CN117304375A - Devolatilization method and system for isobutylene-based polymer - Google Patents
Devolatilization method and system for isobutylene-based polymer Download PDFInfo
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- CN117304375A CN117304375A CN202311481327.0A CN202311481327A CN117304375A CN 117304375 A CN117304375 A CN 117304375A CN 202311481327 A CN202311481327 A CN 202311481327A CN 117304375 A CN117304375 A CN 117304375A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 56
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000001704 evaporation Methods 0.000 claims abstract description 54
- 230000008020 evaporation Effects 0.000 claims abstract description 54
- 238000011084 recovery Methods 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- -1 trace moisture Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000009849 deactivation Effects 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/10—Vacuum distillation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a devolatilization method of an isobutylene-based polymer, which is used for removing unreacted monomers, trace moisture, solvents, oligomers and other low boiling point substances in an isobutylene-based polymer solution, wherein the solvents comprise C1-C20 alkane, C2-C20 alkene, C3-C20 cycloalkane or C1-C20 halohydrocarbon, and the isobutylene-based polymer comprises polyisobutene, liquid butyl, copolymerization products of isobutylene and other alkene and chemical modification products; the method comprises the following steps: concentrating by a first-stage falling strip devolatilization device after the first treatment, increasing the concentration of a polymer solution of a reaction solution to be treated to a second concentration, obtaining a flash evaporation gas phase, cooling, condensing to obtain a recovery condensate, and returning to a recovery system; concentrating by a secondary falling strip devolatilization device, comprising: the polymer solution enters a secondary falling strip devolatilization device after the second treatment to increase the concentration of the polymer solution to a third concentration; concentrating by a double-screw devolatilization unit, comprising: and after being pressurized by a third booster pump, the mixture enters a double-screw devolatilization unit to concentrate to fourth concentration and stripping. A system is also disclosed.
Description
Technical Field
The invention relates to the technical field of polyolefin devolatilization, in particular to a method and a system for devolatilizing an isobutylene-based polymer, belonging to the process technology for devolatilizing polyisobutylene and liquid butyl polymers.
Background
In the production process of the solution method polymer, in order to remove volatile substances such as solvent, unreacted monomers, oligomers and the like in the solution after the polymerization reaction, the existing devolatilization process adopts the technologies such as climbing film devolatilization, falling film devolatilization, film devolatilization or other surface renewal equipment and the like or the combination process thereof. In the actual operation of lifting and lowering the membranes, pretreatment of the liquid is generally required. For example, the property of the liquid is changed by adjusting the concentration, temperature, pH value and the like of the solute, so that the separation effect is improved, and the process complexity is high. And under the condition of high concentration solvent content, the solution after polymerization reaction directly enters a thin film evaporator or surface updating equipment, so that the following problems are caused:
(1) The rising film and falling film are suitable for processing polymer solution with lower viscosity, and the application range is narrow;
(2) The volatile residue in the product is high, thereby affecting downstream applications such as sealant, food, medicine and the like;
(3) The adoption of the liquid vacuum pump (wet vacuum pump) can generate additional waste water or waste liquid, and the method does not belong to an energy-saving and environment-friendly treatment process and does not meet the requirements of the current treatment process.
Accordingly, there is a need in the art for improved polyolefin post-treatment devolatilization processes.
Disclosure of Invention
The invention aims to provide an isobutylene-based polymer devolatilization method and system, which adopt a grading devolatilization process to couple and connect primary flash evaporation and strip falling devolatilization equipment and surface-modified devolatilization equipment (such as double screws and the like) in series, so as to realize efficient devolatilization.
