CN115057953A - Olefin polymerization method and device - Google Patents
Olefin polymerization method and device Download PDFInfo
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- CN115057953A CN115057953A CN202210885367.0A CN202210885367A CN115057953A CN 115057953 A CN115057953 A CN 115057953A CN 202210885367 A CN202210885367 A CN 202210885367A CN 115057953 A CN115057953 A CN 115057953A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 112
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 68
- 238000003860 storage Methods 0.000 claims abstract description 52
- 238000012660 binary copolymerization Methods 0.000 claims abstract description 14
- 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 49
- 239000005977 Ethylene Substances 0.000 claims description 49
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 29
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 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 3
- 229920001577 copolymer Polymers 0.000 claims 1
- -1 polyethylene Polymers 0.000 abstract description 15
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- 229920000573 polyethylene Polymers 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 65
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 38
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 229920000098 polyolefin Polymers 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 13
- 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 12
- 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
- 238000004519 manufacturing process Methods 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
- 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
- 239000000155 melt 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
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier 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
- 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
- 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
- 239000007790 solid phase Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 239000002699 waste material Substances 0.000 description 1
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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
Abstract
The invention discloses a method and a device for olefin polymerization, belonging to the technical field of olefin polymerization. The invention condenses and stores the different components in the storage tank by the gas-liquid separation device on the circulating pipeline. 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, and the switching between olefin copolymerization and homopolymerization or between different copolymerization is realized. In addition, the invention forms a differentiated polymerization environment in the fluidized bed by inputting condensate containing different comonomers at different positions of the reactor, thereby realizing the regulation and control of the molecular chain structure of the polyethylene. The invention can realize the alternating operation of olefin homopolymerization and copolymerization reaction or/and olefin binary copolymerization and ternary copolymerization reaction, and obtain products 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 widely used in olefin polymerization production. The main structure of the device is a section of hollow cylinder and a distribution plate, and the polymerization reaction occurs above the distribution plate. The gas-phase fluidized bed polyolefin production process is gradually developed into one of the main methods of the polyolefin industry due to the advantages of shorter process, lower operation cost, simple product separation process, less three-waste discharge and the like.
Conventional gas phase fluidized bed reactors can only produce a single polyolefin product. To produce polyolefin products having both processability and mechanical properties, for example bimodal polyolefins or polyolefin products with a broad molecular weight distribution. Can be realized by a series reactor process. Chinese patent 102844333a discloses a process for producing bimodal polyethylene for blow molding applications. The polyethylene resin is produced by using at least two slurry loop reactors connected in series under a Ziegler-Natta catalyst, 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 materials need to pass through the two reactors.
The parallel reactor process can also produce bimodal/broad polyethylene. Chinese patent 108530568A discloses a novel parallel reaction process for producing bimodal polyethylene, wherein high molecular weight and low molecular weight polyethylene are respectively prepared in two parallel polymerization reactors with different raw material ratios, and after discharging, mixing is carried out, one part is circulated, and the other part is led 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 in a single reactor, or catalysts having different active sites, has become a new focus of research. Chinese patent 107540767B discloses a preparation method of a metal catalyst for bimodal polyethylene. The two compounds of chromium and vanadium are loaded on a silica gel carrier, so that the obtained catalyst has two active centers. The chromium active center provides a lower molecular weight polyethylene product and the vanadium active center provides 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. A gas-liquid separation device is arranged on a gas circulation pipeline, part or all of condensate is separated from a circulating gas flow and stored in a storage tank, and a condensing agent and/or a comonomer are intermittently introduced into a reactor, so that the homopolymerization and copolymerization of olefin or the switching of different copolymerization reactions are realized. Chinese patent 104628904B discloses a method for preparing a broadly distributed polyolefin product using multiple temperature reaction zones. The components of polymerization monomer, condensing agent and the like are used as circulating media, polymerization reaction zones with different temperatures are formed in a fluidized bed reactor to generate high molecular weight polyolefin with high branched chain and low density and low molecular weight polyolefin with low branched chain and high density, so that polyolefin products with wider distribution and uniform mixing can be obtained. This process lacks flexibility in regulating the molecular weight distribution of the polyolefin product.
