CN116082552A - Method for preparing polyethylene by using batch production equipment - Google Patents
Method for preparing polyethylene by using batch production equipment Download PDFInfo
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- CN116082552A CN116082552A CN202111306030.1A CN202111306030A CN116082552A CN 116082552 A CN116082552 A CN 116082552A CN 202111306030 A CN202111306030 A CN 202111306030A CN 116082552 A CN116082552 A CN 116082552A
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- -1 polyethylene Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 57
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 56
- 238000010923 batch production Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 171
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005977 Ethylene Substances 0.000 claims abstract description 51
- 239000001294 propane Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000005070 sampling Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 79
- 238000001704 evaporation Methods 0.000 claims description 37
- 230000008020 evaporation Effects 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 33
- 238000011084 recovery Methods 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract description 20
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 6
- 229920013716 polyethylene resin Polymers 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 238000007599 discharging Methods 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polyethylene, and discloses a method for preparing polyethylene by using batch production equipment, which comprises the following steps: in the presence of propane and a catalyst, ethylene and a comonomer are contacted in a polymerization kettle to carry out polymerization reaction; in the polymerization reaction process, sampling and analyzing are carried out from a polymerization kettle at regular intervals to obtain the content ratio of ethylene and comonomer in the polymerization kettle, and the content ratio is transmitted to a comonomer feeding system; the comonomer feeding system adjusts the feeding amount of the comonomer according to the content ratio, so that the content ratio of the ethylene to the comonomer in the polymerization kettle is maintained within a preset range. The method can effectively solve the problem that the density of the polyethylene resin is difficult to adjust in the intermittent production of the ultra-high molecular weight polyethylene device, and effectively improve the utilization rate and economic benefit of the production device.
Description
Technical Field
The invention relates to the field of polyethylene, in particular to a method for preparing polyethylene by using batch production equipment.
Background
Polyethylene (PE) resin is the variety with the largest yield in general synthetic resin, has the characteristics of low price and better performance, and is widely applied to the fields of industry, agriculture and the like. Polyethylene production technology has been a coexistence of multiple processes. The current solution process is medium pressure process from Nova, low pressure cooling process from Dow chemical and low pressure adiabatic process from DSM. The slurry process is a loop process of Phillips and Solvi company and a stirred tank process of Hurst, nissan chemical and Midsin chemical. The gas phase process mainly comprises a Unipol process of a Unistation company, an Innovene process of a BP company and a Spherilene process of a Basell company.
Ultra High Molecular Weight Polyethylene (UHMWPE) is a polyethylene resin having a molecular weight of 150 to 800 tens of thousands. UHMWPE has a larger molecular weight than ordinary polyethylene, so that the UHMWPE has excellent properties of impact resistance, wear resistance, self-lubrication, low temperature resistance, chemical corrosion resistance and the like, and is widely applied to the fields of coal mining industry, chemical industry, mechanical industry, textile industry, artificial prostheses, other fields and the like. The UHMW resin production process is similar to the production of common high density polyethylene HDPE, and can be produced by adopting the HDPE production technology, except that the UHMW-PE production process has no granulation process, and the product is in powder form. The preparation method of the ultra-high molecular weight polyethylene resin mainly adopts Ziegler catalyst, triethylaluminum as a cocatalyst, saturated hydrocarbon at 60-120 ℃ as a dispersion medium, and ethylene is polymerized under certain temperature and pressure conditions to prepare products with different molecular weights. However, in the production of polyethylene, the quality of the product is significantly reduced, whether the conventional low molecular weight polyethylene is blended with UHMWPE resin or UHMWPE resin is blended with conventional low molecular weight polyethylene. High quality UHMWPE resins are therefore commonly produced using batch processes.
In addition, the ultra-high molecular weight polyethylene has excellent product performance, and the characteristics of difficult processing limit the application of the ultra-high molecular weight polyethylene. This results in low user and low usage of ultra high molecular weight polyethylene. For enterprises producing ultra-high molecular weight polyethylene, the production cannot be carried out at full load, and considerable idle capacity exists. These idle capacities also typically require the production of common polyethylene products. While conventional polyethylene products generally require adjustment of resin density for their use, devices for producing ultra-high molecular weight polyethylene generally do not have this capability.
