CN114965852A - Ethylene gas phase polymerization evaluation test device - Google Patents
Ethylene gas phase polymerization evaluation test device Download PDFInfo
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- CN114965852A CN114965852A CN202110224240.XA CN202110224240A CN114965852A CN 114965852 A CN114965852 A CN 114965852A CN 202110224240 A CN202110224240 A CN 202110224240A CN 114965852 A CN114965852 A CN 114965852A
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- 238000012685 gas phase polymerization Methods 0.000 title claims abstract description 85
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005977 Ethylene Substances 0.000 title claims abstract description 41
- 238000011156 evaluation Methods 0.000 title claims abstract description 34
- 238000012360 testing method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 28
- -1 polyethylene Polymers 0.000 abstract description 26
- 229920000573 polyethylene Polymers 0.000 abstract description 26
- 230000037048 polymerization activity Effects 0.000 abstract description 6
- 238000011165 process development Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 105
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101100476800 Mus musculus Chgb gene Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical class COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
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Abstract
The invention discloses a test device for evaluating ethylene gas-phase polymerization, which comprises a gas-phase polymerization reaction kettle and a gas circulating compressor; a combined stirrer is arranged in the gas phase polymerization reaction kettle, and the tail end of the stirrer shaft is a circulating gas inlet; the upper part of the gas-phase polymerization kettle is provided with a gas feed inlet, an emptying and vacuumizing port, a catalyst feed inlet, a seed bed feed inlet, a pressure detection port, a temperature detection port and a circulating gas outlet; a temperature control system is arranged outside the gas-phase polymerization reaction kettle; both ends of the gas circulation compressor are provided with a filter and a heat exchanger. The device provided by the invention improves the accuracy of polymerization activity when the gas-phase polyethylene catalyst is evaluated, the correlation between the polymerization evaluation test data result and the gas-phase polymerization pilot plant is strong, basic data is provided for the gas-phase polymerization pilot plant, the efficiency of the pilot plant can be greatly improved, the cost is reduced, and the device has important guiding significance for the operation and process development of the gas-phase polyethylene pilot plant and the evaluation of the catalyst.
Description
Technical Field
The invention relates to an ethylene gas phase polymerization evaluation test device and a method for evaluating a gas phase polyethylene catalyst by using the same.
Background
In the current polyethylene production process technology, a gas phase process is common. The gas phase method refers to that the polymerization monomer gas is directly polymerized in a fluidized bed reactor or a stirred bed reactor to generate solid polyethylene. The gas phase process does not require a solvent and therefore does not require separation to recover the solvent. The gas phase method has the advantages of short flow, small occupied area of the device, low equipment investment, mild operation condition, low production unit consumption, small environmental pollution and the like. Furthermore, the gas phase process is not limited by the solubility of the polymerizing monomers and polymers in the diluent and the solution viscosity during polymerization, allowing the production of PE products with a very broad range of properties, wherein the Melt Flow Rate (MFR) ranges from less than 0.01 g/10min or more than 100g/10min and the density ranges from 0.910 to 0.965g/cm 3. In view of the advantages of the gas phase polyethylene production process, the gas phase polyethylene production process is favored by many enterprises, and more than 60% of domestic newly-built polyethylene devices use the gas phase production process.
The gas phase polymerization process is that monomer is polymerized on solid catalyst particle in gas phase medium, and the produced polyethylene is in the form of catalyst particle, and its particle size, size distribution and bulk density are directly related to the catalyst particle form except that the particle size is amplified in different degrees. In a sense, polyethylene particles are "replicas" of the morphology of the catalyst particles. In order to obtain polymer with ideal particle shape and reasonable distribution, new requirements are provided for the particle shape of the catalyst, and if the catalyst is spherical and is distributed concentratedly, the reaction yield can be improved, the slurry concentration of a polymerization reactor can be improved, the mass transfer and heat transfer capacity of the polymerization reaction can be improved, the unit volume production capacity of a device can be improved, and the safe and stable operation of the device can be improved. The research and development of the gas-phase polyethylene catalyst are always hot spots and cores of domestic and foreign research institutions.
