CN104245088B - Component seperation in polymerization - Google Patents

Component seperation in polymerization Download PDF

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Publication number
CN104245088B
CN104245088B CN201380019547.XA CN201380019547A CN104245088B CN 104245088 B CN104245088 B CN 104245088B CN 201380019547 A CN201380019547 A CN 201380019547A CN 104245088 B CN104245088 B CN 104245088B
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flow
stream
reactor
air
polymer
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CN104245088A (en
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S·E·库费尔德
J·D·浩托威
章艾茀
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Chevron Phillips Chemical Co LLC
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Chevron Phillips Chemical Co LLC
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/001Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00Post-polymerisation treatments
    • C08F6/001Removal of residual monomers by physical means
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/02Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The method of Component seperation in polymer production system, including polymerizate flow separation becomes air-flow and polymer flow, wherein air-flow includes ethane and unreacted ethylene;Airflow distillation becomes lightweight hydrocarbon stream, and wherein lightweight hydrocarbon stream includes ethane and unreacted ethylene;Lightweight hydrocarbon stream is made to contact with lyosoption system, wherein from least some of unreacted ethylene of lightweight hydrocarbon stream by lyosoption Systemic absorption;Reclaiming waste gas stream with from lyosoption system, wherein waste gas stream includes ethane, hydrogen or a combination thereof.

Description

Component seperation in polymerization
Cross-Reference to Related Applications
The application submitted on October 15th, 2010, the entitled " ethylene separation (Improved of improvement Ethylene Separation) " the part of U.S. Patent Application Serial 12/905,966 continue, it is by quoting with it Entirety is expressly incorporated herein for all purposes.
Background
Technical field
The disclosure relates generally to the production of polyethylene.More specifically, it relates to change by reducing ethylene loss The system and method for kind polyethylene production efficiency.
Background technology
Highly purified monomer and comonomer raw material is required by light gas generation polymer such as polyethylene.Due to this Boiling point difference little between light gas in raw material, commercial production high-purity raw may call for multiple distillation column, high pressure and low temperature Operation.So, relevant to purification of raw materials cost of energy accounts for the notable ratio producing this base polymer totle drilling cost.Additionally, produce, The base structure that holding and recirculation high-purity raw require is the signal portion of relevant capital cost.
In order to make up some costs and make production maximize, regain and/or any unreacted unstrpped gas of recirculation, especially It is light hydrocarbon reactant, such as ethylene, can be useful.Including unreacted monomer gas can after polymerization with Polymer separates.Process polymer, reclaim unreacted monomer from the gas regained after polymerization simultaneously.In order to realize This point, the air-flow of withdrawal is conventionally sent through purification process or redirects by other unnecessary process steps.Often In the case of Zhong, the conventional method reclaiming monomer needs process disadvantageous and expensive on energy.
Accordingly it is desirable to ethylene and the high efficiency separation of recirculation flow.
Summary of the invention
Disclosed herein is the method for Component seperation in polymer production system, become air-flow including by polymerizate flow separation And polymer flow, wherein air-flow includes ethane and unreacted ethylene;Airflow distillation is become lightweight hydrocarbon stream, wherein lightweight hydrocarbon stream bag Include ethane and unreacted ethylene;Lightweight hydrocarbon stream is made to contact with lyosoption system, wherein from least one of lightweight hydrocarbon stream Divide unreacted ethylene by lyosoption Systemic absorption;Reclaiming waste gas stream with from lyosoption system, wherein waste gas stream includes second Alkane, hydrogen or a combination thereof.
In polymer production system the method for Component seperation is also disclosed, becomes gas including by polymerizate flow separation Stream and polymer flow, wherein air-flow includes ethane and unreacted ethylene;Hydrocarbon stream and the first tower underflow in the middle of airflow distillation is become Going out thing, wherein middle hydrocarbon stream includes ethane, ethylene and isobutene.;Centre hydrocarbon stream is distilled at the bottom of lightweight hydrocarbon stream and the second tower and flows out Thing, wherein lightweight hydrocarbon stream includes ethane and ethylene;Lightweight hydrocarbon stream is made to contact with lyosoption system, wherein from lightweight hydrocarbon stream At least some of unreacted ethylene is by lyosoption Systemic absorption;Waste gas stream, wherein waste gas is reclaimed with from lyosoption system Stream includes ethane, hydrogen or a combination thereof.
There is further disclosed herein the method for Component seperation in polymer production system, including making olefinic monomer first Polymer reactor is polymerized, with m-polymerizate stream in producing;In Jiang m-polymerizate flow separation become in m-air-flow and in M-polymer flow, wherein in m-air-flow include ethane, unreacted ethylene and hydrogen;With make in m-polymer flow second gather Close in reactor and be polymerized.
There is further disclosed herein the method for Component seperation in polymer production system, including making olefinic monomer first Polymer reactor is polymerized;In Jiang m-polymerizate flow separation become in m-air-flow and in m-polymer flow, wherein in m-gas Stream includes ethane and unreacted ethylene;M-polymer flow is made to be polymerized in the second polymer reactor;Anti-with in the second polymerization Scavenger is introduced before answering device.
There is further disclosed herein the method for Component seperation in polymer production system, including making olefinic monomer first Polymer reactor is polymerized, with m-polymerizate stream in producing;Make from m-polymerizate stream at least some of hydrogen take off Gas, to produce the product stream that hydrogen reduces;By hydrogen reduce product stream be separated in m-air-flow and in m-polymer flow, Qi Zhongzhong M-air-flow includes ethane and unreacted ethylene;With make in m-polymer flow be polymerized in the second polymer reactor.
The aforementioned feature rather broadly outlining open subject matter and technical advantage, in order to be better understood following Describe in detail.When those skilled in the art read the following detailed description of preferred implementation and during referring to accompanying drawing, above-mentioned respectively Plant feature, and other features are apparent from.
Accompanying drawing explanation
In order to describe the preferred implementation of open method and system in detail, description, wherein:
Fig. 1 illustrates the schematic diagram of the first embodiment of polyethylene production system;
Fig. 2 illustrates the schematic diagram of the second embodiment of polyethylene production system;
Fig. 3 illustrates the schematic diagram of the third embodiment of polyethylene production system;
Fig. 4 illustrates the schematic diagram of the 4th kind of embodiment of polyethylene production system;
Fig. 5 illustrates the schematic diagram of the 5th kind of embodiment of polyethylene production system;
Fig. 6 illustrates the flow chart of the first embodiment of polyethylene process;
Fig. 7 illustrates the flow chart of the second embodiment of polyethylene process;
Fig. 8 illustrates the flow chart of the third embodiment of polyethylene process;
Fig. 9 illustrates the flow chart of the 4th kind of embodiment of polyethylene process;
Figure 10 diagram has the schematic diagram of the embodiment absorbing reactor of pressure swing absorption structure;
Figure 11 is the dissolubility of ethylene and the ethane figure to temperature in diagram lyosoption system;
Figure 12 illustrates the schematic diagram of the embodiment of the absorption system of simulation;With
Figure 13 illustrates the schematic diagram of the embodiment of the absorption system of simulation.
Detailed description of the invention
The system relevant to having the polyethylene production improving efficiency, apparatus and method are disclosed herein.This system, device Relate generally to method separate the first chemical constituent or compound from compositions, described source from the production of polyethylene and Including the first chemical constituent or compound and one or more other chemical constituents, compounds or the like.
With reference to Fig. 1, disclose the first polyethylene production (PEP) system 100.PEP system 100 generally comprises depurator 102, reactor 104,106, separator 108, processor 110, distillation column 122, absorption reactor 116 and processing equipment 114.? In PEP embodiment disclosed herein, various system components can through be suitable to transport concrete stream such as by Fig. 1-5,10,12- What the stream numbered in 13 displayed the details of one or more conduits (such as, pipe, tubing, flowline etc.) fluid is even Logical.
In the embodiment of figure 1, feed stream 10 can be communicated to depurator 102.The feed stream 11 purified can be from depurator 102 are communicated to one or more reactor 104,106.The most this system includes two or more reactors, reactor stream 15 can be communicated to reactor 106 from reactor 104.Hydrogen can be introduced to reactor 106 with stream 21.Polymerizate stream 12 can be from one Individual or multiple reactors 104,106 are communicated to separator 108.Polymer flow 14 can be communicated to processor 110 from separator 108. Product stream 16 can send from processor 110.Air-flow 18 can be communicated to distillation column 122 from separator 108.Base product effluent 23 Can send from distillation column 122, and effluent 27 can send from distillation column 122.Lightweight hydrocarbon stream 25 can send from distillation column 122 and connect Pass to absorb reactor 116.Waste gas stream 20 can be communicated to processing equipment 114 from absorbing reactor 116, and recirculation flow 22 can be from Absorbing other positions that reactor 116 is communicated in system 100, such as, separated device 108 is communicated to depurator 102.Through dividing In the case of device 108 is recycled to depurator 102, recirculation flow 22 can be communicated to separator 108 from absorbing reactor 116, Depurator 102 can be communicated to from separator 108 with stream.
With reference to Fig. 2, disclosing the second PEP system 200, it has many system components common with PEP100.At Fig. 2 In the optional embodiment of explaination, the second PEP system 200 comprises additionally in degasifier 118.Replace the first PEP system 100 (as explained in Fig. 1), in the embodiment of Fig. 2 explaination, air-flow 18 can be communicated to degasifier 118.The air-flow 26 processed can be from Degasifier 118 is communicated to distillation column 122.Consider that the embodiment of present subject matter can may be adapted in air-flow 18 being with or without Operate in the case of the degasifier 118 of gas component.
In the optional embodiment of Fig. 2 explaination, the second PEP system 200 comprises additionally in distillation column 124.Including In the embodiment of distillation column 122 and 124, distillation column 122 can be described as the first distillation column or redistillation tower, and distillation column 124 can It is referred to as after-fractionating tower or light distillation column.As shown in Figure 2, the air-flow 26 of process (with optionally, does not has degasifier 118 The air-flow 18 of embodiment) distillation column 122 can be communicated to.Middle hydrocarbon stream 29 can be communicated to distillation column 124 from distillation column 122.Steam Evaporate bottom stream 23 to send from distillation column 122.Base product effluent 33, and optionally, effluent 31 can be from distillation column 124 Send.Lightweight hydrocarbon stream 25 can send to absorbing reactor 116 from distillation column 124.
With reference to Fig. 3, disclosing the third PEP system 300, it has many and the common system of PEP system 100 and 200 Assembly.The system component in polymerizate stream 12 downstream, those shown in such as Fig. 1 and 2, not included in Fig. 3;But, examine Consider this downstream components that the embodiment of such as system 300 may be included in various disclosed embodiment.Fig. 3 explaination can In the embodiment of choosing, the third PEP system 300 includes the separator 105 between reactor 104 and reactor 106 alternatively. Scavenger can be introduced to system through stream 35.Stream 35 can with in m-polymerizate stream 15 be communicated to separator 105, wherein in m-poly- Close during product stream 15 is separable into m-air-flow 19 and in m-polymer flow 17.In m-polymer flow 17 can be communicated to reactor 106, it sends polymerizate stream 12.In m-air-flow 19 can be communicated to absorb reactor 116, it sends waste stream 20, absorbent Stream 30 and recirculation flow 22.Waste stream 20 can be communicated to processing equipment 114 from absorbing reactor 116, and recirculation flow 22 can be from Absorb other positions of being communicated in system 300 of reactor 116, as in Fig. 1 to described by recirculation flow 22.
With reference to Fig. 4, disclosing the 4th kind of PEP system 400, it has many system components common with PEP system 300. The system component in polymerizate stream 12 downstream, those shown in such as Fig. 1 and 2, not included in Fig. 4;But, it is considered to such as The embodiment of system 400 may be included in this downstream components in various disclosed embodiment.That explains in the diagram is optional In embodiment, the 4th kind of PEP system 400 includes separator 126 alternatively.Reactor 104 is m-polymerizate stream in can sending 15, it can be communicated to separator 126.Hydrogen stream 37 can send, from separator 126, the product stream 39 reduced with hydrogen can be from separator 126 It is communicated to separator 105.
With reference to Fig. 5, disclosing the 5th kind of PEP system 500, it has many and the common system of PEP system 300 and 400 Assembly.The system component in polymerizate stream 12 downstream, those shown in such as Fig. 1 and 2, not included in Fig. 5;But, examine Consider this downstream components that the embodiment of such as system 500 may be included in various disclosed embodiment.Fig. 5 explaination can In the embodiment of choosing, the 5th kind of PEP system 500 comprises additionally in regenerator 120 (such as, desorption container).Substitute PEP system 100,200,300 and 400, in the embodiment explained in Figure 5, combined-flow 28 can be communicated to regeneration from absorbing reactor 116 Device 120.Recirculation flow 22 can be communicated to other positions in system 500, and such as, separated device is communicated to depurator 102 (such as figure Discussed in 1).The absorbent stream 30 of regeneration can be communicated to absorb reactor 116 from regenerator 120.Although regenerator 120 combines Absorb reactor 116 and show in Figure 5, but additionally consider that regenerator can be used for combining any suction of the embodiment of Fig. 1 to 4 Receive reactor 116.Additionally, it is contemplated that the absorption reactor 116 of Fig. 5 can be configured to operate in the case of not having regenerator 120.
The stream 30 that the temperature of lean solvent is retrieved from Fig. 5.The temperature absorbing reactor 116 can be depending on the temperature of air-flow 18 The temperature of lean solvent, the heat of solution and the heat of reaction in degree, stream 30.In disclosed embodiment, lean molten in stream 30 Big than the mass velocity of air-flow 18 50 to 300 times of the mass velocity of agent.So, the temperature absorbing reactor 116 can highly take The certainly temperature of the lean solvent in disclosed embodiment.
Have been disclosed for the various embodiments of suitable PEP system, the embodiment of presently disclosed PEP method.Can join Examine PEP system 100, PEP system 200, PEP system 300, one or more descriptions of PEP system 400 and/or PEP system 500 One or more embodiments of PEP method.Although the one or more embodiments referring to PEP system describe given PEP method, this disclosure should not be construed as the most restrictive.Although the various steps of method disclosed herein can be with specifically Order is open or explaination, but should not be construed as and the carrying out of these methods is limited to any concrete order, unless additionally Point out.
With reference to Fig. 6, explain the first PEP method 600.PEP method 600 is commonly included in block 61 purified feed stream, at block 62 make the monomer of purified feed stream be polymerized, and to form polymerizate, at block 63, polymerizate are separated into polymer flow and air-flow, Process polymer flow at block 64, separate at least one gas component at block 65 from air-flow, to form recirculation flow and waste stream, and At block 66 combustion waste stream.
As an example, the first PEP method 600 or its part (can be explained in such as, such as Fig. 1 through the first PEP system 100 Release) enforcement.With reference to Fig. 1 and 6, in embodiments, feed stream 10 can include gas reactant, especially ethylene.Implementing In mode, purified feed stream can produce purification stream 11, and it includes the purest monomer (such as, vinyl monomer), comonomer (such as, butene-1 comonomer) or a combination thereof.Monomer (optionally, the comonomer) polymerization making purification stream 11 can produce polymerization Product stream 12, its generally comprise unreacted monomer (such as, ethylene), optional unreacted comonomer (such as, butylene- 1), by-product (such as, ethane, it can be by the by-product ethane of ethylene and hydrogen evolution) and polymerizate (such as, polymer Optionally, copolymer).Separation of polymeric product stream 12 can produce polymer flow 14 (such as, polyethylene polymer, copolymer) and Air-flow 18, its generally comprise unreacted monomer (such as, vinyl monomer and any optional comonomer such as butene-1) and Various gases (such as, ethane, hydrogen).Process polymer flow 14 and can produce product stream 16.At least one gas is separated from air-flow 18 Component can produce recirculation flow 22, and it generally comprises unreacted vinyl monomer (optionally, unreacted comonomer), With waste gas stream 20.In embodiments, separate at least one gas component from air-flow 18 can include distilling the second from air-flow 18 Alkene, to produce lightweight hydrocarbon stream 25.In embodiments, alternatively, or in addition, separation bubble 18 can include absorbing from air-flow The ethylene of 18, to produce waste gas stream 20 and then to discharge the ethylene of absorption, to form recirculation flow 22.Recirculation flow 22, bag Include ethylene, can pressurized (such as, separated device 108 returns depurator 102 for pressurizeing) and reboot into PEP method (example As, PEP method 600).Burner exhaust stream 20 can apply a torch (flare) carry out as processing equipment 114.
With reference to Fig. 7, explaining the second PEP method 700, it has many method steps common with PEP method 600.PEP Method 700 is commonly included in block 71 purified feed stream, makes the monomer of purified feed stream be polymerized at block 72, with m-polymerization in being formed Product, in polymerizate is separated into by block 73 m-polymer flow and in m-air-flow, the list of m-polymer flow in block 74 makes Body (optionally, comonomer) is polymerized, and separates at least one gas component at the most m-air-flow of block 75, to form recirculation flow With waste stream, with at block 76 combustion waste stream.In the optional embodiment of Fig. 7 explaination, the block 63-64 of Fig. 6 is by block 73-75 Replace.It is said that in general, the method 700 of Fig. 7 occurs between reactor 104 and 106, and the method 600 of Fig. 6 occurs at reactor The downstream of 104 and 106.
