CN115057953B - Olefin polymerization method and device - Google Patents
Olefin polymerization method and device Download PDFInfo
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- CN115057953B CN115057953B CN202210885367.0A CN202210885367A CN115057953B CN 115057953 B CN115057953 B CN 115057953B CN 202210885367 A CN202210885367 A CN 202210885367A CN 115057953 B CN115057953 B CN 115057953B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 126
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 238000003860 storage Methods 0.000 claims abstract description 48
- 238000012660 binary copolymerization Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 53
- 239000005977 Ethylene Substances 0.000 claims description 53
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 29
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 11
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- 229920000573 polyethylene Polymers 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 60
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 43
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 17
- 229920000098 polyolefin Polymers 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000002902 bimodal effect Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 5
- 239000004707 linear low-density polyethylene Substances 0.000 description 5
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- UEEXYHHZSOEEDG-UHFFFAOYSA-N methylaluminum(2+);oxygen(2-) Chemical compound [O-2].[Al+2]C UEEXYHHZSOEEDG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0005—Catalytic processes under superatmospheric pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1809—Controlling processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method and a device for olefin polymerization, and belongs to the technical field of olefin polymerization. The invention condenses and stores the different components in a storage tank by a gas-liquid separation device on a circulation line. By controlling the valve switch on the pipeline between the storage tank and the polymerization reactor, condensate containing different comonomers can be input into the reactor, so that the switching of olefin copolymerization and homopolymerization or different copolymerization reactions can be realized. In addition, the invention realizes the regulation and control of the polyethylene molecular chain structure by inputting condensate containing different comonomers at different positions of the reactor and forming different polymerization environments in the fluidized bed. The invention can realize the alternate process of olefin homo-polymerization and copolymerization reaction or/and olefin binary copolymerization and ternary copolymerization reaction, and obtain the product with excellent performance; and the switching speed of different polymerization products is high, the operation is flexible and convenient, the continuous operation of the reactor is not influenced, and the method has high practical value.
Description
Technical Field
The invention relates to an olefin polymerization method and an olefin polymerization device. In particular to an olefin polymerization device and a method for producing polyolefin and polyolefin copolymer.
Background
Fluidized bed reactors are very widely used in olefin polymerization production. The main structure is a section of hollow cylinder and a distributing plate, and the polymerization reaction occurs above the distributing plate. The gas-phase fluidized bed polyolefin production process has the advantages of shorter flow, lower operation cost, simple product separation flow, less three-waste discharge and the like, and is gradually developed into one of the main methods of the polyolefin industry.
Conventional gas phase fluidized bed reactors can only produce a single polyolefin product. In order to produce polyolefin products having both processability and mechanical properties, for example bimodal polyolefin or polyolefin products of broad molecular weight distribution. This can be achieved by a cascade reactor process. Chinese patent 102844333a discloses a bimodal polyethylene production process for blow molding applications. The polyethylene resin is produced by using at least two slurry loop reactors in series with each other under Ziegler-Natta catalyst, and the obtained product has bimodal molecular weight distribution, but the process flow is complex and the engineering investment cost and the operation cost are high because the materials need to pass through the two reactors.
The reactor parallel process can also produce bimodal/broad-peak polyethylene. Chinese patent 108530568A discloses a novel parallel reaction process for producing bimodal polyethylene, which comprises the steps of respectively preparing polyethylene with high molecular weight and low molecular weight in two parallel polymerization reactors with different raw material ratios, discharging, mixing, recycling one part, and leading the other part out as a product. The process also has the problems of complex process flow and high production cost, and the uniformity of the product quality is difficult to ensure.
With the development of the polyolefin industry, the production of bimodal polyethylene using mixed catalysts, or catalysts with different active sites, in a single reactor has become a new research hotspot. Chinese patent 107540767B discloses a preparation method of a metal catalyst for bimodal polyethylene. Chromium and vanadium compounds are loaded on a silica gel carrier, so that the obtained catalyst has two active centers. Chromium active centers provide a lower molecular weight polyethylene product and vanadium active centers provide a high molecular weight polyethylene product.
