CN107304196A - A kind of method of vacuum distillation-refined glycolide of fusion-crystallization coupling - Google Patents
A kind of method of vacuum distillation-refined glycolide of fusion-crystallization coupling Download PDFInfo
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- CN107304196A CN107304196A CN201610243474.8A CN201610243474A CN107304196A CN 107304196 A CN107304196 A CN 107304196A CN 201610243474 A CN201610243474 A CN 201610243474A CN 107304196 A CN107304196 A CN 107304196A
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- glycolide
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- mixed liquor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
Abstract
The present invention relates to a kind of method of the refined glycolide of vacuum distillation fusion-crystallization coupling, this method is to first pass through impurity of the reduced pressure distillation process by glycolide crude product mid-boiling point higher than glycolide to be separated with glycolide, and boiling point enters in heat exchanger in a gaseous form less than the impurity of glycolide with glycolide, it is condensed to be changed into mixed liquor, it is collected by collecting tank, the mixed liquor that collecting tank is collected is passed directly into melting crystallizer again and purified, that is, purified grade glycolide product is made.Compared with prior art, the present invention is coupled reduced pressure distillation process and fusion-crystallization technique, a large amount of energy consumptions can be saved, reduce equipment investment, separation process is set to be easy to be carried out continuously, the requirement of industrialization large-scale production is disclosure satisfy that, obtained purified grade glycolide purity can reach more than 99.5%, disclosure satisfy that the requirement of downstream application.
Description
Technical field
The invention belongs to chemical industry purification technique field, it is related to a kind of method of refined glycolide, more particularly, to one
The method for planting vacuum distillation-refined glycolide of fusion-crystallization coupling.
Background technology
The polyglycolic acid resin of HMW be it is a kind of it is important can degradable boiomacromolecule medical material.At present,
The polyglycolic acid resin of HMW is handed over by first preparing its corresponding binary cyclic ester glycolide, then by second
It is prepared by the ring-opening polymerization of ester.However, being crystallized by thick cyclic ester made from various methods, typically all contain hydroxyl
The impurity such as oligomer, hydroxyacetic acid and the oxidized aldehydes of guanidine-acetic acid, it is therefore desirable to refined.
Reported process for purification has using a variety of solvents, is carried out by recrystallizing, for example, adopting
With isopropanol (visible European Patent No. 261572), tert-pentyl alcohol (see German Patent Publication the 1808939th),
Carbon tetrachloride (see German Patent Publication the 123473904th), ethyl acetate are (see U.S. Patent No. 4727163
Number), ether (Japanese Patent Laid-Open 6-172341), to recrystallize obtained Crystalline slurry liquid, while entering
The separation of solid and liquid such as row filtering, while after being cleaned with the solvent or cleaning fluid used in recrystallization, solvent is removed through drying
Or cleaning fluid, you can obtain refining crystallization.
CN100999516A discloses a kind of recrystallization method of purification of glycolide, this method be by thick glycolide with
Remove insoluble matter after organic solvent exposure, fully dissolving, then resulting solution is put into cold bath is rapidly cooled to room
Temperature, then suction filtration isolate crystallization, at 40~50 DEG C be dried in vacuo 8-12 hours, obtain glycolide.Used
Organic solvent include methanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, butyl ether, methylisobutylketone,
The mixture or alcohols and the mixture of ethyl acetate of MEK or alcohols and acetone, alcohols and acetone, alcohols
It is 30~100 with ethyl acetate mixed volume percentage：70~0.The addition of the organic solvent is every 10 grams thick
Glycolide 4-15ml.
CN103664866A discloses a kind of recrystallization method of purification of glycolide, mainly solves prior art and exists
The problem of yield of glycolide is not high after repeated recrystallize.The side that this method increases by using solvent ratios gradient
Formula, substep changes the repeated recrystallize that solvent ratios carry out glycolide, and organic solvent is selected from methanol, ethanol, positive third
Alcohol, isopropanol, the tert-butyl alcohol, isobutanol, ethyl acetate or methyl acetate, available in the industrial production of glycolide.
CN1432006A discloses a kind of glycolide method of purification similar to fusion-crystallization, material crystal it is refined
It is to be carried out by the decline melting liquid of refining crystallization component in treating column and the counter current contact of rising material crystal.Will
Cyclic ester is crystallized and crystallization melting liquid counter current contact, while cleaning is attached to the mother liquor and impurity on crystal surface,
The mother liquor and impurity that are mixed into inside crystallization are removed by perspiration.