The process for producing polyethylene by the batch method in the prior art has the advantages that the polymerization rate and polymerization activity fluctuation in the production process are large, the obtained polyethylene product is single, the variety is few, the density of polyethylene resin is uncontrollable, and comonomer is difficult to directly inject into a reactor according to the continuous polyethylene production process, the traditional slurry process uses traditional solvents such as hexane, solvent oil and the like, and the process steps such as centrifugation, filtration, drying and the like are needed.
Disclosure of Invention
The invention aims to solve the technical problems that the product of ultra-high molecular weight polyethylene prepared by an intermittent method in the prior art is single and few in variety, and the traditional slurry process uses traditional solvents such as hexane, solvent oil and the like, and needs the process steps of centrifugation, filtration, drying and the like, and provides a method for preparing polyethylene by adopting intermittent production equipment.
The inventor of the present invention found in experiments that in the presence of propane and a catalyst, ethylene and a comonomer are contacted to carry out polymerization reaction, the density of the produced polyethylene can be adjusted, and the density of a polyethylene product can be controlled on a batch process device for producing ultra-high molecular weight polyethylene, and a medium-high density polyethylene product can be produced, so that the performance range of the polyethylene product can be further enlarged. In addition, the method adopts propane as the suspension solvent to produce the ultra-high molecular weight polyethylene, compared with the traditional slurry process which uses traditional solvents such as hexane, solvent oil and the like, the method does not need the process steps such as centrifugation, filtration, drying and the like, does not need the equipment such as a centrifuge, a dryer and the like, and reduces the production cost.
In order to achieve the above object, the present invention provides a method for producing polyethylene using a batch production apparatus, the method comprising:
in the presence of propane and a catalyst, ethylene and a comonomer are contacted in a polymerization kettle to carry out polymerization reaction;
in the polymerization reaction process, sampling and analyzing are carried out from a polymerization kettle at regular intervals to obtain the content ratio of ethylene and comonomer in the polymerization kettle, and the content ratio is transmitted to a comonomer feeding system; the comonomer feeding system adjusts the feeding amount of the comonomer according to the content ratio, so that the content ratio of the ethylene to the comonomer in the polymerization kettle is maintained within a preset range.
The technical scheme of the invention also has the following advantages:
(1) The method can effectively solve the problem that the device for intermittently producing the ultra-high molecular weight polyethylene is difficult to produce common polyethylene, can increase the variety of products of the device for intermittently producing the ultra-high molecular weight polyethylene, and effectively improves the utilization rate and economic benefit of the production device.
(2) The polypropylene production equipment for reforming the small-body polypropylene production factory is adopted to produce the ultra-high molecular weight polyethylene, and is very suitable for meeting the characteristic that downstream factories need small-batch goods. The ultra-high molecular weight polyethylene has higher price, and the technical scheme of the invention can obviously improve the economic benefit of a small-body polypropylene production factory.
Drawings
FIG. 1 is a schematic view showing the structure of a system for producing polyethylene using a batch production apparatus according to an embodiment of the present invention;
fig. 2 is a schematic structural view of a control system for producing polyethylene using a batch production apparatus according to an embodiment of the present invention.
Description of the reference numerals
100 polymeric kettles, 200 recovery tanks, 300 gas storage equipment, 400 flash tanks, 500 gas chromatographs and 600 control equipment
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing polyethylene using a batch production apparatus, the method allowing the density of a polyethylene resin to be adjusted, the method comprising:
in the presence of propane and a catalyst, ethylene and a comonomer are contacted in a polymerization kettle to carry out polymerization reaction;
in the polymerization reaction process, sampling and analyzing are carried out from a polymerization kettle at regular intervals to obtain the content ratio of ethylene and comonomer in the polymerization kettle, and the content ratio is transmitted to a comonomer feeding system; the comonomer feeding system adjusts the feeding amount of the comonomer according to the content ratio, so that the content ratio of the ethylene to the comonomer in the polymerization kettle is maintained within a preset range.
In some embodiments of the invention, the comonomer is an alpha-olefin; preferably, the alpha-olefin is selected from at least one of butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof, more preferably propylene and/or n-butene.
In some embodiments of the invention, the propane feed contains a comonomer, wherein the comonomer content in the propane feed is lower than the comonomer content in the polymerization reaction.