This patent presents 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 are capable of condensing different components and storing them in a storage tank through a gas-liquid separation device on a recycle 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, and the switching between olefin copolymerization and homopolymerization or between different copolymerization is realized. In addition, the invention forms a differentiated polymerization environment in the fluidized bed by inputting condensate containing different comonomers at different positions of the reactor, thereby realizing the regulation and control of the molecular chain structure of the polyethylene.
One embodiment of the present invention relates to an olefin polymerization apparatus, specifically including:
a polymerization reactor for performing homo-and/or copolymerization of olefins;
the compressor is connected with at least one outlet of the polymerization reactor and is used for receiving the circulating gas at the outlet of the upper end of the polymerization reactor and maintaining the circulating gas to flow in the pipeline;
at least 2 heat exchangers for reducing the temperature of the recycle stream in stages 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 respectively connected with at least one outlet of the first gas-liquid separator and at least one inlet of the second gas-liquid separator; at least 2 gas-liquid separators including a first gas-liquid separator and a second gas-liquid separator for separating a condensate after the cycle gas is condensed from the remaining gas;
and the at least 2 storage tanks are respectively used for receiving and storing the condensate separated from each gas-liquid separator, the storage tanks are connected with at least one inlet of the polymerization reactor, and valves are arranged on pipelines between the storage tanks and the polymerization reactor.
In a preferred embodiment of the invention, said at least 2 tanks comprise:
a first storage tank, which is respectively connected with at least one outlet of the first gas-liquid separator and at least one inlet of the polymerization reactor, and is used for receiving and storing the condensate separated from the first gas-liquid separator;
a second storage tank, which is respectively connected with at least one outlet of the second gas-liquid separator and at least one inlet of the polymerization reactor, and is used for receiving and storing the condensate separated from the second gas-liquid separator;
according to the requirement of the 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 the monomer is accumulated in the storage tank and is not introduced into the polymerization reactor, and the switching between the olefin copolymerization and the homopolymerization or the switching between different copolymerization reactions can be 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 buffer tank separator and a cyclone separator.
In a preferred embodiment of the present invention, the polymerization reactor is connected to the heat exchanger by means of a compressor;
the compressor is connected with at least one outlet of the polymerization reactor and is used for receiving the circulating gas at the outlet at the upper end of the polymerization reactor and maintaining the circulating gas to flow in the pipeline;
in a preferred embodiment of the present invention, the connection between the storage tank and the polymerization reactor is by means of a pump.
In a preferred embodiment of the present invention, the storage tank is connected to at least 1 inlet, preferably 3 to 6 inlets, of the polymerization reactor.
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 present invention, the device can control the input of liquid feed liquid by controlling a valve switch on a pipeline between a storage tank and a polymerization reactor so as to realize the switching of the olefin copolymerization and the homopolymerization 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 above polymerization apparatus;
2) introducing a polymerization monomer into the polymerization reactor from a feed inlet of the polymerization reactor for homopolymerization and/or copolymerization reaction, 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, condensate separated by each stage of gas-liquid separator is stored in different storage tanks, and the rest gas is circulated to the reactor through the feed port of the reactor to continue to react, so that a circulating loop is formed;
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, so that part of polymerization monomers are introduced or not introduced into the polymerization reactor, or comonomers are introduced into the polymerization reactor at intervals, and the switching of olefin copolymerization and homopolymerization or the switching of different copolymerization reactions 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 high, heavy components are condensed and enter the first storage tank, and the heavy components are introduced into different positions of the polymerization reactor through the feed pump. The residual gas stream continues to pass through a second heat exchanger and a second gas-liquid separator, the outlet temperature of the second heat exchanger is lower, and the lighter components are condensed and enter a second storage tank and are introduced into different positions of the polymerization reactor through a feed pump. The remaining gas stream is passed into the polymerization reactor from the bottom.
When the copolymerization reaction is switched from ternary polymerization reaction to binary polymerization reaction, valves on pipelines between the two storage tanks and the polymerization reactor are controlled according to different target products so as to withdraw partial comonomers.