However, because glycolide has thermal sensitivity, coking and hydrolysis easily occur for high temperature, it is difficult to be applicable rectification and purification,
And impurity component is complicated in thick glycolide, therefore single process for purification has significant limitation.Using organic solvent
Means re-crystallization, then can be not economic and environment-friendly enough because introducing a large amount of solvents, and the method for single fusion-crystallization can not
Separate the impurity that crude product mid-boiling point is higher than glycolide.In addition, the glycolide used as polymerized monomer is, it is necessary to second
The purity of lactide reaches more than 99%.Therefore, in order to meet the application requirement of glycolide, it is necessary to find a kind of height
Imitate feasible economic glycolide method of purification.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind distillation energy consumption it is small,
Production cost is low, non-environmental-pollution, easy to operate, can meet vacuum distillation-melting of industrialization large-scale production
The method of the refined glycolide of crystallization coupling.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method of vacuum distillation-refined glycolide of fusion-crystallization coupling, this method is to first pass through vacuum distillation work
Impurity of the skill by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity and glycolide enter in a gaseous form in heat exchanger, it is condensed to be changed into mixed liquor, be collected by collecting tank,
The mixed liquor that collecting tank is collected is passed directly into melting crystallizer again and purified, that is, the production of purified grade glycolide is made
Product.
A kind of method of vacuum distillation-refined glycolide of fusion-crystallization coupling, this method specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device, it is 100-280 DEG C to control temperature, and absolute pressure is 1Pa-10KPa, carries out vacuum distillation；
(2) it is condensed to be changed into mixing by the mixed gas delivery isolated by vacuum distillation into heat exchanger
Liquid, collects mixed liquor, and the temperature of mixed liquor is maintained into 70-100 DEG C by collecting tank；
(3) melting crystallizer is first subjected to biofilm processing, one layer of crystalline film is formed on melting crystallizer surface, then
The temperature of melting crystallizer is maintained 40-75 DEG C, the mixed liquor that collecting tank is collected then is passed directly into fused junction
In brilliant device, the glycolide in mixed liquor is set to separate out and continue to grow as crystal layer along crystalline film, then crystallized, sent out
Sweat, after sweating terminates, continues to raise the temperature of melting crystallizer, until crystal layer fusing, discharge is collected, that is, made
Obtain purified grade glycolide product.
Weight/mass percentage composition≤2% of moisture in dehydration mixed liquor described in step (1).
Flow regime of the dehydration mixed liquor in vacuum distillation reactor described in step (1) is complete mixing flow state
Or horizontal sliding stream mode.
As preferred technical scheme, the temperature described in step (1) is 160-250 DEG C, described absolute pressure
Power is 100Pa-3KPa.
As preferred technical scheme, the temperature of the mixed liquor described in step (2) maintains 80-90 DEG C.
Described in step (3) biofilm processing condition be：The molten state glycolide of purity >=99% is passed through temperature
In the melting crystallizer that not higher than 80 DEG C of degree, 1-10min is stopped, treats molten state glycolide on melting crystallizer surface
Formed after one layer of crystalline film, release remaining molten state glycolide, you can.
The treatment conditions of crystallization described in step (3) are：With 0.5-5 DEG C/h rate of temperature fall, to fused junction
Brilliant device cooling 2-8h, after cooling terminates, discharges remaining uncrystallized liquid.
The treatment conditions of sweating described in step (3) are：With 0.1-10 DEG C/h heating rate, to fused junction
Brilliant device carries out heating sweating, and controls sweating outlet temperature to be 60-85 DEG C.
Using purity >=99.5% of purified grade glycolide product made from the above method.
In the present invention, described reduced pressure distillation process can be distilled using continuous feed, also can be using disposable
Charging, it is to be distilled it is complete after feed again.
Described vacuum distillation reactor can be vacuum distillation tank, vacuum distillation kettle or de- with vacuum
The piston flow reactor of the gas port either extruder with vacuum deaerator plant.
The inventive method is mainly by reduced pressure distillation process the impurity and second higher than glycolide by crude product mid-boiling point
Lactide is separated, and the glycolide without high-boiling-point impurity leaves vacuum distillation reactor with gaseous state, cold by heat exchanger
It is solidifying to collect；Fusion-crystallization is used to the crude product for removing high-boiling-point impurity, overcomes that second distillation energy consumption is big, production
Cost is high, and solvent crystallization uses organic solvent, and cost is high, easily causes environmental pollution, harm operating personnel and is good for
The shortcomings of health.