In the invention, the density of the polyethylene is reduced by adopting a mode of copolymerizing ethylene and comonomer, the content ratio of the ethylene and the comonomer is automatically controlled and stabilized by adopting feeding, and the phenomenon that the content of the comonomer is too high to cause excessive soluble matters and the phenomenon that the comonomer sticks to a kettle in a flash evaporation process is prevented. The polyethylene resin which can be produced is medium-high density polyethylene with the density ranging from 0.926 g/cm to 0.97g/cm 3 Preferably 0.93-0.97g/cm 3 Still more preferably 0.935 to 0.970g/cm 3 . The molar ratio of ethylene to comonomer (e.g., 1:0.04-0.06) is determined according to the copolymerization capability of the catalyst, so that the density of the polyethylene product reaches the preset requirement. In the present invention, the content ratio of ethylene to α -olefin used means a molar ratio.
The amount of propane used in the present invention is determined according to the volume of the polymerizer used, and is generally 40 to 90% of the volume of the polymerizer. The ethylene and comonomer are continuously added along with the reaction, the yield of the polyethylene in the kettle can be measured according to the consumption of the ethylene and the comonomer, and the volume concentration of the polyethylene in propane during discharging is lower than 70 percent, preferably lower than 50 percent, and the discharging is difficult due to the excessive concentration. For safety reasons, the total volume of propane and polyethylene in the reactor should not be less than 95%, preferably less than 90% of the volume of the ultra-high polymerization reactor at the time of discharge. The catalyst dosage is determined according to the activity of the catalyst and the single kettle yield. The single pot polymerization time is generally from 0.5 to 12 hours depending on the active life of the catalyst.
In some embodiments of the invention, the contacting is performed in the presence of hydrogen in an amount such that the pressure within the system increases by 0.01 to 1.5MPa (this pressure refers to the partial pressure of hydrogen). The feeding order of the hydrogen gas is not limited in the present invention, and for example, the hydrogen gas may be fed into the polymerization vessel before feeding the propane and the catalyst into the polymerization vessel, or may be fed into the polymerization vessel after feeding the propane and the catalyst into the polymerization vessel and before introducing the ethylene gas.
In some embodiments of the invention, the polymerization conditions include: the temperature is 50-90 ℃, preferably 60-80 ℃; the pressure is 2.3-3.8MPa, preferably 2.8-3.6MPa. In the present invention, the amount of ethylene relative to propane can be such that the pressure of the polymerization reaction system is controlled within the above-mentioned range.
In some embodiments of the invention, the method further comprises:
(a) After the polymerization reaction is finished, the pressure of the polymerization kettle is reduced, unreacted ethylene, comonomer and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into a liquid phase material through a recovery condenser, and the liquid phase material enters a recovery tank.
In some embodiments of the invention, preferably, the vaporization pressure is from 0.8 to 1.8MPa, more preferably from 1 to 1.5MPa.
In some embodiments of the invention, the method further comprises:
and (c) after the step (a) is finished, injecting materials in the kettle into a flash tank by utilizing residual pressure in the polymerization kettle to perform flash evaporation, and obtaining flash evaporation gas and polyethylene powder. Specifically, after the flash evaporation is completed, vacuum is pumped in the flash tank and nitrogen is used for replacement, and the replacement air is also discharged out of the flash tank and enters the gas storage device.
In some embodiments of the invention, the conditions of the flash distillation include: the pressure is 0-0.1MPa.
In some embodiments of the invention, the apparatus used for sampling analysis from the polymerizer is a gas chromatograph. Preferably, the sampling analysis interval is less than 30 minutes, preferably less than 10 minutes, more preferably the sampling interval is less than 5 minutes.
In the present invention, the catalyst is a polyethylene catalyst, and may be any catalyst capable of polymerizing ethylene into high molecular weight polyethylene, preferably a Ziegler-Natta catalyst.
According to the process of the present invention, the Ziegler-Natta catalyst comprises: (1) The active component of the titanium-containing solid catalyst comprises magnesium, titanium, halogen and an internal electron donor as main components; (2) an organoaluminum compound cocatalyst component; and (3) optionally an external electron donor component.
Solid catalysts available for use are commercially available from beijing aoda division, chinese petrochemical catalyst limited, such as: BCE catalyst, CM catalyst.
