CN106519231A - Polyphenylene sulfide waste liquid recovery and separation process - Google Patents
Polyphenylene sulfide waste liquid recovery and separation process Download PDFInfo
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- CN106519231A CN106519231A CN201510570807.3A CN201510570807A CN106519231A CN 106519231 A CN106519231 A CN 106519231A CN 201510570807 A CN201510570807 A CN 201510570807A CN 106519231 A CN106519231 A CN 106519231A
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- polyphenylene sulfide
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Abstract
The invention discloses a polyphenylene sulfide waste liquid recovery and separation process, which uses three centrifuges, three dryers, and a set of three-tower low pressure rectification system. The invention relates to a new polyphenylene sulfide waste liquid recovery and separation process, which is characterized in that the new process is developed, and the special three-tower low pressure rectification method is set, such that the separation of the components in the raw materials is fine, the product separation purity is high, and the operability is good; by matched use of the centrifuge and the forced circulation drying equipment, the loss caused by the attachment of the product to the liquid phase is avoided; in order to promote the LiCl crystallization, ensure the rapid precipitation of the LiCl product, and reduce the heat loss, the evaporation crystallization equipment is additionally arranged between the centrifugal separation and the dryer; and with the application of the new process, the product separation is energy-saving and efficient, the product collection is fine, the purity is good, and the good industrial prospects are provided.
Description
Technical field
The invention belongs to a kind of chemical engineering Material Field, is specifically exactly the innovation for being related to polyphenylene sulfide devil liquor recovery separating technology
And improvement.
Background technology
Polyphenylene sulfide is a kind of thermoplastic special engineering plastic, has developed into the sixth-largest kind and extraordinary work of engineering plastics
First big kind of engineering plastics.Its molecular backbone is by constituting to penylene base and sulphur atom, rotten with good thermostability, chemically-resistant
Corrosion, anti-flammability, electrical insulating property, mechanical strength and processing characteristics, have been widely used for automobile, electronics, Aero-Space,
The industrial departments such as precision instrument.
Although the method for synthesis polyphenylene sulfide is a lot, realize that industrialized main method is pressurization synthesis polyphenyl both at home and abroad
Sulfide resin.Pressurization synthesis technique is to adopt sodium sulfide and paracide for raw material, and lithium chloride is catalyst, N- methyl -2- pyrroles
Network alkanone (NMP) is solvent, Jing after polycondensation reaction of pressurizeing in a kettle., isolates PPS products.In the process of production PPS
In, synthesis, washing etc. unit can produce a large amount of waste liquids, in waste liquid containing 35% water, 5% paracide, 50% NMP (N-
N-methyl-2-2-pyrrolidone N) and 10% Sodium Chloride and the solid compounds such as lithium chloride.The dehydration of one tower of its filtrate Jing rectification separates chlorine
After changing sodium, then two tower of Jing rectification reclaims most of solvent, and the toughness residual liquid that bottom of towe is excluded is curable useless into pitchy after cooling
Slag.Jing is analyzed, the residual liquid (residue) mainly contain can not by rectification recovered solvent, catalyst, salt and a small amount of oligomer or
Its carbonized product and other impurities.
At present, domestic PPS manufacturers adopt it is mostly be that water washing polycondensation reaction thing filter cake reclaims NMP techniques, the technique compared with
Other organic solvent extraction and recovery NMP techniques have that extractant is cheap and easy to get, nonflammable explosive, the nontoxic, ring of extraction phase
Little, water is polluted in border and solvent NMP is easily separated, solvent slop, technological process be not short for extractant, solvent recovery cost is low excellent
Point.But in actual application process, its shortcoming is also than more significant：Mixed solution when vacuum batch distillation is dehydrated, due to NMP
NaCl is not dissolved in solvent, and in dehydration, with the reduction of moisture in dehydration tower bottom of rectifying tower, a large amount of NaCl crystallizations are separated out,
Crystal salt is easy to block tower reactor and pipeline when generating.Such case had both reduced the efficiency of heating surface, made NaCl be difficult to timely emptying again,
Reduce the utilization rate of equipment.The NMP adhered on NaCl planes of crystal and kettle wall during cleaning tower reactor in kettle is rinsed water and takes away,
The consumption of nmp solvent is not only increased, excessively, is subject to the utilization of effluent brine simultaneously because discharging content of organics in saline
Considerable restraint.