The present invention is coupled reduced pressure distillation process and fusion-crystallization technique, can save a large amount of energy consumptions, reduction is set
Standby investment, makes separation process be easy to be carried out continuously, and disclosure satisfy that the requirement of industrialization large-scale production.By this
Technique is refining to obtain sterling glycolide purity and reaches more than 99.5%, disclosure satisfy that the requirement of downstream application.
Compared with prior art, handed over present invention employs the refined purification second of mode of vacuum distillation-fusion-crystallization coupling
Ester, eliminates the impurity that thick glycolide product mid-boiling point is higher than glycolide, Ran Houjin using reduced pressure distillation process first
Impurity of one step by fusion-crystallization technique by boiling point less than glycolide is separated with glycolide, reaches that purification second is handed over
The purpose of ester.Operate by this method, not only avoid the substantial amounts of solvent used in solvent recrystallization, save
A large amount of energy consumptions, and due to the low-temperature operation of later stage fusion-crystallization, it is thus also avoided that glycolide it is rotten, obtain pure
Degree reaches more than 99.5% sterling glycolide, meets the demand of glycolide downstream application.
Brief description of the drawings
Fig. 1 is present invention process schematic flow sheet；
Description of symbols in figure：
1-vacuum distillation reactor, 2-heat exchanger, 3-collecting tank, 4-melting crystallizer.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
The present embodiment technological process as shown in figure 1, the glycolide crude product of material quality content 65% is dehydrated,
It is less than 2% that moisture, which is controlled in mass percent, then weighs the thick glycolide dehydration products of 1Kg and is conveyed into decompression steaming
Evaporate in reactor 1, carry out vacuum distillation：Thick glycolide is heated to 140 DEG C, is then vacuumized, control decompression is steamed
It is 100Pa to evaporate absolute pressure in reactor 1.The low boiling fraction distilled out is condensed into mixed liquor through heat exchanger 2, through receiving
Collection tank 3 is collected, and is maintained at 75 DEG C, and then the mixed liquor of collection is conveyed into the melting of biofilm processing
In crystallizer 4, stop 3 hours, after being cooled 5 hours with 3 DEG C/h rate of temperature fall, uncrystallized liquid is arranged
Release melting crystallizer 4；Sweating is carried out with 5 DEG C/h heating rate, sweating outlet temperature is 80 DEG C, is drained molten
The liquid of change, continuing rise temperature collects crystal layer fusing discharge.
Sampling carries out gas chromatographic analysis purified grade glycolide, and purity is 99.75%, and refined products 585g is collected altogether.
Embodiment 2：
The glycolide crude product of material quality content 40% is dehydrated, moisture control mass percent be 2% with
Under, then weigh the thick glycolide dehydration products of 1Kg and be conveyed into vacuum distillation reactor 1, carry out vacuum distillation：
Thick glycolide is heated to 180 DEG C, is then vacuumized, it is 156Pa to control absolute pressure in vacuum distillation reactor 1.Steam
The low boiling fraction distillated is condensed into mixed liquor by heat exchanger 2, is collected through collecting tank 3, is maintained at 70 DEG C,
Then the mixed liquor of collection is conveyed into the melting crystallizer 4 of biofilm processing, stopped 5 hours, with 5 DEG C
After/h rate of temperature fall cools 4 hours, uncrystallized liquid is given off into melting crystallizer 4；With 2 DEG C/h liter
Warm speed carries out sweating, and sweating outlet temperature is 78 DEG C, drains the liquid of fusing, and continuing rise temperature makes crystal layer
Fusing discharge is collected.
Sampling carries out gas chromatographic analysis purified grade glycolide, and purity is 99.56%, and refined products 332g is collected altogether.
Embodiment 3：
The glycolide crude product of material quality content 80% is dehydrated, moisture control mass percent be 2% with
Under, then weigh the thick glycolide dehydration products of 1Kg and be conveyed into vacuum distillation reactor 1, carry out vacuum distillation：
Thick glycolide is heated to 220 DEG C, is then vacuumized, it is 2KPa to control absolute pressure in vacuum distillation reactor 1.Steam
The low boiling fraction distillated is condensed into mixed liquor by heat exchanger 2, is collected through collecting tank 3, is maintained at 85 DEG C,
Then the mixed liquor of collection is conveyed into the melting crystallizer 4 of biofilm processing, stopped 1.5 hours, with 5 DEG C
After/h rate of temperature fall cools 3 hours, uncrystallized liquid is given off into melting crystallizer 4；With 4 DEG C/h liter
Warm speed carries out sweating, and sweating outlet temperature is 82 DEG C, drains the liquid of fusing, and continuing rise temperature makes crystal layer
Fusing discharge is collected.