As an example, the second PEP method 700 or its part can be through the third PEP system 300 (institutes in such as, such as Fig. 3 Explaination) enforcement.With reference to Fig. 3 and 7, in embodiments, feed stream 10 can include gas reactant, especially ethylene.In reality Executing in mode, purified feed stream can produce purification stream 11, and it includes the purest monomer (such as, vinyl monomer) and optional Ground, comonomer (such as, butene-1).Make purification stream 11 monomer polymerization can produce in m-polymerizate stream 15, it typically wraps Include unreacted monomer (such as, ethylene), optional unreacted comonomer (such as, butene-1), by-product (such as, second Alkane, it can be by the by-product ethane of ethylene and hydrogen evolution) and polymerizate (such as, polymer and optionally, copolymer). Fig. 1 polymerizate stream 12 its in the replacement in the downstream of polymer reactor 104 and 106, embodiment in Fig. 3 In m-polymerizate stream 15 can polymer reactor (one or more) 104 and polymer reactor (one or more) 106 it Between.In separation m-polymerizate stream 15 in can producing m-polymer flow 17 its generally comprise unreacted ethylene, ethane (it can be by the by-product ethane of ethylene and hydrogen evolution) and polymer (such as, polyethylene), and in m-air-flow 19, one As include unreacted monomer (such as, vinyl monomer), the most unreacted comonomer (such as, butene-1 monomer) and each Plant gas (such as, ethane, hydrogen).In making, monomer (optionally, the comonomer) polymerization of m-polymer flow 17 can produce polymerization product Logistics 12.The component of polymerizate stream 12 can process according to the embodiment of system in Fig. 1 and 2 100 and 200.The most m-air-flow 19 at least one gas component of separation can produce recirculation flow 22, and (optionally, it generally comprise unreacted vinyl monomer Comonomer), and waste gas stream 20.In embodiments, the most m-air-flow 19 separates at least one gas component and can include therefrom M-air-flow 19 absorbs ethylene, to produce waste gas stream 20 and then to discharge the ethylene of absorption, to form recirculation flow 22.Follow again Circulation 22, including ethylene, can be pressurized and reboot and (such as, as depicted in figure 1) enter PEP method (such as, PEP side Method 700).Burner exhaust stream 20 can apply a torch and carry out as processing equipment 114.
With reference to Fig. 8, explaining the third PEP method 800, it has many method steps common with PEP method 600 (i.e., Block 61,62,63,64,65 and 66).In the optional embodiment of Fig. 8 explaination, PEP method 800 includes that block 81 processes air-flow, The air-flow processed with formation separates at least one gas component with at block 65 ' from the air-flow processed, to form recirculation flow and to give up Logistics.
In embodiments, the third PEP method 800 or its part can be through the second PEP system 200 (in such as such as Fig. 2 Explained) enforcement.The embodiment of alternate figures 1 and 6, in the embodiment of Fig. 2 and 8, processes air-flow 18 and can produce process Air-flow 26.In embodiments, process air-flow 18 to include making air-flow 18 deoxidation.At least one gas is separated from the air-flow 26 processed Body component can produce recirculation flow 22, and it generally comprises unreacted vinyl monomer (optionally, comonomer), waste gas stream 20, base product effluent 23, base product effluent 33 and effluent 31.
With reference to Fig. 9, explaining the 4th kind of PEP method 900, it has many method steps common with PEP method 700.? In the optional embodiment of Fig. 9 explaination, PEP method 900 includes that block 91 processes air-flow (m-air-flow 19 in such as) to be formed The air-flow processed.The block 75 of Fig. 7 changes at block 75 ', for separating at least one gas component from the air-flow processed, multiple to be formed Interflow and waste gas stream.At block 92, PEP method 900 includes being separated into combined-flow absorbent stream and recirculation flow.
In embodiments, the 4th kind of PEP method 900 or its part can be through the 5th kind of PEP system 500 (in such as such as Fig. 5 Explained) enforcement.Replace Fig. 3 and 7 embodiment, in the embodiment of Fig. 5 and 9, from process air-flow 41 separate to Few a kind of gas component can produce unreacted monomer-absorbent (such as, ethylene-absorbent) in combined-flow 28.Implementing In mode, separate the ethylene that unreacted monomer-absorbent combined-flow 28 includes that release absorbs, to form recirculation flow 22 and to inhale Receive agent stream 30.In the embodiment of Fig. 5 and 9, separating at least one gas component from the air-flow 26 processed can be at combined-flow 28 Unreacted comonomer-the absorbent of middle generation (such as, butene-1-absorbent).In embodiments, separate in combined-flow 28 Unreacted comonomer-absorbent includes the comonomer that release absorbs, to form recirculation flow 22 and the absorbent of regeneration Stream 30.
In one or more embodiments disclosed herein, purified feed stream (such as, at block 61 or 71) can include Undesired compound and element is separated, to form purified feed stream from the feed stream including ethylene.In embodiments, charging Stream can include ethylene and other gases various, is such as but not limited to methane, ethane, acetylene, propylene, has three or more carbon Other hydrocarbon various of atom, or a combination thereof.In embodiments, purified feed stream can include any suitable method or technique, Filter including non-limitative example, membrane choosing reacts with various chemicals, absorption and sorption, distillation (one or more) or its group Close.
In the embodiment that such as Fig. 1-5 explains, purified feed stream can include sending feed stream 10 to depurator 102.? In one or more embodiments disclosed herein, depurator 102 can include that being suitable to purification includes multiple potential undesired The equipment of one or more reactant gas or device in the feed stream of gaseous compound, element, pollutant or the like.Suitably The non-limitative example of depurator 102 can include filter, film, reactor, absorbent, molecular sieve, one or more distillation Tower or a combination thereof.Depurator 102 can be configured to from including separating ethene following stream: methane, ethane, acetylene, propane, third Alkene, water, oxygen other gaseous hydrocarbons various, various pollutant and/or a combination thereof.
In embodiments, purified feed stream can produce the purified feed 11 including the purest ethylene.Embodiment party In formula, purified feed stream can include less than 25% based on the gross weight of this stream, alternatively, and less than about 10%, alternatively, less than about Nitrogen, oxygen, methane, ethane, propane or a combination thereof of 1.0% any one or more of." the purest second as used herein Alkene " refer to the ethylene that fluid stream includes based on the gross weight of this stream at least about 60%, alternatively, the ethylene of at least about 70%, optional Ground, the ethylene of at least about 80%, alternatively, the ethylene of at least about 90%, alternatively, the ethylene of at least about 95%, alternatively, extremely The ethylene of few about 99%, alternatively, the ethylene of based on the gross weight of this stream at least about 99.5%.In embodiments, feed stream 11 ethane that can farther include trace, such as, by come into question from recirculation flow.
In one or more embodiments disclosed herein, can make feed stream 11, in m-polymerizate stream 15 and in Monomer polymerization in m-polymer flow 17.In one or more embodiments, the monomer making purified feed is polymerized and (such as, exists Block 62 and 72) can include so that by a kind of monomer or various of monomer with antigravity system under conditions of suitably forming polymer Contact polyreaction between multiple monomers.In one or more embodiments disclosed herein, make being total to of purified feed Poly-monomer polymerization (such as, at block 62 and 72) can include so that by a kind of comonomer or multiple comonomer and catalyst system System contacts polyreaction between multiple comonomers under conditions of suitably forming copolymer.Similarly, disclosed herein One or more embodiments in, in making m-polymer flow monomer polymerization (such as, at block 74) can include so that by one Plant monomer or various of monomer contacts under conditions of suitably forming polymer with antigravity system and is polymerized instead between multiple monomers Should.In one or more embodiments disclosed herein, in making, the comonomer of m-polymer flow is polymerized (such as, at block 74) can include so that suitably forming the condition of copolymer by a kind of comonomer or multiple comonomer with antigravity system Lower contact polyreaction between multiple comonomers.The most similarly, in one or more embodiments disclosed herein, In making, the monomer polymerization of m-polymerizate can include so that being suitable to shape by a kind of monomer or various of monomer with antigravity system Polyreaction between multiple monomers is contacted under conditions of becoming polymer.At one or more embodiments disclosed herein In, in making the comonomer polymerization of m-polymerizate can include so that by a kind of comonomer or multiple comonomer with urge Agent system contacts polyreaction between multiple comonomers under conditions of suitably forming copolymer.
In the embodiment that such as Fig. 1-5 is explained, make purified feed monomer polymerization can include send feed stream 11 to One or more polymer reactors or " reactor " 104,106.In the embodiment that such as Fig. 1-2 explains, in making, m-polymerization is produced The monomer polymerization of thing can include m-polymerizate stream 15 to polymer reactor (one or more) 106 in transmission.Such as Fig. 1-2 In the embodiment of explaination, in making, the monomer polymerization of m-polymerizate can include sending from polymer reactor (or many Individual) m-polymerizate stream 15 to polymer reactor (one or more) 106 in 104.At the embodiment explained such as Fig. 3-5 In, m-polymer flow 17 to polymer reactor (or many during the monomer polymerization of m-polymer flow 17 can include sending in making Individual) 106.In the embodiment that such as Fig. 3-5 explains, in making, the monomer polymerization of m-polymer flow 17 can include sending from dividing M-polymer flow 17 to polymer reactor (one or more) 106 in device 105.
In embodiments, any suitable antigravity system can be used.Suitable antigravity system can include catalyst With, optionally, promoter and/or accelerator.The non-limitative example of suitable antigravity system includes that metallocene is urged Agent, Ziegler catalyst, chrome catalysts, chromium oxide catalyst, two chromium catalysts, metallocene catalyst, Raney nickel or A combination thereof.Be suitable to the antigravity system of disclosure use at such as U.S. Patent number 7,619,047 and U.S. Patent application Publication No. 2007/0197374,2009/0004417,2010/0029872,2006/0094590 and 2010/0041842 is retouched Stating, its each piece is integrally incorporated herein with it by quoting.
In one or more embodiments disclosed herein, reactor 104,106 can include following any container or The combination of container, it is suitable to be configured to provide for for monomer in the presence of a catalyst (such as, ethylene) and/or polymer (such as, " active " or growing polymer chain), and optionally chemistry between comonomer (such as, butene-1) and/or copolymer React to produce polymer (such as, polyethylene polymer) and/or the environment (such as, contact area) of copolymer.Although Fig. 1,2 and In 3, the embodiment of explaination illustrates the various PEP systems with two tandem reactors, but reads this area skill of the disclosure Art personnel are it will be recognized that a reactor can be used, alternatively, and any suitable quantity and/or the reactor of structure.
As used herein, term " polymer reactor " or " reactor " include can polymerization of olefin monomers or comonomer To produce homopolymer or any polymer reactor of copolymer.This homopolymer and copolymer are referred to as resin or polymer.Various The reactor of type includes can be described as batch reactor, slurry-phase reactor, Gas-phase reactor, solution reactor, reaction under high pressure Those of device, tubular reactor or autoclave reactor.Gas-phase reactor can include fluidized-bed reactor or classification horizontal reacting Device.Slurry-phase reactor can include vertical or horizontal loop.High-pressure reactor can include autoclave or tubular reactor.Reactor class Type can include method in batches or continuously.Continuation method can use intermittently or serially product withdraw.Method may also comprise unreacted The partially or completely direct recirculation of monomer, unreacted comonomer and/or diluent.
The polymerization reactor system of the disclosure can include a type of reactor in system or identical or different type Multiple reactors.Several rank during the production of polymer can include at least two separation of polymeric reactor in multiple reactors Section, described at least two separation of polymeric reactor is by transfer stream (one or more), pipeline (one or more), device ( Individual or multiple) (such as, separation container (one or more)) and/or equipment (one or more) (such as, valve or other mechanisms) It is connected with each other so that second may be transferred to by the polymer produced in the first polymer reactor (such as, reactor 104) anti- Answer device (such as, reactor 106).Desired polymerizing condition in one reactor likely differs from the operation bar of other reactors Part.Alternatively, the polymerization in multiple reactors can include, from a reactor manual transfer polymer to reactor subsequently, using In continuing polymerization.Multiple reactor assemblies can include any combination, and it includes but not limited to multiple loop reactor, multiple gas The combination of reactor, loop and gas reactor, multiple high-pressure reactor or high pressure and loop and/or the group of gas reactor Close.Multiple reactors can be operated in parallel or in series.
In such as Fig. 1-5 in the embodiment of explaination, multiple reactors produce polymer and can include that at least two is polymerized Reactor 104,106, it passes through one or more equipment or device (such as, valve, continuous delivery valve (take-off valve) And/or continuous output machine structure) be connected with each other.In such as Fig. 1-2 in the embodiment of explaination, multiple reactors produce polymer Can include at least two polymer reactor 104,106, it is by one or more streams or pipeline (m-polymerizate stream in such as, 15) it is connected with each other.In the embodiment explained in such as Fig. 3-5, multiple reactors produce polymer and can include at least two Individual polymer reactor 104,106, it passes through one or more separators (such as, separator 105 and/or separator 126) through two Individual or more stream (in such as, m-polymerizate stream 15 and in m-polymer flow 17) is connected with each other.
According to an aspect, polymerization reactor system can include that at least one includes the loop slurry of vertical or horizontal loop Reactor.Monomer, diluent, catalyst and the most any comonomer can continuous feed to wherein occur polymerization loop anti- Answer device.It is said that in general, continuation method can include monomer, optional comonomer, catalyst and diluent are continually introduced into polymerization Reactor and be continuously removed the suspension including polymer beads and diluent from this reactor.Reactor effluent can be dodged Steam, to remove solid polymer from the liquid including diluent, monomer and/or comonomer.Various technology can be used for this point From step, including but not limited to flash distillation, it can include heating and any combination of decompression;By cyclone separator or rotary filter press The separation of whirlwind effect in device;Or by centrifugal separation.
In one or more embodiments, comonomer can include the unsaturated hydrocarbons with 3 to 12 carbon atoms.Example As, comonomer can include propylene, butene-1, hexene-1, octene or a combination thereof.
Such as, at U.S. Patent number 3,248,179,4,501,885,5,565,175,5,575,979,6,239,235,6, 262,191 and 6, disclose typical slurry phase polymerisation process (also referred to as method for forming particles) in 833,415, its each piece passes through Quote and be integrally incorporated herein with it.
In one or more embodiments, the suitable diluent used in slurry polymerization includes but not limited to be polymerized Monomer, and optionally comonomer, and be the hydrocarbon of liquid at reaction conditions.The example of suitable monomer diluent include but It is not limited to hydrocarbon such as propane, hexamethylene, iso-butane, normal butane, pentane, isopentane, neopentane and normal hexane.At embodiment In, comonomer diluent can include the unsaturated hydrocarbons with 3 to 12 carbon atoms.The example of suitable comonomer diluent Include, but are not limited to propylene, butene-1, hexene-1, octene or a combination thereof.The reaction of some Loop Polymerizations can the most not use Carry out under the bulk conditions of diluent.One example is the polymerization of propylene monomer, such as U.S. Patent number 5, disclosed in 455,314 , it is integrally incorporated herein with it by quoting.
According to still on the other hand, polymer reactor can include at least one Gas-phase reactor.This type of system can use continuously Recirculation flow, it comprises one or more being continuously circulated through fluid bed the most in the presence of a catalyst Monomer.Recirculation flow can be fetched from fluid bed and be recycled back into reactor.Meanwhile, polymer product can be fetched from reactor And new or fresh monomer can be added, to replace the monomer of polymerization.Similarly, optionally copolymer is fetched from reactor Product and can add new or fresh comonomer, to replace comonomer, the monomer of polymerization or a combination thereof of polymerization.This Kind of Gas-phase reactor can include the method for alkene multistep gas-phase polymerization, wherein alkene with gas phase at the gas of at least two independence Phase-polymerization district is polymerized, feeds the polymer comprising catalyst formed in the first polymeric area to the second polymeric area simultaneously.Beautiful State's patent No. 5,352,749,4588,790 and 5, discloses a type of Gas-phase reactor in 436,304, its each piece leads to Cross to quote and be integrally incorporated herein with it.
According to still on the other hand, reactors for high pressure polymerisation can include tubular reactor or autoclave reactor.Tubular reactor Device can have several district, wherein can add fresh monomer (optionally, comonomer), initiator or catalyst.Monomer is (optionally Ground, comonomer) can be entrained in inert gas and introduce in a district of reactor.Initiator, catalyst and/or catalysis Agent component can carry secretly in the gas flow and introduce in another district of reactor.Air-flow can be mixed for polymerization.Can suitably adopt By heat with pressure to obtain optimum polymerizating reacting condition.
According to still on the other hand, polymer reactor can include solution polymerization reactor, wherein monomer (optionally, copolymerization list Body) can be contacted with carbon monoxide-olefin polymeric by suitable stirring or other means.Can use and include inert organic diluent or mistake The carrier of amount monomer (optionally, comonomer).If so desired, in the case of presence or absence fluent material, monomer and/ Or optional comonomer can contact with catalytic reaction products in the gas phase.Polymeric area is maintained at so that being formed in reaction medium Under the temperature and pressure of polymer solution.Agitation can be used to obtain the control of more preferable temperature and to maintain uniformly throughout polymeric area Polyblend.Suitable means are used for dissipating polymerization exotherm.