In a first aspect, the present invention provides a process for devolatilizing an isobutylene-based polymer comprising polyisobutylene, liquid butyl, co-polymerization products of isobutylene and other olefins, and chemically modified products; the devolatilization method is used for removing volatile matters in the isobutylene-based polymer solution, wherein the volatile matters are low-boiling matters, the low-boiling matters comprise one or more of unreacted monomers, trace moisture, solvents and oligomers, and the solvents comprise one or more of C1-C20 alkanes, C2-C20 alkenes, C3-C20 cycloalkanes and C1-C20 halohydrocarbons;
the isobutylene-based polymer devolatilization process comprises:
s1, concentrating by primary flash evaporation equipment, comprising: feeding the reaction solution to be treated into a primary flash evaporation device to remove the unreacted monomers and a small amount of the solvent, and increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration after the removal;
s2, concentrating by a first-stage falling strip devolatilization device, wherein the method comprises the following steps of: the polymer solution concentrated by the primary flash evaporation equipment enters a first-stage falling bar devolatilization equipment for concentration by the first-stage falling bar devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, the flash evaporation gas phase is cooled by a coupling heat exchanger and then condensed to obtain a recovery condensate, and the recovery condensate is returned to a recovery system for recovery;
s3, concentrating by a secondary falling strip devolatilization device, wherein the concentrating comprises the following steps: the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration;
s4, concentrating the double-screw devolatilization unit, including: the polymer solution concentrated by the secondary falling strip devolatilization equipment enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping after being pressurized by a third booster pump; the double-screw devolatilization component comprises a double-screw first section and a double-screw second section, wherein the double-screw first section is a high vacuum recovery section, a polymer solution concentrated by the secondary falling strip devolatilization equipment is subjected to high vacuum recovery section to form a double-screw first section polymer melt, the double-screw first section polymer melt contains trace solvent, monomer and low boiling point substances, the double-screw first section polymer melt is sent into the double-screw second section to form a stripped polymer product as a final product, the double-screw second section adopts a stripping process, and the stripping medium comprises nitrogen, water and CO 2 And air; and pumping the polymer product after gas stripping to a tail gas treatment unit for treatment after passing through a dry vacuum equipment unit III.
Preferably, the reaction solution to be treated is a reaction solution subjected to solution polymerization reaction or a polymer solution subjected to catalyst deactivation and water washing; wherein the solvent content is 60% -90% and the monomer content is 1% -10%.
Preferably, the reaction solution to be treated is heated to 40-90 ℃ by a coupling heat exchanger and then is sent to primary flash evaporation equipment; after entering the primary flash evaporation equipment, the operating pressure in the primary flash evaporation equipment is 10-100kpa, and a conventional jacket, coil heat tracing or external circulation heater is arranged outside the primary flash evaporation equipment for heating; the first concentration is 20% -40%.
Preferably, the first process includes: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; sending the first pressurized polymer solution into a preheater to exchange heat to 100-200 ℃ to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device; the operating pressure of the primary falling strip devolatilization equipment is 10-100kpa, a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilization equipment, and heat exchange is performed through a first heating medium; the second concentration is 70% -90%.
Preferably, the second process includes: the polymer solution concentrated by the primary falling strip devolatilization equipment enters the secondary falling strip devolatilization equipment after being pressurized by a second booster pump, the operating pressure of the secondary falling strip devolatilization equipment is-90 to-40 kpa, a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilization equipment, and heat exchange is carried out through a second heating medium; the third concentration is 95% -99.9%.
Preferably, the secondary falling strip devolatilization device is connected with a dry vacuum device unit I to realize vacuum, and is combined by a screw, a Roots and a rotary vane vacuum device, and corresponding cooling and condensing devices are arranged in the secondary falling strip devolatilization device, and extracted solvent and low boiling point substances are sent to a solvent recovery system for recovery after being condensed; the double-screw devolatilization unit is connected with the dry vacuum equipment unit II to realize vacuum, the dry vacuum equipment unit I and the dry vacuum equipment unit II are combined by screw, roots and rotary-vane vacuum equipment, corresponding cooling and condensing equipment is arranged in the equipment, extracted solvent and low-boiling point substances are condensed and then sent to the solvent recovery system to be recovered, the condensing equipment comprises three condensers, wherein the first condenser is connected between the primary flash evaporation equipment and the solvent condensate tank, the second condenser is connected between the coupling heat exchanger and the solvent condensate tank, and the third condenser is connected between the dry vacuum equipment unit I, the dry vacuum equipment unit II and the solvent condensate tank.