Chinese patent 201410748891 discloses an apparatus and method for producing a wide distribution of polyolefin products using a single fluidized bed reactor. By arranging a gas-liquid separation device on a gas circulation pipeline, part or all of condensate is separated from the circulating gas flow and stored in a storage tank, and condensing agent and/or comonomer is intermittently introduced into the reactor so as to realize olefin homo-polymerization and copolymerization or switching of different copolymerization reactions. Chinese patent 104628904B discloses a process for preparing a wide distribution of polyolefin products using a multi-temperature reaction zone. The components such as polymerized monomer and condensing agent are used as circulating medium, and polymerization reaction areas with different temperatures are formed in the fluidized bed reactor to generate high-molecular-weight polyolefin with high branched chains and low density and low-molecular-weight polyolefin with low branched chains and high density, so that polyolefin products with wider distribution and uniform mixing can be obtained. The process lacks flexibility in regulating the molecular weight distribution of the polyolefin product.
The present patent proposes a process for producing broad-peak polyethylene using a single fluidized bed reactor, which is expected to solve the above-mentioned problems in the art.
Disclosure of Invention
The object of the present invention is to provide a novel apparatus and process for olefin polymerization which enables the different components to be condensed by a gas-liquid separation device on a recycle line and stored in a storage tank. By controlling the valve switch on the pipeline between the storage tank and the polymerization reactor, condensate containing different comonomers can be input into the reactor, so that the switching of olefin copolymerization and homopolymerization or different copolymerization reactions can be realized. In addition, the invention realizes the regulation and control of the polyethylene molecular chain structure by inputting condensate containing different comonomers at different positions of the reactor and forming different polymerization environments in the fluidized bed.
One embodiment of the present invention relates to an olefin polymerization apparatus, specifically comprising:
a polymerization reactor for carrying out homo-and/or copolymerization of olefins;
a compressor connected to at least one outlet of the polymerization reactor for receiving the recycle gas at the upper outlet of the polymerization reactor and maintaining the recycle gas flowing in the pipeline;
at least 2 heat exchangers for stepwise reducing the temperature of the recycle stream to condense the different components separately; the first heat exchanger is connected with at least one outlet of the compressor and at least one inlet of the first gas-liquid separator, and the second heat exchanger is connected with at least one outlet of the first gas-liquid separator and at least one inlet of the second gas-liquid separator respectively; at least 2 gas-liquid separators including a first gas-liquid separator and a second gas-liquid separator for separating condensate and remaining gas after condensing the recycle gas;
and at least 2 storage tanks which are respectively used for receiving and storing condensate separated from each gas-liquid separator, wherein the storage tanks are connected with at least one inlet of the polymerization reactor, and a valve is arranged on a pipeline between each storage tank and the polymerization reactor.
In a preferred embodiment of the invention, the at least 2 reservoirs comprise:
a first storage tank connected to at least one outlet of the first gas-liquid separator and at least one inlet of the polymerization reactor, respectively, for receiving and storing condensate separated in the first gas-liquid separator;
a second storage tank connected to at least one outlet of the second gas-liquid separator and at least one inlet of the polymerization reactor, respectively, for receiving and storing condensate separated in the second gas-liquid separator;
according to the requirement of a target product, a valve on a pipeline between the first storage tank or the second storage tank and the polymerization reactor can be opened or closed, so that part of monomers are gathered in the storage tank and are not introduced into the polymerization reactor any more, and the switching between olefin copolymerization and homopolymerization or the switching between different copolymerization reactions is realized.
In a preferred embodiment of the present invention, the polymerization reactor is a fluidized bed reactor;
in a preferred embodiment of the present invention, the gas-liquid separator includes a surge tank separator and a cyclone separator.
In a preferred embodiment of the invention, the polymerization reactor is connected to the heat exchanger by a compressor;
a compressor connected to at least one outlet of the polymerization reactor for receiving the recycle gas at the upper outlet of the polymerization reactor and maintaining the recycle gas flowing in the pipeline;
in a preferred embodiment of the invention, the reservoir is connected to the polymerization reactor by a pump.
In a preferred embodiment of the invention, the storage tank is connected to at least 1 inlet of the polymerization reactor, preferably 3-6 inlets.