The organoaluminum compound as the cocatalyst component of the catalyst is preferably an alkylaluminum compound, more preferably at least one selected from trialkylaluminums (e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, trioctylaluminum, etc.), diethylaluminum chloride, diisobutylaluminum chloride, monoethylaluminum dichloride and ethylaluminum dichloride.
The ratio of the titanium-containing solid catalyst active component to the organoaluminum compound promoter component may be from 0.1:25 to 0.1:1000 in terms of Ti/Al molar ratio.
In the present invention, referring to fig. 1 and 2, the following are specific embodiments of the present invention:
1) Propane and catalyst are charged into polymerizer 100;
2) Heating the polymerization kettle 100 to a preset polymerization temperature, and introducing ethylene gas and comonomer into the polymerization kettle 100 to perform polymerization reaction; sampling and analyzing the mixture from the polymerization kettle at regular intervals by a gas chromatograph 500 in the reaction process to obtain the content ratio of ethylene and comonomer in the polymerization kettle 100, and transmitting the content ratio to a comonomer feeding system; the comonomer feed control apparatus 600 adjusts the comonomer feed amount according to the content ratio so that the ethylene-to-comonomer content ratio in the polymerizer 100 is maintained within a predetermined range, thereby producing a polyethylene product of a predetermined density.
3) After the polymerization reaction is finished, the pressure of the polymerization kettle is reduced, unreacted ethylene, comonomer and propane are vaporized in the polymerization kettle 100, the obtained gas phase is condensed into a liquid phase material through a recovery condenser, and the liquid phase material enters a recovery tank 200;
4) After recovery, the materials in the kettle are sprayed into a flash tank 400 by utilizing the residual pressure in the polymerization kettle to obtain flash gas and polyethylene powder, the flash gas is discharged and then is conveyed to the gas storage device 300, the flash tank is vacuumized and replaced by nitrogen, and the replacement gas is also conveyed to the gas storage device 300. And discharging the polyethylene powder from the bottom end of the polymerizer 100 to obtain the polyethylene.
In addition, optionally, hydrogen is fed into the polymerizer 100 in step 1) or into the polymerizer 100 before ethylene gas is fed in step 2). The amount of hydrogen is such that the pressure in the system increases by 0.01 to 1.5MPa (this pressure means hydrogen partial pressure). In step 2), the device for heating and removing heat of the polymerization kettle 100 is conventional equipment, and the typical heating equipment for heating the polymerization kettle 100 is to introduce hot water into a jacket of the polymerization kettle; the heat removal from the polymerizer 100 is achieved by feeding cold water into the polymerizer jacket. In step 3), the liquid phase material which is vaporized and condensed in the polymerization kettle 100 and enters the recovery tank 200 is mainly propane, contains a small amount of ethylene and comonomer, and can be reused as a polymerization raw material.
In the method of the present invention, in step 3, the gas in the flash tank 400 is discharged into the gas storage device 300. The gas evacuated in the flash tank 400 and replaced with nitrogen also enters the gas storage device 300. The gas in the gas storage device 300 is recovered or harmlessly treated according to the production plant equipment.
More specifically, in the present invention, step 1) is fed, usually by first adding metered amounts of hydrogen to the polymerization vessel, preferably by introducing hydrogen so that the pressure in the system is from 0.01 to 1.0MPa. The Ziegler Natta catalyst component is then fed to the polymerization vessel 100 using liquid propane; and finally, supplementing propane required by the process. Step 2) heating the polymerization kettle 100, and adopting a hot water pump to send hot water to a jacket of the polymerization kettle 100 for heating, wherein the kettle temperature is increased from normal temperature to polymerization temperature. The polymerization temperature is 50 to 90℃and preferably 60 to 80 ℃. At this time, ethylene gas and a comonomer were introduced into the polymerizer 100 to start the polymerization reaction. The polymerization rate is increased to a predetermined polymerization rate by controlling the pressure of the polymerization vessel 100 with ethylene, hot water (gradually closed in an automatic state) is switched to circulating cooling water (automatically adjusting the opening of a circulating cooling water valve), heat released by the polymerization reaction is removed, and the reaction temperature is controlled to be stable. Sampling and analyzing from the polymerization kettle at regular intervals by using a gas chromatograph 500 to obtain the content ratio of ethylene to comonomer in the polymerization kettle 100; the comonomer feed system adjusts the feed amount of the comonomer according to the content ratio, so that the content ratio of ethylene to the comonomer in the polymerization kettle is maintained within a preset range. In step 3), when the polymerization time or the polyethylene yield reaches the requirement, the recovery system is started, unreacted ethylene, comonomer and propane are vaporized in the polymerization kettle 100, the gas phase is condensed into a liquid phase material by the condenser, and the liquid phase material enters the recovery tank 200. The liquid propane which is vaporized and condensed in the polymerization vessel and then enters the recovery tank 200 contains ethylene and comonomer, and this liquid material can be used again as a raw material. After recovery, the materials in the kettle are sprayed into the flash tank 400 by using residual pressure in the kettle, and the gas in the flash tank 400 is discharged and enters the gas storage device 300. Vacuum is drawn in the flash tank 400 and replaced with nitrogen, and the replacement gas is also vented out of the flash tank 400 into the gas storage device 300. The gas in the gas storage device 300 is recovered or subjected to harmless treatment according to the plant equipment. In the step 4), after the combustible gas content in the flash tank 400 is qualified, the polyethylene powder is discharged out of the flash tank 400 and enters a powder bin or is packaged. And (5) testing the melt index and the like of the powder product, and grading the product according to the test result. Thus, a polyethylene powder product was obtained.
