is 5~20KPaA, and tower reactor is boiled again
Device E1143 is heated using steam, and top gaseous phase is after the E1144 condensations of azeotropic distillation tower reactor reboiler, into weight-removing column return tank
V1144, lime set produce pump P1145A/B through weight-removing column top and are partly refluxed to weight-removing column T1142.Rest part is as dimethyl second
Amide products produce.Weight-removing column T1142 kettles obtain heavy constituent, and producing pump P1144A/B through weight-removing column kettle is sent into collection system.
Azeotropic distillation process includes the capital equipments such as azeotropy rectification column T1141, oil water separator V1142.
Embodiment 1
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 1.Azeotropy rectification column
T1141 has 21 blocks of theoretical trays.Using water as entrainer, it is added from the 1st piece of theoretical plate (number of plates is from top to bottom), addition
For 5000kg/hr, the waste oil containing dimethylacetylamide, cyclohexanol, a small amount of light component and heavy constituent is added by the 3rd block of tower top plate
Enter, the mass fraction of total flow 1000kg/hr, wherein dimethylacetylamide and cyclohexanol are 17wt% and 35wt%.Azeotropic
Rectifying column operating pressure is 15kPaA, and overhead reflux ratio is 13, and tower top temperature is 54 DEG C, and bottom temperature is 126 DEG C, overhead stream
After oil water separator, cyclohexanol (aqueous) product and mass fraction 97.5wt% of mass fraction 90.5wt% is obtained
Water.The water isolated sends azeotropy rectification column recycling back to, and cyclohexanol (aqueous) product can obtain mass fraction through dry water removal
The product of >=99.0wt%.The dimethylacetylamide and heavy constituent mixture of tower reactor are sent into weight-removing column T1142, tower top operating pressure
For 15kPaA, overhead reflux ratio is 4, and tower top temperature is 106 DEG C, and bottom temperature is 161 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
Embodiment 2
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 1.Azeotropy rectification column
T1141 has 21 blocks of theoretical trays.Using water as entrainer, it is added from the 1st piece of theoretical plate (number of plates is from top to bottom), addition
For 6000kg/hr, the waste oil containing dimethylacetylamide, cyclohexanol, a small amount of light component and heavy constituent is added by the 3rd block of tower top plate
Enter, the mass fraction of total flow 1000kg/hr, wherein dimethylacetylamide and cyclohexanol are 17wt% and 35wt%.Azeotropic
Rectifying column operating pressure is 10kPaA, and overhead reflux ratio is 15, and tower top temperature is 46 DEG C, and bottom temperature is 115 DEG C, overhead stream
After oil water separator, cyclohexanol (aqueous) product and mass fraction 97.5wt% of mass fraction 91.0wt% is obtained
Water.The water isolated sends azeotropy rectification column recycling back to, and cyclohexanol (aqueous) product can obtain mass fraction through dry water removal
The product of >=99.5wt%.The dimethylacetylamide and heavy constituent mixture of tower reactor are sent into weight-removing column T1142, tower top operating pressure
For 10kPaA, overhead reflux ratio is 4, and tower top temperature is 95 DEG C, and bottom temperature is 149 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
Embodiment 3
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 1.Azeotropy rectification column
T1141 has 21 blocks of theoretical trays.Using water as entrainer, it is added from the 1st piece of theoretical plate (number of plates is from top to bottom), addition
For 4000kg/hr, the waste oil containing dimethylacetylamide, cyclohexanol, a small amount of light component and heavy constituent is added by the 3rd block of tower top plate
Enter, the mass fraction of total flow 1000kg/hr, wherein dimethylacetylamide and cyclohexanol are 17wt% and 35wt%.Azeotropic
Rectifying column operating pressure is 10kPaA, and overhead reflux ratio is 10, and tower top temperature is 45 DEG C, and bottom temperature is 115 DEG C, overhead stream
After oil water separator, cyclohexanol (aqueous) product and mass fraction 97.5wt% of mass fraction 90.0wt% is obtained
Water.The water isolated sends azeotropy rectification column recycling back to, and cyclohexanol (aqueous) product can obtain mass fraction through dry water removal