When the heavy component monomer is required to be withdrawn from the reaction system, the 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, so that a liquid phase stream condensed by the first gas-liquid separator is gradually accumulated in the first storage tank, and meanwhile, part of light component monomer and/or condensing agent is supplemented into a circulating pipeline from an inlet of a compressor to maintain the load stability of the reactor.
When the light component monomer is required to be withdrawn from the reaction system, a valve on a pipeline between the first storage tank and the polymerization reactor is kept opened, a valve on a 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 the heavy component monomer and/or condensing agent is supplemented to a circulating pipeline from a compressor inlet to maintain the load stability of the reactor.
When the copolymerization reaction is switched from binary copolymerization reaction to ternary copolymerization reaction, a valve on a pipeline between the two storage tanks and the polymerization reactor is opened, and a polymerization monomer and/or a condensing agent are supplemented from an inlet of the compressor to maintain the load stability 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 between 55 and 80 ℃ and the outlet temperature of the second heat exchanger is between 35 and 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 copolymerization or ternary copolymerization, and the polymerization monomer comprises at least 1 of ethylene, butene, hexene or other alpha-olefins with less than 18 carbon atoms. The comonomer tank can be used for storing one or a mixture of butene, hexene or other alpha-olefins with less than 18 carbon atoms and a condensing agent 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, chromium metal catalysts, metallocene catalysts, late transition metal catalysts, preferably ziegler-natta catalysts.
In a preferred embodiment of the present invention, a certain switching frequency should be maintained between the olefin copolymerization and the terpolymerization. Specifically, the frequency of switching between reactions is 1 to 8 times/hour, preferably 5 times/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 circulating component of the polymerization process.
In a preferred embodiment of the present invention, at least one of a cocatalyst, a polymerization monomer, an antistatic agent, a chain transfer agent, a condensing agent and an inert gas is passed into the reactor and/or the circulation loop during the polymerization.
The cocatalyst mainly comprises alkyl aluminum and alkoxy aluminum, preferably selected from methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum. In the present embodiment, proper measures must be taken to avoid spontaneous combustion in the presence of air when using the cocatalyst.
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 5 MPa; 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 the comonomer, the alternating operation of olefin homopolymerization and copolymerization reaction or/and olefin binary copolymerization and ternary copolymerization reaction can be realized, and a product with excellent performance is 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 the condensate H in the outlet of the two-stage gas-liquid separator in accordance with one embodiment of the present invention 2 /C 2 、Cx/C 2 The value of (c) varies with temperature.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations included within the spirit of the invention are within the scope of the invention.
FIG. 1 is a simplified schematic diagram of an olefin polymerization apparatus and process, comprising:
a fluidized bed reactor 1 for performing homopolymerization and/or copolymerization and a distribution plate 2 thereof;
a gas circulation line 12 for circulating gaseous materials from the reactor outlet to the gas phase distribution zone of the fluidized bed reactor 1;
a fluid pipe 17 for introducing a monomer, a low-boiling comonomer, etc. into the fluidized bed reactor 1, a fluid pipe 18 for introducing a molecular weight modifier, etc. into the fluidized bed reactor 1, a fluid pipe 19 for introducing a high-boiling comonomer, a condensing agent, etc. into the fluidized bed reactor 1;
a fluid conduit 15 for introducing a polymerization catalyst into the fluidized bed reactor 1;
a fluid conduit 16 for withdrawing a polyolefin product from the fluidized bed reactor 1;
a compressor 3 for receiving the circulating gas from the upper outlet of the fluidized bed reactor 1 and maintaining the circulating gas flowing in the pipeline;
heat exchange means 4 for cooling the gaseous material exiting the fluidized bed reactor 1 and heat exchange means 8 for cooling the gaseous material exiting the separation means 5;
a separation device 5 and a separation device 9 for recovering condensate from the cooled gaseous material;
a first reservoir 6 and a second reservoir 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;
the reacted circulating gas flow with reaction products is led out from the top of the fluidized bed reactor 1, enters a gas circulating pipeline 12, flows through a compressor 3 and a heat exchanger 4, the partially condensed circulating gas flow flowing out of the heat exchanger 4 enters a gas-liquid separator 5, part or all of liquid materials in the gas-liquid separator 5 are separated and enter a first storage tank 6, the rest material flow passes through a heat exchanger 8, the flowing partially condensed circulating gas flow enters a gas-liquid separator 9, and part or all of liquid materials in the gas-liquid separator 9 are separated and enter a second storage tank 10. The remaining gas-rich stream enters the gas phase distribution zone of reactor 1, completing one cycle.