The gas phase polyethylene catalyst comprises Ziegler-Natta catalyst (Z-N), chromium-based catalyst and metallocene catalyst, most typically, the dry powder type catalyst UCAT-A, the slurry type catalyst UCAT-J, the chromium-based catalyst UCAT-B, UCAT-G and the metallocene catalyst PRODIGY series bimodal catalyst developed by Univation company. In recent years, domestic research and development organizations have also performed a great deal of work on Z-N catalysts, and certain achievements have been achieved. The Shanghai chemical research institute and Shanghai Li De catalyst Co., Ltd develop dry powder type SCG-1 catalyst and slurry type SLC-S catalyst. The Beijing chemical research institute and the Beijing Orda company develop dry powder type BCG-I, BCG-II catalyst and slurry type BCS-01 and BCS-02 catalyst. XY-L catalysts and XY-S catalysts have been developed by the Yingkou Yankee group. The TH-1L type high-efficiency gas phase method slurry catalyst is developed by the cooperation of China petrochemical industry scientific research institute and Qilu petrochemical company. The petrochemical research institute of China Petroleum products, Inc. developed slurry type catalyst PGE-101 and dry powder type catalyst PGE-201.
During the development of the catalyst, the polymerization performance evaluation of the catalyst is of great importance. The existing ethylene polymerization evaluation device adopting a slurry method is used for evaluating a gas-phase polyethylene catalyst, and because a liquid dispersing agent is adopted, the polymerization process is different from the gas-phase process, and impurities in the liquid dispersing agent can influence the performance of the catalyst, particularly a metallocene catalyst, the activity of the catalyst is evaluated inaccurately; in the polymerization evaluation process of the catalyst for producing the low-density polyethylene by the slurry method, the low-density polymer is swelled due to the action of the dispersing agent, so that the particle morphology is poor, the activity of the catalyst is further influenced, the performance of the catalyst cannot be truly reflected, and effective data support cannot be provided for the gas-phase pilot polymerization process research of the catalyst.
Disclosure of Invention
Aiming at the problems existing in the process of evaluating the ethylene polymerization catalyzed by a gas-phase polyethylene catalyst, the invention provides an ethylene gas-phase polymerization evaluation test device.
The invention provides an ethylene gas phase polymerization evaluation device, which comprises a gas phase polymerization reaction kettle (1) and a gas circulating compressor (2); a stirring device is arranged in the gas-phase polymerization reaction kettle and comprises a stirring shaft and a combined stirring paddle, and the upper end of the stirring shaft is a circulating gas inlet; the upper part of the gas-phase polymerization kettle is provided with a gas feed port (6), a vent and vacuum-pumping port (7), a catalyst feed port (8), a seed bed feed port (9), a pressure detection port (10), a temperature detection port (12) and a circulating gas outlet (13); a temperature control system (14) is arranged outside the gas-phase polymerization reaction kettle; the outlet of the gas circulation compressor is connected with a circulating gas inlet at the upper end of the stirring shaft, the inlet of the gas circulation compressor is connected with the circulating gas outlet (13), and the front end of the gas circulation compressor is provided with a filter (15); and the rear end of the gas circulation compressor is provided with a heat exchanger (16).
In one embodiment, the bottom of the gas phase polymerization reactor is a "convex" structure.
In one embodiment, the combined stirring paddle (3) is one or more of a propeller type stirring paddle, a turbine type stirring paddle, a paddle type stirring paddle, a propeller type stirring paddle, a ribbon type stirring paddle and a hinge type stirring paddle.
In one embodiment, the stirring shaft is provided with a gas channel along the axial direction, the recycle gas inlet is communicated with the gas channel, and the gas pressurized by the gas recycle compressor enters the bottom of the gas phase polymerization reactor from the recycle gas inlet through the gas channel.