Sampling carries out gas chromatographic analysis purified grade glycolide, and purity is 99.92%, and refined products 716g is collected altogether.
Embodiment 4：
The glycolide crude product of material quality content 89% is dehydrated, moisture control mass percent be 2% with
Under, then weigh the thick glycolide dehydration products of 1Kg and be conveyed into vacuum distillation reactor 1, carry out vacuum distillation：
Thick glycolide is heated to 240 DEG C, is then vacuumized, it is 150Pa to control absolute pressure in vacuum distillation reactor 1.Steam
The low boiling fraction distillated is condensed into mixed liquor by heat exchanger 2, is collected through collecting tank 3, is maintained at 85 DEG C,
Then the mixed liquor of collection is conveyed into the melting crystallizer 4 of biofilm processing, stopped 1 hour, with 1.5 DEG C
After/h rate of temperature fall cools 3 hours, uncrystallized liquid is given off into melting crystallizer 4；With 1 DEG C/h liter
Warm speed carries out sweating, and sweating outlet temperature is 83 DEG C, drains the liquid of fusing, and continuing rise temperature makes crystal layer
Fusing discharge is collected.
Sampling carries out gas chromatographic analysis purified grade glycolide, and purity is 99.97%, and refined products 803g is collected altogether.
Embodiment 5：
The method of the present embodiment vacuum distillation-refined glycolide of fusion-crystallization coupling, is to first pass through reduced pressure distillation process
Impurity by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity enters in heat exchanger 2 in a gaseous form with glycolide, condensed to be changed into mixed liquor, is received by collecting tank 3
Collection, then the mixed liquor that collecting tank 3 is collected are passed directly into melting crystallizer 4 and purified, that is, purified grade is made
Glycolide product, specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device 1, it is 100 DEG C to control temperature, and absolute pressure is 1Pa, carries out vacuum distillation；
(2) by the mixed gas delivery isolated by vacuum distillation into heat exchanger 2, it is condensed be changed into it is mixed
Liquid is closed, mixed liquor is collected by collecting tank 3, and the temperature of mixed liquor is maintained 70 DEG C；
(3) melting crystallizer 4 is first subjected to biofilm processing, one layer of crystalline film is formed on the surface of melting crystallizer 4,
The temperature of melting crystallizer 4 is maintained 40 DEG C again, the mixed liquor for then collecting collecting tank 3 is passed directly into molten
Melt in crystallizer 4, the glycolide in mixed liquor is separated out and is continued to grow as crystal layer along crystalline film, then tied
Brilliant, sweating, after sweating terminates, continues to raise the temperature of melting crystallizer 4, until crystal layer fusing, discharge is received
Collection, that is, be made purified grade glycolide product.
In step (1), weight/mass percentage composition≤2% of moisture in dehydration mixed liquor, dehydration mixed liquor is in decompression
Flow regime in distillation reactor 1 is complete mixing flow state.
In step (3), the condition of biofilm processing is：The molten state glycolide of purity >=99% is passed through temperature not
In melting crystallizer 4 higher than 80 DEG C, 1min is stopped, treats molten state glycolide in the surface shape of melting crystallizer 4
Into after one layer of crystalline film, remaining molten state glycolide is released, you can.
In step (3), the treatment conditions of crystallization are：With 0.5 DEG C/h rate of temperature fall, to melting crystallizer 4
Cool 8h, after cooling terminates, and discharges remaining uncrystallized liquid.
In step (3), the treatment conditions of sweating are：With 0.1 DEG C/h heating rate, to melting crystallizer 4
Heating sweating is carried out, and controls sweating outlet temperature to be 60 DEG C.
The purity of purified grade glycolide product made from the present embodiment method is 99.65%.