The polymer reactor of the system and method being suitable to the disclosure can farther include following any combination: at least one is former Material feed system, catalyst or at least one feed system of catalytic component and/or at least one polymer recovery system. Suitable reactor assembly can farther include for following system: purification of raw materials, catalyst storage and preparation, extrusion, anti- Answer device cooling, polymer recovery, fractional distillation, recirculation, storage, discharging, lab analysis and process control.
Control for polymerization efficiency and provide the condition of resin properties to include temperature, pressure and the concentration of various reactant. Polymerization temperature can affect catalyst production, polymer molecular weight and molecular weight distribution.Suitable polymerization temperature can be less than root Any temperature according to the temperature that depolymerizes of Gibbs Free energy equation.Generally this includes from about 60 DEG C to about 280 DEG C, such as, and From about 70 DEG C to about 110 DEG C, this depends on the type of polymer reactor.
Suitable pressure also will change according to reactor and polymeric type.The pressure of liquid phase polymerization in loop reactor Power is typically smaller than 1000psig.For the pressure of gas-phase polymerization generally at about 200 500psig.In tubulose or autoclave reactor High pressure polymerisation typically carry out under about 20,000 to 75,000psig.Polymer reactor also can be in general higher temperature and pressure The critical zone occurred under power operates.On the critical point of Pressure/Temperature figure, the operation of (supercritical phase) can provide advantage.? In embodiment, polymerization can occur in the environment with suitable temperature and pressure combination.Such as, polymerization can be in scope from about 550psi is to about 650psi, alternatively, with scope from about 170 to about 230 under the pressure of about 600psi to about 625psi, and can Selection of land, from about 195 to about 220 at a temperature of carry out.
The concentration of various reactant can be controlled to produce the resin with some Physical and mechanical properties of polyoropylene.Recommend by tree The whole purposes product that the method for fat and this product of formation is formed determines desired resin properties.Engineering properties include stretching, curved Song, impact, creep, stress relaxation and hardness test.Physical property include density, molecular weight, molecular weight distribution, melting temperature, Glass transition temperature, the melting temperature (temperature melt of crystallization) of crystallization, density, solid Stereoregularity, crack growth, long chain branching and rheology measurement value.
The concentration of monomer, comonomer, hydrogen, promoter, modifying agent and electron donor and/or dividing potential drop are for producing these Resin properties is important.Comonomer can be used for controlling product density.Hydrogen can be used for controlling molecular weight of product.Promoter can For alkylation, remove poisonous substance and control molecular weight.Modifying agent can be used for controlling product characteristics and influenced By Electron Donors is three-dimensional Stereoregularity, molecular weight distribution or molecular weight.It addition, because poisonous substance impact reaction and product characteristics, make the concentration of poisonous substance minimize.
In embodiments, can to include that suitable antigravity system is introduced first and/or second respectively anti-for polymerization monomer Answer device 104,106, in order to form slurry.Alternatively, suitable antigravity system can residue in the first and/or second reaction respectively In device 104,106.
As explained above, polymerization monomer can include that selectivity manipulates one or more polymeric reaction conditions, given to produce Polymer product, with produce have one or more desirable properties polymer product, with realize desired efficiency, with realize Desired productivity etc. or a combination thereof.The non-limitative example of this parameter includes the class of temperature, pressure, catalyst or promoter Type and/or amount and the concentration of various reactant and/or dividing potential drop.In embodiments, the monomer polymerization making purified feed 52 can be wrapped Include the one or more polymeric reaction conditions of adjustment.In embodiments, polymerization monomer can include vinyl monomer and/or copolymerization list Body such as butylene adds to polymer reactor 106.
In embodiments, polymerization monomer keeps suitable temperature, pressure and/or dividing potential drop during may be included in polyreaction (one or more), alternatively in a series of suitable temperature, pressure and/or dividing potential drop (one or more) during polyreaction Between circulate.
In embodiments, polymerization monomer can include introducing the hydrogen into one or more reactor 104 and 106.Such as, Fig. 1 Reactor 106 can be introduced to by stream 21 with 2 explaination hydrogen.Adjustable introduces the amount of the hydrogen of reactor 106 to obtain in dilution In agent, hydrogen is 0.001 to 0.1 with the mol ratio of ethylene.This mol ratio can be at least 0.004 in reactor 106.Implementing In mode, this mol ratio can be less than 0.05.In the diluent of reactor 104, the concentration of hydrogen is dense with the hydrogen of polymer reactor 106 The ratio of degree can be at least 20, alternatively, at least 30, alternatively, at least 40, alternatively, no more than 300, alternatively, is not more than 200.At U.S. Patent number 6, disclosing suitable hydrogen concentration control method and system in 225,421, it is incorporated by reference into this Literary composition.
In embodiments, polymerization monomer can include monomer (optionally, comonomer), antigravity system and/or slurry In reactor 104,106 and/or between circulate, flow, operate, mix, stir or a combination thereof.Monomer is (optionally, wherein Comonomer), in the embodiment that circulated of antigravity system and/or slurry, the speed (such as, slurry rate) of circulation can be From about 1m/s to about 30m/s, alternatively, from about 2m/s to about 17m/s, alternatively, from about 3m/s to about 15m/s.
In embodiments, polymerization monomer can include configuring reactor 104,106, multi-modal (such as, bimodal to produce ) polymer (such as, polyethylene).Such as, resulting polymers can include relatively high molecular weight, low-density (HMWLD) polyethylene Polymer and relatively low molecular weight, high density (LMWHD) polyethylene polymer.Such as, various types of suitable polymer can It is characterized as that there is various density.Such as, I type may be characterized as having scope from about 0.910g/cm3To about 0.925g/cm3Density, Alternatively, II type may be characterized as having from about 0.926g/cm3To about 0.940g/cm3Density, alternatively, type III may be characterized as Have from about 0.941g/cm3To about 0.959g/cm3Density, alternatively, IV type may be characterized as having greater than about 0.960g/cm3 Density.
In embodiments, polymerization monomer can include making comonomer at one or more polymer reactors 104, in 106 Polymerization.
In the embodiment explained in figs. 1-5, m-polymerizate stream 15 in making the monomer polymerization of purified feed to produce And/or polymerizate stream 12.In this m-polymerizate stream 15 and/or polymerizate stream 12 can generally comprise various solid, half Solid, volatility and non-volatile liquid, gas and a combination thereof.In embodiments, m-polymerizate stream 15 and/or poly-in Close product stream 12 can include hydrogen, nitrogen, methane, ethylene, ethane, propylene, propane, butane, iso-butane, pentane, hexane, hexene-1 and Heavy hydrocarbon.In embodiments, the scope that ethylene exists can be from about 0.1% to about 15% based on the gross weight of stream, alternatively, from about 1.5% to about 5%, alternatively, about 2% to about 4%.Ethane exist scope by stream gross weight based on can from about 0.001% to About 4%, alternatively, from about 0.2% to about 0.5%.The scope that iso-butane exists can be from about 80% to about based on the gross weight of stream 98%, alternatively, from about 92% to about 96%, alternatively, about 95%.
Solid and/or liquid can include polymer product (such as, polyethylene polymer), lead in this stage of PEP method It is frequently referred to " polymer fluff (fluff) ".Gas can include unreacted, gas reactant monomer or optional comonomer (such as, unreacted vinyl monomer, unreacted butene-1 monomer), off-gas product, gaseous contaminant or a combination thereof.
In one or more embodiments disclosed herein, polymerizate is separated into polymer flow and air-flow (example As, at block 63) can generally comprise and be appointed from liquid and/or solid (such as, polymer fluff) removal by any suitable method What gas.
In the embodiment that such as Fig. 1-2 explains, polymerizate is separated into polymer flow and air-flow can include that transmission is poly- Close product stream 12 to separator 108.
In embodiments, air-flow 18 can include hydrogen, nitrogen, methane, ethylene, ethane, propylene, propane, butane, iso-butane, Pentane, hexane, hexene-1 and heavy hydrocarbon.In embodiments, ethylene exist scope by stream gross weight based on can from about 0.1% to About 15%, alternatively, from about 1.5% to about 5%, alternatively, about 2% to about 4%.The scope that ethane exists is by the gross weight of stream Meter can be from about 0.001% to about 4%, alternatively, from about 0.2% to about 0.5%.The scope that iso-butane exists is by the gross weight of stream Meter can be from about 80% to about 98%, alternatively, from about 92% to about 96%, alternatively, and about 95%.
In one or more embodiments, by m-polymerizate be separated in m-polymer and in m-air-flow (example As, at block 73) can generally comprise and be appointed from liquid and/or solid (such as, polymer fluff) removal by any suitable method What gas.
In the embodiment explained in such as Fig. 3 and 5, by m-polymerizate be separated in m-polymer flow and in M-air-flow can complete in separating in including sending in the single step of m-polymerizate stream 15 to separator 105.
In embodiment as illustrated in fig. 3, by m-polymerizate be separated in m-polymer flow and in m- Air-flow can include that the most m-polymerizate stream 15 separates at least one gas component.The most m-polymerizate stream 15 separates at least A kind of gas component in can producing m-air-flow 19 and in m-polymer flow 17.In m-polymerizate stream 15 can include hydrogen, second Alkene, ethane, polymer, iso-butane or a combination thereof.In m-air-flow 19 can include hydrogen, ethylene, ethane or a combination thereof.In m-polymerization Logistics 17 can include polymer, iso-butane or a combination thereof.
In embodiment as illustrated in fig. 3, by m-polymerizate be separated in m-polymer flow and in m- Air-flow can include reducing in the pressure of m-polymerizate so that flash distillation ethylene, hydrogen, ethane or a combination thereof.In m-polymerizate stream 15 can include hydrogen, ethylene, ethane, polymer, iso-butane or a combination thereof.Separator 105 can produce pressure to be reduced, thus ethylene, Hydrogen polymerizate the most m-with ethane separates or flash distillation, in order to produces and includes m-air-flow 19 in hydrogen, ethylene and ethane.
In the embodiment explained in such as Fig. 5, by m-polymerizate be separated in m-polymer flow and in m- Air-flow introduces scavenger before may be included in reactor 106.In embodiments, scavenger can reduce the dense of component such as hydrogen Degree.The embodiment display stream 35 of Fig. 3 and 5 explaination can before reactor 106 in such as m-polymerizate stream 15 introduce. Alternatively, stream 35 can introduce separator 105 or in m-polymer flow 17.Stream 35 can include scavenger.In embodiments, Scavenger can include catalyst.In embodiments, catalyst can include hydrogenation catalyst.Undesirably it is limited by theory, clearly Except agent can be used for consuming hydrogen, to form ethane, it is possible to decrease hydrogen concentration is even to zero-dose.In embodiments, hydrogenation catalyst Polymerization for polyethylene can have low activity.Hydrogenation catalyst can include the metallocene catalyst of following formula:
Cp2MXn
Wherein Cp is substituted cyclopentadienyl group;M is the transition metal of the periodic table of elements Group IVB from vanadium;X is halogen Element or there is the alkyl of 1 to 10 carbon atom;And n is that the quantivalence of metal M subtracts 2.In embodiments, metallocene catalyst Cp can be included2TiCl2, also referred to as cyclopentadienyl titanium dichloride.The amount that metallocene catalyst can introduce is lazy in m-polymerizate stream 15 in pressing The weight meter of property diluent can be 2 to 50ppm, alternatively, and 2 to 20ppm.
In the embodiment explained in such as Fig. 5, before the second polymer reactor 106, reduce hydrogen in stream by scavenger Concentration can improve polymer production ability, such as, compared with in polymer reactor 104, can produce in polymer reactor 106 Raw relative higher molecular weight polymer.Such as, wherein in expected response device 106 relative to the embodiment party of higher molecular weight polymer In formula, generally without extra hydrogen to reactor 106, because the hydrogen concentration increased in reactor 106 is generally higher to producing Polydispersity polymer is harmful to.The most not introducing hydrogen, hydrogenation catalyst can introduce in reactor 106 or at reactor Introduced before 106.The embodiment display hydrogenation catalyst of Fig. 3 and 5 explaination can be with stream 35 introducing before reactor 106.? In one or more embodiments, the polymer of generation can include polyethylene.In this embodiment, ziegler-natta catalyzed Agent can be used as polymerization catalyst, and can include metallocene catalyst by the hydrogenation catalyst of stream 35 introducing.The cyclopentadienyl gold used The amount of metal catalyst may be such that metallocene catalyst and Ziegler-Natta catalyst mass ratio (that is, g metallocene/neat lattice of g Le-Baunatal) scope can be from about 0.1 to about 2.0, preferably from about 0.25 to about 1.5, the most about 0.5-1.0.In reality Executing in mode, metallocene catalyst can include the metallocene of non-bridging.In embodiments, the metallocene of non-bridging can include two Double (cyclopentadienyl group) titanium of chlorination, also referred to as cyclopentadienyl titanium dichloride.U.S. Patent number 6,730,751,6,221,982 and 6,291, Disclosing suitable hydrogenation catalyst in 601, it is expressly incorporated herein by reference.
In the embodiment explained in such as Fig. 5, by m-polymerizate be separated in m-polymer flow and in m- Air-flow can farther include the most m-at least one gas component of polymerizate flow separation.In this embodiment, separation is entered In device 105 m-polymerizate stream 15 can include unreacted hydrogen, unconverted ethylene, ethane, polymer, iso-butane or its Combination.In m-air-flow 19 can include hydrogen, ethylene, ethane or a combination thereof;In and, m-polymer flow 17 can include polymer, different Butane or a combination thereof.In in m-air-flow 19 amount of ethane can be more than unreacted hydrogen and/or the amount of unconverted ethylene.
In the embodiment explained in such as Fig. 4, by m-polymerizate be separated in m-polymer flow and in m- Air-flow (such as, at block 73) can in including sending m-polymerizate stream 15 to separator 126 and sending from separator Two steps of product stream 39 to the separator 105 that the hydrogen of 126 reduces realize in separating.
In the embodiment explained in such as Fig. 4, by m-polymerizate be separated in m-polymer flow and in m- Air-flow can include making from least some of hydrogen degassing of m-polymerizate.Embodiment display separation device such as Fig. 4 explaination 126 can produce stream 37 and 39.Stream 37 can include the hydrogen of removal, and flow 39 and can include the product that hydrogen reduces.Separator 126 can make In from, at least some of hydrogen of m-polymerizate stream 15 is through decompression degassing.Decompression can be less than or equal in reactor 104 Polymerization temperature, alternatively, more than 20 DEG C, alternatively, occurs at a temperature of at least 40 DEG C.Decompression can be less than in reactor 104 Occur under the pressure of pressure.Decompression is smaller than 1.5MPa.Decompression can be at least 0.1MPa.The stream 39 that in Fig. 4, hydrogen reduces remains The amount of hydrogen based on the weight in the amount of the hydrogen being initially present from the mixture that reactor 104 reclaims, be smaller than 1%, optional Ground, by weight less than 0.5%, alternatively, 0wt% by weight.U.S. Patent number 6,225,412 discloses suitable degassing Condition and device, it is incorporated herein by.
In the embodiment explained in such as Fig. 4, by m-polymerizate be separated in m-polymer flow and in m- The product stream that air-flow can farther include from hydrogen reduces separates at least one gas component.In this embodiment, entrance point The product stream 39 reduced from the hydrogen of device 105 can include hydrogen, ethylene, ethane, polymer, iso-butane or a combination thereof.In m-air-flow 19 Hydrogen, ethylene, ethane or a combination thereof can be included;In and, m-polymer flow 17 can include polymer, iso-butane or a combination thereof.Fig. 4 In present in m-air-flow 19 amount of hydrogen by the weight of the amount at the hydrogen being initially present from the mixture that reactor 104 reclaims Gauge is smaller than 1%, alternatively, by weight less than 0.5%, alternatively, and 0wt% by weight.
In one or more embodiments disclosed herein, separator 105,108 and 126 can be configured to stream (example As, the product that the polymerizate that including polymerizate m-in polyethylene, includes polyethylene, the hydrogen including polyethylene reduce) point From becoming gas, liquid, solid or a combination thereof.Product stream 12,15 and 39 can include unreacted, gaseous monomer or optional copolymerization Monomer (such as, unreacted vinyl monomer, unreacted butene-1 monomer), off-gas product and/or gaseous contaminant.? As in the embodiment explained in Fig. 4, in m-polymerizate stream 15 can include hydrogen.The embodiment of explaination in such as Fig. 1-2 In, polymerizate stream 12 can include hydrogen.As used herein, " unreacted monomer ", such as, ethylene, during referring to polyreaction It is introduced into polymer reactor but is not incorporated to the monomer of polymer.As used herein, " unreacted comonomer ", example As, butene-1, introduce polymer reactor during referring to polyreaction but be not incorporated to the comonomer of polymer.
