CN106554434B - A kind of aftertreatment technology of the ethylenic copolymer based on polymerisation in solution - Google Patents
A kind of aftertreatment technology of the ethylenic copolymer based on polymerisation in solution Download PDFInfo
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Abstract
The invention discloses a kind of aftertreatment technologies of ethylenic copolymer based on polymerisation in solution, terminate solutions of vinyl polymers polymerization reaction in the case where not using deactivation agent, then the polymer solution by polymer separation and etc. obtain polymer, liquid phase part containing cocatalyst send to time liquid storage tank and then is circulated back to polymeric kettle, when polymerization initiation conditions have again, it can be used as active component and continue initiated polymerization.The invention avoids the inactivations of co-catalyst, realize the recycling of co-catalyst, are effectively saved production cost, particularly with co-catalyst expensive in the case where it is more applicable.
Description
Technical field
The invention belongs to polymer treatment fields, and in particular to after a kind of ethylenic copolymer based on polymerisation in solution
Treatment process.
Background technique
Polymerisation in solution is important one of polymerization, has polymer reactor small in size, and polymerization reaction time is short, switching
Transition Materials are few when product grade, and production chains are big, and monomer conversion per pass is higher, and gel content is low, and monomer distribution is uniform, produce
Quality is stablized, the advantages that can producing the product of property, therefore, polymerisation in solution be always the direction paid close attention to of people it
One.
There are mainly three types of techniques for the current polymerisation in solution for being related to alpha-olefin in the world: middle pressure solution polymerization process, low pressure are exhausted
Hot solution polymerization technique and hypotonic solution polymerization technique.No matter which kind of production technology its aftertreatment technology be all key problem in technology it
One.Polymer solution is to prevent continuing for polymerization reaction before carrying out next step process after polymeric kettle outflow, is led to
Chang Bixu carries out deactivation first to terminate the catalyst of reaction and inactivating residual.The method of the most frequently used deactivation is that deactivation agent is added, such as
Acetylacetone,2,4-pentanedione, fatty acid, water etc..In the ethylene-norbornene copolymerization technique of Hirst (existing Celanese), polymer solution
It is continuously fed to reaction terminating device from polymer reactor bottom through pressure reducing valve, a small amount of terminator is added to terminate reaction and mistake
Remaining catalyst living.Product stream is transported to polymer settling vessel via the cooling heat exchanger of water from reaction terminating device bottom,
Polymer settling vessel is added with the ethylene-NB copolymerization after precipitation reaction in the desiccant dryness acetone stream that supplement and reuse merge
Object.As Hirst patent US5623039 in the technology that uses be to use very small amount of water as reaction terminating agent, Shao Liangshui
It can simply be removed by desiccant dryness.And used in the patent US5602219 of Hirst it is then the mixed of hydrochloric acid and ethyl alcohol
Object is closed as reaction terminating agent, subsequent step needs hydrochloric acid neutralization procedure, dehydration (may pass through azeotropic distillation) and second
Alcohol recycling step, it is relatively complicated.The middle pressure solwution method (also known as Sclair technique or Sclairtech technique) of NOVA company is main
Produce LLDPE.The technique is using hexamethylene as solvent, and using Ziegler high activated catalyst, butene-1 and octene-1 make copolymerization list
Body.The deactivations agent such as acetylacetone,2,4-pentanedione, fatty acid are added to terminate and react, after inactivation in the technique in the material that polymer reactor exports
Polymer solution be heated to 290 DEG C or more through heat exchanger, flow through solution absorber absorption fall polymer solution in catalyst
Residue and acidic materials, to guarantee the quality of polyethylene.The polymer solution come out in patent EP0416815A2 to reactor makes
It is inactivated with methanol, the method used in patent ZL200510059771.9 polymer inactivation is that addition ethyl alcohol and hydrochloric acid are molten
Liquid.
Above-mentioned no matter any deactivation or inactivation to catalyst all will lead to the inactivation of co-catalyst, in co-catalyst spy
Not in the case where valuableness, the raising of cost caused by co-catalyst inactivates is very significant.For expensive co-catalysis must be used
The system of agent selects high active major catalyst all generally to reduce the cost of co-catalyst, and such as metallocene catalyst system gathers
Closing activity can be close to or reach 108g/molM.h.For co-catalyst, extra high feelings are not achieved in expensive, polymerization activity again
Condition also only rests on the laboratory research stage at present, has no the report of related process.