If the residue is discharged in production, environmental pollution certainly will be caused, and solvent therein and catalyst are expensive, it is necessary to
Reclaimed, to reduce the production cost of PPS.With the production-scale expansions of current PPS, solvent NMP subsequently how is improved
The response rate, reclaim paracide, NaCl and LiCl, improve side-product separation purity, it has also become reduce production cost, carry
High PPS resin produces competitiveness, strengthens enterprise's production economy benefit, reduces key subjects of environmental pollution.
The content of the invention
Present invention is generally directed in waste liquid produced by polyphenylene sulfide process units the by-product such as solvent, catalyst recovery separating technology,
Develop a kind of brand-new continuous production processes flow process.The application of the flow process, makes the separation of product more efficient, separation component
Purity is higher, realizes that effect is more preferable.The present invention passes through innovative technology scheme and equipment occupation mode, improves nmp solvent
Organic efficiency, reduces pollution of the salt to solvent, realizes the classification to salt component and reclaims, with significant economic benefit
And environmental benefit.
For solving the above problems, the technical solution used in the present invention is：
Waste liquid raw material initially enters centrifuge, and liquid parts are got rid of into dashpot, containing oligomer, other carbonized products or insoluble
The dehydration underflow of solid impurity enters exsiccator, and the moisture that drying is evaporated enters dashpot, and dried solid impurity is discharged to
Out-of-bounds.Solution in dashpot enters three tower low-pressure distillation systems, by three group of three tower rectification under vacuum, isolates moisture, to two
Chlorobenzene and nmp solvent.The NaCl concentrated solutions that bottom of towe is isolated enter centrifugal separator, and liquid parts return three-tower rectification system,
NaCl underflows are dried process into exsiccator, are dried boil-off gas and return dashpot, and dry NaCl is collected process.
Another product LiCl that bottom of towe is isolated is introduced into centrifuge and removes most liquid composition, is then evaporated crystallization, crystallizes
Product afterwards carries out further depth drying, and the collection for then carrying out LiCl products is processed；Liquid composition and knot that centrifugation is separated out
The gaseous component steamed when brilliant evaporation, depth drying carries out rectification separating treatment again into dashpot.
Polyphenylene sulfide process units devil liquor recovery separating technology of the present invention, mainly including three desk centrifuges, three exsiccators, one
Crystallizing and drying device and three proprietary tower low-pressure distillation systems.Whole technological process, is provided with three proprietary tower low-pressure distillation modes,
The separation of component in raw material is made more to refine, product separation purity is higher, operability more preferably, has fully demonstrated chemical process
The net Advanced Idea of dry squeezing is eaten, the further lifting and optimization of polyphenylene sulfide nmp solvent recovery process flow process is realized.
Description of the drawings
The present invention is further described below in conjunction with the accompanying drawings：
Accompanying drawing is to separate production procedure schematic diagram using polyphenylene sulfide devil liquor recovery of the present invention；
Specific embodiment
Device and embodiment below in conjunction with the accompanying drawings is further elaborated to the present invention, but does not produce any restriction to the present invention.
The described polyphenylene sulfide process units devil liquor recovery separating technology of invention, by impurity removed system, three tower rectification under vacuum systems and from
Heart drying system is constituted.
Waste liquid produced by PPS production processes first carries out remove impurity process.Waste liquid enters centrifuge, and the liquid phase isolated enters slow
Jet-bedding, the insoluble solid impurities isolated, for preventing solid impurity attachment solvent and other components, cause solvent recovery to lose,
Further in addition dried, the gas phase for evaporating return the dashpot before distillation system, and solid impurity is collected to deliver to and out-of-bounds processed；
Solution in dashpot delivers to three tower rectification under vacuum units, respectively is isolated by moisture, highly purified paracide and solvent NMP
And NaCl solution and LiCl solution.NaCl solution enters centrifuge, and the liquid phase of removing enters dashpot and continues to separate, sticky
Solid phase be further dried, cause solvent loss to prevent NaCl from taking away partial solvent；In the same manner, LiCl solution enters centrifuge,
Liquid composition is isolated, according to the difference of NaCl and LiCl physical property, the LiCl underflows for throwing away centrifuge need further to be steamed
Crystallization treatment is sent out, depth drying is finally carried out again, could the highly purified LiCl crystal of output.Produced by LiCl solution centrifugals are separated
Liquid composition and evaporative crystallization and depth drying during produced by steam component be back to surge tank and carry out doing further
Separating treatment.So, in both having ensure that waste liquid, all components can obtain most sufficient recovery, also ensure that detached NaCl
There can be very high product purity with LiCl.