In embodiments, separator 105,108 and/or 126 can include gas-liquid separator.This separator suitable Example can include distillation column, flash tank, filter, film, reactor, absorbent, adsorbent, molecular sieve or a combination thereof.Implementing In mode, separator includes flash tank.Undesirably be limited by theory, this flash tank can include being configured to from high temperature and/or High-pressure fluid evaporates and/or removes the container of low vapor pressure component.Separator 105,108 and/or 126 may be configured so that entrance Stream is separable into liquid stream (such as, condensate flow) and gas (such as, steam) stream.Liquid or condensate flow can include product (such as, polyethylene, commonly referred to " polymer fluff ").Gas or steam stream can include volatile solvent, gaseous state, unreacted Monomer and/or optional comonomer, waste gas (secondary response product, such as pollutant etc.), or a combination thereof.Separator 105, 108 and 126 may be configured so that feed stream passes through heating, decompression or the two flash distillation so that the enthalpy of stream increases.This can heater via, Flash line heater, other operations various commonly known in the art or a combination thereof realize.Such as, including two-tube flash pipe Line heater can pass through hot water or steam heat-exchanging.This flash line heater can increase the temperature of stream and reduce its pressure simultaneously.
In one or more embodiments, in polymerizate being separated into polymer flow and air-flow or inciting somebody to action, m-polymerization is produced Thing in being separated into m-polymer flow and in m-air-flow can include making polymerizate distillation, evaporation, flash distillation, filtration, membrane choosing, suction Receive, adsorb or a combination thereof.In the embodiment of Fig. 1-2 explaination, polymerizate is separated into polymer flow gentle miscarriage anger Stream 18 and polymer flow 14.Fig. 3-5 explaination embodiment in, by m-polymerizate be separated in m-polymer flow and In m-air-flow produce in m-air-flow 19 and in m-polymer flow 17.
In one or more embodiments disclosed herein, process polymer flow (such as, at block 64) and include any Suitable method or serial of methods, it is configured to production and may be adapted to business or industrial application, stores, transports, processes further Or the polymer product of a combination thereof.
In the embodiment that such as Fig. 1-2 explains, process polymer flow and can include sending polymer flow 14 to processor 110.Processor 110 is configurable to perform suitable process means, and its non-limitative example includes cooling down, is molded, melts, makes Grain, blowing, extrusion molding, rotational molding, thermoforming, cast molding, similar means or a combination thereof.Various additives and modifying agent May be added to that polymer, to provide preferably process and the desirable properties for end-product during manufacture.This additive Non-limitative example can include surface modifier such as slip agent, anti-caking agent, viscosifier;Antioxidant is such as primary with two Level antioxidant;Pigment;Processing aid such as paraffin/oil and fluoroelastomer;With specialist additive such as fire retardant, antistatic Agent, scavenger, absorbent, odor enhancers and degradation agent.
In embodiments, processor 110 can be configured to form suitable polymer product.May originate from the suitable of this process When the non-limitative example of polymer product include thin film, powder, bead, resin, liquid or any other art technology Personnel it will be recognized that suitable form.This suitable output can be used for such as one or more different consumer products or industry and produces Thing.Such as, polymer product may utilize any one or more of different goods, includes but not limited to bottle, drum, object for appreciation Tool, household receptacle, utensil, film product, drum, fuel tank, pipe, geomembrane (geomembrane) and lining.Specifically Embodiment in, processor be configured to formed bead, for transport to consumer product manufacturers.Such as, in Fig. 1-2 explaination In embodiment, process polymer flow and produce polymer product 16 (such as, the polyethylene of granulating).
In one or more embodiments disclosed herein, m-gas in processing air-flow (such as, at block 81) and processing Stream (such as, at block 91) can include for from air-flow go deoxygenation, oxygen containing (oxygenated) compound, the compound of oxidation or Any suitable method of a combination thereof (being herein collectively referred to as " oxygen ") or reaction.The those skilled in the art reading the disclosure will recognize that To suitable method or reaction.For going the non-limitative example of the proper method of deoxygenation to include, various catalytic reaction is with known The chemical species reacted with oxygen contacts, filters, absorption and sorption, heat, cool down or a combination thereof.
In the embodiment that such as Fig. 2 explains, process air-flow and can include sending air-flow 18 to degasifier 118.Explain at such as Fig. 5 In the embodiment released, m-air-flow 19 to degasifier 118 during m-air-flow can include sending in process.
In one or more embodiments disclosed herein, degasifier 118 can include being configured to go deoxygenation from air-flow Equipment or device.The non-limitative example of suitable degasifier includes various reactor (such as, fluidized-bed reactor or fixing Bed), filter or a combination thereof.Suitable degasifier 118 can be configured to reduce, prevent from or get rid of to have making lyosoption be poisoned The compound of effect and/or element (such as, oxygen) avoid arriving absorption reactor (such as, as herein by disclosed).
In the embodiment of Fig. 2 explaination, process air-flow and produce the air-flow 26 of the process being substantially free of oxygen.Explain at Fig. 5 In the embodiment released, in process, m-air-flow produces the air-flow 41 of the process being substantially free of oxygen.As used herein " basic On the most oxygen-containing " refer to fluid stream to include based on the gross weight of stream to be not more than at least about 5% oxygen, alternatively, no more than about 1% Oxygen, alternatively, the oxygen of no more than about 0.1%, alternatively, the oxygen of no more than about 0.01%.
In one or more embodiments disclosed herein, it is referred to as gas from the air-flow of air-flow and/or process At least one gas component of flow separation (such as, at block 65,65 ', 75 or 75 ') generally comprises from including the first chemical constituent Or Selective Separation at least the first chemical constituent or change in the stream of compound and one or more other chemical constituent, compounds etc. Any suitable method of compound.In various embodiments, the gas component separated from air-flow can include one or more hydrocarbon. The non-limitative example of this hydrocarbon includes alkane (such as, ethane, butane, iso-butane, hexane or a combination thereof) and alkene or alkene list Body (such as, ethylene, hexane or a combination thereof) or optional comonomer (such as, butene-1).In embodiments, divide from air-flow From gas component can include unreacted hydrocarbon monomer, such as ethylene.Optionally, the gas component separated from air-flow can include not The hydrocarbon comonomer of reaction, such as propylene.In embodiments, the gas component separated from air-flow can include unreacted hydrocarbon list Body (such as, ethylene, individually or combine with other hydrocarbon, such as, ethane, iso-butane, hexane or a combination thereof), or optionally hydrocarbon copolymerization Monomer (such as, propylene, individually or combine with other hydrocarbon, such as, iso-butane, hexane or a combination thereof).In embodiments, from gas The gas component of flow separation can include ethylene, individually or with iso-butane combines.In embodiments, capture iso-butane can make joint The cost of the iso-butane about captured and reduce the amount of iso-butane in flare discharge.The non-limiting example of suitable separation means Attached bag includes distillation, evaporation, flash distillation, filtration, membrane choosing, absorption and sorption, MW exclusion, size exclusion, separation based on polarity Or a combination thereof.
In embodiments, separate at least one gas component from air-flow and may be included in distillation air-flow (example a step As, the air-flow 18 of Fig. 1, the air-flow 26 of the process of Fig. 2), in order to make at least one gas component according to the temperature (of boiling Or multiple) separate with other gas components.In this embodiment, from air-flow separate at least one gas component can include by Airflow distillation becomes to include the lightweight hydrocarbon stream of ethylene, ethane, optionally hydrogen or a combination thereof.In this embodiment, divide from air-flow May be included in from least one gas component and base product effluent is collected hexane, hexene, optionally iso-butane or a combination thereof. In other and/or optional embodiment, separate at least one gas component from air-flow and can include the effluent from distillation column Collect iso-butane.
In the embodiment of the system 100 shown in FIG, distillation column 122 may be configured to separated at least Plant gas component.Air-flow 18 can be communicated to distillation column 122, and air-flow 18 can include the non-of the polymerizate stream 12 for steam phase Solid constituent (such as, nitrogen, methane, ethylene, ethane, propylene, propane, butane, iso-butane, pentane, hexane, hexene-1, heavy hydrocarbon or A combination thereof).Air-flow 18 optionally includes hydrogen, and it can be removed in such as separator between two polymer reactors or pass through Hydrogenation catalyst in polymer reactor (one or more) is removed.At least one gas component can be from distillation column 122 with lightweight Hydrocarbon stream 25 sends, and other gas components can send with base product effluent 23 from distillation column 122.At Fig. 1 from distillation column 122 at least one gas component sent with lightweight hydrocarbon stream 25 can include ethylene and can farther include other light gases (such as, Ethylene, ethane, methane, carbon dioxide, nitrogen, hydrogen or a combination thereof).Such as, lightweight hydrocarbon stream 25 exists the amount of ethylene by light hydrocarbon The gross weight meter of stream 25 can be from about 50% to about 99%, alternatively from about 60% to about 98%, alternatively, from about 70% to about 95%.Other gas components sent with base product effluent 23 from distillation column 122 can include propylene, propane, butane, isobutyl Alkane, pentane, hexane, hexene-1, heavy hydrocarbon or a combination thereof.In embodiments, base product effluent 23 can be free of alkene, optional Ground, is substantially free of alkene, alternatively, and the most not olefin-containing.Such as, the amount of alkene present in base product effluent 23 About 1.0%, alternatively, less than about 0.5% it is smaller than, alternatively, less than about based on the gross weight of base product effluent 23 0.1%.In embodiments, the effluent 27 including iso-butane can send with effluent 27 from distillation column 122.
In such as Fig. 1 in the embodiment of explaination, effluent 27 or at least some of base product effluent 23 can be followed again Ring.Recirculation effluent 27 or at least some of base product effluent 23 can include, such as, through suitable pump or compressor, send out Effluent 27 or at least some of base product effluent 23 is sent to return PEP system 100 and/or by effluent 27 or steam at least partially Evaporate bottom stream 23 and introduce PEP system 100, such as, for reusing in the polymerization.In embodiments, effluent 27 or at least some of base product effluents 23 can be in conjunction with various other components (catalyst, promoter etc.), can with formation It is introduced to the catalyst slurry of one or more reactor 104,106.It is not intended to be limited by theory, because effluent 27 or at least Part base product effluent 23 can include not olefin-containing isobutane stream (alternatively, be substantially free of alkene, disclosed above ), effluent 27 or at least some of base product effluent 23 can mix with catalyst component (such as, catalyst, promoter etc.) Close and there is no the risk (such as, at the pre-polymerization introducing one or more reactors) of unexpected polyreaction.So, effluent 27 Or base product effluent 23 can be used as the iso-butane source of not olefin-containing at least partially, for polyreaction.Make effluent 27 Or base product effluent 23 (including the iso-butane of not olefin-containing) recirculation can provide effective and/or cost at least partially Effective supply iso-butane is for the means of polymerisation process operation.In alternative embodiments, can send effluent 27 or At least some of base product effluent 23 is to store for using the most in the polymerization or in any other suitable side Method uses.
In embodiments, at least some of effluent 27 or at least some of base product effluent 23 can return to distillation column 122.Such as, effluent 27 or at least some of base product effluent 23 to distillation column 122 can be sent through reboiler, for additionally Process.
Distillation column 122 can be configured to and/or be dimensioned to provide gas (such as, the lightweight hydrocarbon stream of Fig. 1 of proper volume 25) separation.Such as, distillation column 122 can be alternatively, from about 40 DEG C to about 10 DEG C, optional in scope from about 50 DEG C to about 20 DEG C Ground, from about 30 to about 5 DEG C at a temperature of, and in scope from about 14.7psia to about 529.7psia, alternatively, from about 15.7psia is to about 348psia, alternatively, operates to the pressure of about 290psia from about 85psia.Distillation column 122 can configure For and/or be designed and sized to the separation of air-flow (such as, the stream 26 of Fig. 2) air-flow 18 of proper volume being provided or processing.Such as this Skilled person is it will be realized that air-flow 18 (optionally, the air-flow of process) can retain and/or remain in distillation column 122 Any reasonable time amount, as provided enough air-flow 18 (optionally, the air-flow of process) Component seperation required.Implementing In mode, distillation column 122 can be equipped with at least two outlet.
In embodiments, distillation column 122 is configurable and/or operates so that the lightweight hydrocarbon stream 25 of Fig. 1, optional effluent 27 and base product effluent 23 each component including air-flow 18 (optionally, the air-flow of process) desired part, Number or subset.Such as, as it would be recognized by those skilled in the art that with the help of the disclosure, concrete inflow entrance or outlet Position, the operating parameter of distillation column 122, the composition of air-flow 18 (optionally, the air-flow of process), or a combination thereof can be manipulated so that Given stream can include concrete one or more components of air-flow 18 (optionally, the air-flow of process).
In alternative embodiments, separate at least one gas component from air-flow and may be included in distillation gas two steps Stream (such as, air-flow 18 or the air-flow 26 of process), in order at least one gas component and other gases in making to separate first Component according to boiling temperature (one or more) separate, and so that second separate at least another gas component and other Gas component separates according to boiling temperature (is each or multiple).In this embodiment, first separate in from air-flow separate to Few a kind of gas component can include making airflow distillation, and with hydrocarbon stream in the middle of being formed, it includes ethylene, ethane, hydrogen, iso-butane or its group Close.In this embodiment, separate, from air-flow, the distillation column that at least one gas component may be included in the distillation column of the first separation Bottom effluent is collected hexane, optionally hexene or a combination thereof.It addition, separate at least one gas from air-flow in separating second Component can include making ethylene, ethane, optionally hydrogen or a combination thereof distill from middle hydrocarbon stream;In the second distillation column underflow separated Go out collection hexane, optionally hexene, optionally iso-butane or a combination thereof in thing;Optionally from the side of the second distillation column separated Stream collects iso-butane.
In the embodiment of the system 200 shown at Fig. 2, distillation column 126 and 124 can be configured to from the air-flow 26 processed or Air-flow 18 separates at least one gas component.The air-flow 26 and the air-flow 18 that process can include the polymerizate stream 12 with steam phase Non-solid component (such as, nitrogen, methane, ethylene, ethane, propylene, propane, butane, iso-butane, pentane, hexane, hexene-1, heavy hydrocarbon Or a combination thereof).The air-flow 26 and the air-flow 18 that process optionally include hydrogen, and it can such as dividing between two polymer reactors Remove in device or removed by the dehydrogenation of polymer reactor (one or more).The air-flow 26 or the air-flow 18 that process can It is distilled, with hydrocarbon stream 29 in the middle of being formed.Non-distillation component in distillation column 126 can be from distillation column 126 with base product effluent 43 send.Effluent 45 optionally sends from distillation column 126.
Middle hydrocarbon stream 29 may be characterized as including following, alternatively, consists essentially of following, alternatively, substantially by following Composition, alternatively, is made up of following: C4Lighter hydrocarbon (such as, butane, iso-butane, propane, ethane or methane) and any gently Gas (such as, hydrogen or nitrogen).Such as, C4Lighter hydrocarbon and gas is total by middle hydrocarbon stream of amount present in the middle hydrocarbon stream 29 Weight meter can be from about 80% to about 100%, alternatively from about 90% to about 99.999999%, alternatively from about 99% to about 99.9999%, alternatively, C5With heavy hydrocarbon measure present in middle hydrocarbon stream 29 based on the gross weight of middle hydrocarbon stream can from 0% to About 20%, alternatively from about 10% to about 0.000001%, alternatively from about 1.0% to about 0.0001%.The most such as, by processing Air-flow 26 or the weight meter at least 90% of air-flow 18, alternatively, at least 98%, alternatively, the C of at least 99%4Lighter Hydrocarbon and gas may be present in middle hydrocarbon stream 29.
In embodiments, base product effluent 43 may be characterized as including C6Heavier component such as alkane, i.e. big Alkane (such as, heptane and/or other big alkane) in hexane.In embodiments, C6Hydrocarbon outside more heavy paraffin hydrocarbon is pressed The gross weight meter of base product effluent 43 can be with less than about 15%, alternatively, and less than about 10%, alternatively, less than about 5% Amount be present in base product effluent 43.In embodiments, base product effluent 43 can be guided to other place Reason step or method, or they can be appropriately processed alternatively.In embodiments, base product effluent 43 can be drawn It is directed at torch for disposing.
In embodiments, effluent 45 may be characterized as including hexene.Such as, hexene can be from based on the gross weight of effluent 45 The amount of about 20% to about 98% is present in effluent 45, alternatively from about 40% hexene to about 95% hexene, alternatively from about 50% hexene is to about 95% hexene.
In embodiments, effluent 45 can be recycled.In the embodiment of Fig. 2, effluent 45 recirculation is made to include, Such as, through suitable pump or compressor, send effluent 45 and return PEP system 200 and/or effluent 45 is introduced PEP system 200, Such as, for reusing in the polymerization.Make effluent 45 (such as, including hexene) recirculation can provide effective and/or Cost-effective supply hexene is for the means of polymerisation process operation.In embodiments, the hexene of effluent 45 can be poly- Close in reaction and be used as, such as, the comonomer in reaction.In alternative embodiments, can send effluent 45 with store, be used for Use the most in the polymerization or use in the method that any other is suitable.