Summary of the invention
The purpose of the present invention is to solve solution polymerization deactivations in the prior art using the method that deactivation agent is added
The problem of will lead to co-catalyst inactivation provides a kind of method that can interrupt solution polymerization, i.e., based on polymerisation in solution
The aftertreatment technology of ethylenic copolymer, the technique can interrupt solution polymerization, and retain the activity of co-catalyst.This
The purpose of invention also resides in the recycling that co-catalyst may be implemented.
Technical solution: the aftertreatment technology of the ethylenic copolymer of the present invention based on polymerisation in solution, including it is as follows
Several steps:
(1) gas removal, using vacuum or the method for flash distillation by copolymer gaseous monomer and partial solvent remove,
Middle vacuum pressure control is in -0.09~-0.01Mpa, and wherein flashing pressure control is in -0.08~0.05Mpa；；
(2) polymer precipitates, and the polymer solution after gas removal enters polymer precipitation unit, with precipitating reagent phase
Mixing, while being rapidly cooled to -60 DEG C~50 DEG C, polymer is largely precipitated, and the slurry with number of polymers precipitating is formed
Liquid；
(3) polymer separates, and the polymer slurries that step (2) obtains are entered separative unit, realizes and is separated by solid-liquid separation；
(4) liquid phase for obtaining step (1) and (3) is sent into liquid phase separation unit, will be precipitated by the method for vacuum distillation
Agent, reaction monomers and partial solvent are separated and are separately recovered into corresponding storage tank, the remaining liquid containing cocatalyst
It is mutually delivered to corresponding storage tank after chromatography, realizes and recycles；The isolated solid of step (3) is washed, is done
Dry, granulation and packaging process obtain ethylenic copolymer.
Further, in order to precipitate polymer well, the polymer low precipitating of solubility in a solvent is chosen
Agent, so, precipitating reagent in the step (2) is one or more of C5-C8 linear chain or branched chain alkane, preferably n-hexane,
One or more of pentane, hexamethylene, 2- methylpentane, hexahydrotoluene.
Further, the separative unit in the step (3) is centrifugal separation system, filtration system, in sedimenting system
One kind, these types of separation method may be implemented to be separated by solid-liquid separation.
Further, the step (3) can also include polymer dissolution, deliming processing step, after this step, gather
The purity for closing object can further be got higher, and can be suitable for the occasions high to polymer purity requirements such as medical field.
Further, the polymer that step (3) is as separated to by the polymer dissolution, deliming processing step is in solvent
In further dissolve, removing attachment catalyst residue on polymer is then handled by deliming.
Further, the deliming processing step is filled with the pillar of activated alumina using one.
The utility model has the advantages that can make vinyl poly- in the case where not using deactivation agent using aftertreatment technology of the invention
Polymer solution polymerization reaction terminate, then the polymer solution by polymer separation, and etc. obtain polymer, urged containing helping
The liquid phase part of agent send to time liquid storage tank and then is circulated back to polymeric kettle, when polymerization initiation conditions have again, Ke Yizuo
Continue initiated polymerization for active component.The invention avoids the inactivations of co-catalyst, realize the repetition benefit of co-catalyst
With, be effectively saved production cost, particularly with co-catalyst expensive in the case where it is more applicable.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, these implementations
Example for explaining only the invention, is not intended to limit the scope of the present invention..
In following embodiment, the synthesis of ethylenic copolymer, major catalyst is urged using metallocene catalyst or Nonmetallocene
Agent, co-catalyst using methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triisobutyl aluminium hydrolysate (BAO),
One of triethyl aluminum hydrolysate (EAO) or trimethyl aluminium hydrolysate (SMAO) are several.
Embodiment 1:
The polymerization reaction of ethylene-norbornene copolymer uses toluene for solvent, co-catalyst MAO, specific to post-process
Process are as follows:
The ethylene-norbornene copolymer toluene solution come out from polymeric kettle initially enters gas removal unit, and gas is de-
Except unit includes 2 flash tanks, the pressure control of flash tank is in -0.05MPa~0.05MPa, in this quilt of the unit medium vinyl
Removing, part toluene and norbornene enter liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, is converged herein with n-hexane logistics
It closes, while polymer stream is rapidly cooled to -20 DEG C~20 DEG C, polymer is largely precipitated, and has number of polymers later
The slurry logistics of precipitating enters polymer separative unit.
Polymer stream initially enters settler in polymer separative unit, is divided into thick slurry stream and almost solids-free
Overflow logistics.Overflow substance streams to fine filter to recycle remaining fine powder solid.All liquid phase streams collect send to
Liquid phase separation unit.Thick slurry streams to filter, realizes be separated by solid-liquid separation herein.