In a preferred embodiment of the invention, the comonomer is ethylene, butene, hexene or other alpha olefins having less than 18 carbon atoms.
In a preferred embodiment of the invention, the device can control the input of liquid feed by controlling the valve switch on the pipeline between the storage tank and the polymerization reactor, so as to realize the switching of olefin copolymerization and homo-polymerization reaction or the switching of different copolymerization reactions.
A second embodiment of the present invention provides a process for the polymerization of olefins, in particular:
1) Providing the polymerization reaction device;
2) Introducing a polymerization monomer into a polymerization reactor from a feed inlet of the polymerization reactor to carry out homopolymerization and/or copolymerization, and leading out circulating gas from a discharge outlet of the polymerization reactor;
3) After the circulating gas is subjected to multiple heat exchange and gas-liquid separation, storing condensate separated by each stage of gas-liquid separator in different storage tanks, and circulating the residual gas to the reactor through a reactor feed inlet for continuous reaction, so as to form a circulating loop;
according to the requirement of a target product, a valve on a pipeline between the storage tank and the polymerization reactor can be opened or closed to enable part of polymerization monomers to be introduced into the polymerization reactor or not, or comonomer is introduced into the polymerization reactor at intervals, so that the switching of olefin copolymerization and homopolymerization or different copolymerization is realized.
Specifically, when the polymerization reaction device is used for producing a ternary polymerization product, circulating gas at the outlet of the top end of the polymerization reactor enters the first heat exchanger and the first gas-liquid separator after being pressurized by the compressor, the outlet temperature of the first heat exchanger is higher, heavy components are condensed into the first storage tank, and the heavy components are introduced into different positions of the polymerization reactor through the feed pump. The remaining gas stream continues through a second heat exchanger and a second gas-liquid separator, the second heat exchanger having a lower outlet temperature, the lighter components condensing into a second storage tank and being introduced into different locations of the polymerization reactor by a feed pump. The remaining gas stream is passed from the bottom into the polymerization reactor.
When the copolymerization is switched from the ternary polymerization to the binary copolymerization, valves on the pipelines between the two storage tanks and the polymerization reactor are controlled according to the difference of target products so as to withdraw part of the comonomer.
When heavy component monomer is required to be withdrawn from the reaction system, a first storage tank is used as a storage tank of the heavy component monomer, a valve on a pipeline between the first storage tank and the polymerization reactor is closed, the valve on the pipeline between the second storage tank and the polymerization reactor is kept open, a liquid phase flow condensed by the first gas-liquid separator is gradually accumulated in the first storage tank, and meanwhile, part of the light component monomer and/or condensing agent is fed into a circulating pipeline from a compressor inlet so as to maintain the stability of the load of the reactor.
When light component monomers are required to be withdrawn from the reaction system, a valve on a pipeline between the first storage tank and the polymerization reactor is kept open, and the valve on the pipeline between the second storage tank and the polymerization reactor is closed, so that a liquid phase flow condensed by the second gas-liquid separator is gradually accumulated in the second storage tank, and meanwhile, part of heavy component monomers and/or condensing agents are supplemented into a circulating pipeline from a compressor inlet to maintain the stability of the load of the reactor.
When the copolymerization is switched from binary copolymerization to ternary copolymerization, a valve on a pipeline between two storage tanks and a polymerization reactor is opened, and simultaneously, polymerization monomers and/or condensing agents are fed in from an inlet of a compressor so as to maintain the stability of the load of the reactor.
In a preferred embodiment of the present invention, the polymerization reactor is a fluidized bed reactor.
In a preferred embodiment of the invention, the outlet temperature of the first heat exchanger is 55-80 ℃ and the outlet temperature of the second heat exchanger is 35-55 ℃.
In a preferred embodiment of the invention, the comonomer is ethylene, butene, hexene or other alpha olefins having less than 18 carbon atoms.
The olefin polymerization method provided by the invention can be used for olefin homopolymerization, binary or ternary polymerization, and the polymerization monomer comprises at least 1 of ethylene, butene, hexene or other alpha-olefins with less than 18 carbon atoms. The comonomer tanks may be used to store one or a mixture of butenes, hexenes, or other alpha-olefins having less than 18 carbon atoms, and condensing agents, respectively.