The product of >=98.5wt%.The dimethylacetylamide and heavy constituent mixture of tower reactor are sent into weight-removing column T1142, tower top operating pressure
For 10kPaA, overhead reflux ratio is 4, and tower top temperature is 95 DEG C, and bottom temperature is 149 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
As shown in Fig. 2, when using " water+ethyl alcohol " as when binary azeotropic agent：
The technique of dimethylacetylamide is in azeotropic distillation recycling pimelinketone device waste oil of the present invention:
Be sent into the middle part of azeotropy rectification column T1141 containing the waste oil of dimethylacetylamide and cyclohexanol, entrainer ethyl alcohol+water by
Tower top is added, and 20~30KPaA of operating pressure of azeotropy rectification column, azeotropic distillation tower reactor reboiler E1141 is added using steam
Heat, top gaseous phase is after the E1142 condensations of azeotropic distillation tower top condenser, into azeotropic distillation tower top surge tank V1141, lime set warp
Azeotropic distillation tower top extraction pump P1142A/B is sent into entrainer recovery tower T1142.It is detached by entrainer recovery tower, overhead product
It is sent into entrainer after entrainer recycling overhead condenser E1145 condensations and recycles tower buffer tank V1142, is returned by entrainer
It receives an overhead extraction pump P1144A/B parts and is back to entrainer recovery tower T1142, a part is sent to azeotropy rectification column return tank
V1144 is recycled；Tower reactor product is sent after entrainer recycling tower reactor cooler E1144 coolings to oil water separator V1143,
The water phase product isolated is sent into azeotropy rectification column return tank V1144 and is recycled, and oil phase product is sent to pimelinketone device.Azeotropic
The dimethylacetylamide and recombination lease making azeotropy rectification column kettle extraction pump P1141A/B of rectifying column T1141 tower reactors are sent into weight-removing column
T1143 continues to detach.The operating pressure of weight-removing column is 5~20KPaA, and weight-removing column kettle reboiler E1146 is heated using steam, tower
Top gas is mutually after weight-removing column top condenser E1148 condensations, and into weight-removing column return tank V1145, lime set is produced through weight-removing column top and pumped
P1147A/B is partly refluxed to weight-removing column T1143.Rest part is produced as dimethylacetamide amine product.Weight-removing column kettle obtains weight
Component produces pump P1146A/B through weight-removing column kettle and is sent into collection system.
Azeotropic distillation process includes azeotropy rectification column T1141, entrainer recovery tower T1142, oil water separator V1143 etc. main
Want equipment.
Embodiment 4
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 2.Azeotropy rectification column
T1141 has 30 blocks of theoretical trays.Using ethyl alcohol+water as binary azeotropic agent, the mass ratio of water and ethyl alcohol is 4:1, it is managed from the 1st piece
It is added by plate (number of plates is from top to bottom), addition 1500kg/hr, contains dimethylacetylamide, cyclohexanol, heavy constituent and micro-
The waste oil for measuring light component is added by the 16th block of plate in the middle part of tower, total flow 500kg/hr, wherein dimethylacetylamide and cyclohexanol
Mass fraction be 20wt% and 35wt%.Azeotropy rectification column operating pressure is 25kPaA, and overhead reflux ratio is 4, tower top temperature
It it is 56 DEG C, bottom temperature is 138 DEG C, is sent after overhead product is condensed to entrainer recovery tower T1142.Entrainer recovery tower operates
Pressure is 101kPaA, and overhead reflux ratio is 4,78 DEG C of tower top temperature, 98 DEG C of column bottom temperature, and theoretical plate quantity is 30, feed entrance point
15th piece of theoretical plate.The mixing of the entrainer isolated ethyl alcohol of recovery tower T1142 tower tops (93.45wt%) and water (6.54wt%)
Object is back to T1142 tower tops through pumping a P1144 parts, and part extraction, which is sent to V1144 azeotropy rectification column return tanks cycle, to be made
With；T1142 tower reactors product obtains oil phase product (cyclohexanol 91wt%+ water 9.3wt%) after oil water separator detaches and send to ring
Hexanone device, water phase product (water 97wt%+ cyclohexanol 2.9wt%) send to V1144 azeotropy rectification column return tanks and recycle.