In embodiments, distillation column 126 can be equipped with one or more entrance and at least two outlet.Distillation column 126 can Suitable, such as, may be adapted to operate under the temperature and pressure of the air-flow 26 of realization process or the Component seperation of air-flow 18.Such as, Distillation column 126 can be in scope from about 15 DEG C to about 233 DEG C, alternatively, from about 20 DEG C to about 200 DEG C, alternatively, from about 20 DEG C to At a temperature of about 180 DEG C, and/or in scope from about 14.7psi to about 527.9psi, alternatively, from about 15.7psi to about 348psi, alternatively, operates to the pressure of about 290psi from about 85psi.Distillation column 126 can be configured to and/or size design For providing the separation of the gas (such as, flash vapor stream) of proper volume.Will recognize that as read those skilled in the art of the disclosure Arriving, the air-flow 26 of process or air-flow 18 can retain and/or remain in any reasonable time amount in distillation column 126, such as, carry The time quantum required for being sufficiently separated the component of distillation column 126.
In embodiments, air-flow 26 or the air-flow 18 of process can be introduced to distillation column 126 and without compression step, i.e. Process need not be compressed after separator 108 sends and before introducing distillation column 126 at the air-flow 26 processed or air-flow 18 Air-flow 26 or air-flow 18.In another embodiment, air-flow 26 or the air-flow 18 of process can be in the outlet pressure with separator 108 Under the pressure that power is substantially the same, (such as, the outlet pressure at flash chamber 130 is to about 527.9psia from about 14.7psia, can Selection of land, from about 15.7psia to about 348psia, alternatively, from about 85psia to about 290psia) it is introduced to distillation column 126.? Still in another embodiment, air-flow 26 or the air-flow 18 of process can be introduced to distillation column 126, and do not have obvious compression step. In embodiments, air-flow 26 or the air-flow 18 of process can introduce distillation column 126 under the pressure of following ranges: from less than air-flow The 18 pressure about 25psi sent from separator 108 are to the pressure about 25psi sent from separator 108 more than air-flow 18, optional Ground, from the pressure about 15psi sent from separator 108 less than air-flow 18 to the pressure sent from separator 108 more than air-flow 18 About 15psi, alternatively, from the pressure about 5psi sent from separator 108 less than air-flow 18 to more than air-flow 18 from separator 108 The pressure sent about 5psi.In embodiments, air-flow 26 or the air-flow 18 of process can introduce distillation under following ranges pressure Tower 126: from about 14.7psia to about 527.8psia, alternatively, from about 15.7psia to about 348psia, from about 85psia to about 290psia。
In embodiments, distillation column 126 is configurable and/or operation makes middle hydrocarbon stream 29, base product effluent 43 Air-flow 18 or expectation part, number or the subset of the component of air-flow 26 that process is included with optional effluent 45 each.Example As, as it would be recognized by those skilled in the art that with the help of the disclosure, the position of concrete flow export, the behaviour of distillation column 126 Make parameter, the air-flow 26 of process or the composition of air-flow 18 or a combination thereof can be manipulated so that given stream can include the air-flow processed 26 or concrete one or more components of air-flow 18.
In the embodiment of the system 200 shown at Fig. 2, middle hydrocarbon stream 29 can separate in distillation column 124, to be formed gently Matter hydrocarbon stream 25, base product effluent 33 and optionally effluent 31.Lightweight hydrocarbon stream 25 can include ethylene, ethane, optionally hydrogen or A combination thereof.Base product effluent 33 can include iso-butane.Effluent 31 can include iso-butane.The isobutyl of base product effluent 33 Alkane can include and the iso-butane of effluent 31 different stage.Such as, base product effluent 33 can include being substantially free of alkene Iso-butane, and effluent 31 can include secondary recycle isobutane, it can include alkene.
At least one gas component can send with lightweight hydrocarbon stream 25 from distillation column 124, and other gas components can be from distillation Tower 124 sends with base product effluent 33.At least one the gas group sent with lightweight hydrocarbon stream 25 from the distillation column 124 of Fig. 2 Divide and can include ethylene and other light gases (such as, ethylene, ethane, methane, carbon dioxide, nitrogen, hydrogen or its group can be farther included Close).Such as, ethylene can be with from about 50% to about 99% based on the gross weight of lightweight hydrocarbon stream 25, alternatively from about 60% to about 98%, alternatively, it is present in lightweight hydrocarbon stream 25 from the amount of about 70% to about 95%.
From distillation column 124 with other gas components that base product effluent 33 sends can include propylene, propane, butane, Iso-butane, pentane, hexane, hexene-1, heavy hydrocarbon or a combination thereof.In embodiments, base product effluent 33 can be free of alkene, Alternatively, it is substantially free of alkene, alternatively, the most not olefin-containing.Such as, alkene can total by base product effluent 33 Weight meter is with less than about 1.0%, alternatively, less than about 0.5%, alternatively, the amount of less than about 0.1% is present in distillation column underflow Go out in thing 33.In embodiments, including iso-butane, the effluent 31 being made up of iso-butane alternatively can be from distillation column 124 with side Stream 31 sends.
In embodiments, effluent 31 or at least some of base product effluent 33 can be recycled.Make effluent 31 or At least some of base product effluent 33 recirculation can include, such as, through suitable pump or compressor, send effluent 31 or extremely Few a part of base product effluent 33 returns PEP system 200 and/or by effluent 31 or at least some of base product effluent 33 introduce PEP system 200, such as, for reusing in the polymerization.In embodiments, effluent 31 or at least one Point base product effluent 33 can in conjunction with various other components (catalyst, promoter etc.), with formed can be introduced to one or The catalyst slurry of multiple reactors 104,106.It is not intended to be limited by theory, because at least some of base product effluent 33 Can be free of alkene and can include iso-butane, base product effluent 33 can be with catalyst component (such as, catalyst, promoter Deng) mixing, and there is no the risk (such as, being introduced to the pre-polymerization of one or more reactor) of unexpected polyreaction.So, At least some of base product effluent 33 can be used as the source of the iso-butane of the not olefin-containing of polyreaction.Make effluent 31 Or at least some of base product effluent 33 recirculation can provide effective and/or cost-effective supply iso-butane for gathering Close the means of reaction method operation.In alternative embodiments, effluent 31 can be sent or at least some of base product flows out Thing 33 is to store, for using the most in the polymerization or using in the method that any other is suitable.
In embodiments, at least some of effluent 31 or at least some of base product effluent 33 can return to distillation column 124.Such as, effluent 31 or at least some of base product effluent 33 to distillation column 124 can be sent through reboiler, for additionally Process.
Distillation column 124 can be configured to and/or be designed and sized to provide gas (such as, the lightweight hydrocarbon stream of Fig. 2 of proper volume 25) separation.Such as, distillation column 124 can be alternatively, from about 40 DEG C to about 10 DEG C, optional in scope from about 50 DEG C to about 20 DEG C Ground, from about 30 to about 5 DEG C at a temperature of, and in scope from about 14.7psia to about 529.7psia, alternatively, from about 15.7psia is to about 348psia, alternatively, operates to the pressure of about 290psia from about 85psia.Distillation column 124 can configure For and/or be designed and sized to the separation of air-flow 26 air-flow 18 of proper volume being provided or processing.As those skilled in the art will Recognizing, the air-flow 26 of process or air-flow 18 can retain and/or remain in any reasonable time amount in distillation column 124, as The component being sufficiently separated the air-flow 26 of process or air-flow 18 can be provided required.In embodiments, distillation column 124 can be equipped with to Few two outlets.
In embodiments, distillation column 124 is configurable and/or operates so that the lightweight hydrocarbon stream 25 of Fig. 2 and distillation column underflow Go out each air-flow 26 including processing of thing 33 or expectation part, number or the subset of the component of air-flow 18.Such as, as at this It would be recognized by those skilled in the art that with the help of Gong Kai, concrete inflow entrance or the position of outlet, the operation ginseng of distillation column 124 Number, the air-flow 26 processed or the composition of air-flow 18 or a combination thereof can be manipulated so that air-flow 26 that given stream can include processing or Concrete one or more components of air-flow 18.
In optional and/or other embodiment, separate at least one gas component from air-flow and can include making air-flow With absorbent (such as, lyosoption system, as disclosed herein) contact, such as, in order to gas component is inhaled by absorbent Receive.In this embodiment, separate at least one gas component from air-flow to include optionally absorbing at least one from air-flow Gas component.In this embodiment, absorb at least one gas component from air-flow to generally comprise and make air-flow and suitable suction Receipts agent contacts so that at least one component is absorbed by absorbent, and optionally, removes the refuse including unabsorbed gas Stream.In other embodiment, separate at least one gas component from air-flow and can farther include to absorb from absorbent release Gas component.
In embodiments, make air-flow contact with absorbent and can include ensuring that be fully contacted between air-flow and absorbent appoints What suitable means.The non-limitative example providing the suitable means being fully contacted between air-flow and absorbent includes various reactor The use of system such as those disclosed above (such as, absorption tower or spraying or blending tank).It is not intended to be limited by theory, suitably Reactor assembly by stirring or mix two components in the presence of each other, circulate, disperse or make the first compositions Diffuse through the second compositions or diffusion or various other technologies well known by persons skilled in the art can be true in the second compositions Protect two or more gaseous states, liquid and or solid composite between contact.In embodiments, air-flow and absorbent are permissible With suitable ratio contact.The scope of this air-flow and the suitable ratio of absorbent can from about 1,000lb/hr:1000gpm to about 2, 500lb/hr:25gpm, alternatively, from about 1000lb/hr:250gpm to about 2500lb/hr:100gpm, alternatively, about 1875lbs/hr:250gpm。
In the embodiment that such as Fig. 1-5 is explained, from air-flow (such as, the air-flow of the process of the air-flow 18 or Fig. 2 of Fig. 1 M-air-flow 19 in 26 or Fig. 3-5) separate at least one gas component can include send air-flow to absorb reactor 116.At this In one or more embodiments disclosed in literary composition, absorbing reactor 116 and can include reactor, it is configured to from including the first change Learn and the stream of component or compound and one or more other chemical constituent, compounds etc. optionally absorbs at least the first chemistry Component or compound.The suitable non-limitative example absorbing reactor and/or absorption reactor configurations includes absorbing (distillation) Tower, pressure swing absorption (PSA) structure, aerosol can, agitation reactor, one or more compressor, one or more recirculation pump or A combination thereof.
In embodiments, absorb reactor to can be configured to dissipate in a liquid (such as, by making gas bubble gas Pass through liquid).Such as, in embodiments, absorbing reactor 116 and can include solvent circulation, it is configured to make solvent follow Ring is by absorbing reactor 116.Solvent rate of circulating flow can be determined by the operating condition of absorption system, as disclosed in herein below. In embodiments, absorb reactor 116 and can include one or more pump and/or be in fluid communication with one or more pumps, described Pump be configured to make solvent through absorb reactor 116 and/or in absorbing reactor 116 recirculation.Other and/or optional In embodiment, absorbing reactor 116 and can include packed bed or post, it is configured to such as, maintains less bubble size (example As, dissipate the bubble size of gas in a liquid), such as, in order to maintain the relatively large surface of contact between gas and liquid Long-pending, such as, in order to maintain gas transfer and/or be absorbed into the efficiency of liquid.In embodiments, packed bed or the filling of post Material can include polymeric material, metal material or a combination thereof.In embodiments, absorb reactor 116 and can have multiple filling Bed or post.In embodiments, only only a part absorption reactor 116 can have packing material.In embodiments, filling The packing material of absorption reactor 116 can have random filling and maybe can have structurized filling.Suitable absorption reactor Example is illustrated in gas processer association, " through engineering approaches data book " the tenth edition (Gas Processors Association, “Engineering Data Book”10thEd), Figure 19-16.
In absorption reactor 116 includes the embodiment of solvent reaction device, absorb reactor and can include suitable absorption Solvent system, as disclosed herein.This absorption reactor 116 can be configured to keep lyosoption system.Such as, lyosoption System can as liquid, as fixed bed or as fluid bed keep in the reactor.
In embodiments, suitable lyosoption system can reversibly with ethylene and/or iso-butane complexation.This Lyosoption system can generally comprise chelating agent and solvent.In embodiments, lyosoption system may be characterized as having ethylene Selectivity to ethane, wherein ethylene and ethane under the identical dividing potential drop of about 14psi with about 40:1, at identical point of about 20psi Pressure, with about 12:1, with about 6:1 under the identical dividing potential drop of about 40psi, is deposited with about 3:1 with under the identical dividing potential drop of about 180psi ?.In embodiments, solvent system can be further characterised as having high pollutant tolerance and in increase and/or variation Temperature and/or pressure or a combination thereof under show high stability.
In embodiments, chelating agent can include slaine.In this embodiment, slaine can include one or many Plant transition metal and the salt of weak ion halogen.The non-limitative example of suitable transition metal include silver, gold, copper, platinum, palladium or Nickel.The non-limitative example of suitable weak ion halogen includes chlorine and bromine.In embodiments, suitable transition metal salt can table Levy as having the high specific to alkene.The non-limitative example of suitable transition metal-haloid includes silver chloride (AgCl) With copper chloride (CuCl).In a particular embodiment, the salt used in lyosoption system includes CuCl.It is not intended to theoretical Being limited, this slaine can interact with double carbon bonds of alkene (such as, ethylene).
In embodiments, chelating agent can include copper carboxylate (I).In this embodiment, suitable copper carboxylate (I) can Including copper (I) with comprise the monocarboxylic acid of 1-20 carbon atom, dicarboxylic acids and/or tricarboxylic salt.The carboxyl acid component of salt can include Aliphatic character, ring-type composition, aryl elements or a combination thereof.Other suitable examples of copper carboxylate (I) include formic acid Cu (I), second Acid Cu (I), propanoic acid Cu (I), butanoic acid Cu (I), valeric acid Cu (I), caproic acid Cu (I), octanoic acid Cu (I), capric acid Cu (I), 2-ethyl-own Acid Cu (I), Palmic acid Cu (I), tetradecylic acid Cu (I), toluic acid Cu (I), ethyl acetic acid Cu (I), n-pro-pyl acetic acid Cu (I), Normal-butyl acetic acid Cu (I), propionic acid ethyl copper Cu (I), cupric octoate Cu (I), benzoic acid Cu (I), p-p t butylbenzoic acid Cu (I) and Analog.In other embodiment, chelating agent can include the adduct of copper carboxylate (I), such as, as disclosed herein, and Boron trifluoride (BF3) adduct.
In other and/or optional embodiment, chelating agent can include sulfonic acid copper (I).Suitable sulfonic acid copper (I) Non-limitative example includes copper (I) salt with the sulfonic acid of 4 to 22 carbon atoms.The sulfonic acid component of salt can include that aliphatic becomes Point, ring-type composition, aryl elements or a combination thereof.Aliphatic sulfonic can be straight chain or side chain.Suitable aliphatic sulfonic Example include but not limited to n-butanesulfonic acid, 2-ethyl-1-hexane sulfonic acid, 2-methylnonane sulfonic acid, dodecane sulfonic acid, 2-second Base-5-n-pentyl tridecane sulfonic acid, AI3-28404 sulfonic acid and analog.The example of suitable aromatic sulfonic acid includes benzenesulfonic acid, alkane Base benzenesulfonic acid, wherein moieties comprises 1 to 16 carbon atom, such as p-methyl benzenesulfonic acid, DBSA (o-, m-and Right), p-cetyl benzenesulfonic acid and analog, LOMAR PWA EINECS 246-676-2, phenolsulfonic acid, naphtholsulfonic acid and halogeno-benzene sulfonic acid, the most p-chlorine Benzenesulfonic acid, p-bromo-benzene sulfonic acid and analog.
In embodiments, chelating agent can farther include hindered olefins.Such as, in embodiments, chelating agent can wrap Including such hindered olefins, its complexing agent forms the copper complex with insufficient dissolubility.The example of this hindered olefins It is propylene tetramer (i.e. laurylene).Being not intended to be limited by theory, hindered olefins can increase copper complex formazan dissolubility to be held simultaneously Easily replaced by ethylene.
In various embodiments, chelating agent can include U.S. Patent number 5,104,570;5,191,153;5,259,986; With 5, one or more chelating agent disclosed in 523,512, its each piece is integrally incorporated herein with it by quoting.
In embodiments, solvent can include amine or amine complex, aromatic hydrocarbon, alkene or a combination thereof.The non-limit of solvent amine Property example processed includes pyridine, benzylamine and aniline.Such as, amine can include aniline (phenyl amine, aminobenzene);Alternatively, replace with diformazan The aniline that Methanamide (DMF) combines, and in embodiments, aniline and N-Methyl pyrrolidone (NMP).Solvent bag wherein Including in the embodiment of aromatic hydrocarbon, aromatic hydrocarbon can include the substituted aryl of unsubstituted or alkyl.In this embodiment, aromatics Hydrocarbon can be in liquid phase under ambient environment.Suitable non-limitative example includes toluene, dimethylbenzene etc..Solvent bag wherein Including in the embodiment of alkene, non-limitative example includes the alkene with 10 to 16 carbon atoms.Such as, alkene can include third Alkene tetramer, laurylene, tetradecene, hexadecylene or a combination thereof.