Preferably, the operating pressure of the high vacuum recovery section is-100 to-95 kpa, and a conventional jacket or a coil or electric tracing is arranged outside one section of the double screw; the fourth concentration is 99.98% or more.
Preferably, the stripped polymer product portion is sent to a final storage/packaging unit.
A second aspect of the present invention is to provide an isobutylene-based polymer devolatilization system comprising: primary flash evaporation equipment, primary falling strip devolatilization equipment, secondary falling strip devolatilization equipment, double-screw devolatilization units and auxiliary equipment; the auxiliary assembly includes a coupled heat exchanger, a preheater, and a plurality of booster pumps, wherein:
feeding the reaction solution to be treated into a primary flash evaporation device to remove unreacted monomers and a small amount of solvent, and after the removal, increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration;
the polymer solution concentrated by the primary flash evaporation equipment enters a first-stage falling bar devolatilization equipment for concentration by the first-stage falling bar devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, the flash evaporation gas phase is cooled by a coupling heat exchanger and then condensed to obtain a recovery condensate, and the recovery condensate is returned to a recovery system for recovery; the first process includes: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; feeding the first pressurized polymer solution into a preheater for heat exchange to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device;
the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration; the second process includes: the polymer solution concentrated by the first-stage falling bar devolatilization equipment enters the second-stage falling bar devolatilization equipment after being pressurized by a second booster pump;
and (3) after the polymer solution concentrated by the secondary falling strip devolatilization equipment is pressurized by a third booster pump, the polymer solution enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping.
Preferably, the device further comprises a plurality of dry vacuum equipment units which are respectively connected with the secondary falling strip devolatilization equipment, the secondary falling strip devolatilization equipment and the screw devolatilization unit to realize vacuum.
The method and the system have the beneficial effects that:
(1) The final formation is a high quality polymer with low solvent, monomer and oligomer residues;
(2) The devolatilization process is a step-by-step, efficient, reliable and long-period running devolatilization system, the step-by-step devolatilization is performed, the devolatilization efficiency is high, and the quality of the produced product is high;
(3) The method belongs to a low-carbon energy-saving treatment process; low carbon, energy saving, high treatment capacity, high equipment stability, environmental protection, no extra waste water and high solvent recovery efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings that are required to be used in the description of the embodiments or the related art will be briefly described, and it is apparent that the drawings in the description below are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort for those skilled in the art.
Fig. 1 is a flowchart of a polyolefin post-treatment devolatilization method according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
As shown in fig. 1, the present example provides a devolatilization process for isobutylene-based polymers including, but not limited to, the following products: polyisobutene, liquid butyl, isobutylene and other olefin copolymerization products and chemically modified products; the devolatilization method is used for removing volatile matters of the isobutylene-based polymer solution, wherein the volatile matters are low-boiling matters, the low-boiling matters comprise one or more of unreacted monomers, trace moisture, solvents and oligomers, and the solvents comprise one or more of C1-C20 alkanes, C2-C20 alkenes, C3-C20 cycloalkanes and C1-C20 halohydrocarbons;
the devolatilization method comprises the following steps:
s1, concentrating by primary flash evaporation equipment, comprising: feeding the reaction solution to be treated into a primary flash evaporation device to remove unreacted monomers and a small amount of solvent, and after the removal, increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration;
in this embodiment, the reaction solution to be treated is a reaction solution subjected to solution polymerization reaction or a polymer solution subjected to catalyst deactivation and water washing; wherein the solvent content is 60% -90% and the monomer content is 1% -10%.
In this embodiment, the first concentration is 20% -40%.
In a preferred embodiment, the reaction solution to be treated is heated to 40-90 ℃ by a coupling heat exchanger and then sent to a primary flash evaporation device.