In a preferred embodiment of the present invention, the catalyst used in the polymerization process is selected from the group consisting of conventional Ziegler-Natta catalysts, metal chromium catalysts, metallocene catalysts, post-transition metal catalysts, preferably Ziegler-Natta catalysts.
In a preferred embodiment of the invention, a certain switching frequency is maintained between the olefin binary copolymerization and ternary copolymerization. In particular, the switching frequency between reactions is between 1 and 8 times per hour, preferably 5 times per hour.
In a preferred embodiment of the present invention, at least one of a cocatalyst, a regulator, and an inert component may be further included in the recycle component of the polymerization process.
In a preferred embodiment of the invention, at least one of cocatalyst, polymerization monomer, antistatic agent, chain transfer agent, condensing agent and inert gas is introduced into the reactor and/or the circulation loop during the polymerization.
The cocatalyst mainly comprises alkyl aluminum and alkoxy aluminum, preferably methyl aluminum oxide, trimethyl aluminum, triethyl aluminum and triisobutyl aluminum. In embodiments of the present invention, proper handling is necessary to avoid spontaneous combustion in air when cocatalysts are used.
The regulator is used for regulating the molecular weight and molecular weight distribution of the olefin polymer and is selected from one of propylene, propionaldehyde and hydrogen, preferably hydrogen. The inert component is preferably nitrogen.
In a preferred embodiment of the present invention, the reaction pressure of the polymerization reaction is 0.5 to 8MPa, preferably 1 to 5MPa; the reaction temperature is 50 to 140℃and preferably 55 to 120 ℃. The separation efficiency of the gas-liquid separator is 20 to 100%, preferably 50 to 100%.
Compared with the prior art, the invention has the following advantages:
1) By introducing and extracting comonomer, the olefin homo-polymerization and copolymerization reaction or/and olefin binary copolymerization and ternary copolymerization reaction can be alternately carried out, and a product with excellent performance can be obtained;
2) The switching speed of different polymerization products is high, the operation is flexible and convenient, the continuous operation of the reactor is not influenced, and the method has high practical value.
Drawings
FIG. 1 is a simplified flow diagram of a polymerization reaction system in one embodiment of the present invention.
FIG. 2 shows H in condensate at the outlet of a two-stage gas-liquid separator in accordance with one embodiment of the present invention 2 /C 2 、Cx/C 2 The change in value with temperature.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
FIG. 1 is a simplified schematic diagram of an olefin polymerization apparatus and process comprising:
a fluidized bed reactor 1 and a distribution plate 2 for carrying out homo-polymerization and/or copolymerization reactions;
a gas circulation line 12 for circulating gaseous material from the reactor outlet to the gas phase distribution zone of the fluidized bed reactor 1;
fluid lines 13 and 14 for liquid material to be introduced into the fluidized bed reactor 1;
a fluid conduit 17 for introducing monomers, low boiling point comonomers, etc. into the fluidized bed reactor 1, a fluid conduit 18 for introducing molecular weight regulators, etc. into the fluidized bed reactor 1, a fluid conduit 19 for introducing high boiling point comonomers, condensing agents, etc. into the fluidized bed reactor 1;
a fluid conduit 15 for introducing polymerization catalyst into said fluidized bed reactor 1;
a fluid conduit 16 for withdrawing polyolefin product from said fluidized bed reactor 1;
a compressor 3 for receiving the recycle gas at the upper outlet of the fluidized bed reactor 1 and maintaining the flow of the recycle gas in the pipeline;
heat exchange means 4 for cooling the gaseous material at the outlet of said fluidized bed reactor 1 and heat exchange means 8 for cooling the gaseous material at the outlet of the separation means 5;
a separation device 5 and a separation device 9 for recovering condensate in the cooled gaseous material;
a first tank 6 and a second tank 10 for storing condensate and comonomer;
a first feed pump 7 and a second feed pump 11 for introducing condensate and comonomer into the fluidized bed reactor 1;
wherein, the recycle gas flow with reaction products after reaction is led out from the top of the fluidized bed reactor 1, enters a gas recycle pipeline 12, flows through a compressor 3 and a heat exchanger 4, and enters a gas-liquid separator 5 from the partially condensed recycle gas flow flowing out of the heat exchanger 4, wherein liquid materials in the gas-liquid separator 5 are partially or completely separated and enter a first storage tank 6, the rest material flow passes through the heat exchanger 8, the flowing partially condensed recycle gas flow enters a gas-liquid separator 9, and the liquid materials in the gas-liquid separator 9 are partially or completely separated and enter a second storage tank 10. The remaining gas phase enriched stream enters the gas phase distribution zone of reactor 1, completing a cycle.