In embodiments, solvent may be characterized as sprotic, i.e. does not include dissociable hydrogen atom.Be not intended to by Theory is limited, and dissociable hydrogen solvent may result in the double bond hydrogenation in alkene such as ethylene between carbon.Additionally, solvent can table Levy for polarity, there is slight polarity or there is unidirectional electric charge.Being not intended to be bound by theory, polar solvent can interact with salt Salt is at least partly made to dissolve.
In embodiments, solvent may be characterized as with relatively large volume of industrial production, there is relatively low cost, Easily transport or the liquid of a combination thereof.Solvent can be further characterised as keeping the alkene-slaine of complexation or keep weak from The slaine of son, no matter how are temperature and/or pressure oscillation.
In embodiments, lyosoption system can include copper chloride, aniline and dimethyl formamide (CuCl/ aniline/ DMF).In alternative embodiments, lyosoption system can include copper chloride, aniline and N-Methyl pyrrolidone (CuCl/ benzene Amine/NMP).In this embodiment, CuCl/ aniline/nmp solvent system may be characterized as in lower pressure and higher temperature There is under degree the volatilization stability of increase.In alternative embodiments, lyosoption system can include copper carboxylate (I) and aromatics Solvent such as toluene or dimethylbenzene.In alternative embodiments, lyosoption system can include sulfonic acid copper (I) and arsol Such as toluene or dimethylbenzene.In alternative embodiments, lyosoption system can include arsol such as toluene or diformazan Copper carboxylate (I) and BF in benzene3Adduct.
In embodiments, lyosoption system can include 2-ethyl-hexanoic copper (I) and propylene tetramer.Embodiment party In formula, lyosoption system can include 2-ethyl-hexanoic copper (I) and laurylene.In embodiments, lyosoption system can be wrapped Include copper palmitate (I) and hexadecylene.In embodiments, lyosoption system can include tetradecylic acid copper (I) and tetradecene.
In embodiments so that at least one component is absorbed by absorbent and can include so that at least one component such as warp Form various bonding, key, attraction, complex or a combination thereof reversibly to combine, connect, be bonded or a combination thereof is to absorbent or its portion Point.Such as, wherein absorbent include lyosoption system (such as, CuCl/ aniline/DMF solvent system or CuCl/ aniline/ Nmp solvent system) embodiment in so that absorb at least one component and can include so that in absorbent and at least one component Between formed complex, referred to as absorbent components complex (such as, the alkene complex of absorption).
Make to absorb at least one component and can farther include to provide and/or keep the suitable of air-flow and absorbent contact environment When pressure, the suitable dividing potential drop providing and/or keeping gas, the suitable temperature that provides and/or keep air-flow and absorbent contact environment Degree, catalytic absorption or a combination thereof.Be not intended to be limited by theory, absorbent absorb at least one component can suitable temperature and/ Or improve under pressure.
In embodiments, absorbing reactor 116 can selective induction heat and/or pressure oscillation, change or circulate. In embodiments, absorb reactor 116 to can be configured to from the group including other gases various (such as, ethane, optionally hydrogen) Compound optionally absorbs and/or the unreacted vinyl monomer of induced absorption (with optionally, comonomer).Another embodiment party In formula, the compositions that absorption reactor 116 can be configured to from including other gases various optionally absorbs and/or induced absorption Butane, especially iso-butane.In still another embodiment, absorb reactor 116 and can be configured to from including other gases various The compositions of (such as, ethane, optionally hydrogen) optionally absorbs both unreacted ethylene and butane, especially iso-butane.
In embodiments, absorb the temperature that reactor 116 can be configured to provide or maintain suitable, such as, can be depending on Absorb the phase that reactor operates in preset time.Such as, absorb the temperature that reactor 116 can be configured to provide or maintain suitable, Such as, it is used for increasing the desired chemical species of absorption, the minimizing desired chemical species of absorption, not absorbing from reactor 116 flash distillation Gas, from absorb reactor 116 reclaim unreacted ethylene, make the absorbent regeneration absorption reactor 116 or a combination thereof Purpose.In embodiments, this suitable temperature range can be from about 40 to about 110, alternatively, from about 40 to about 60, alternatively, from about 45 to about 55, alternatively, from about 50 to about 55, the most about 50.Such as, sent out Existing temperature range is from about 40 to about 110, alternatively, from about 40 to about 60, and the absorption reactor of the most about 50 The beat all increase that can produce ethylene absorption relative to ethane absorption of the operation temperature of 116 (with lyosoption system). It is not intended to be limited by theory, it would be recognized by those skilled in the art that (such as, based on the dividing potential drop concept from Raoult's law) is pre- Phase ethylene and ethane dissolubility in absorbent solvent at a temperature of being gradually lowered increases.But, contrary with this expectation, send out Now along with at a temperature of be reduced to 50 time, in the absorbent solvent and/or absorbent solvent system of disclosed embodiment inhale The ethylene volume received reduces.Because this beat all phenomenon, the absorption of ethylene can in scope from about 40 to about 110, optional Ground, in the scope temperature from about 40 to about 60, alternatively, maximum at a temperature of about 50.Figure 11 is shown in difference At a temperature of ethylene and the figure of ethane dissolubility in copper chloride, aniline, NMP absorbent solvent system.This figure is illustrated in above-mentioned The intended dissolubility trend of ethane and the beat all dissolubility trend of ethylene under the temperature range discussed.
In embodiments, absorb reactor 116 to can be configured in one or more components (such as, the second absorbing air-flow Alkene and/or iso-butane) period provides or maintains proper temperature from the scope of about 40 to about 110.Disclosed above, It is found that ethylene dissolution degree scope from about 40 to about 60 at a temperature of unexpectedly maximum.In embodiments, exist During air-flow absorbs ethylene and/or isobutene., absorbing reactor 116 can be in the temperature from about 40 to about 60, alternatively Operate at a temperature of about 50.In alternative embodiments, during absorbing ethylene and/or isobutene. from air-flow, absorb anti- Answer device can from about 60 to about 110, or from about 70 to about 90 at a temperature of operate.Such as, reactor 116 is absorbed This absorption temperature can be suitably as the warp operating (it may require the energy expenditure such as cooled down) at lower temperatures Ji alternative scheme.Such as, in scope from about 60 to about 110, or from about 70 to about 90 at a temperature of operation absorb Reactor, can operate and requirement under the ambient temperature in given geographical position by making absorption reactor as absorbed reactor 116 Less energy, it can produce cost savings.
In embodiments, the pressure that reactor 116 can be configured to provide during operation or maintain suitable is absorbed.This Suitably the scope of pressure can be from about 5psig to about 500psig, alternatively, from about 50psig to about 450psig, alternatively, from about 75psig to about 400psig.In other embodiment, absorb reactor 116 and can be configured to provide during operation or tie up Hold suitable ethylene partial pressure.The scope of this suitable ethylene partial pressure can be from about 1psia to about 400psia, alternatively, from about 30psia is to about 200psia, alternatively, from about 40psia to about 250psia, alternatively, from about 40psia to about 75psia, and can Selection of land, from about 40psig to about 60psig, the most about 40psig, alternatively, about 60psig.It is not intended to be limited by theory, makes Absorb reactor 116 supercharging can beneficially absorb ethylene and/or form ethylene and lyosoption system (such as, CuCl/ aniline/NMP System) complex.And, it is not intended to be bound by theory, along with the pressure absorbing reactor declines, lyosoption system is to ethylene Selectivity can increase.
In embodiments, absorb reactor 116 to be configurable in batches and/or continuation method.Such as, embodiment party In formula, PEP system can include that two or more absorb reactor (such as, such as absorb reactor 116), and each of which can configure For for batch operation.Such as, by using two or more to absorb reactor, this system is configurable to allow by inciting somebody to action Air-flow component absorbs to the first " first batch " absorbing in reactor to absorb to prepare in reactor second simultaneously and is used for absorbing " the second batch " and operate continuously.So, by circulating between the reactor suitable at two or more, system can be continuous Operation.
Such as, in embodiments, two or more absorption reactors (such as, absorbing reactor assembly) can be configured to Using liquid flux, such as, lyosoption system disclosed herein or lyosoption carry out the pressure swing absorption (PSA) of ethylene.? In this embodiment, absorbing reactor 116 and can include that two or more absorb reactor, (such as, it be configured for PSA Absorb reactor assembly).Figure 10, display absorbs reactor assembly 1000, has four and absorbs reactor 1010,1020,1030 With 1040, it is configured for PSA.Although the embodiment of Figure 10 illustrates four absorbs reactor (such as, absorption reactor 1010,1020,1030 and 1040), those skilled in the art, read the disclosure time it will be recognized that can use similarly two, Three, five, six, seven, eight or more absorption reactor.In this embodiment, each absorption reactor can base Configuration as disclosed herein in basis.In embodiments, one or more reactors 1010,1020,1030 and 1040 can be through following Loop systems (such as, including one or more pumps, valve, conduit etc.) connect with during absorbing at reactor 1010,1020,1030 With 1040 in circulating liquid solvent.Absorb reactor 1010,1020,1030 and 1040 can the absorption stage (wherein gas component, Such as ethylene and/or iso-butane, by lyosoption and/or lyosoption Systemic absorption) and regeneration stage (wherein absorb and/ Or the gas component of complexation discharges from lyosoption system and/or lyosoption system, prepare to reuse, as herein by public affairs Open) between circulate.Such as, reactor 1010,1020,1030 and 1040 tunable ground is at absorption stage and regeneration stage (such as, Through one or more interstages) between circulate, thus not all reactor 1010,1020,1030,1040 is the most all Carry out absorbing or regenerating.Absorb reactor 1010,1020,1030 and 1040 wherein to be configured to the embodiment of PSA operation In, reactor 1010,1020,1030 and 1040 had both been used as absorber and had also served as regenerator.In this embodiment, for again Raw separation container is not likely to be required (such as, as disclosed herein).
As the example of the PSA operation coordinated, the given stage during this kind of operation, reactor 1010 can be to absorb Stages operating, such as, under acceptance condition as disclosed herein.In the substantially the same time, reactor 1020 can be pressurized To intermediate pressure, such as, less than absorption pressure.And, in the substantially the same time, reactor 1030 can subtract from intermediate pressure Be depressed into regeneration pressure, and simultaneous reactions device 1040 can from absorption pressure (from before be in the absorption stage) be decompressed to intermediate pressure Power.Being not intended to be limited by theory, after absorption, the decompression of each reactor 1010,1020,1030 and/or 1040 is (such as, from suction Receive pressure to intermediate pressure and from intermediate pressure to regeneration pressure) gas component (such as, the ethylene and/or different that absorbs can be made Butane) (such as, prepare to be used for reusing, as disclosed herein) from absorbent release and/or absorbent regeneration.Implementing In mode, the pressure from one or more reactors (such as, reactor 1010,1020,1030 and/or 1040) can be used for making Another pressurization of these reactors.Such as, in the embodiment of Figure 10, in reactor 1040, the pressure of gas can be used for making Reactor 1020 is forced into intermediate pressure by pipeline 1050, and valve 1058 and 1084 is in an open position and valve 1082 and 1056 In the closed position.Valve 1062,1064,1066 and 1068 can be changed between open and closed positions, so that stream Nitrogen in Products in 1060 flows in and out reactor 1010,1020,1030 and 1040.Valve 1052,1054,1056 and 1058 can be Change between open position and closed position, so that reactor 1010,1020,1030 and 1040 by stream 1050 pressurization and subtracts Pressure.Valve 1082,1084,1086 and 1088 can be changed between open and closed positions, so that light gas stream 1080 is worked as During the absorption stage, charging is to reactor 1010,1020,1030 and 1040.Valve 1092,1094,1096 and 1098 can be at open position And change between closed position, to remove any purging gas from reactor 1010,1020,1030 and 1040 by stream 1090.
In embodiments, during regeneration stage, stripping gas, such as iso-butane or nitrogen, can such as be added by stream 1070 Add to absorb reactor 1010,1020,1030 and 1040.Stream 1070 can be located at the end of reactor 1010,1020,1030 and 1040 Portion, so stripping gas can be bubbled through reactor 1010,1020,1030 or 1040 (and by any filling material therein Material).Valve 1072,1074,1076 and 1078 can be changed between the open and closed positions, to add desorption gas during regenerating To reactor 1010,1020,1030 and 1040.Being not intended to be limited by theory, during regeneration, stripping gas can reduce absorption reactor 1010, the dividing potential drop of the ethylene in 1020,1030 and 1040.
In embodiments, one or more absorption reactors 1010,1020,1030 and 1040 can include internals, With by liquid lyosoption distributing gas and prevent channel.Suitable internals can include that distillation is filled, and it is distributed gas Body and reduce the axial backmixing of liquid.Internals can prevent from absorbing the liquid in reactor 1010,1020,1030 and 1040 Lyosoption mixes thus solvent flow general is the most saturated and then saturation front (saturation front) can pass through Absorb reactor 1010,1020,1030 and 1040 to move vertically upward.
In embodiments, separate at least one gas component from air-flow to include removing waste stream.In embodiments, residual The unabsorbed air-flow component stayed forms waste stream.Include that in absorbent components the embodiment of ethylene and absorbent includes CuCl/ aniline/DMF or CuCl/ aniline/nmp solvent system, this waste stream can include hydrogen, methane, ethane, acetylene, propylene, Other hydrocarbon various, volatile contaminant or a combination thereof.Additionally, this waste stream can be substantially free of unreacted vinyl monomer Or, optionally, comonomer.As used herein, " being substantially free of unreacted vinyl monomer " meaning be waste gas include by The gross weight meter of this stream is less than 50% unreacted vinyl monomer, alternatively, less than 10% unreacted vinyl monomer, optional Ground, less than 1.0% unreacted vinyl monomer, alternatively, less than 0.1% unreacted vinyl monomer, alternatively, is less than 0.01% unreacted vinyl monomer.
In embodiments, remove waste stream and can include cooling down waste stream, and/or reduce or the pressure of increase waste stream, Waste stream is made to flow to processing equipment 114.Such as, in embodiments, waste stream can be by under sufficient pressure, under speed Or a combination thereof suitable purge gas of transport (such as, inertia or unreacted gas, disclosed above) by comprising the appearance of waste gas Device (such as, absorbing reactor 116) is with from its discharge waste gas " cleaning ".Such as, the embodiment explained in figs. 1-5 In, separate the generation of at least one gas component from air-flow and be substantially free of unreacted vinyl monomer (optionally, comonomer) Waste gas stream 20, alternatively, there is the waste gas stream of unreacted vinyl monomer (optionally, comonomer) reducing concentration.Example As, waste gas stream can include based on the gross weight of this stream less than about 30%, alternatively, less than about 25%, alternatively, less than about 20%, alternatively, less than about 15%, alternatively, the unreacted vinyl monomer of less than about 10%.At other embodiment In, ethylene can reduce before separating at least one gas component from air-flow the percent of ethylene present in air-flow.Such as, useless Air-flow can include based on the gross weight of this stream less than about 40%, alternatively, less than about 30%, alternatively, less than about 20% divide Unreacted vinyl monomer present in the air-flow before.
In embodiments, separate at least one gas component from air-flow can farther include from absorbent release absorption Gas component (such as, absorbs reactor 116 situ and/or in another container of such as regenerator 120).Release from absorbent Put the gas component of absorption and generally comprise any suitable means: its reverse combined by its at least one gas component, connect, Bonding or a combination thereof are to absorbent or various bondings, key, attraction, complex or a combination thereof of its part.Absorbed by its release The non-limitative example of suitable means of the gas component absorption dynamics that includes changing absorbent or absorption equilibrium, heating or Decompression absorbent, the dividing potential drop changing the gas absorbed or a combination thereof.
In embodiments, in regeneration and/or desorption phase, the gas component of absorption can be from one or more this absorptions Absorbent in reactor discharges (such as, desorbing and/or solution complexation).In embodiments, regeneration stage can include making suction Receive solvent system to regenerate to produce unreacted ethylene;In embodiments, regeneration stage can include making absorption reactor 116 In lyosoption system regeneration, in order to produce unreacted ethylene.Such as, in the embodiment of Fig. 1 and 2 (and/or, Wherein absorb in the embodiment that reactor 116 is configured to PSA structure, as herein with reference to disclosed in Figure 10), absorb reactor 116 can be configured to induce from lyosoption absorb or complexation gas release gas (such as, absorption and/or the second of complexation Alkene and/or the desorbing of iso-butane and/or solve complexation), such as this paper detailed disclosure.It is not intended to be limited by theory, induced absorption Or the release of the gas of complexation can include the kinetics changing lyosoption system or gas-solvent balance, absorb reaction The temperature of device 116, the dividing potential drop absorbing the gas of the pressure of reactor 116, absorption or a combination thereof.In this embodiment, inhale Receive reactor 116 can include being configured to change kinetics, gas-solvent balance, absorb the temperature of reactor 116, absorption The pressure of reactor 116 or the controller of a combination thereof, heat pipe, conductivity cell, compressor, vacuum pump etc. or a combination thereof.