The dimethylacetylamide and heavy constituent mixture of azeotropic distillation tower reactor are sent into weight-removing column T1143, tower top operating pressure
For 15kPaA, overhead reflux ratio is 4, and tower top temperature is 106 DEG C, and bottom temperature is 161 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
Embodiment 5
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 2.Azeotropy rectification column
T1141 has 30 blocks of theoretical trays.Using ethyl alcohol+water as binary azeotropic agent, the mass ratio of water and ethyl alcohol is 9:1, it is managed from the 2nd piece
It is added by plate (number of plates is from top to bottom), addition 2000kg/hr, contains dimethylacetylamide, cyclohexanol, heavy constituent and micro-
The waste oil for measuring light component is added by the 16th block of plate in the middle part of tower, total flow 500kg/hr, wherein dimethylacetylamide and cyclohexanol
Mass fraction be 20wt% and 35wt%.Azeotropy rectification column operating pressure is 30kPaA, and overhead reflux ratio is 2, tower top temperature
It it is 62 DEG C, bottom temperature is 144 DEG C, is sent after overhead product is condensed to entrainer recovery tower T1142.Entrainer recovery tower operates
Pressure is 101kPaA, and overhead reflux ratio is 6,78 DEG C of tower top temperature, 98 DEG C of column bottom temperature, and theoretical plate quantity is 30, feed entrance point
18th piece of theoretical plate.The mixing of the entrainer isolated ethyl alcohol of recovery tower T1142 tower tops (90.9wt%) and water (9.09wt%)
Object is back to T1142 tower tops through pumping a P1144 parts, and part extraction, which is sent to V1144 azeotropy rectification column return tanks cycle, to be made
With；T1142 tower reactors product obtained after oil water separator detaches oil phase product (cyclohexanol 90.7wt%+ water 9.26wt%) send to
Pimelinketone device, water phase product (water 97wt%+ cyclohexanol 2.98wt%), which is sent to V1144 azeotropy rectification column return tanks cycle, to be made
With.
The dimethylacetylamide and heavy constituent mixture of azeotropic distillation tower reactor are sent into weight-removing column T1143, tower top operating pressure
For 15kPaA, overhead reflux ratio is 4, and tower top temperature is 106 DEG C, and bottom temperature is 161 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
Embodiment 6
A kind of technological process for recycling dimethylacetylamide in pimelinketone device waste oil is as shown in Figure 2.Azeotropy rectification column
T1141 has 30 blocks of theoretical trays.Using ethyl alcohol+water as binary azeotropic agent, the mass ratio of water and ethyl alcohol is 4:1, it is managed from the 3rd piece
It is added by plate (number of plates is from top to bottom), addition 1500kg/hr, contains dimethylacetylamide, cyclohexanol, heavy constituent and micro-
The waste oil for measuring light component is added by the 15th block of plate in the middle part of tower, total flow 500kg/hr, wherein dimethylacetylamide and cyclohexanol
Mass fraction be 30wt% and 50wt%.Azeotropy rectification column operating pressure is 20kPaA, and overhead reflux ratio is 4, tower top temperature
It it is 52 DEG C, bottom temperature is 120 DEG C, is sent after overhead product is condensed to entrainer recovery tower T1142.Entrainer recovery tower operates
Pressure is 101kPaA, and overhead reflux ratio is 4,78 DEG C of tower top temperature, 97 DEG C of column bottom temperature, and theoretical plate quantity is 30, feed entrance point
16th piece of theoretical plate.The mixing of the entrainer isolated ethyl alcohol of recovery tower T1142 tower tops (93.57wt%) and water (6.42wt%)
Object is back to T1142 tower tops through pumping a P1144 parts, and part extraction, which is sent to V1144 azeotropy rectification column return tanks cycle, to be made
With；T1142 tower reactors product obtained after oil water separator detaches oil phase product (cyclohexanol 90.7wt%+ water 9.26wt%) send to
Pimelinketone device, water phase product (water 96.96wt%+ cyclohexanol 2.98wt%) send to V1144 azeotropy rectification column return tanks and recycle
It uses.
The dimethylacetylamide and heavy constituent mixture of azeotropic distillation tower reactor are sent into weight-removing column T1143, tower top operating pressure
For 15kPaA, overhead reflux ratio is 4, and tower top temperature is 106 DEG C, and bottom temperature is 161 DEG C, and tower top obtains mass fraction
The dimethylacetamide amine product of 99.9wt%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of method of dimethylacetylamide in recycling pimelinketone device waste oil, it is characterised in that：Including with water or water and second
The mixture of alcohol is entrainer, the method being combined using azeotropic distillation and rectification under vacuum, by the ring in pimelinketone device waste oil
The step of hexane and dimethylacetylamide separation, the dimethylacetamide amine product of acquisition mass concentration >=99.9wt%.
2. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 1, it is characterised in that：When
When entrainer is water, include the following steps：
(1) it will be sent into azeotropy rectification column containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component,
Azeotropic distillation is carried out as entrainer using water；
(2) the azeotropic distillation tower top material returns to azeotropy rectification column by the water phase that oil water separator is isolated and recycles,
Oil phase material sends pimelinketone device back to；The recombination dispensing of azeotropy rectification column tower reactor is dense through the isolated quality of rectification under vacuum to weight-removing column
Degree >=99.9wt% dimethylacetylamides.
3. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 2, it is characterised in that：Institute
The theoretical tray quantity for stating azeotropy rectification column is 20~30, and feed entrance point is the 2nd~5 block of theoretical tray；The weight-removing column is theoretical
Plate quantity is 35~45, and feed entrance point is described in the 18th~25 piece of theoretical plate.
4. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 2, it is characterised in that：Institute
It is 5~20kPaA to state azeotropy rectification column and use vacuumizing, rectifying column operating pressure, and reflux ratio is 10~15, and tower top temperature is
40~58 DEG C, 110~130 DEG C of bottom temperature.
5. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 2, it is characterised in that：Institute
It is 3.0~6.0 to state weight-removing column and use vacuumizing, reflux ratio, and rectifying column operating pressure is 5~20kPaA, tower top temperature 100
~120 DEG C, 140~170 DEG C of bottom temperature.
6. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 2, it is characterised in that：Step
Suddenly in (1), the entrainer is 3.0~7.0 with material liquid mass flow ratio；In step (2), the azeotropic distillation tower top is light
Component is sent into oil water separator after condensation, and after being layered by liquid-liquid, water phase material is back to the azeotropy rectification column cycle
It uses, oil phase material sends pimelinketone device back to.
7. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 1, it is characterised in that：When
When entrainer is the mixture of water and ethyl alcohol, include the following steps：
(1) it will be sent into azeotropy rectification column containing the waste oil raw material of cyclohexanol, dimethylacetylamide, heavy constituent and micro light component,
Azeotropic distillation is carried out as binary azeotropic agent using second alcohol and water；
(2) the azeotropic distillation tower top material is sent to entrainer recovery tower, and it is isolated containing a small amount of water that entrainer recycles column overhead
Alcohol product, the isolated product based on hexamethylene alcohol and water of entrainer recovery tower tower reactor detaches by oil water separator
After obtain satisfactory cyclohexanol product and return to pimelinketone device；
(3) the water phase product after the entrainer recovery tower overhead product and tower reactor water-oil separating is collected and returns to the azeotropic
Rectifying column recycles；Azeotropic distillation tower reactor heavy constituent send to weight-removing column through the isolated mass concentration of rectification under vacuum >=
99.9wt% dimethylacetylamides.
8. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 7, it is characterised in that：Institute
The theoretical tray quantity for stating azeotropy rectification column is 28~36, and feedstock position is the 10th~18 piece of theoretical plate, entrainer charging
Position is the 1st~5 piece of theoretical plate；The weight-removing column theoretical plate quantity is 35~45, and feed entrance point is the 18th~25 piece of theoretical plate；
The entrainer recovery tower theoretical plate quantity is 25~35, and feed entrance point is the 12nd~18 piece of theoretical plate.
9. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 7, it is characterised in that：Institute
The entrainer stated is 1.0~5.0 with material liquid mass flow ratio；In the entrainer mass ratio of water and ethyl alcohol be 1.0~
10.0；In step (3), water phase product is the water containing a small amount of cyclohexanol.
10. the method for dimethylacetylamide in recycling pimelinketone device waste oil according to claim 7, it is characterised in that：
It is 20~40kPaA that the azeotropy rectification column, which uses vacuumizing, rectifying column operating pressure, and reflux ratio is 1~5, and tower top temperature is
50~60 DEG C, 115~150 DEG C of bottom temperature；It is 2.0~8.0 that the entrainer recovery tower, which uses atmospheric operation, reflux ratio, essence
It is 101kPaA to evaporate tower operating pressure, and tower top temperature is 70~85 DEG C, 90~110 DEG C of bottom temperature；The weight-removing column uses vacuum
Operation, reflux ratio are 3.0~6.0, and rectifying column operating pressure is 5~20kPaA, and tower top temperature is 100~120 DEG C, bottom temperature
140~170 DEG C；Preferably, azeotropy rectification column operating pressure is 20~30kPaA.
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