When producing the ternary copolymer product, the heavy component condensate and the light component condensate in the first storage tank 6 and the second storage tank 10 are respectively introduced into the fluidized bed reactor 1 from the pipeline 13 and the pipeline 14 above the distribution plate 2 through the first feed pump 7 and the second feed pump 11; when the reaction is switched to binary copolymerization reaction, partial comonomer is withdrawn according to different target products. When the heavy component monomer is 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 any more; when it is desired to withdraw the light component monomer from the reaction system, the light component condensate in the second reservoir 10 is not introduced into the reactor 1 any more.
Fresh reaction raw material gas required by the reaction enters a gas circulation pipeline 12 through a pipeline 17, a molecular weight regulator enters the gas circulation pipeline 12 through a pipeline 18, a condensing agent enters the gas circulation pipeline 12 through a pipeline 19, a catalyst intermittently or continuously enters the reactor 1 through a pipeline 15, and solid-phase polymer generated in the polymerization reaction is intermittently or continuously discharged from a pipeline 16 and conveyed to a downstream working section 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 88 ℃ and a pressure of 2.45MPa with a superficial reactor gas velocity of 0.65 m/s.
When the terpolymerization (copolymerization of ethylene, butene, hexene) is switched to the bipolymerization (copolymerization of ethylene, butene), the recycle gas stream in line 12 comprises hydrogen, nitrogen, ethylene, butene, hexene, and isopentane. The valves on the pump 7 to the fluidized bed reactor 1 are closed, keeping the remaining valves open. The outlet temperature of the heat exchanger 4 was 65 ℃ and the outlet stream contained 15.0% (mass fraction, the same applies hereinafter) of condensate, which mainly comprised hexene and isopentane, with a liquid phase density of 600.2kg/m 3 Gas phase density of 24.8kg/m 3 After passing through the gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters the comonomer tank 6 and is stored for later use, and the rest of the stream enters the heat exchanger 8 along with the recycle gas. The outlet temperature of the heat exchanger 8 was 42 ℃, and after multiple cycles, the outlet gas stream of the heat exchanger 8 contained 11.1% condensate, with a liquid phase density of 617.7kg/m 3 Gas phase density of 24.6kg/m 3 The copolymerization of ethylene, butene and hexene in the reactor is converted into the copolymerization of ethylene and butene, and meanwhile, partial polymerization monomers and/or condensing agents are supplemented into the circulating pipeline to maintain the load stability of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is switched into ternary copolymerization (ethylene, butene and hexene copolymerization), a pump 7 is opened to a valve on the fluidized bed reactor 1, 60% of condensate at the outlet of the gas-liquid separator 5 enters the comonomer tank 6, and the rest enters the fluidized bed reactor for ethylene, butene and hexene ternary copolymerization after passing through a heat exchanger 8 and the gas-liquid separator 9. The above binary and ternary copolymerization reactions were repeated 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 failure weight was 144 g.
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 a polymerization temperature of 86 deg.C, a pressure of 2.3MPa and a reactor superficial velocity of 0.61 m/s.