As a preferred embodiment, after entering the primary flash evaporation equipment, the operating pressure in the primary flash evaporation equipment is 10-100kpa, and a conventional jacket, coil heat tracing or external circulation heat exchanger is arranged outside the primary flash evaporation equipment for heating.
Of course, other conventional heating forms may be employed by those skilled in the art and are within the scope of the present invention.
S2, concentrating by a first-stage falling strip devolatilization device, wherein the method comprises the following steps of: and (3) enabling the polymer solution concentrated by the primary flash evaporation equipment to enter a first-stage falling strip devolatilization equipment for concentration by the first-stage falling strip devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, cooling the flash evaporation gas phase by a coupling heat exchanger and then condensing to obtain a recovery condensate, and returning the recovery condensate to a recovery system for recovery.
As a preferred embodiment, the first process includes: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; sending the first pressurized polymer solution into a preheater to exchange heat to 100-200 ℃ to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device; the operating pressure of the primary falling strip devolatilizing equipment is 10-100kpa, a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilizing equipment, and heat exchange is performed through a heating medium 1.
In a preferred embodiment, the second concentration is 70% -90%.
S3, concentrating by a secondary falling strip devolatilization device, wherein the concentrating comprises the following steps: the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration;
as a preferred embodiment, the second process includes: the polymer solution concentrated by the primary falling strip devolatilization equipment enters the secondary falling strip devolatilization equipment after being pressurized by the second booster pump, the operating pressure of the secondary falling strip devolatilization equipment is-90 to-40 kpa, and a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilization equipment and exchanges heat through a heating medium 2.
In a preferred embodiment, the third concentration is 95% -99.9%.
As a preferred implementation mode, the secondary falling strip devolatilizing device is connected with a dry vacuum device unit I to realize vacuum, the dry vacuum device unit I is formed by combining a screw, a Roots vacuum device and a rotary-vane vacuum device, and corresponding cooling and condensing devices are arranged in the dry vacuum device unit I, and extracted solvent and low-boiling point substances are sent to a solvent recovery system for recovery after being condensed; the condensing device comprises a condenser 1, a condenser 2 and a condenser 3.
S4, concentrating the double-screw devolatilization unit, including: the polymer solution concentrated by the secondary falling strip devolatilization equipment enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping after being pressurized by a third booster pump; the double-screw devolatilization component is divided into a double-screw first section and a double-screw second section, the double-screw first section is a high vacuum recovery section, a polymer solution concentrated by the secondary falling strip devolatilization equipment is subjected to the high vacuum recovery section to form a double-screw first section polymer melt, the double-screw first section polymer melt contains a trace amount of solvent, monomer and low boiling point substances, and in order to realize the production requirement of high-quality products, the double-screw first section polymer melt needs to be further removed, therefore, the double-screw first section polymer melt is sent into the double-screw second section to form a stripped polymer product as a final product, the double-screw second section adopts a stripping process, and stripping mediums include but are not limited to the following mediums: nitrogen, water, CO 2 And air, low solvent residue in the polymer product after strippingThe content of monomers and oligomers is less than 20ppm at 100ppm, and the purity of the product is high; and pumping the polymer product after gas stripping to a tail gas treatment unit for treatment after passing through a dry vacuum equipment unit III.
As a preferable implementation mode, the operation pressure of the high vacuum recovery section is-100 to-95 kpa, and a conventional jacket or a coil or electric tracing is arranged outside one section of the double screw.
As a preferred embodiment, the stripped polymer product portion is sent to a finished storage/packaging unit for application in electronics, food, high-end building seals, and the like.
In a preferred embodiment, the fourth concentration is 99.98% or more.