Such as, in embodiments, the gas component that release absorbs can include the solution decompression making to include the ethylene of complexation To suitable dividing potential drop.In other embodiment, the gas component that release absorbs can include adding heat absorption reactor 116 (can Selection of land, in regenerator 120, as disclosed in herein below) include that the solution of ethylene of complexation is to suitable temperature.This suitably Temperature range can be from about 110 to about 200, alternatively, from about 140 to about 160, alternatively, from about 160 to about 200, alternatively, from about 180 to about 200, to promote that absorption compound (such as, ethylene and/or iso-butane) is from absorption Solvent discharges.Such as, in a particular embodiment, release from lyosoption in absorbent components (such as, ethylene and/or isobutene .) Putting period, absorbing reactor 116 (alternatively, regenerator 120) can be from about 160 to about 200, alternatively, from about 180 Operate at a temperature of about 200.In alternative embodiments, in absorbent components (such as, ethylene and/or isobutene .) from suction Receiving solvent deenergized period, absorbing reactor 116 (alternatively, regenerator 120) can be at a temperature of from about 140 to about 160 Operation.Such as, this release temperature can be suitably as economic alternative scheme.Such as, at absorbent components deenergized period, operation is inhaled Receive reactor, as absorbed reactor 116 (alternatively, regenerator, such as regenerator 120) in scope from about 140 to about 160 At a temperature of can be by making to be derived from other source (such as, polymer reactor coolant, low-pressure stream, heat exchange of regenerator upstream Heat exchanger in device, absorbent recirculation line, polymer reactor, flash line heater, flash chamber etc. or a combination thereof) Heat is for adding heat absorption reactor and/or regenerator and needing less energy, and it can produce cost savings.
It addition, in this embodiment, absorption reactor 116 can be configured to discharge gas and (such as, absorbs with right before The gas of rear release, such as ethylene) and/or it is beneficial to the gas absorbed through pressure reduction release.Absorb reactor 116 to can be configured to provide Or maintain suitable dividing potential drop.The scope of this suitable dividing potential drop can be from about 0.1psig to about 40psig, alternatively, from about 5psig To about 30psig, alternatively, from about 5psig to about 15psig.In embodiments, absorb reactor 116 to can be configured to provide Or maintain ethylene partial pressure scope from about 0psia to about 5psia.
In alternative embodiments, from air-flow separate at least one gas component can farther include removal include absorb The solution of component complex (such as, the alkene complex of absorption), for processing further.This optional embodiment party Formula, the absorption complex including the gas component absorbed can be moved to regenerator 120 from absorbing reactor 116, be used for discharging suction Receive gas component and/or make absorption complex be regenerated as combined-flow 28.In embodiments, regenerator 120 can make absorption molten Agent system regeneration is to produce unreacted ethylene;In embodiments, the absorption during regenerator 120 can make regenerator 120 is molten Agent system regeneration is to produce unreacted ethylene.
In this embodiment, combined-flow 28 can include ethylene, ethane and/or iso-butane.The scope that ethylene exists is pressed The gross weight meter of this stream can be from about 0.1% to about 10%, alternatively, from about 0.4% to about 5%, alternatively, from about 0.5% to About 2.5%.The scope that ethane exists can be from about 0.1% to about 1% based on the gross weight of this stream, alternatively, from about 0.2% to about 0.5%.The scope that iso-butane exists can be from about 0.1% to about 1% based on the gross weight of this stream, alternatively, from about 0.2% to about 0.5%.
In one or more embodiments disclosed herein, combined-flow is separated into recirculation flow and absorbent stream (such as, at block 92) includes the gas component absorbed from absorbent release.As explained above, the gas group absorbed from absorbent release Point generally comprise any suitable means, its reverse combined by its at least one gas component, connect, be bonded or a combination thereof extremely Absorbent or various bondings, key, attraction, complex or a combination thereof of its part.Public above with reference to the release absorbed in reactor Various methods and/or the parameter of the gas component that release absorbs are opened.
In the embodiment of Fig. 5 explaination, combined-flow is separated into recirculation flow and absorbent stream can include that transmission is compound Stream 28 to regenerator 120.In one or more embodiments disclosed herein, regenerator 120 can include being configured to reclaiming, The equipment of the gas that regeneration, recirculation and/or purification lyosoption and/or release absorb or device.Suitable regenerator non- Limitative examples includes flashing reactor, Depressor response device, solvent reclamation reactor or a combination thereof.
In embodiments, regenerator 120 can be configured to operate based on pressure reduction.In this embodiment, regenerator 120 Can be configured to provide or maintain suitable intrinsic pressure.This suitable intrinsic pressure scope can be from about 0psig to about 150psig, alternatively, From about 5psig to about 30psig, alternatively, from about 5psig to about 15psig, alternatively, from about 0psig to about 10psig.? In embodiment, regenerator 120 can be configured to provide or maintain suitable dividing potential drop.This suitable partial pressure range can be from about 0psia to about 50psia.
In embodiments, regenerator 120 can be configured to based on the temperature operation raised.This regenerator 120 can configure For providing or maintain suitable temperature.This suitable temperature range can be from about 110 to about 200, alternatively, from about 140 To about 200, alternatively, from about 140 to about 160, alternatively, from about 160 to about 200, alternatively, from about 180 to about 200, with the compound (such as, ethylene and/or iso-butane) absorbed from lyosoption evaporation and/or release.? In embodiment, regenerator 120 (such as, as absorbed reactor 116) can use and include cooling down water, low-pressure steam or a combination thereof Thermal source carries out heating with desorbing or regenerable absorbent solvent system.Cooling water, low-pressure steam or a combination thereof may be adapted to thermal regeneration device 120 (or absorb reactor 116, and disclosed above) to the temperature from about 140 to about 200.
In embodiments, regenerator 120 is configurable in batches and/or continuation method.Such as, in embodiments, PEP system can include two or more absorption and regeneration devices (such as, the regenerator 1220 and 1222 of such as Figure 12), and each of which can It is configured to batch operation.As explained above, by using two or more to absorb reactor, this system is operable such that suction Receive agent cyclic regeneration.
In embodiments, combined-flow is separated into recirculation flow and absorbent stream can produce the absorbent stream of regeneration It can reuse and include the recirculation flow of unreacted monomer (optionally, comonomer) in absorbing reaction, its PEP method can be reintroduced back to or reuse in PEP method.Such as, in the embodiment of Fig. 5 explaination, by combined-flow 28 It can return to such as depurator 102, and the absorption of regeneration to be separated into recirculation flow and the raw recirculation flow 22 of absorbent miscarriage Agent stream 30, it can return to such as absorb reactor 116.
In embodiments, the gas that release absorbs also can produce and include unreacted monomer (optionally, comonomer) Recirculation flow, it can return to separator 108 for pressurizeing (such as, through being positioned at the one or more compressions at separator 108 Machine).Such as, in the embodiment of Fig. 1-5 explaination, the gas that release absorbs produces recirculation flow 22, and it can return to separator 108,105.Making recirculation flow 22 supercharging to produce to be reintroduced back to flow (not shown), it can be reintroduced back to PEP method or in PEP side Method is reused.Such as, in the embodiment of Fig. 1-5 explaination, it is reintroduced back to stream and can be introduced to depurator 102.Optional Embodiment in, recirculation flow (such as recirculation flow 22) can be pressurized and/or be reintroduced back to PEP method, and does not return point From device 108,105.In embodiments, recirculation flow 22 can include the purest ethylene;Alternatively, recirculation flow 22 can wrap Include ethylene and butane, especially iso-butane.In embodiments, air-flow can include nitrogen, ethylene, ethane and/or iso-butane.Ethylene The scope existed can be from about 65% to about 99% based on the gross weight of stream, alternatively, from about 70% to about 90%, alternatively, about 75% to about 85%.The scope that ethane exists can be from about 1% to about 20% based on the gross weight of stream, alternatively, from about 5% to about 15%, alternatively, from about 7.5% to about 12.5%.The scope that iso-butane exists can be from about 1% to about based on the gross weight of stream 20%, alternatively, from about 5% to about 15%, alternatively, from about 7.5% to about 12.5%.
In one or more embodiments disclosed herein, burner exhaust stream (such as, at block 66 or 76) can be general Including burning or one or more gas components of incineration waste gas stream 20.In embodiments, burner exhaust stream 20 can be further Or include waste gas stream 20 or the cracking of combustion product, catalytic cracking, pyrolysis, dehydrogenation alternatively, wash, convert, process or its group Close.
As disclosed herein, waste gas stream 20 can include the solvent of volatilization, unreacted gas, secondary products, pollutant, hydrocarbon Or a combination thereof.In embodiments, waste gas stream 20 can include hydrogen, nitrogen, methane, ethylene, ethane, propylene, propane, butane, isobutyl Alkane, heavy hydrocarbon or a combination thereof.The scope that ethylene exists can be from about 1% to about 40% based on the gross weight of stream, alternatively, from about 2.5% to about 20%.Ethane exist scope by stream gross weight based on can be from about 5% to about 50%, alternatively, from about 30% to About 40%.The scope that iso-butane exists can be from about 1% to about 20% based on the gross weight of stream, alternatively, from about 1.5% to about 5%, alternatively, from about 2% to about 3%.The scope that nitrogen exists can be optional from about 10% to about 80% based on the gross weight of stream Ground, from about 35% to about 50%, alternatively, from about 40% to about 45%.
In the embodiment that such as Fig. 1-5 is explained, burner exhaust stream can include sending waste gas stream 20 to processing equipment 114.In one or more embodiments disclosed herein, processing equipment 114 can include combustion apparatus or device, such as fire Torch.The suitably non-limitative example of torch includes torch, incinerator etc. or a combination thereof.Torch can suitably include one or more Controlled nozzle, incendiary source, bypass valve, pressure relief valve or a combination thereof.Torch can be configured to provide for various waste product, Such as, atomic gas (such as nitrogen, oxygen), oxide (such as carbon monoxide, nitrogen or sulfur oxide), various undesired gaseous state Product or the environment of a combination thereof burning.In embodiments, torch can comprise additionally in equipment or device, and it is configured in burning Before, period and/or the most optionally remove one or more pollutant (such as so that given combustion product do not discharge to Air).
In one or more embodiments disclosed herein, processing equipment 114 can include such as cracking unit, catalysis Cracking unit, scrubber, converter, processing means, dehydrogenator, degasifier or a combination thereof.In embodiments, processing equipment 114 can include ethylene cracker device.In processing equipment 114, from one or more gas components of waste gas stream 20, such as ethane Desired product, such as vinyl monomer can be changed into.The expectation product formed in processing equipment 114 can be recirculated to such as Depurator 102, reactor 104, reactor 106 one or more.
In other optional embodiments, waste gas stream 20 can be used as fuel and (such as produces for steam or common property is raw (co-gen) operation, and/or can be used as fuel and/or feed to thermal cracking unit, to form ethylene (such as, to form charging Stream 10).In another optional embodiment, the waste gas from waste gas stream 20 can export to monomer unit from device.
In embodiments, one or more disclosed systems (such as, PEP system 100,200,300,400 and/or 500) and/or the enforcement of method (such as, PEP method 600,700,800 and/or 900) can make to reclaim major part vinyl monomer, It otherwise due to this system or the operation of method, such as, is lost by burning.In embodiments, one or more public affairs The system opened can make to reclaim based on the gross weight of stream up to about 75%, alternatively, up to about 85%, alternatively, up to about 90%, alternatively, up to about the vinyl monomer otherwise will lost of 95%.In embodiments, one or more open systems Can make to reclaim based on the gross weight of stream up to about 75%, alternatively, up to about 85%, alternatively, up to about 90%, optional Ground, up to about the iso-butane otherwise will lost of 95%.Reclaim the unreacted vinyl monomer of this part, such as, by improving second The capital input that the utilization ratio of alkene monomer is relevant to obtaining vinyl monomer with minimizing, can produce significant economic benefit.Similar Ground, reclaims this part iso-butane, such as, by reducing the capital input relevant to obtaining iso-butane and/or by reducing torch The existence of iso-butane in discharge, can produce significant economic benefit.
In embodiments, the enforcement of one or more disclosed systems and/or method can reduce and is transferred to polyreaction The ethane of device 106 and/or the amount of hydrogen.In embodiments, the enforcement of one or more disclosed systems and/or method can reduce Recycled stream returns ethane and/or the amount of hydrogen of polymer reactor (such as reactor 104 and/or 106).In being flowed by minimizing The amount of the ethane to polymer reactor comprised, can improve polyethylene production aggregate efficiency (such as, by increase ethylene concentration, And the bubbling point being not up in loop reactor).Such as, reduce the amount of ethane in stream and can improve polymer reactor efficiency, improvement Catalyst efficiency, reduce Polymeric Soil, reduce the polymerization downtime, improve the production of bimodal polymers type, improve copolymer Production or a combination thereof.
In figure display various embodiments can be simplified and may not explain general device such as heat exchanger, pump and Compressor;But, the skilled person will appreciate that disclosed method and system may be included in whole polymers manufacturing and generally use This device.
The skilled person will appreciate that industry and commercial polyethylene manufacture method may required one or more usual several pressures Contracting machine or similar device.This compressor whole polyethylene manufacture in use, such as make during being polymerized reactor 104, 106 pressurizations.Additionally, the skilled person will appreciate that preparation method for polythene includes one or more degasifier and/or similar taking off Oxidation unit, such as purifying solvent or reactant and/or for cleaning the reactor of oxygen.Because such as providing power supply and maintaining pressure The base structure of contracting machine and/or degasifier and support in commercial polyethylene manufacturer exist, reallocation a part this Some available resources may need the most other capital cost in disclosed system so that In conjunction with disclosed system and or method.
Additionally, because having used compressor, degasifier and other assemblies various in various polyethylene process and system, The chance increasing the operation of this device can improve the aggregate efficiency of polyethylene production system and method.Such as, when a part of PEP method Or system off-line is when being used for keeping in repair and/or repairing, the system (such as, compressor, degasifier, reactor etc.) of other parts can continue Continuous offer according to current method services.Operation and/or reallocation resource are used for the operation of open PEP system and/or method can Thus improve the efficiency using conventional system.
Description additionally
Have been described with the method and system of Component seperation in paradigmatic system.There is provided terms hereinafter as further retouching State:
Embodiment A is the method for Component seperation in polymer production system, including:
Polymerizate flow separation becomes air-flow and polymer flow, and wherein air-flow includes ethane and unreacted ethylene;
Airflow distillation becomes lightweight hydrocarbon stream, and wherein lightweight hydrocarbon stream includes ethane and unreacted ethylene;
Lightweight hydrocarbon stream is made to contact with lyosoption system, wherein from least some of unreacted ethylene of lightweight hydrocarbon stream By lyosoption Systemic absorption;With
Reclaiming waste gas stream from lyosoption system, wherein waste gas stream includes ethane, hydrogen or a combination thereof.
The method of embodiment B embodiment A, farther includes:
Make lyosoption system regeneration to produce the ethylene reclaimed.
The method of embodiment C embodiment A, farther includes:
Become to include the effluent of iso-butane by airflow distillation.
The method of embodiment D embodiment A, farther includes:
Process waste gas stream in processing.
The method of embodiment E embodiment D, wherein processing equipment includes cracking unit, catalytic cracking unit, washing Device, converter, processing means, dehydrogenator, degasifier, torch or a combination thereof.
The method of embodiment F embodiment A, wherein absorbent solvent system is configured in scope from about 40 to about Operate at a temperature of 110.
The method of embodiment G embodiment A, wherein absorbent solvent system includes copper chloride, aniline and N-methyl pyrrole Pyrrolidone.
Embodiment H is the method for Component seperation in polymer production system, including:
Polymerizate flow separation becomes air-flow and polymer flow, and wherein air-flow includes ethane and unreacted ethylene;
Hydrocarbon stream and the first bottom stream in the middle of being become by airflow distillation, wherein middle hydrocarbon stream includes ethane, ethylene and isobutyl Alkane;
Centre hydrocarbon stream is distilled into lightweight hydrocarbon stream and the second bottom stream, and wherein lightweight hydrocarbon stream includes ethane and ethylene;
Lightweight hydrocarbon stream is made to contact with lyosoption system, wherein from least some of unreacted ethylene of lightweight hydrocarbon stream By lyosoption Systemic absorption;With
Reclaiming waste gas stream from lyosoption system, wherein waste gas stream includes ethane, hydrogen or a combination thereof.
The method of embodiment I embodiment H, farther includes:
Make lyosoption system regeneration to produce the ethylene reclaimed.
The method of embodiment J embodiment H, farther includes:
Middle hydrocarbon stream is distilled into the effluent including iso-butane, and wherein the second bottom stream includes iso-butane, Qi Zhong Two bottom streams are substantially free of alkene.
Embodiment K is the method for Component seperation in polymer production system, including:
Olefinic monomer is made to be polymerized in the first polymer reactor, with m-polymerizate stream in producing;
In Jiang m-polymerizate flow separation become in m-air-flow and in m-polymer flow, wherein in m-air-flow include second Alkane, unreacted ethylene and hydrogen;With
M-polymer flow is made to be polymerized in the second polymer reactor.