Embodiment 6：
The method of the present embodiment vacuum distillation-refined glycolide of fusion-crystallization coupling, is to first pass through reduced pressure distillation process
Impurity by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity enters in heat exchanger 2 in a gaseous form with glycolide, condensed to be changed into mixed liquor, is received by collecting tank 3
Collection, then the mixed liquor that collecting tank 3 is collected are passed directly into melting crystallizer 4 and purified, that is, purified grade is made
Glycolide product, specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device 1, it is 280 DEG C to control temperature, and absolute pressure is 10KPa, carries out vacuum distillation；
(2) by the mixed gas delivery isolated by vacuum distillation into heat exchanger 2, it is condensed be changed into it is mixed
Liquid is closed, mixed liquor is collected by collecting tank 3, and the temperature of mixed liquor is maintained 100 DEG C；
(3) melting crystallizer 4 is first subjected to biofilm processing, one layer of crystalline film is formed on the surface of melting crystallizer 4,
The temperature of melting crystallizer 4 is maintained 75 DEG C again, the mixed liquor for then collecting collecting tank 3 is passed directly into molten
Melt in crystallizer 4, the glycolide in mixed liquor is separated out and is continued to grow as crystal layer along crystalline film, then tied
Brilliant, sweating, after sweating terminates, continues to raise the temperature of melting crystallizer 4, until crystal layer fusing, discharge is received
Collection, that is, be made purified grade glycolide product.
In step (1), weight/mass percentage composition≤2% of moisture in dehydration mixed liquor, dehydration mixed liquor is in decompression
Flow regime in distillation reactor 1 is complete mixing flow state.
In step (3), the condition of biofilm processing is：The molten state glycolide of purity >=99% is passed through temperature not
In melting crystallizer 4 higher than 80 DEG C, 10min is stopped, treats molten state glycolide on the surface of melting crystallizer 4
Formed after one layer of crystalline film, release remaining molten state glycolide, you can.
In step (3), the treatment conditions of crystallization are：With 5 DEG C/h rate of temperature fall, melting crystallizer 4 is dropped
Warm 2h, after cooling terminates, discharges remaining uncrystallized liquid.
In step (3), the treatment conditions of sweating are：With 10 DEG C/h heating rate, to melting crystallizer 4
Heating sweating is carried out, and controls sweating outlet temperature to be 85 DEG C.
The purity of purified grade glycolide product made from the present embodiment method is 99.82%.
Embodiment 7：
The method of the present embodiment vacuum distillation-refined glycolide of fusion-crystallization coupling, is to first pass through reduced pressure distillation process
Impurity by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity enters in heat exchanger 2 in a gaseous form with glycolide, condensed to be changed into mixed liquor, is received by collecting tank 3
Collection, then the mixed liquor that collecting tank 3 is collected are passed directly into melting crystallizer 4 and purified, that is, purified grade is made
Glycolide product, specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device 1, it is 250 DEG C to control temperature, and absolute pressure is 3KPa, carries out vacuum distillation；
(2) by the mixed gas delivery isolated by vacuum distillation into heat exchanger 2, it is condensed be changed into it is mixed
Liquid is closed, mixed liquor is collected by collecting tank 3, and the temperature of mixed liquor is maintained 90 DEG C；
(3) melting crystallizer 4 is first subjected to biofilm processing, one layer of crystalline film is formed on the surface of melting crystallizer 4,
The temperature of melting crystallizer 4 is maintained 65 DEG C again, the mixed liquor for then collecting collecting tank 3 is passed directly into molten
Melt in crystallizer 4, the glycolide in mixed liquor is separated out and is continued to grow as crystal layer along crystalline film, then tied
Brilliant, sweating, after sweating terminates, continues to raise the temperature of melting crystallizer 4, until crystal layer fusing, discharge is received
Collection, that is, be made purified grade glycolide product.
In step (1), weight/mass percentage composition≤2% of moisture in dehydration mixed liquor, dehydration mixed liquor is in decompression
Flow regime in distillation reactor 1 is horizontal sliding stream mode.
In step (3), the condition of biofilm processing is：The molten state glycolide of purity >=99% is passed through temperature not
In melting crystallizer 4 higher than 80 DEG C, 5min is stopped, treats molten state glycolide in the surface shape of melting crystallizer 4
Into after one layer of crystalline film, remaining molten state glycolide is released, you can.
In step (3), the treatment conditions of crystallization are：With 2 DEG C/h rate of temperature fall, melting crystallizer 4 is dropped
Warm 5h, after cooling terminates, discharges remaining uncrystallized liquid.