In the production of the ternary polymerization product, heavy and light component condensate in the first storage tank 6 and the second storage tank 10 are respectively introduced above the distribution plate 2 of the fluidized bed reactor 1 through a pipeline 13 and a pipeline 14 by a first feed pump 7 and a second feed pump 11; and when the reaction is switched to binary copolymerization reaction, the partial comonomer is withdrawn according to different target products. When heavy component monomers are required to be withdrawn from the reaction system, the heavy component condensate in the first storage tank 6 is not introduced into the reactor 1; when it is desired to withdraw the light fraction monomer from the reaction system, the light fraction condensate in the second tank 10 is not introduced into the reactor 1.
Fresh reaction feed gas required for the reaction is introduced into the gas circulation line 12 via line 17, molecular weight regulator is introduced into the gas circulation line 12 via line 18, condensing agent is introduced into the gas circulation line 12 via line 19, catalyst is introduced into the reactor 1 intermittently or continuously via line 15, and solid polymer produced in the polymerization is discharged intermittently or continuously from line 16 and fed to downstream stages for further processing.
Example 1:
linear Low Density Polyethylene (LLDPE) was produced in a fluidized bed olefin polymerization reactor as shown in FIG. 1 using a Ziegler-Natta (Z-N) catalyst at a polymerization temperature of 88℃and a pressure of 2.45MPa, with an apparent gas velocity of 0.65m/s.
When the terpolymer (ethylene, butene, hexene copolymerization) is cut into the binary copolymer (ethylene, butene copolymerization), the recycle gas stream in line 12 comprises hydrogen, nitrogen, ethylene, butene, hexene, and isopentane. The pump 7 was closed to the valve on the fluidized bed reactor 1, keeping the remaining valves open. The outlet temperature of the heat exchanger 4 was 65℃and the outlet stream contained 15.0% by mass of condensate comprising mainly hexene and isopentane with a liquid phase density of 600.2kg/m 3 The gas phase density was 24.8kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, 11.1 percent of condensate is contained in the outlet airflow of the heat exchanger 8, and the liquid phase density is 617.7kg/m 3 The gas phase density was 24.6kg/m 3 The reactor is changed from ethylene, butene and hexene copolymerization into ethylene and butene copolymerization, and partial polymerization monomer and/or condensing agent are fed into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is cut into ternary copolymerization (ethylene, butene and hexene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 60% of condensate at the outlet of a gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor to carry out ternary copolymerization of ethylene, butene and hexene after passing through a heat exchanger 8 and a gas-liquid separator 9. Repeatedly switching the above binary and ternaryThe meta-copolymerization is switched 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9228g/cm 3 The melt flow index was 0.98g/10min and the dart impact breakage weight was 144g.
Example 2:
linear Low Density Polyethylene (LLDPE) was produced in a fluidized bed olefin polymerization reactor as shown in FIG. 1 using a Ziegler-Natta (Z-N) catalyst at 86℃and a pressure of 2.3MPa and a reactor space velocity of 0.61m/s.