In one embodiment, the stirring device is further provided with a stirring motor, the stirring motor is positioned at the upper end of the stirring shaft, and the stirring rotating speed range of the stirring device is 0-1000 r/min.
In one embodiment, the temperature control system (14) comprises a jacket and coils of a reaction vessel: the jacket is sleeved on the outer surface of the gas phase polymerization reaction kettle, and heat conducting oil is arranged between the jacket and the outer surface of the gas phase polymerization reaction kettle to provide heat required by the initial polymerization reaction; the coil pipe is surrounded on the outer surface of the gas phase polymerization reaction kettle, and cold water is introduced into the coil pipe.
The application also provides an evaluation method of the ethylene gas-phase polymerization evaluation test device, which comprises the following steps:
step S1, adding a certain amount of seedbed into a reaction kettle (1) through a seedbed feeding port (8), opening a stirring device in the reaction kettle (1) to a certain rotating speed, and heating the temperature in the reaction kettle (1) to 70-90 ℃ by using a temperature control system (14);
step S2, adding nitrogen into the reaction kettle from a gas feed inlet (6) until the gauge pressure is 0.3MPa, vacuumizing the reaction kettle through an emptying and vacuumizing port (7), repeatedly replacing for 8-10 times, and then introducing nitrogen until the gauge pressure is 0 MPa;
step S3, adding hydrogen required by the test through a gas feed inlet (6), adding polymerized monomer ethylene to a certain pressure, opening a gas circulation compressor (2), and adjusting the circulation gas speed to 0.05-0.5 m/S;
step S4, utilizing a temperature control system (14) to raise the temperature of the gas-phase polymerization reaction kettle to a set reaction temperature; adding a certain amount of cocatalyst aluminum alkyl and a main catalyst into the reaction kettle through a catalyst feeding port (8); the rotating speed of the stirring device is adjusted to 100-400 r/min;
step S5, adding a polymerization monomer ethylene into the reaction kettle through a gas feed inlet (6) to a reaction set pressure, and starting a polymerization reaction; and after the reaction set time is reached, stopping adding the polymerization monomer ethylene, cooling to room temperature by using a temperature control system (14), closing the circulating compressor, opening a vent (7) to vent the gas in the reaction kettle, adding nitrogen for replacement for 3-5 times, disassembling the reaction kettle cover, and taking out a reaction product.
The invention provides an ethylene gas-phase polymerization evaluation test device, wherein a catalyst catalyzes ethylene polymerization reaction in a gas-phase environment, the ethylene gas-phase polymerization evaluation test device is closer to the gas-phase polymerization environment of a gas-phase process, the accuracy of polymerization activity during evaluation of the gas-phase catalyst is improved, the correlation between a polymerization evaluation test data result and a gas-phase polymerization pilot plant is strong, basic data can be provided for the gas-phase polymerization pilot plant, and the ethylene gas-phase polymerization evaluation test device has important guiding significance for operation and process development of the gas-phase polymerization pilot plant and evaluation of the catalyst.
Drawings
FIG. 1 is a schematic view of the structure of an ethylene gas phase polymerization evaluation test apparatus according to the present invention.
Detailed Description
The detailed description and technical contents of the invention are described as follows with the accompanying drawings: the invention is further described with reference to the following figures and examples: the following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
As shown in the figure, the ethylene gas phase polymerization evaluation test device of the present invention comprises: comprises a gas-phase polymerization reaction kettle 1 and a gas circulating compressor 2; a stirring device is arranged in the gas-phase polymerization reaction kettle, the stirring device comprises a stirring shaft 5 and a combined stirring paddle, and the upper end of the stirring shaft is a circulating gas inlet; the upper part of the gas-phase polymerization kettle is provided with a gas feed inlet 6, an emptying and vacuumizing port 7, a catalyst feed inlet 8, a seed bed feed inlet 9, a pressure detection port 10, a stirring motor 11, a temperature detection port 12 and a circulating gas outlet 13; a temperature control system 14 is arranged outside the gas-phase polymerization reaction kettle; the outlet of the gas circulation compressor is connected with a circulating gas inlet at the upper end of the stirring shaft, the inlet of the gas circulation compressor is connected with the circulating gas outlet 13, and the front end of the gas circulation compressor is provided with a filter 15; the rear end of the gas circulation compressor is provided with a heat exchanger 16.