Polymer solids obtained after separation successively use toluene and n-hexane thorough in polymer treatment, drying and packaging unit
Bottom washing is sent to the vacuum drier for having steam jacket later, the Solid Conveying and Melting after drying to granulation and packaging process.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, here by the method for vacuum distillation by n-hexane, norbornene and portion
Toluene is divided to separate and respectively enter corresponding storage tank, the remaining toluene stream containing MAO is delivered to phase after chromatography
Storage tank is answered, can be directly used for polymerized unit.
Embodiment 2:
The polymerization reaction of ethylene-norbornene copolymer uses toluene/n -nonane for solvent, co-catalyst MMAO, tool
Body last handling process are as follows:
Ethylene-norbornene copolymer toluene/n -nonane the solution come out from polymeric kettle initially enters gas removal unit,
Gas removal unit includes 2 flash tanks, and the pressure of flash tank is controlled in -0.05MPa~0.02MPa, the ethylene in the unit
Substantially it is removed, (part) toluene and part norbornene enter liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, is converged herein with pentane logistics
It closes, while polymer stream is rapidly cooled to -30 DEG C~30 DEG C, polymer is largely precipitated, and has number of polymers later
The slurry logistics of precipitating enters polymer separative unit.
Polymer stream initially enters filtration system in polymer separative unit, and filter cake successively uses toluene and pentane thorough
Bottom washing can also be washed only with pentane.It is sent to polymer dissolution unit later, polymer solids and toluene are mixed herein
It closes, is completely dissolved at 80-110 DEG C, solution deliming unit removing wherein catalyst residue is then flowed through, to be further ensured that product
Quality.Wherein the main body of solution deliming unit is the pillar for being filled with activated alumina.It is come out from solution deliming unit
Polymer solution is dry and packaging unit back warp crosses flash distillation and removes most of solvent in polymer, subsequently into there is steam jacket
Vacuum drier, it is dry after Solid Conveying and Melting to granulation and packaging process.All liquid phase streams including filtrate and washing lotion
It collects and send to liquid phase separation unit.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, here by vacuum distillation method by pentane, norbornene and/or
Corresponding storage tank is separated and respectively enterd to part toluene or n -nonane, the remaining toluene containing MMAO/n -nonane logistics (or
N -nonane logistics) corresponding storage tank is delivered to after chromatography, it can be directly used for polymerized unit after being further concentrated under reduced pressure.
Embodiment 3:
Ethylene-ethylidene norbornene copolymer polymerization reaction, uses toluene for solvent, co-catalyst MAO, after specific
Treatment process are as follows:
Ethylene-ethylidene norbornene the copolymer toluene solution come out from polymeric kettle initially enters gas removal unit, gas
Body removal unit includes 1 flash tank and a set of surge tank with vacuum system, and the pressure of flash tank is controlled in -0.07MPa
The pressure of~0.02MPa, surge tank are controlled in -0.06MPa~-0.01MPa, are originally removed in the unit medium vinyl, part
Toluene and ethylidene norbornene enter liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, is converged herein with hexamethylene logistics
It closes, while polymer stream is rapidly cooled to -20 DEG C~20 DEG C, polymer is largely precipitated, and has number of polymers later
The slurry logistics of precipitating enters polymer separative unit.
Polymer stream initially enters settler in polymer separative unit, is divided into thick slurry stream and almost solids-free
Overflow logistics.Overflow substance streams to fine filter to recycle remaining fine powder solid.All liquid phase streams collect send to
Liquid phase separation unit.Thick slurry streams to filter, realizes be separated by solid-liquid separation herein.
Polymer solids obtained after separation successively use toluene and hexamethylene thorough in polymer treatment, drying and packaging unit
Bottom washing is sent to the vacuum drier for having steam jacket later, the Solid Conveying and Melting after drying to granulation and packaging process.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, here by the method for vacuum distillation by hexamethylene, norbornene and portion
Toluene is divided to separate and respectively enter corresponding storage tank, the remaining toluene stream containing MAO is delivered to phase after chromatography
Storage tank is answered, can be directly used for polymerized unit.