The method of embodiment L embodiment K, separating step includes the pressure of m-polymerizate stream in reduction, in order to dodge Steam ethylene, ethane, hydrogen or a combination thereof.
Embodiment M is the method for Component seperation in polymer production system, including:
Olefinic monomer is made to be polymerized in the first polymer reactor;
In Jiang m-polymerizate flow separation become in m-air-flow and in m-polymer flow, wherein in m-air-flow include ethane With unreacted ethylene;
M-polymer flow is made to be polymerized in the second polymer reactor;With
Scavenger was introduced before the second polymer reactor.
The method of embodiment N embodiment M, introduced scavenger before the second polymer reactor and includes drawing scavenger M-polymerizate stream in entering.
The method of embodiment O embodiment M, wherein scavenger includes hydrogenation catalyst.
The method of embodiment P embodiment M, wherein separating step includes:
The pressure of m-polymerizate stream in reduction, in order to flash distillation ethylene and ethane.
The method of embodiment Q embodiment M, wherein scavenger reduced the concentration of hydrogen before the second polymer reactor.
Embodiment R is the method for Component seperation in polymer production system, including:
Olefinic monomer is made to be polymerized in the first polymer reactor, with m-polymerizate stream in producing;
Make from m-polymerizate stream at least some of hydrogen degassing, with produce hydrogen reduce product stream;
By hydrogen reduce product stream be separated in m-air-flow and in m-polymer flow, wherein in m-air-flow include ethane With unreacted ethylene;With
M-polymer flow is made to be polymerized in the second polymer reactor.
The method of embodiment S embodiment R, separating step includes the pressure reducing the product stream that hydrogen reduces, in order to dodge Steam ethylene and ethane.
The method of embodiment T embodiment R, wherein in m-air-flow the amount of hydrogen account for less than about 1wt%.
The method of embodiment U embodiment R, farther includes:
In making, m-air-flow contacts with lyosoption system, wherein from least some of unreacted second of m-air-flow Alkene is by lyosoption Systemic absorption;With
Make lyosoption system regeneration to produce the ethylene reclaimed.
The method of embodiment V embodiment R, farther includes:
Reclaiming waste gas stream from lyosoption system, wherein waste gas stream includes ethane.
Embodiment
Generally described the disclosure, provide the following embodiment detailed description of the invention as the disclosure, to show Its practice and advantage.It should be understood that these are given by the way of explaination and are not intended to limit description or right by any way Claim.
Use the business method simulator calculated, to produce defeated from the model according to system disclosed herein and/or method Go out.The model used is explained in fig. 12, and it shows the embodiment of absorption system 1200 as disclosed herein, and is applied to The following examples are described.In the embodiment shown in fig. 12, from the PEP system 100,200,300,400 at Fig. 1 to 5 Or 500 embodiment disclosed in the light gas stream 1218 of polymerizate flow separation of polyethylene reactor 104,106 feed to Absorb reactor 1216.Total mole of light gas stream 1218 and mass flow and component molar and mass flow show table 1 below In:
Table 1
The unreacted ethylene entering absorption reactor 1216 is absorbed in the lyosoption system absorbing reactor 1216 In.The unreacted ethylene absorbed flow to the first regenerator 1220 as combined-flow 1228.In stream 1228, the ethylene quilt of absorption Heat exchanger REG1HEAT heats, subsequently into the first regenerator 1220.Ethylene is from the lyosoption system of the first regenerator 1220 Solvent desorption and flow through 1229 to Second reactivator 1222.Stream 1229 can cool down with heat exchanger REG2COOL, then enters Enter Second reactivator 1222.Ethylene reclaims in stream 1224.Lyosoption in stream 1232 and 2134 is at heat exchanger FEEDCOOL Middle combination is to be recycled to absorb reactor 1216 in stream 1230.
Table 2 display uses the operating condition of embodiment 1-44 of the ethylene recovery of the system 1200 of Figure 12.For aobvious in table 2 The embodiment shown, lyosoption system includes copper chloride, aniline and NMP system, as disclosed herein, and the group of purified product Compound ethylene recovery based on 90%.The compositions of the purified product reclaimed from the stream 1224 of Figure 12 include ethylene, ethane, nitrogen, Hydrogen and iso-butane.The wt% of each of these components of purified product shows in table 2.Selection is discussed further below from table The embodiment of 2.
Embodiment 3
In the embodiment 3 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 15, and wherein 14 Lean solvent temperature and the pressure of 40psig.First regenerator 120 operates at the temperature of 150 and the pressure of 0psig.Second again Raw device 122 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, system 900 reclaims the ethylene of 90% and molten Agent rate of circulating flow is to the amount of ethylene in 344,776lb/hr and purified product to 64.5%.
Embodiment 4
In the embodiment 4 of table 2, operating condition is same as in Example 3, and except for the difference that the first regenerator 1220 is 200 Temperature and 0psig pressure under operate.Under these conditions, for 143, the solvent rate of circulating flow of 736lb/hr, system 900 Reclaim the ethylene of 90%, and purified product comprises the ethylene of 77.5%.
Embodiment 7
In the embodiment 7 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 53, wherein lean solvent Temperature is 50.Absorb reactor 1216 also to operate under the pressure of 40psig.First regenerator 120 150 temperature and Operate under the pressure of 0psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, For 53, the solvent rate of circulating flow of 920lb/hr, system 900 reclaims the ethylene of 90%.The purified product compositions of embodiment 7 shows Show in table 2.
When comparing embodiment 7 and embodiment 3 and 4, in embodiment 7 53, the solvent rate of circulating flow of 920lb/hr is less than real Execute the flow velocity of 143,736lb/hr and 344,776lb/hr in example 3 and 4.Therefore, embodiment 7 shows the absorption temperature for 53 Comparing the absorption temperature of 15, the solvent rate of circulating flow absorbing ethylene requirement in copper chloride aniline NMP lyosoption system is less Much, this is because ethylene in lyosoption system dissolubility for below about 50 the beat all decline of temperature.
Embodiment 8
In the embodiment 8 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 55, wherein lean solvent Temperature is 50.Absorb reactor 1216 also to operate under the pressure of 40psig.First regenerator 1220 200 temperature and Operate under the pressure of 0psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, For 47, the solvent rate of circulating flow of 785lb/hr, system 800 reclaims the ethylene of 90%.The purified product compositions of embodiment 8 shows Show in table 2.
Embodiment 8 confirms in embodiment 7 result of display, when absorb reactor 1216 at a temperature of 55 rather than Lower solvent rate of circulating flow is needed during operation at a temperature of less than 50.Embodiment 2 additionally shows that regenerator 1220 is from 150 Change temperature to 200 and do not affect solvent rate of circulating flow with significance degree.
Embodiment 19
In the embodiment 19 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 53, wherein lean solvent Temperature is 50.Absorb reactor 1216 also to operate under the pressure of 40psig.First regenerator 1220 200 temperature and Operate under the pressure of 10psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 10psig.In these conditions Under, for 59, the solvent rate of circulating flow of 272lb/hr, system 1200 reclaims the ethylene of 90%.Purified product compositions shows In table 2.
Embodiment 19 confirms the lower solvent circulation rates discussed in embodiment 7 and 8 when comparing with embodiment 3 and 4. Embodiment 19 displays that changing pressure in the first and second regeneratoies 1220 and 1222 between 0psig and 10psig does not significantly changes Result.The regenerator 1220 and 1222 operation under 0psig can provide the product of lower solvent circulation rates and raising pure Spend, and the operation that regenerator 1220 and 1222 is under 10psig can provide safer design, because regenerator 1220 He Malleation in 1222 reduces in system and method air and the chance of water penetration through seepage, and this infiltration can be with lyosoption system Copper chloride reaction and suppression in system are carried out.
Embodiment 28
In the embodiment 28 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 52, wherein lean solvent Temperature is 50.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 100 temperature and Operate under the pressure of 0psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, For 58, the solvent rate of circulating flow of 613lb/hr, system 1200 reclaims the ethylene of 90%.Purified product compositions shows at table 2 In.
Under conditions of embodiment 28, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies In product, the amount of ethylene is significantly higher.
Embodiment 29
In the embodiment 29 of table 2, the absorption reactor 1216 in Figure 12 is 55 times operations, and wherein lean solvent temperature is 50℉.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 150 temperature and 0psig Pressure under operate.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, for The solvent rate of circulating flow of 51,106lb/hr, system 1200 reclaims the ethylene of 90%.Purified product compositions shows in table 2.
Under conditions of embodiment 29, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies In product, the amount of ethylene is significantly higher.
Embodiment 30
In the embodiment 30 of table 2, the absorption reactor 1216 in Figure 12 is 56 times operations, and wherein lean solvent temperature is 50℉.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 200 temperature and 0psig Pressure under operate.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.Under these conditions, for The solvent rate of circulating flow of 46,744lb/hr, system 1200 reclaims the ethylene of 90%.Purified product compositions shows in table 2.
Under conditions of embodiment 30, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies In product, the amount of ethylene is significantly higher.
Embodiment 33
In the embodiment 33 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 102, the leanest molten Agent temperature is 100.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 200 temperature Operate under the pressure of degree and 0psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 0psig.At these Under part, for 63, the solvent rate of circulating flow of 435lb/hr, system 900 reclaims the ethylene of 90%.The purified product group of embodiment 33 Compound shows in table 2.
Under conditions of embodiment 33, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies In product, the amount of ethylene is significantly higher.And, embodiment 33 display absorbs reactor 116 more molten than the maximum that dissolubility picture shows Operate at the higher temperature of temperature of Xie Du, such as, at 102 times as shown in embodiment 33, can still prove economically feasible Property, because such as, the condition that solvent rate of circulating flow compares embodiment 3 and 4 is the most relatively low.
Embodiment 40
In the embodiment 40 of table 2, the absorption reactor 1216 in Figure 12 operates at a temperature of 52, wherein lean solvent Temperature is 50.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 150 temperature and Operate under the pressure of 10psig.Second reactivator 1222 operates at the temperature of 50 and the pressure of 10psig.In these conditions Under, for 57, the solvent rate of circulating flow of 441lb/hr, system 1200 reclaims the ethylene of 90%.The purified product group of embodiment 40 Compound shows in table 2.
Under conditions of embodiment 40, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies In product, the amount of ethylene is significantly higher.
Embodiment 41
In the embodiment 41 of table 2, the absorption reactor 1216 in Figure 12 is 55 times operations, and wherein lean solvent temperature is 50℉.Absorb reactor 1216 also to operate under the pressure of 60psig.First regenerator 1220 200 temperature and 10psig Pressure under operate.Second reactivator 1222 operates at the temperature of 50 and the pressure of 10psig.Under these conditions, for The solvent rate of circulating flow of 51,482lb/hr, system 900 reclaims the ethylene of 90%.Purified product compositions shows in table 2.
Under conditions of embodiment 41, solvent rate of circulating flow is less than the solvent rate of circulating flow of embodiment 3 and 4, and purifies product In thing, the amount of ethylene is significantly higher.
Embodiment is simulated
Use the business method simulator calculated, to produce from the alternate model according to system disclosed herein and/or method Raw output.The model used is illustrated at Figure 13, the air-flow (such as, light gas stream disclosed herein) of the most named VAPFEED Charging is to absorbing reactor A SORB1.The output produced by business method simulator is material balance and thermally equilibrated, and display exists In table 3.The stream of explaination in name correspondence Figure 10 naming various streams enumerated in table 3.In Figure 13, ASORB1 is to absorb reaction Device, it is shown as the four stage absorbers 90 times operations.
Disclose at least one embodiment, and the embodiment (one or more) made by those skilled in the art And/or the modification of the feature (one or more) of embodiment, combine and/or revise and fall within the scope of this disclosure.By group Close, integrate and/or omit the optional embodiment of feature generation of embodiment (one or more) also at the model of the disclosure In enclosing.When clearly expressing numerical range or boundary, this expression scope or boundary are understood to include at the model clearly expressed Enclose or the iteration ranges of same number level in boundary or boundary (such as, include 2,3,4 etc. from about 1 to about 10;More than 0.10 bag Include 0.11,0.12,0.13 etc.).Such as, no matter when disclose there is lower limit RlWith upper limit RuNumerical range, specifically public Open any numerical value within the range.In particular, following numerical value within the range: R=R is specifically disclosedl+k* (Ru-Rl), wherein k be scope from 1% to 100%, the variable of 1% increment, i.e. k is 1%, 2%, 3%, 4%, 5% ... 50%, 51%, 52% ... 95%, 96%, 97%, 98%, 99% or 100%.And, also specifically disclose as defined above Any numerical range of two R numerical definitenesses.Term " optionally " meaning is used to be needs with regard to any key element in claim This key element or optionally need not this key element, two kinds of replacement schemes are all intended to fall within the scope of the appended claims.The use of wider term, Such as comprise, include and have the term being interpreted as narrower, such as by ... composition, substantially by ... composition, and base On Ben by ... constitute provide support.Therefore, the description that protection domain is not illustrated above limits, but by appended right Requiring to limit, this scope includes all equivalents of claim theme.Each and all of claim is as further Disclosure is incorporated in description, and claim is the embodiment (one or more) of invention disclosed theme.In the disclosure The discussion of list of references does not approve that it is prior art, the especially publication date any reference after the priority of the application Document.All patents, patent application and the publication quoted in the disclosure are incorporated herein by, and are the disclosure to them Exemplary, procedural or that other details are supplementary degree is provided.

Claims (16)

1. the method for Component seperation in polymer production system, including:
A. olefinic monomer is made to be polymerized in the first polymer reactor, with m-polymerizate stream in producing;
B. in m-polymerizate flow separation in described being become m-air-flow and in m-polymer flow, wherein said in m-air-flow bag Include ethane, unreacted ethylene and hydrogen;
C. make described in m-polymer flow be polymerized in the second polymer reactor;
D. make described in m-air-flow contact with lyosoption system, wherein from m-air-flow at least some of described in described Unreacted ethylene is included copper chloride, aniline and N-first by described lyosoption Systemic absorption, wherein said lyosoption system Base ketopyrrolidine;With
E. make described lyosoption system regeneration to produce the ethylene reclaimed.
2. the method described in claim 1, described separating step include reducing described in the pressure of m-polymerizate stream, in order to Flash distillation ethylene, ethane, hydrogen or a combination thereof.
3. the method for Component seperation in polymer production system, including:
A. olefinic monomer is made to be polymerized in the first polymer reactor;
B. will in m-polymerizate flow separation become in m-air-flow and in m-polymer flow, wherein said in m-air-flow include second Alkane and unreacted ethylene;
C. make described in m-polymer flow be polymerized in the second polymer reactor;
D. before described second polymer reactor, introduce scavenger;
E. make described in m-air-flow contact with lyosoption system, wherein from m-air-flow at least some of described in described Unreacted ethylene is included copper chloride, aniline and N-first by described lyosoption Systemic absorption, wherein said lyosoption system Base ketopyrrolidine;With
F. make described lyosoption system regeneration to produce the ethylene reclaimed.
4. the method described in claim 3, described before described second polymer reactor introduce scavenger include by described clearly Except agent introduce described in m-polymerizate stream.
5. the method described in claim 3, wherein said scavenger includes hydrogenation catalyst.
6. the method described in claim 3, wherein said separating step includes:
Reduce described in the pressure of m-polymerizate stream, in order to flash distillation ethylene and ethane.
7. the method described in claim 3, wherein said scavenger reduced the concentration of hydrogen before described second polymer reactor.
8. the method for Component seperation in polymer production system, including:
A. olefinic monomer is made to be polymerized in the first polymer reactor, with m-polymerizate stream in producing;
B. make from least some of hydrogen degassing of m-polymerizate stream in described, to produce the product stream that hydrogen reduces;
C. in the product stream that described hydrogen reduces being separated into m-air-flow and in m-polymer flow, wherein said in m-air-flow bag Include ethane and unreacted ethylene;
D. make described in m-polymer flow be polymerized in the second polymer reactor;
E. make described in m-air-flow contact with lyosoption system, wherein from m-air-flow at least some of described in described Unreacted ethylene is included copper chloride, aniline and N-first by described lyosoption Systemic absorption, wherein said lyosoption system Base ketopyrrolidine;With
F. make described lyosoption system regeneration to produce the ethylene reclaimed.
9. the method described in claim 8, described separating step includes the pressure reducing the product stream that described hydrogen reduces, in order to dodge Steam ethylene and ethane.
10. the method described in claim 8, wherein said in m-air-flow the amount of hydrogen account for less than 1wt%.
The method described in any one of 11. claim 1,3 and 8, farther includes:
Reclaiming waste gas stream from described lyosoption system, wherein said waste gas stream includes ethane.
Method described in 12. claim 11, farther includes:
Process described waste gas stream in processing.
Method described in 13. claim 12, wherein said processing equipment includes processing means.
Method described in 14. claim 12, wherein said processing equipment includes cracking unit, scrubber, converter, dehydrogenation Device, degasifier, torch or a combination thereof.
Method described in 15. claim 12, wherein said processing equipment includes catalytic cracking unit.
The method described in any one of 16. claim 1,3 and 8, wherein said lyosoption system is configured in scope from 40 Operate at a temperature of 110.
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