In step (3), the treatment conditions of sweating are：With 6 DEG C/h heating rate, melting crystallizer 4 is entered
Row heating sweating, and control sweating outlet temperature to be 72 DEG C.
The purity of purified grade glycolide product made from the present embodiment method is 99.78%.
Embodiment 8：
The method of the present embodiment vacuum distillation-refined glycolide of fusion-crystallization coupling, is to first pass through reduced pressure distillation process
Impurity by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity enters in heat exchanger 2 in a gaseous form with glycolide, condensed to be changed into mixed liquor, is received by collecting tank 3
Collection, then the mixed liquor that collecting tank 3 is collected are passed directly into melting crystallizer 4 and purified, that is, purified grade is made
Glycolide product, specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device 1, it is 160 DEG C to control temperature, and absolute pressure is 100Pa, carries out vacuum distillation；
(2) by the mixed gas delivery isolated by vacuum distillation into heat exchanger 2, it is condensed be changed into it is mixed
Liquid is closed, mixed liquor is collected by collecting tank 3, and the temperature of mixed liquor is maintained 80 DEG C；
(3) melting crystallizer 4 is first subjected to biofilm processing, one layer of crystalline film is formed on the surface of melting crystallizer 4,
The temperature of melting crystallizer 4 is maintained 60 DEG C again, the mixed liquor for then collecting collecting tank 3 is passed directly into molten
Melt in crystallizer 4, the glycolide in mixed liquor is separated out and is continued to grow as crystal layer along crystalline film, then tied
Brilliant, sweating, after sweating terminates, continues to raise the temperature of melting crystallizer 4, until crystal layer fusing, discharge is received
Collection, that is, be made purified grade glycolide product.
In step (1), weight/mass percentage composition≤2% of moisture in dehydration mixed liquor, dehydration mixed liquor is in decompression
Flow regime in distillation reactor 1 is horizontal sliding stream mode.
In step (3), the condition of biofilm processing is：The molten state glycolide of purity >=99% is passed through temperature not
In melting crystallizer 4 higher than 80 DEG C, 8min is stopped, treats molten state glycolide in the surface shape of melting crystallizer 4
Into after one layer of crystalline film, remaining molten state glycolide is released, you can.
In step (3), the treatment conditions of crystallization are：With 4 DEG C/h rate of temperature fall, melting crystallizer 4 is dropped
Warm 4h, after cooling terminates, discharges remaining uncrystallized liquid.
In step (3), the treatment conditions of sweating are：With 2 DEG C/h heating rate, melting crystallizer 4 is entered
Row heating sweating, and control sweating outlet temperature to be 65 DEG C.
The purity of purified grade glycolide product made from the present embodiment method is 99.66%.
Embodiment 10：
The method of the present embodiment vacuum distillation-refined glycolide of fusion-crystallization coupling, is to first pass through reduced pressure distillation process
Impurity by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and boiling point is less than glycolide
Impurity enters in heat exchanger 2 in a gaseous form with glycolide, condensed to be changed into mixed liquor, is received by collecting tank 3
Collection, then the mixed liquor that collecting tank 3 is collected are passed directly into melting crystallizer 4 and purified, that is, purified grade is made
Glycolide product, specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device 1, it is 200 DEG C to control temperature, and absolute pressure is 1KPa, carries out vacuum distillation；
(2) by the mixed gas delivery isolated by vacuum distillation into heat exchanger 2, it is condensed be changed into it is mixed
Liquid is closed, mixed liquor is collected by collecting tank 3, and the temperature of mixed liquor is maintained 85 DEG C；
(3) melting crystallizer 4 is first subjected to biofilm processing, one layer of crystalline film is formed on the surface of melting crystallizer 4,
The temperature of melting crystallizer 4 is maintained 58 DEG C again, the mixed liquor for then collecting collecting tank 3 is passed directly into molten
Melt in crystallizer 4, the glycolide in mixed liquor is separated out and is continued to grow as crystal layer along crystalline film, then tied
Brilliant, sweating, after sweating terminates, continues to raise the temperature of melting crystallizer 4, until crystal layer fusing, discharge is received
Collection, that is, be made purified grade glycolide product.
In step (1), weight/mass percentage composition≤2% of moisture in dehydration mixed liquor, dehydration mixed liquor is in decompression
Flow regime in distillation reactor 1 is horizontal sliding stream mode.