When the terpolymerization (copolymerization of ethylene, butene and octene) is switched into the bipolymerization (copolymerization of ethylene and butene), the valves from the pump 7 to the fluidized bed reactor 1 are closed, the remaining 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 consisting mainly of octenes and isopentane and having a density of 559.3kg/m 3 Gas phase density of 24.8kg/m 3 Passing through a gas-liquid separator 5, 100% of the condensate in the recycle gas stream enters a comonomer tank 6 and is stored for use, whichThe residual stream enters the heat exchanger 8 along with the circulating gas. The outlet temperature of the heat exchanger 8 was 42 ℃, after multiple cycles, the outlet stream of the heat exchanger 8 contained 2.4% condensate, with a gas phase density of 26.7kg/m 3 The copolymerization of ethylene, butene and octene in the reactor is converted into the copolymerization of ethylene and butene, and partial polymerized monomer and/or condensing agent are supplemented into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butylene copolymerization) is switched into ternary copolymerization (ethylene, butylene and octene copolymerization), a pump 7 is opened to a valve on the fluidized bed reactor 1, 80% of condensate at the outlet of the gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor for ethylene, butylene and octene ternary copolymerization after passing through a heat exchanger 8 and a gas-liquid separator 9. The above binary and ternary copolymerization reactions were repeated 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9136g/cm 3 The melt flow index was 0.95g/10min, and the dart impact failure weight was 148 g.
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 85 ℃ and 2.5MPa and a reactor superficial velocity of 0.68 m/s.
When the terpolymerization (copolymerization of ethylene, butene and octene) is switched into the bipolymerization (copolymerization of ethylene and butene), the valves from the pump 7 to the fluidized bed reactor 1 are closed, the remaining 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 consisting essentially of octene and isopentane and a liquid phase density of 550.9kg/m 3 The gas phase density was 26.5kg/m 3 And after passing through a gas-liquid separator 5, 100% of the condensate in the circulating gas flow enters a comonomer tank 6 and is stored for standby application, and the rest of the flow enters a heat exchanger 8 along with the circulating gas. The outlet temperature of the heat exchanger 8 was 42 ℃, after multiple cycles, the outlet gas stream of the heat exchanger 8 contained 4.2% condensate, and the liquid phase density was 588kg/m 3 Gas phase density of 28.7kg/m 3 The copolymerization of ethylene, butene and octene in the reactor is converted into the copolymerization of ethylene and butene, and partial polymerized monomer and/or condensing agent are supplemented into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butylene copolymerization) is switched into ternary copolymerization (ethylene, butylene and octene copolymerization), a pump 7 is opened to a valve on the fluidized bed reactor 1, 80% of condensate at the outlet of the gas-liquid separator 5 enters a comonomer tank 6, and the rest enters the fluidized bed reactor for ethylene, butylene and octene ternary copolymerization after passing through a heat exchanger 8 and a gas-liquid separator 9. The above binary and ternary copolymerization reactions were repeated 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 failure weight was 162 g.
In this embodiment, the outlet temperature of the heat exchanger 4 is changed, the outlet temperature of the heat exchanger 8 is kept at 42 ℃, and the obtained H of the outlet liquid phase streams of the gas-liquid separator 5 and the gas-liquid separator 9 2 /C 2 、Cx/C 2 The variation is shown in figure 2. Under the operating conditions of the examples herein, H in the two gas-liquid separator outlet streams 2 /C 2 、Cx/C 2 All had 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 a polymerization temperature of 92 deg.C, a pressure of 2.1MPa and a reactor superficial velocity of 0.61 m/s.
When the terpolymerization (copolymerization of ethylene, butene and hexene) is switched into the bipolymerization (copolymerization of ethylene and butene), the valves from the pump 7 to the fluidized bed reactor 1 are closed, the remaining valves are kept open, and the circulating gas stream 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% condensate comprising mainly octene and isopentane, the liquid phase density was 600.2kg/m 3 Gas phase density of 24.8kg/m 3 In the circulating gas flow through a gas-liquid separator 5100% of the condensate enters a comonomer tank 6 and is stored for standby, and the rest of the stream enters a heat exchanger 8 along with the circulating gas. The outlet temperature of the heat exchanger 8 was 42 ℃, and after multiple cycles, the outlet gas stream of the heat exchanger 8 contained 12.1% condensate, with a liquid phase density of 617.7kg/m 3 Gas phase density of 24.6kg/m 3 The copolymerization of ethylene, butene and hexene in the reactor is converted into the copolymerization of ethylene and butene, and meanwhile, partial polymerization monomers and/or condensing agents are supplemented into the circulating pipeline to maintain the load stability of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is switched into ternary copolymerization (ethylene, butene and hexene copolymerization), a pump 7 is opened to a valve on the fluidized bed reactor 1, 70% of condensate at the outlet of the gas-liquid separator 5 enters the comonomer tank 6, and the rest enters the fluidized bed reactor through the heat exchanger 8 and the gas-liquid separator 9 to carry out ternary copolymerization reaction of ethylene, butene and hexene. The binary and ternary copolymerization reactions were switched repeatedly 6 times per hour. The medium density polyethylene produced according to this example had a density of 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 100 deg.C, a pressure of 2.1MPa and a reactor superficial velocity of 0.61 m/s.