When ternary polymerization (ethylene, butene and octene copolymerization) is cut into binary copolymerization (ethylene and butene copolymerization), the valve on the pump 7 to the fluidized bed reactor 1 is closed, and the rest valves are kept open, and the circulating gas flow in the pipeline 12 comprises hydrogen, nitrogen, ethylene, butene, octene and isopentane. The outlet temperature of the heat exchanger 4 was 65℃and the outlet stream contained 28.4% of condensate comprising mainly octene and isopentane with a density of 559.3kg/m 3 The gas phase density was 24.8kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, the outlet airflow of the heat exchanger 8 contains 2.4 percent of condensate, and the gas phase density is 26.7kg/m 3 The reactor is internally changed from ethylene, butene and octene copolymerization reaction into ethylene and butene copolymerization reaction, and meanwhile, partial polymerization monomer and/or condensing agent are fed into a circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is cut into ternary polymerization (ethylene, butene and octene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 80% of condensate at the outlet of a gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor to carry out ternary polymerization of ethylene, butene and octene after passing through a heat exchanger 8 and a gas-liquid separator 9. The above binary and ternary polymerization reactions were repeatedly switched 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9136g/cm 3 Melt flow index of 0.95g/10min, dart impact breakage weight of 148g。
Example 3:
linear Low Density Polyethylene (LLDPE) was produced in a fluidized bed olefin polymerization reactor as shown in FIG. 1 using a Ziegler-Natta (Z-N) catalyst at a polymerization temperature of 85℃and a pressure of 2.5MPa and a reactor space velocity of 0.68m/s.
When ternary polymerization (ethylene, butene and octene copolymerization) is cut into binary copolymerization (ethylene and butene copolymerization), the valve on the pump 7 to the fluidized bed reactor 1 is closed, and the rest valves are kept open, and the circulating gas flow in the pipeline 12 comprises hydrogen, nitrogen, ethylene, butene, octene and isopentane. The outlet temperature of the heat exchanger 4 was 75℃and the outlet stream contained 26.7% of condensate comprising mainly octene and isopentane with a liquid phase density of 550.9kg/m 3 The gas phase density was 26.5kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, the outlet airflow of the heat exchanger 8 contains 4.2 percent of condensate, and the liquid phase density is 588kg/m 3 The gas phase density was 28.7kg/m 3 The reactor is internally changed from ethylene, butene and octene copolymerization reaction into ethylene and butene copolymerization reaction, and meanwhile, partial polymerization monomer and/or condensing agent are fed into a circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is cut into ternary polymerization (ethylene, butene and octene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 80% of condensate at the outlet of a gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor to carry out ternary polymerization of ethylene, butene and octene after passing through a heat exchanger 8 and a gas-liquid separator 9. The above binary and ternary polymerization reactions were repeatedly switched 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9189g/cm 3 The melt flow index was 0.88g/10min and the dart impact breaking weight was 162g.
In this example, the outlet temperature of the heat exchanger 4 was varied, and the outlet temperature of the heat exchanger 8 was maintained at 42℃to obtainH of gas-liquid separator 5 and gas-liquid separator 9 outlet liquid phase flow 2 /C 2 、Cx/C 2 The variation is shown in fig. 2. Under the operating conditions of the examples herein, H in the outlet streams of the two gas-liquid separators 2 /C 2 、Cx/C 2 There are significant differences.
Example 4:
medium Density Polyethylene (MDPE) was produced in a fluidized bed olefin polymerization reactor as shown in fig. 1 using a ziegler-natta (Z-N) catalyst at 92 c and a pressure of 2.1MPa at a reactor superficial velocity of 0.61m/s.
When ternary polymerization (ethylene, butene and hexene copolymerization) is cut into binary copolymerization (ethylene and butene copolymerization), the valve on the pump 7 to the fluidized bed reactor 1 is closed, and the rest valves are kept open, and the circulating gas flow in the pipeline 12 comprises hydrogen, nitrogen, ethylene, butene, hexene and isopentane. The outlet temperature of the heat exchanger 4 was 65℃and the outlet stream contained 12.6% of condensate comprising mainly octene and isopentane with a liquid phase density of 600.2kg/m 3 The gas phase density was 24.8kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, the outlet airflow of the heat exchanger 8 contains 12.1 percent of condensate, and the liquid phase density is 617.7kg/m 3 The gas phase density was 24.6kg/m 3 The reactor is changed from ethylene, butene and hexene copolymerization into ethylene and butene copolymerization, and partial polymerization monomer and/or condensing agent are fed into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is cut into ternary copolymerization (ethylene, butene and hexene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 70% of condensate at the outlet of a gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor through a heat exchanger 8 and a gas-liquid separator 9 to carry out ternary copolymerization of ethylene, butene and hexene. The above binary and ternary polymerization reactions were repeatedly switched 6 times per hour. The medium density polyethylene produced according to this exampleDensity is 0.9324g/cm 3 。
Example 5:
high Density Polyethylene (HDPE) was produced in a fluidized bed olefin polymerization reactor as shown in FIG. 1 using a Ziegler-Natta (Z-N) catalyst at a polymerization temperature of 100deg.C and a pressure of 2.1MPa and a reactor superficial velocity of 0.61m/s.