Evaluation method of the ethylene gas phase polymerization evaluation test apparatus: adding a certain amount of seedbed into a gas-phase polymerization reaction kettle through a seedbed feeding port, opening and stirring to a certain rotating speed, and heating a reaction system to 70-90 ℃ by using a temperature control system; adding nitrogen into the polymerization reaction kettle from the gas feed inlet until the gauge pressure is 0.3MPa, vacuumizing the reaction kettle through a vacuumizing port, repeatedly replacing for 8-10 times, and then introducing nitrogen until the gauge pressure is 0 MPa; adding hydrogen required by the test through a gas feed inlet, adding polymerized monomer ethylene to a certain pressure, opening a circulating compressor, and adjusting the circulating gas speed to 0.05-0.5 m/s; the temperature of the gas-phase polymerization reaction kettle is raised to the set reaction temperature by using a temperature control system 14; adding a certain amount of cocatalyst aluminum alkyl and a main catalyst into a reaction kettle through a catalyst feeding port; the stirring speed is increased to 100-400 r/min; adding a polymerization monomer ethylene into the reaction kettle through a gas charging opening to a reaction set pressure, and starting a polymerization reaction; and after the reaction set time is reached, stopping adding the polymerization monomer ethylene, reducing the temperature to room temperature by using a temperature control system, closing the circulating compressor, opening a vent to vent the gas in the reaction kettle, adding nitrogen for replacement for 3-5 times, disassembling the reaction kettle cover, and taking out a reaction product.
The bottom of the gas-phase polymerization reaction kettle 1 is of a convex structure, the structure ensures that a seed bed and a catalyst added into the reaction kettle keep a good motion state under the actions of gas pushing and combined stirring, the seed bed and the catalyst are uniformly dispersed, no dead angle exists, and the motion state of materials in the gas-phase polymerization reaction kettle is closer to the motion state of the materials in the polymerization process of a gas-phase fluidized bed. The inside of the gas-phase polymerization reaction kettle is provided with a combined stirring paddle, and the combined stirring paddle and the bottom structure of the reaction kettle cooperate to ensure that the seed bed and the catalyst are dispersed more uniformly, so that the material motion state is closer to the material motion state in the polymerization process of the gas-phase fluidized bed. The combined stirring paddle comprises a first stirring paddle 3 and a second stirring paddle 4, the first stirring paddle 3 is located above the second stirring paddle 4, the first stirring paddle 3 and the second stirring paddle 4 are both connected with the stirring shaft 5, the first stirring paddle 3 is one or a combination of a propeller stirrer, a turbine stirrer, a paddle stirrer, a propelling stirrer, a helical ribbon stirrer and a folding blade stirrer, and the preferred propeller stirrer and the preferred paddle stirrer are selected from the propeller stirrer and the paddle stirrer. The second stirring paddle 4 is one of a blade stirrer, a paddle stirrer and a propeller stirrer, and is preferably a blade stirrer. The stirring device is also provided with the stirring motor, the stirring motor is positioned at the upper end of the stirring shaft, and the stirring rotating speed range of the stirring device is 0-1000 r/min.