When the ternary polymerization (ethylene, butene, hexene copolymerization) is switched into the binary polymerization (ethylene, butene copolymerization), the valves from the pump 7 to the fluidized bed reactor 1 are closed, the remaining 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, the liquid phase density was 598.5kg/m 3 Gas phase density of 24.6kg/m 3 And after passing through a gas-liquid separator 5, 100% of the condensate in the circulating gas flow enters a comonomer tank 6 and is stored for standby application, and the rest of the flow enters a heat exchanger 8 along with the circulating gas. The outlet temperature of the heat exchanger 8 was 42 ℃, and after multiple cycles, the outlet gas stream of the heat exchanger 8 contained 13.4% condensate, and the liquid phase densityIs 617.8kg/m 3 Gas phase density of 24.2kg/m 3 The copolymerization of ethylene, butene and hexene is converted into the copolymerization of ethylene and butene in the reactor, and part of polymerization monomer and/or condensing agent is added into the circulating pipeline to maintain the stable load of the reactor.
When binary copolymerization (ethylene and butene copolymerization) is switched into ternary copolymerization (ethylene, butene and hexene copolymerization), a pump 7 is opened to a valve on the fluidized bed reactor 1, 70% of circulating stream at the outlet of the gas-liquid separator 5 enters 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 ethylene, butene and hexene ternary copolymerization. The above binary and ternary copolymerization reactions were repeated 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 85 ℃ and 2.3MPa and a reactor superficial velocity of 0.63 m/s.
When the ethylene homopolymerization is switched in (ethylene, hexene copolymerization), the valves from the pump 7 to the fluidized bed reactor 1 and from the pump 11 to the fluidized bed 1 are closed, the remaining valves are kept open, and the circulating gas stream in the 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 a condensate comprising mainly hexene and isopentane and a liquid phase density of 594.3kg/m 3 The gas phase density was 26.9kg/m 3 And after passing through a gas-liquid separator 5, 100% of the condensate in the circulating gas flow enters a comonomer tank 6 and is stored for standby application, and the rest of the flow enters a heat exchanger 8 along with the circulating gas. The outlet temperature of the heat exchanger 8 was 42 ℃, after multiple cycles, the outlet gas stream of the heat exchanger 8 contained 11.4% condensate, and the liquid phase density was 598.6kg/m 3 The gas phase density was 27.5kg/m 3 The ethylene and hexene copolymerization reaction in the reactor is converted into ethylene homopolymerization reaction, and simultaneously, partial ethylene and/or condensing agent is supplemented into the circulating pipeline to maintain the load stability of the reactorAnd (4) determining.