When ternary polymerization (ethylene, butene and hexene copolymerization) is cut into binary copolymerization (ethylene and butene copolymerization), the valve on the pump 7 to the fluidized bed reactor 1 is closed, and the rest valves are kept open, and the circulating gas flow in the pipeline 12 comprises hydrogen, nitrogen, ethylene, butene, hexene and isopentane. The outlet temperature of the heat exchanger 4 was 67℃and the outlet stream contained 11.3% of condensate comprising mainly octene and isopentane with a liquid phase density of 598.5kg/m 3 The gas phase density was 24.6kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, the outlet airflow of the heat exchanger 8 contains 13.4 percent of condensate, and the liquid phase density is 617.8kg/m 3 The gas phase density was 24.2kg/m 3 The reactor is changed from ethylene, butene and hexene copolymerization into ethylene and butene copolymerization, and partial polymerization monomer and/or condensing agent are fed into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is cut into ternary copolymerization (ethylene, butene and hexene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 70% of circulating flow streams at the outlet of a gas-liquid separator 5 enter a comonomer tank 6, and the rest part is finally introduced into the fluidized bed reactor through a heat exchanger 8 and a gas-liquid separator 9 to carry out ternary copolymerization of ethylene, butene and hexene. The above binary and ternary polymerization reactions were repeatedly switched 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9479g/cm 3 。
Example 6:
linear Low Density Polyethylene (LLDPE) was produced in a fluidized bed olefin polymerization reactor as shown in FIG. 1 using a Ziegler-Natta (Z-N) catalyst at a polymerization temperature of 85℃and a pressure of 2.3MPa and a reactor space velocity of 0.63m/s.
When copolymerization (ethylene, hexene copolymerization) is switched into ethylene homopolymerization, the valves from pump 7 to fluidized bed reactor 1 and from pump 11 to fluidized bed 1 are closed, the remaining valves are kept open, and the recycle gas stream in line 12 comprises hydrogen, nitrogen, ethylene, hexene and isopentane. The outlet temperature of the heat exchanger 4 was 65℃and the outlet stream contained 10.7% of condensate comprising mainly hexene and isopentane with a liquid phase density of 594.3kg/m 3 The gas phase density was 26.9kg/m 3 Through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for use, and the remaining stream enters the heat exchanger 8 with the recycle gas. The outlet temperature of the heat exchanger 8 is 42 ℃, after multiple circulation, 11.4% of condensate is contained in the outlet airflow of the heat exchanger 8, and the liquid phase density is 598.6kg/m 3 The gas phase density was 27.5kg/m 3 The reactor is changed from ethylene and hexene copolymerization reaction to ethylene homopolymerization reaction, and part of ethylene and/or condensing agent is fed into a circulating pipeline to maintain the stable load of the reactor.