The upper end of the stirring shaft 5 is a circulating gas inlet, the stirring shaft is provided with a gas channel along the axial direction, the circulating gas inlet is communicated with the gas channel, and the gas pressurized by the gas circulating compressor passes through the circulating gas inlet from the bottom of the gas channel entering the gas phase polymerization reaction kettle. The gas pressurized by the circulating compressor enters the reaction kettle from the circulating gas inlet, the circulating gas enters from the bottom of the gas-phase polymerization reaction kettle by the structure, the dispersing effect of the circulating gas is facilitated, the circulating gas blows materials in the reaction kettle to move uniformly, so that the polymerization monomers and the copolymerization monomers are in full and uniform contact with the catalyst, and the moving state of the materials in the gas-phase polymerization reaction kettle is closer to the moving state of the materials in the polymerization process of the gas-phase fluidized bed.
The gas feed inlet 6 at the upper part of the gas phase polymerization reaction kettle is used for feeding gas comprising polymerization monomers of ethylene, hydrogen and nitrogen. The upper part of the gas-phase polymerization reaction kettle is provided with an emptying and vacuumizing port 7, and the emptying and vacuumizing port 7 is used for emptying gas and vacuumizing the reaction kettle during purification treatment. The upper part of the gas phase polymerization reaction kettle is provided with a catalyst feed port 8, and the catalyst feed port 8 is used for adding a catalyst for catalyzing olefin polymerization. The upper part of the gas phase polymerization reaction kettle is provided with a seed bed feed port 9, and the seed bed feed port 9 is used for feeding a seed bed required in gas phase polymerization. The upper part of the gas-phase polymerization reaction kettle is provided with a pressure detection port 10, the pressure detection port 10 is used for measuring the pressure of a reaction system and controlling the pressure, and the polymerization reaction pressure range is 0.5-2.5 MPa.
The upper part of the gas-phase polymerization reaction kettle is provided with a stirring motor 11, the stirring motor 11 is used for regulating and controlling the stirring rotating speed during the polymerization reaction, and the stirring rotating speed range is 0-1000 r/min. The upper part of the gas phase polymerization reaction kettle is provided with a temperature detection port 12, the temperature detection port 12 is used for measuring the temperature of the polymerization reaction, and the reaction temperature range is 70-100 ℃. The upper part of the gas-phase polymerization reaction kettle is provided with a circulating gas outlet 13, and gas in the reaction kettle enters a gas circulating compressor through the circulating gas outlet 13 to be pressurized and completes the circulation of the gas between the reaction kettle and the gas compressor together with a circulating gas inlet. The outside of the gas phase polymerization reaction kettle is provided with a temperature control system 14, the temperature control system 14 is composed of a jacket and a coil pipe of the reaction kettle: the temperature control system 14 includes the jacket and coils of the autoclave: the jacket is sleeved on the outer surface of the gas phase polymerization reaction kettle, and heat conducting oil is arranged between the jacket and the outer surface of the gas phase polymerization reaction kettle to provide heat required by the initial polymerization reaction; the coil pipe is surrounded on the outer surface of the gas phase polymerization reaction kettle, and cold water is introduced into the coil pipe. Heat conducting oil is arranged in the jacket to provide heat required in the initial stage of polymerization reaction; the coil is a cold water system used for removing heat generated by the polymerization reaction. The control system 14 maintains the stability of the polymerization temperature, which is 70-100 deg.C and + -2 deg.C.
The gas circulating compressor 2 pressurizes the gas from the gas phase polymerization reactor 1 to maintain the pressure inside the reactor stable, so that the gas inside the polymerization system is dynamically circulated and is near the gas circulating state in the gas phase fluidized bed polymerization process, and the circulating gas speed is 0.05-0.5 m/s. The front end of the gas circulation compressor 2 is provided with a filter 15, and the filter 15 is used for filtering solid particles entrained in the circulating gas and preventing the solid particles from entering a subsequent system. The gas circulation compressor 2 is provided at the rear end thereof with a heat exchanger 16, and the heat exchanger 16 is used for maintaining the temperature of the circulating gas closer to the gas phase polymerization reaction temperature. The front end and the rear end are based on the flow direction of the compressed gas of the gas circulation compressor, and a pipeline where the compressed gas entering the gas circulation compressor 2 is located is defined as the front end of the gas circulation compressor 2, and a pipeline where the compressed gas flowing out of the gas circulation compressor 2 is located is defined as the rear end.