As a preferred embodiment, the double-screw devolatilization unit is connected with a dry vacuum equipment unit II to realize vacuum, the dry vacuum equipment unit II is formed by combining a screw, a Roots type vacuum equipment and a rotary vane type vacuum equipment, corresponding cooling and condensing equipment is arranged in the equipment, extracted solvent and low boiling point substances are condensed and then sent to a solvent recovery system for recovery, and the condensing equipment comprises a condenser 1, a condenser 2 and a condenser 3.
The present embodiment also provides an isobutylene-based polymer devolatilization system comprising: primary flash evaporation equipment, primary falling strip devolatilization equipment, secondary falling strip devolatilization equipment, double-screw devolatilization units and auxiliary equipment; the auxiliary assembly includes a coupled heat exchanger, a preheater, and a plurality of booster pumps, wherein:
feeding the reaction solution to be treated into a primary flash evaporation device to remove unreacted monomers and a small amount of solvent, and after the removal, increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration;
the polymer solution concentrated by the primary flash evaporation equipment enters a first-stage falling bar devolatilization equipment for concentration by the first-stage falling bar devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, the flash evaporation gas phase is cooled by a coupling heat exchanger and then condensed to obtain a recovery condensate, and the recovery condensate is returned to a recovery system for recovery; the first process includes: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; feeding the first pressurized polymer solution into a preheater for heat exchange to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device;
the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration; the second process includes: the polymer solution concentrated by the first-stage falling bar devolatilization equipment enters the second-stage falling bar devolatilization equipment after being pressurized by a second booster pump;
and (3) after the polymer solution concentrated by the secondary falling strip devolatilization equipment is pressurized by a third booster pump, the polymer solution enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping.
As a preferred embodiment, the device also comprises a plurality of dry vacuum equipment units which are respectively connected with the secondary falling strip devolatilization equipment, the secondary falling strip devolatilization equipment and the screw devolatilization unit to realize vacuum.
Example 1
The polymer solution contained 8.56% isobutylene, 2.59% water, 63% hexane, 64.06% polymer and trace amounts of other impurities, wherein the polymer was polyisobutylene and the viscosity average molecular weight was 65000g/mol.
After entering a coupling heat exchanger and heating to 61 ℃, entering a primary flash evaporation device (the operating temperature is 50.3 ℃ and the pressure is 30 kpa), and then pressurizing to 1020kpa by a first booster pump;
heating to 130 ℃ through a preheater, entering a falling strip devolatilizer 1 (the operating temperature is 91 ℃, the operating pressure is 42 kapg), and then pressurizing to 396kpa through a second booster pump;
hexane and isobutene residues in the final product were 67ppm and 32ppm, respectively.
Example 2
The polymer solution contains 8.35 percent of isobutene, 1.62 percent of isoprene, 2.9 percent of water, 64.44 percent of hexane, 22.68 percent of polymer and trace amounts of other impurities, wherein the polymer is liquid butyl, and the weight average molecular weight is 43000g/mol.
After entering a coupling heat exchanger and heating to 57 ℃, entering a primary flash evaporation device (the operating temperature is 48 ℃ and the pressure is 30 kpa), and then pressurizing to 935kpa through a first booster pump;
after being heated to 126 ℃ by a preheater, the mixture enters a falling strip devolatilizer 1 (the operating temperature is 85 ℃ and the operating pressure is 36 kapg);
after being pressurized to 380kpa by a second booster pump, the mixture enters a falling strip devolatilizer 2 (the operation temperature is 132 ℃ and the pressure is-55 kpa);
after being pressurized to 456kpa by a pump, the mixture enters a double-screw unit; the first-stage operation temperature of the twin-screw is 142 ℃, the pressure is-94 kpa, and the second-stage operation temperature of the twin-screw is 142 ℃, and the absolute pressure is 700pa;
the hexane, isobutene and isoprene residues in the final product were 43ppm, 21ppm and 5ppm, respectively.