When ethylene homopolymerization is switched into binary copolymerization (ethylene and hexene copolymerization), a valve on a pump 7 to a fluidized bed reactor 1 is opened, 70% of circulating flow at the outlet of a gas-liquid separator 5 enters a comonomer tank 6, and the rest part is introduced into the fluidized bed reactor through a heat exchanger 8 and a gas-liquid separator 9 to carry out ethylene and hexene binary copolymerization. The above homo-and copolymerization reactions were repeated 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9156g/cm 3 。
Claims (5)
1. A process for the polymerization of olefins, said process comprising:
1) There is provided an olefin polymerization plant, comprising:
a polymerization reactor for carrying out homo-and/or copolymerization of olefins;
a compressor connected to at least one outlet of the polymerization reactor for receiving the recycle gas at the upper outlet of the polymerization reactor and maintaining the recycle gas flowing in the pipeline;
at least 2 heat exchangers for stepwise reducing the temperature of the recycle stream to condense the different components separately; the first heat exchanger is connected with at least one outlet of the compressor and at least one inlet of the first gas-liquid separator, and the second heat exchanger is connected with at least one outlet of the first gas-liquid separator and at least one inlet of the second gas-liquid separator respectively; at least 2 gas-liquid separators including a first gas-liquid separator and a second gas-liquid separator for separating condensate and remaining gas after condensing the recycle gas;
at least 2 storage tanks for receiving and storing the condensate separated in each gas-liquid separator, respectively, the storage tanks being connected to at least one inlet of the polymerization reactor;
2) Introducing a polymerization monomer into a polymerization reactor from a feed inlet of the polymerization reactor to carry out homopolymerization and/or copolymerization, and leading out circulating gas from a discharge outlet of the polymerization reactor;
3) After the circulating gas is subjected to multiple heat exchange and gas-liquid separation, storing condensate separated by each stage of gas-liquid separator in different storage tanks, and circulating the residual gas to the reactor through a reactor feed inlet for continuous reaction, so as to form a circulating loop;
according to the requirement of a target product, a valve on a pipeline between the storage tank and the polymerization reactor is opened or closed to enable part of polymerization monomers to be introduced into the polymerization reactor or not, or comonomer is introduced into the polymerization reactor at intervals, so that the switching between olefin copolymerization and homopolymerization or the switching between different copolymerization reactions is realized;
when the copolymerization is switched from the ternary polymerization to the binary copolymerization, valves on a pipeline between the two storage tanks and the polymerization reactor are controlled according to the difference of target products so as to withdraw part of comonomer;
when heavy component monomers are required to be withdrawn from the reaction system, a first storage tank is used as a storage tank of the heavy component monomers, a valve on a pipeline between the first storage tank and the polymerization reactor is closed, the valve on the pipeline between the second storage tank and the polymerization reactor is kept open, a liquid phase flow condensed by the first gas-liquid separator is gradually accumulated in the first storage tank, and meanwhile, part of the light component monomers and/or condensing agents are fed into a circulating pipeline from a compressor inlet so as to maintain the stability of the load of the reactor;
when light component monomers are required to be withdrawn from the reaction system, a valve on a pipeline between a first storage tank and a polymerization reactor is kept open, a valve on the pipeline between a second storage tank and the polymerization reactor is closed, a liquid phase flow condensed by a second gas-liquid separator is gradually accumulated in the second storage tank, and meanwhile, part of heavy component monomers and/or condensing agents are supplemented into a circulating pipeline from a compressor inlet so as to maintain the stable load of the reactor;
when the copolymerization is switched from binary copolymerization to ternary copolymerization, a valve on a pipeline between two storage tanks and a polymerization reactor is opened, and simultaneously, polymerization monomers and/or condensing agents are fed in from an inlet of a compressor so as to maintain the stability of the load of the reactor.
2. The process according to claim 1, characterized in that the polymerized monomers are selected from ethylene and/or α -olefins; the comonomer is butene, hexene or other alpha-olefins having less than 18 carbon atoms.
3. The method of claim 1, wherein the outlet temperature of the first heat exchanger is higher than the outlet temperature of the second heat exchanger; the outlet temperature of the first heat exchanger is 55-80 ℃; the outlet temperature of the second heat exchanger is 35-55 ℃.
4. The method of claim 1, wherein the frequency of switching between the binary copolymerization and the ternary copolymerization of the olefin is at least 1 time/hour.
5. A process according to any one of claims 1-3, wherein the process is also applicable for switching between homo-and co-polymerization of olefins, the frequency of switching between homo-and co-polymerization being at least 1 time/hour.
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| CN107405593A (en) * | 2014-12-09 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of olefinic polymerization device and olefine polymerizing process |
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| CN107405593A (en) * | 2014-12-09 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of olefinic polymerization device and olefine polymerizing process |
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