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention is further described below with reference to examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any modifications made on the basis of the present invention do not depart from the spirit of the present invention.
In the following examples, the polymerization activity was calculated by the following method:
the polymerization activity was expressed in g PE/(g Cat. h).
Example 1:
adding 100g of seedbed into a gas-phase polymerization reaction kettle, opening and stirring to 100r/min, and heating a reaction system to 85 ℃; repeatedly replacing the reaction kettle for 10 times by using nitrogen and vacuumizing, and then introducing nitrogen until the gauge pressure is 0 MPa; adding polymerized monomer ethylene to 0.5MPa, opening a gas circulation compressor, and adjusting the circulation gas velocity to 0.15 m/s; raising the temperature of the reaction system to 88 ℃; adding a cocatalyst of triethylaluminum and 20mg of titanium Z-N catalyst through a catalyst feeding port, wherein the adding amount of the triethylaluminum is Al/Ti (mol) ═ 100; adjusting the stirring speed to 300 r/min; adding ethylene to 1.8MPa, and starting polymerization reaction; after reacting for 1h, stopping introducing the polymerized monomer ethylene, closing the gas circulating compressor, cooling, discharging the gas in the gas phase reaction kettle, replacing for 3 times by nitrogen, disassembling the reaction kettle cover, and taking out the polyethylene product. The test results are shown in Table 1.
Examples 2 to 4:
the gas phase polyethylene catalyst was evaluated in the same manner as in example 1, except that hydrogen was added, and the specific experimental conditions and experimental results are shown in table 1.
Example 5:
the gas phase polyethylene catalyst was evaluated in the same manner as in example 1, except that the Z-N catalyst was replaced with a metallocene catalyst and triethylaluminum was not added as a cocatalyst, and specific experimental conditions and experimental results were shown in Table 1.
Comparative example 1:
heating a 2L slurry polymerization reaction kettle to 85 ℃, vacuumizing, adding nitrogen, vacuumizing again for purification treatment, repeatedly replacing for 4 times by using nitrogen and vacuumizing, and then adding 1L dispersant n-hexane; stirring the mixture to 100r/min, and then adding a cocatalyst of triethylaluminum and 20mg of a titanium-based Z-N catalyst, wherein the adding amount of the triethylaluminum is 100 mol/Ti; stirring and rotating speed is adjusted to 300r/min, reaction temperature is adjusted to 88 ℃, ethylene gas is added to 1.8MPa, and polymerization reaction is started; after reacting for 1h, stopping introducing raw material ethylene, emptying gas in the reaction kettle, cooling, replacing for 3 times by nitrogen, discharging, separating liquid dispersant, and drying to obtain a polyethylene product. The test results are shown in Table 1.
Comparative examples 2 to 4:
the gas phase polyethylene catalyst was evaluated in the same manner as in comparative example 1, except that hydrogen was added, and the specific experimental conditions and experimental results are shown in table 1.
Comparative example 5:
the gas phase polyethylene catalyst was evaluated in the same manner as in comparative example 1, except that the Z-N catalyst was replaced with a metallocene catalyst and triethylaluminum as a cocatalyst was not added, and specific experimental conditions and experimental results are shown in Table 1.
TABLE 1 Experimental conditions and results of examples and comparative examples
As can be seen from the data in Table 1, compared with the ethylene polymerization evaluation device by the slurry method, the ethylene gas phase polymerization evaluation test device provided by the invention can be used for more accurately evaluating the polymerization activity of a gas phase polyethylene catalyst, can be used for providing basic data for the operation of a gas phase polyethylene pilot polymerization device, and can be used for effectively improving the service efficiency and the operation safety of the gas phase polyethylene pilot polymerization device.