In step (3), the condition of biofilm processing is：The molten state glycolide of purity >=99% is passed through temperature not
In melting crystallizer 4 higher than 80 DEG C, 7min is stopped, treats molten state glycolide in the surface shape of melting crystallizer 4
Into after one layer of crystalline film, remaining molten state glycolide is released, you can.
In step (3), the treatment conditions of crystallization are：With 1 DEG C/h rate of temperature fall, melting crystallizer 4 is dropped
Warm 7h, after cooling terminates, discharges remaining uncrystallized liquid.
In step (3), the treatment conditions of sweating are：With 4 DEG C/h heating rate, melting crystallizer 4 is entered
Row heating sweating, and control sweating outlet temperature to be 80 DEG C.
The purity of purified grade glycolide product made from the present embodiment method is 99.74%.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and herein
The General Principle of explanation is applied in other embodiment without passing through performing creative labour.Therefore, the present invention is not limited
In above-described embodiment, those skilled in the art are according to the announcement of the present invention, and do not depart from that scope made changes
Entering and change all should be within protection scope of the present invention.
Claims (10)
1. the method for a kind of vacuum distillation-refined glycolide of fusion-crystallization coupling, it is characterised in that this method is first
Impurity by reduced pressure distillation process by glycolide crude product mid-boiling point higher than glycolide is separated with glycolide, and
Boiling point enters in heat exchanger in a gaseous form less than the impurity of glycolide with glycolide, condensed to be changed into mixed liquor, by
Collecting tank is collected, then the mixed liquor that collecting tank is collected is passed directly into melting crystallizer purified, that is, is made
Obtain purified grade glycolide product.
2. a kind of method of vacuum distillation according to claim 1-refined glycolide of fusion-crystallization coupling, its
It is characterised by, this method specifically includes following steps：
(1) glycolide crude product dehydrate and dehydration mixed liquor is made, and be delivered to vacuum distillation reaction
In device, it is 100-280 DEG C to control temperature, and absolute pressure is 1Pa-10KPa, carries out vacuum distillation；
(2) it is condensed to be changed into mixing by the mixed gas delivery isolated by vacuum distillation into heat exchanger
Liquid, collects mixed liquor, and the temperature of mixed liquor is maintained into 70-100 DEG C by collecting tank；
(3) melting crystallizer is first subjected to biofilm processing, one layer of crystalline film is formed on melting crystallizer surface, then
The temperature of melting crystallizer is maintained 40-75 DEG C, the mixed liquor that collecting tank is collected then is passed directly into fused junction
In brilliant device, the glycolide in mixed liquor is set to separate out and continue to grow as crystal layer along crystalline film, then crystallized, sent out
Sweat, after sweating terminates, continues to raise the temperature of melting crystallizer, until crystal layer fusing, discharge is collected, that is, made
Obtain purified grade glycolide product.
3. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, weight/mass percentage composition≤2% of moisture in the dehydration mixed liquor described in step (1).
4. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, flow regime of the dehydration mixed liquor in vacuum distillation reactor described in step (1) is complete mixed
Stream mode or horizontal sliding stream mode.
5. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, the temperature described in step (1) is 160-250 DEG C, described absolute pressure is 100Pa-3KPa.
6. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, the temperature of the mixed liquor described in step (2) maintains 80-90 DEG C.
7. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, the condition of the biofilm processing described in step (3) is：By the molten state glycolide of purity >=99%
It is passed through temperature to be not higher than in 80 DEG C of melting crystallizer, stops 1-10min, treat molten state glycolide in fusion-crystallization
Device surface is formed after one layer of crystalline film, releases remaining molten state glycolide, you can.
8. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, the treatment conditions of the crystallization described in step (3) are：It is right with 0.5-5 DEG C/h rate of temperature fall
Melting crystallizer cooling 2-8h, after cooling terminates, discharges remaining uncrystallized liquid.
9. a kind of method of vacuum distillation according to claim 2-refined glycolide of fusion-crystallization coupling, its
It is characterised by, the treatment conditions of the sweating described in step (3) are：It is right with 0.1-10 DEG C/h heating rate
Melting crystallizer carries out heating sweating, and controls sweating outlet temperature to be 60-85 DEG C.
10. a kind of vacuum distillation-refined second of fusion-crystallization coupling according to any one of claim 1 to 9 is handed over
The method of ester, it is characterised in that using purity >=99.5% of purified grade glycolide product made from described method.
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