Present invention has the advantages that polyphenylene sulfide process units devil liquor recovery separating technology is changed by innovating arrangement layout and technological process
Enter, reasonable in design, the extraction of various components in product is more refined, the purity of various component extraction is greatly improved, disposable to receive
Rate reaches more than 90%, and product purity reaches more than 98%；To sum up several process innovations, whole device solvent recovery flow process can
Good economic benefit and environmental benefit is obtained in operation.
A kind of polyphenylene sulfide process units devil liquor recovery separating technology proposed by the present invention, is carried out by preferred embodiment
Description, the part wherein do not addressed in detail is the common knowledge of those skilled in the art.Protection scope of the present invention is with right
The content of requirement is defined, the similar replacement and change of all technology enlightenments based on the present invention, is considered as being included in the present invention
In spirit, scope and content.
Claims (3)
1. a kind of devil liquor recovery separating technology of polyphenylene sulfide process units, comprises the following steps：Waste liquid is first centrifuged
Solid impurity composition is removed, solid impurity is further dried process；The liquid being centrifuged out carries out three tower low pressure
Rectification, produces different products, various products is centrifuged and drying crystalline is processed, and centrifugal liquid is steamed with being dried
The gas for going out returns dashpot and continues with.
2. technique as claimed in claim 1, during whole technological process, in the centrifugation of LiCl and dry
Evaporation crystallization equipment is increased between dry, is conducive to LiCl salinities preferably to crystallize precipitation, is reduced drying
During crystallization difficulty and thermal losses.
3. technique as claimed in claim 1, at three, drying unit is forced-circulation evaporation unit.
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| CN201510570807.3A CN106519231B (en) | 2015-09-09 | 2015-09-09 | A kind of polyphenylene sulfide devil liquor recovery separating technology |
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| CN201510570807.3A CN106519231B (en) | 2015-09-09 | 2015-09-09 | A kind of polyphenylene sulfide devil liquor recovery separating technology |
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| CN106519231B CN106519231B (en) | 2019-03-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586746A (en) * | 2017-10-17 | 2018-09-28 | 天津普莱化工技术有限公司 | By-product separation and recovery method in polyphenylene sulfide production |
| CN110668989A (en) * | 2019-10-21 | 2020-01-10 | 南京佳华工程技术有限公司 | Energy-saving separation method and system for DCB-NMP mixture |
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| EP0477964A2 (en) * | 1990-09-28 | 1992-04-01 | Idemitsu Petrochemical Co. Ltd. | Method for recovering lithium chloride |
| CN101205298A (en) * | 2006-12-20 | 2008-06-25 | 自贡鸿鹤化工股份有限公司 | Method for recovering distillation residual liquid of polyphenylene sulfide resin synthesis by compression process |
| CN101239730A (en) * | 2008-01-30 | 2008-08-13 | 江西赣锋锂业股份有限公司 | Method and device for producing crystal anhydrous lithium chloride |
| CN101429288A (en) * | 2008-12-09 | 2009-05-13 | 江苏新中投资有限公司 | Method for treating process liquid generated in production process of polyphenylene sulfide |
| CN104447480A (en) * | 2014-11-06 | 2015-03-25 | 中国科学院过程工程研究所 | Continuous recycling method of NMP (N-methyl pyrrolidone) solvent for polyphenylene sulfide production device |
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| EP0477964A2 (en) * | 1990-09-28 | 1992-04-01 | Idemitsu Petrochemical Co. Ltd. | Method for recovering lithium chloride |
| CN101205298A (en) * | 2006-12-20 | 2008-06-25 | 自贡鸿鹤化工股份有限公司 | Method for recovering distillation residual liquid of polyphenylene sulfide resin synthesis by compression process |
| CN101239730A (en) * | 2008-01-30 | 2008-08-13 | 江西赣锋锂业股份有限公司 | Method and device for producing crystal anhydrous lithium chloride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586746A (en) * | 2017-10-17 | 2018-09-28 | 天津普莱化工技术有限公司 | By-product separation and recovery method in polyphenylene sulfide production |
| CN110668989A (en) * | 2019-10-21 | 2020-01-10 | 南京佳华工程技术有限公司 | Energy-saving separation method and system for DCB-NMP mixture |
| CN110668989B (en) * | 2019-10-21 | 2023-04-07 | 南京佳华科技股份有限公司 | Energy-saving separation method and system for DCB-NMP mixture |
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