The invention provides an ethylene gas-phase polymerization evaluation test device, wherein a catalyst catalyzes ethylene polymerization reaction in a gas-phase environment, the ethylene gas-phase polymerization evaluation test device is closer to the gas-phase polymerization environment of a gas-phase process, the accuracy of evaluating the polymerization activity of the gas-phase catalyst is improved, the correlation between the polymerization evaluation test data result and a gas-phase polymerization pilot plant is strong, basic data can be provided for the gas-phase pilot plant, and the ethylene gas-phase polymerization evaluation test device has important guiding significance for the operation and process development of the gas-phase polyethylene pilot plant. The ethylene gas-phase polymerization evaluation test device is adopted to carry out gas-phase polyethylene catalyst screening and evaluation tests, the catalyst performance is comprehensively mastered, the use efficiency of a gas-phase pilot polymerization device is improved, the production cost is reduced, and the risk caused by unclear catalyst activity in the gas-phase polymerization test process can be reduced. Therefore, the invention has important significance for accelerating the research and development of the polyethylene catalyst and the development process of new products and improving the technical service quality.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications may be made without departing from the invention, and such modifications are intended to be included within the scope of the invention.
Claims (6)
1. A test device for evaluating ethylene gas phase polymerization is characterized by comprising a gas phase polymerization reaction kettle (1) and a gas circulating compressor (2); a stirring device is arranged in the gas-phase polymerization reaction kettle and comprises a stirring shaft and a combined stirring paddle, and the upper end of the stirring shaft is a circulating gas inlet; the upper part of the gas-phase polymerization kettle is provided with a gas feed port (6), a vent and vacuum-pumping port (7), a catalyst feed port (8), a seed bed feed port (9), a pressure detection port (10), a temperature detection port (12) and a circulating gas outlet (13); a temperature control system (14) is arranged outside the gas-phase polymerization reaction kettle; the outlet of the gas circulation compressor is connected with a circulating gas inlet at the upper end of the stirring shaft, the inlet of the gas circulation compressor is connected with the circulating gas outlet (13), and the front end of the gas circulation compressor is provided with a filter (15); and the rear end of the gas circulation compressor is provided with a heat exchanger (16).
2. The apparatus for the evaluation and testing of the gas phase polymerization of ethylene according to claim 1, wherein the bottom of the gas phase polymerization reactor has a "convex" shape.
3. The ethylene gas phase polymerization evaluation test device according to claim 1, wherein the combined stirring paddle (3) is one or a combination of several of a propeller type stirring paddle, a turbine type stirring paddle, a paddle type stirring paddle, a propeller type stirring paddle, a ribbon type stirring paddle and a flap type stirring paddle.
4. The ethylene gas-phase polymerization evaluation test device according to claim 1, wherein the stirring shaft is provided with a gas passage along the axial direction, the recycle gas inlet is communicated with the gas passage, and the gas pressurized by the gas recycle compressor enters the bottom of the gas-phase polymerization reaction vessel from the recycle gas inlet through the gas passage.
5. The ethylene gas phase polymerization evaluation test device according to claim 1, wherein the stirring device is further provided with a stirring motor, the stirring motor is positioned at the upper end of the stirring shaft, and the stirring speed of the stirring device is in the range of 0 to 1000 r/min.
6. The ethylene gas-phase polymerization evaluation test device according to claim 1, wherein the temperature control system (14) comprises a jacket and a coil of a reaction vessel: the jacket is sleeved on the outer surface of the gas phase polymerization reaction kettle, and heat conducting oil is arranged between the jacket and the outer surface of the gas phase polymerization reaction kettle to provide heat required by the initial polymerization reaction; the coil pipe is surrounded on the outer surface of the gas phase polymerization reaction kettle, and cold water is introduced into the coil pipe.
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