When ethylene homopolymerization cuts into binary copolymerization (ethylene and hexene copolymerization), a valve from a pump 7 to the fluidized bed reactor 1 is opened, 70% of circulating stream at the outlet of the 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 homopolymerization and copolymerization reactions were repeatedly switched 5 times per hour. The linear low density polyethylene produced according to this example had a density of 0.9156g/cm 3 。
Claims (10)
1. A process for the polymerization of olefins, characterized in that it comprises:
1) there is provided an olefin polymerization apparatus, the apparatus comprising:
a polymerization reactor for performing homopolymerization and/or copolymerization of olefins;
the compressor is connected with at least one outlet of the polymerization reactor and is used for receiving the circulating gas at the outlet of the upper end of the polymerization reactor and maintaining the circulating gas to flow in the pipeline;
at least 2 heat exchangers for reducing the temperature of the recycle stream in stages 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 respectively connected with at least one outlet of the first gas-liquid separator and at least one inlet of the second gas-liquid separator; at least 2 gas-liquid separators including a first gas-liquid separator and a second gas-liquid separator for separating a condensate after the cycle gas is condensed from the remaining gas;
at least 2 storage tanks, each for receiving and storing the condensate separated in each gas-liquid separator, the storage tanks being connected to at least one inlet of the polymerization reactor;
2) introducing a polymerization monomer into the polymerization reactor from a feed inlet of the polymerization reactor for homopolymerization and/or copolymerization reaction, 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, condensate separated by each stage of gas-liquid separator is stored in different storage tanks, and the rest gas is circulated to the reactor through the feed port of the reactor to continue to react, so that a circulating loop is formed;
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, so that part of polymerization monomers are introduced or not introduced into the polymerization reactor, or comonomers are introduced into the polymerization reactor at intervals, and the switching of olefin copolymerization and homopolymerization or the switching of different copolymerization reactions is realized.
2. The method of claim 1, wherein the polymerized monomer is selected from ethylene and/or alpha-olefins; the comonomer is butene, hexene or other alpha-olefins with 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 when the copolymerization reaction is switched from the ternary copolymerization reaction to the binary copolymerization reaction, valves on pipelines between the two storage tanks and the polymerization reactor are operated according to different target products to withdraw partial comonomers.
5. The method of claim 4, wherein when the heavy component monomer is required to be withdrawn from the reaction system, the first storage tank is used as a storage tank for the heavy component monomer, a valve on a pipeline between the first storage tank and the polymerization reactor is closed, the valve on a 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, a part of light component monomer and/or condensing agent is supplemented into a circulating pipeline from a compressor inlet so as to maintain the load of the reactor to be stable.
6. The method of claim 4, wherein when the light component monomer is required to be withdrawn from the reaction system, the valve on the pipeline between the first storage tank and the polymerization reactor is kept open, the valve on the pipeline between the second storage tank and the polymerization reactor is closed, and the liquid phase flow condensed by the second gas-liquid separator is gradually accumulated in the second storage tank, and meanwhile, part of the heavy component monomer and/or the condensing agent is supplemented into the circulating pipeline from the inlet of the compressor to maintain the load stability of the reactor.
7. The method of claim 1, wherein when the copolymerization reaction is switched from the binary copolymerization reaction to the ternary copolymerization reaction, a valve on a pipeline between the two storage tanks and the polymerization reactor is opened, and a polymerization monomer and/or a condensing agent is fed from an inlet of the compressor to maintain the load of the reactor to be stable.
8. The process according to any one of claims 4 to 7, wherein the frequency of switching between the copolymeric and terpolymeric reactions of the olefin is at least 1 time/hour.
9. A process according to any one of claims 1 to 7, wherein the process is also applicable for switching between homo-and copolymerization of olefins, the frequency of switching between homo-and copolymerization being at least 1 time/hour.
10. An olefin polymerization plant, characterized in that the plant comprises:
a polymerization reactor for performing homopolymerization and/or copolymerization of olefins;
the compressor is connected with at least one outlet of the polymerization reactor and is used for receiving the circulating gas at the outlet of the upper end of the polymerization reactor and maintaining the circulating gas to flow in the pipeline;
at least 2 heat exchangers for reducing the temperature of the recycle stream in stages to condense 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 respectively connected with at least one outlet of the first gas-liquid separator and at least one inlet of the second gas-liquid separator; at least 2 gas-liquid separators including a first gas-liquid separator and a second gas-liquid separator for separating a condensate after the cycle gas is condensed from the remaining gas;
and the at least 2 storage tanks are respectively used for receiving and storing the condensate separated from each gas-liquid separator, the storage tanks are connected with at least one inlet of the polymerization reactor, and valves are arranged on pipelines between the storage tanks and the polymerization reactor.
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