Embodiment 4:
The polymerization reaction of ethylene-vinyl norbornene copolymer, uses toluene/normal octane for solvent, and co-catalyst is
MMAO, specific last handling process are as follows:
The ethylene-vinyl norbornene copolymer toluene/normal octane solution come out from polymeric kettle initially enters gas removal
Unit, gas removal unit include a set of surge tank with vacuum system, the pressure of surge tank control -0.08MPa~-
0.01MPa, temperature are controlled at 80-110 DEG C, are originally removed in the unit medium vinyl, (part) toluene, part normal octane and portion
Point ethylidene norbornene enters liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, herein with 2- methylpentane logistics
Converge, while polymer stream is rapidly cooled to -30 DEG C~30 DEG C, polymer is largely precipitated, later with a large amount of polymerizations
The slurry logistics of object precipitating enters polymer separative unit.
Polymer stream enters centrifugal separation system in polymer separative unit, realizes the solid-liquid point of polymer stream
From.Polymer solids obtained after separation successively use toluene and 2- methylpentane thorough in polymer treatment, drying and packaging unit
Bottom washing can also be washed only with 2- methylpentane.It is sent to drying machine later, the Solid Conveying and Melting after drying to granulation and packaging
Process.All liquid phase streams, which collect, to be sent to liquid phase separation unit.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, here by vacuum distillation method by 2- methylpentane, norbornene,
Corresponding storage tank, remaining toluene/normal octane containing MMAO are separated and respectively enterd to part toluene and/or part normal octane
Logistics (or normal octane logistics) is delivered to corresponding storage tank after chromatography, can be directly used for polymerized unit.
Embodiment 5:
The polymerization reaction of ethylene-butene copolymer uses paraxylene/n-decane for solvent, co-catalyst be MMAO and
BAO, specific last handling process are as follows:
Ethylene-butene copolymer paraxylene/the n-decane solution come out from polymeric kettle initially enters gas removal unit,
Gas removal unit includes 3 flash tanks, and the pressure of flash tank is controlled in -0.06MPa~0.03MPa, the ethylene in the unit
It is removed substantially with butylene, (part) paraxylene and n-decane enter liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, herein with hexahydrotoluene logistics
Converge, while polymer stream is rapidly cooled to -30 DEG C~20 DEG C, polymer is largely precipitated, later with a large amount of polymerizations
The slurry logistics of object precipitating enters polymer separative unit.
Polymer stream enters centrifugal separation system in polymer separative unit, realizes the solid-liquid point of polymer stream
From.Polymer obtained after separation is sent to polymer dissolution unit, herein polymer solids and paraxylene mixing,
90-130 DEG C is completely dissolved, and the removing of solution deliming unit wherein catalyst residue and acidic materials is then flowed through, further to protect
Demonstrate,prove product quality.Wherein the main body of solution deliming unit is the pillar for being filled with molecular sieve.It is come out from solution deliming unit
Polymer solution it is dry and packaging unit back warp crosses flash distillation and removes most of solvent in polymer, subsequently into there is steam jacket
Vacuum drier, it is dry after Solid Conveying and Melting to granulation and packaging process.All liquid phase objects including filtrate and washing lotion
Stream, which collects, to be sent to liquid phase separation unit.All liquid phase streams, which collect, to be sent to liquid phase separation unit.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, here by vacuum distillation method by hexahydrotoluene, norbornene,
Corresponding storage tank is separated and respectively enterd to part paraxylene and/or part n-decane, and remaining containing MMAO and BAO, (three is different
Butyl aluminium hydrolysate) paraxylene/n-decane logistics (or n-decane logistics) corresponding storage tank is delivered to after chromatography,
It can be directly used for polymerized unit.
Embodiment 6:
The polymerization reaction of ethylene-propylene copolymer uses hexamethylene for solvent, co-catalyst MMAO, specific to post-process
Process are as follows:
The ethylene-propylene copolymer cyclohexane solution come out from polymeric kettle initially enters gas removal unit, gas removal
Unit includes 2 flash tanks, and the pressure of flash tank is controlled in -0.05MPa~0.05MPa, ethylene and acrylic in the unit
Originally it is removed, hexamethylene enters liquid phase separation unit.
Enter polymer precipitation unit by the polymer solution of gas removal unit, is converged herein with hexamethylene logistics
It closes, while polymer stream is rapidly cooled to -50 DEG C~-30 DEG C, polymer is largely precipitated, and has number of polymers later
The slurry logistics of precipitating enters polymer separative unit.
Polymer stream enters centrifugal separation system in polymer separative unit, realizes the solid-liquid point of polymer stream
From.Polymer solids obtained after separation are thoroughly washed in polymer treatment, drying and packaging unit with hexamethylene, are sent later
To drying machine, it is dry after Solid Conveying and Melting to granulation and packaging process.All liquid phase streams, which collect, to be sent to liquid phase separation
Unit.