As can be seen from the above two examples, the final formation is a high quality polymer with low solvent, monomer and oligomer residues; the devolatilization process is a step-by-step, efficient, reliable and long-period running devolatilization system, the step-by-step devolatilization is performed, the devolatilization efficiency is high, and the quality of the produced product is high; belongs to a low-carbon energy-saving treatment process; low carbon, energy saving, high treatment capacity, high equipment stability, environmental protection, no extra waste water and high solvent recovery efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A devolatilization method of isobutene-based polymer is characterized in that,
the isobutylene-based polymer comprises polyisobutylene, liquid butyl, isobutylene and other olefin copolymer products and chemically modified products; the devolatilization method is used for removing volatile matters in the isobutylene-based polymer solution, wherein the volatile matters are low-boiling matters, the low-boiling matters comprise one or more of unreacted monomers, trace moisture, solvents and oligomers, and the solvents comprise one or more of C1-C20 alkanes, C2-C20 alkenes, C3-C20 cycloalkanes and C1-C20 halohydrocarbons;
the devolatilization method comprises the following steps:
s1, concentrating by primary flash evaporation equipment, comprising: feeding the reaction solution to be treated into a primary flash evaporation device to remove the unreacted monomers and a small amount of the solvent, and increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration after the removal;
s2, concentrating by a first-stage falling strip devolatilization device, wherein the method comprises the following steps of: the polymer solution concentrated by the primary flash evaporation equipment enters a first-stage falling bar devolatilization equipment for concentration by the first-stage falling bar devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, the flash evaporation gas phase is cooled by a coupling heat exchanger and then condensed to obtain a recovery condensate, and the recovery condensate is returned to a recovery system for recovery;
s3, concentrating by a secondary falling strip devolatilization device, wherein the concentrating comprises the following steps: the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration;
s4, concentrating the double-screw devolatilization unit, including: the polymer solution concentrated by the secondary falling strip devolatilization equipment enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping after being pressurized by a third booster pump; the double-screw devolatilizing component comprises a double-screw first section and a double-screw second section, wherein the double-screw first section is a high vacuum recovery section, the polymer solution concentrated by the secondary falling strip devolatilizing equipment is subjected to high vacuum recovery section to form a double-screw first section polymer melt, and the double-screw first section polymer melt contains trace solvent, monomer and low boiling point substancesFeeding the polymer melt of the first section of the double screw into a second section of the double screw to form a stripped polymer product as a final product, wherein the second section of the double screw adopts a stripping process, and the stripping medium comprises nitrogen, water and CO 2 And air; and pumping the polymer product after gas stripping to a tail gas treatment unit for treatment after passing through a dry vacuum equipment unit III.
2. The method for devolatilizing an isobutylene-based polymer according to claim 1, wherein the reaction solution to be treated is a reaction solution subjected to a solution polymerization reaction or a polymer solution subjected to catalyst deactivation and water washing; wherein the solvent content is 60% -90% and the monomer content is 1% -10%.
3. The method for devolatilizing an isobutylene-based polymer according to claim 2, wherein the reaction solution to be treated is fed into a primary flash evaporation device after being heated to 40-90 ℃ by a coupling heat exchanger; after entering the primary flash evaporation equipment, the operating pressure in the primary flash evaporation equipment is 10-100kpa, and a conventional jacket or coil heat tracing is arranged outside the primary flash evaporation equipment; the first concentration is 20% -40%.
4. A method of devolatilizing an isobutylene-based polymer according to claim 3, wherein said first treatment comprises: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; sending the first pressurized polymer solution into a preheater to exchange heat to 100-200 ℃ to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device; the operating pressure of the primary falling strip devolatilization equipment is 10-100kpa, a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilization equipment, and heat exchange is performed through a first heating medium; the second concentration is 70% -90%.
5. The method for devolatilizing an isobutylene-based polymer according to claim 4, wherein said second treatment comprises: the polymer solution concentrated by the primary falling strip devolatilization equipment enters the secondary falling strip devolatilization equipment after being pressurized by a second booster pump, the operating pressure of the secondary falling strip devolatilization equipment is-90 to-40 kpa, a conventional jacket or coil heat tracing is arranged outside the primary falling strip devolatilization equipment, and heat exchange is carried out through a second heating medium; the third concentration is 95% -99.9%.