Gas removal unit, polymer precipitation unit, polymer separative unit and polymer treatment, drying and packaging unit
The liquid phase part of collection enters liquid phase separation unit, isolates most of hexamethylene here by the method for vacuum distillation
It goes, the remaining hexamethylene logistics containing MMAO is delivered to corresponding storage tank after chromatography, can be directly used for polymerized unit.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of aftertreatment technology of the ethylenic copolymer based on polymerisation in solution, which is characterized in that comprise the following steps:
(1) gas removal, using vacuum or the method for flash distillation by copolymer gaseous monomer and partial solvent remove, wherein very
The control of pneumatics power is in -0.09~-0.01MPa, and wherein flashing pressure control is in -0.08~0.05MPa；
(2) polymer precipitates, and the polymer solution after gas removal enters polymer precipitation unit, mutually mixes with precipitating reagent
It closes, while being rapidly cooled to -60 DEG C~50 DEG C, polymer is largely precipitated, and the slurries with number of polymers precipitating are formed；
(3) polymer separates, and the polymer slurries that step (2) obtains are entered separative unit, realizes and is separated by solid-liquid separation；
(4) liquid phase obtained step (1) and (3) is sent into liquid phase separation unit, by the method for vacuum distillation by precipitating reagent, anti-
It answers monomer and partial solvent to separate and is separately recovered into corresponding storage tank, the remaining liquid phase containing cocatalyst is through color
It is delivered to corresponding storage tank after spectrum analysis, realizes and recycles；The isolated solid of step (3) is washed, dried, is granulated
Ethylenic copolymer is obtained with packaging process.
2. the aftertreatment technology of the ethylenic copolymer according to claim 1 based on polymerisation in solution, which is characterized in that institute
Stating the precipitating reagent in step (2) is one or more of C5-C8 linear chain or branched chain alkane.
3. the aftertreatment technology of the ethylenic copolymer according to claim 2 based on polymerisation in solution, which is characterized in that institute
Stating the precipitating reagent in step (2) is one or more of n-hexane, pentane, 2- methylpentane.
4. the aftertreatment technology of the ethylenic copolymer according to claim 1 based on polymerisation in solution, which is characterized in that institute
Stating the precipitating reagent in step (2) is hexamethylene or hexahydrotoluene.
5. the aftertreatment technology of the ethylenic copolymer according to claim 1 based on polymerisation in solution, which is characterized in that institute
Stating the separative unit in step (3) is one of centrifugal separation system, filtration system, sedimenting system.
6. the aftertreatment technology of the ethylenic copolymer according to claim 1 based on polymerisation in solution, which is characterized in that institute
Stating step (3) further includes polymer dissolution, deliming processing step.
7. the aftertreatment technology of the ethylenic copolymer according to claim 6 based on polymerisation in solution, which is characterized in that institute
State polymer dissolution, deliming processing step be the polymer that step (3) is separated to further is dissolved in a solvent, then into
Enter the catalyst residue of deliming processing removing attachment on polymer.
8. the aftertreatment technology of the ethylenic copolymer according to claim 7 based on polymerisation in solution, which is characterized in that institute
Deliming processing step is stated using a pillar filled with activated alumina or molecular sieve.
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Citations (3)
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|---|---|---|---|---|
| WO2005058979A1 (en) * | 2003-12-11 | 2005-06-30 | Basell Poliolefine Italia S.R.L. | Liquid phase process for polymerizing olefins |
| CN101260167A (en) * | 1997-12-23 | 2008-09-10 | 陶氏环球技术公司 | Finishing design to increase the polymer content in an olefin solution polymerization process |
| CN103374089A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Method for removing catalysts from ethylene-alpha olefin copolymer solution and preparation method of copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260167A (en) * | 1997-12-23 | 2008-09-10 | 陶氏环球技术公司 | Finishing design to increase the polymer content in an olefin solution polymerization process |
| WO2005058979A1 (en) * | 2003-12-11 | 2005-06-30 | Basell Poliolefine Italia S.R.L. | Liquid phase process for polymerizing olefins |
| CN1890269A (en) * | 2003-12-11 | 2007-01-03 | 巴塞尔聚烯烃意大利有限责任公司 | Liquid phase process for polymerizing olefins |
| CN103374089A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Method for removing catalysts from ethylene-alpha olefin copolymer solution and preparation method of copolymer |
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