6. The method for devolatilizing an isobutylene-based polymer according to claim 5, wherein the secondary falling strip devolatilization device is connected with a dry vacuum device unit I to realize vacuum, and is composed of a screw, a Roots and a rotary vane vacuum device, and corresponding cooling and condensing devices are arranged in the device, and extracted solvent and low boiling point substances are condensed and then sent to a solvent recovery system for recovery; the double-screw devolatilization unit is connected with the dry vacuum equipment unit II to realize vacuum, the dry vacuum equipment unit I and the dry vacuum equipment unit II are combined by screw, roots and rotary-vane vacuum equipment, corresponding cooling and condensing equipment is arranged in the equipment, extracted solvent and low-boiling point substances are condensed and then sent to the solvent recovery system to be recovered, the condensing equipment comprises three condensers, wherein the first condenser is connected between the primary flash evaporation equipment and the solvent condensate tank, the second condenser is connected between the coupling heat exchanger and the solvent condensate tank, and the third condenser is connected between the dry vacuum equipment unit I, the dry vacuum equipment unit II and the solvent condensate tank.
7. The method for devolatilizing an isobutylene-based polymer according to claim 6, wherein the operation pressure of the high vacuum recovery section is-100 to-95 kpa, and a conventional jacket or coil or electric tracing is provided outside one section of the twin screw; the fourth concentration is 99.98% or more.
8. The isobutylene-based polymer devolatilization process of claim 7, wherein said stripped polymer product portion is sent to a final storage/packaging unit.
9. An isobutylene-based polymer devolatilization system for carrying out the process of any of claims 1-8, comprising: primary flash evaporation equipment, primary falling strip devolatilization equipment, secondary falling strip devolatilization equipment, double-screw devolatilization units and auxiliary equipment; the auxiliary assembly includes a coupled heat exchanger, a preheater, and a plurality of booster pumps, wherein:
feeding the reaction solution to be treated into a primary flash evaporation device to remove unreacted monomers and a small amount of solvent, and after the removal, increasing the concentration of the polymer solution in the reaction solution to be treated to a first concentration;
the polymer solution concentrated by the primary flash evaporation equipment enters a first-stage falling bar devolatilization equipment for concentration by the first-stage falling bar devolatilization equipment after first treatment, so that the concentration of the polymer solution in the reaction solution to be treated is increased to a second concentration and a flash evaporation gas phase is obtained, the flash evaporation gas phase is cooled by a coupling heat exchanger and then condensed to obtain a recovery condensate, and the recovery condensate is returned to a recovery system for recovery; the first process includes: the polymer solution concentrated by the primary flash evaporation equipment is pressurized by a first booster pump to obtain a first pressurized polymer solution; feeding the first pressurized polymer solution into a preheater for heat exchange to form a first pressurized preheated solution; performing decompression operation on the first pressurized preheating solution to form a first pressurized preheating decompression solution; feeding the first pressurized, preheated and depressurized solution into a first-stage falling strip devolatilization device for concentration by the first-stage falling strip devolatilization device;
the polymer solution concentrated by the first-stage falling strip devolatilization equipment enters the second-stage falling strip devolatilization equipment after being subjected to second treatment, and the concentration of the polymer solution is increased to a third concentration; the second process includes: the polymer solution concentrated by the first-stage falling bar devolatilization equipment enters the second-stage falling bar devolatilization equipment after being pressurized by a second booster pump;
and (3) after the polymer solution concentrated by the secondary falling strip devolatilization equipment is pressurized by a third booster pump, the polymer solution enters a double-screw devolatilization unit to be concentrated to fourth concentration and stripping.
10. The system of claim 9, further comprising a plurality of dry vacuum equipment units to respectively connect the secondary falling bar devolatilizer, and screw devolatilizer to achieve vacuum.
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