In the present invention, the pressures refer to gauge pressure.
The present invention will be described in detail by examples.
The experimental results in the examples were obtained according to the following test methods, in which the operations were performed under room temperature environments without particular limitation:
the main catalyst is BCE catalyst, which is obtained from Beijing Orda division of China petrochemical catalyst Co.
The promoter component is triethylaluminum, and the catalyst component is prepared into 0.35mol/L by dehydrated hexane for use.
Melt index (MFR): measured according to GB/T3682.1-2018 at 190℃under a load of 2.16 kg.
Density: measured according to the method in GB/T1033.2-2010.
Example 1
The polymerization was carried out in a batch liquid phase polymerization vessel having a volume of 5 liters. Hydrogen was added to the polymerization vessel to raise the pressure of the vessel by 0.4MPa, and 23.5mg of BCE catalyst and 10mL of triethylaluminum solution were charged into the polymerization vessel with 2 liters of liquid propane at 20 ℃. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 70 ℃, the gauge pressure of the polymerization kettle is raised to 3.2MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.5MPa, adding propylene, and controlling the molar ratio of propylene to ethylene to be 0.06 according to the analysis value of gas chromatography (sampling analysis every 3 min). The flow rate of the cooling water was adjusted to maintain the polymerization temperature at 70℃and thus the polymerization rate. After the polymerization reaction is carried out for 150 minutes, the pressure of the polymerization kettle is reduced, propane in the polymerization kettle is recovered, unreacted ethylene, propylene and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into liquid phase materials through a recovery condenser, and the liquid phase materials enter a recovery tank. When the polymerization vessel pressure was reduced to 1.5MPa, recovery was stopped. Discharging gas in the polymerization kettle and polyethylene powder into a flash evaporation kettle for flash evaporation (the pressure is 0.01 MPa), discharging the gas after flash evaporation into a gas holder, and replacing the gas in the flash evaporation tank with nitrogen, specifically, discharging the flash evaporation kettle to 0.01MPa; and (3) filling nitrogen into the flash evaporation kettle to 0.4MPa, emptying to normal pressure, discharging the replaced gas into a gas holder, filling nitrogen for 3 times, and discharging and weighing the powder in the kettle to obtain 414g of polyethylene powder. The powder was tested and the results are shown in Table 1.
Example 2
The polymerization was carried out in a batch liquid phase polymerization vessel having a volume of 5 liters. Hydrogen was added to the polymerization vessel to raise the pressure of the vessel by 0.6MPa, and 24.2mg of BCE catalyst and 10mL of triethylaluminum solution were charged into the polymerization vessel with 2 liters of liquid propane at 20 ℃. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 65 ℃, the gauge pressure of the polymerization kettle is raised to 3MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.3MPa, adding propylene, and controlling the molar ratio of the propylene to the ethylene to be 0.05 according to the analysis value of gas chromatography (sampling analysis every 3 min). The flow rate of the cooling water was adjusted to maintain the polymerization temperature at 65 ℃. After the polymerization reaction is carried out for 150 minutes, the pressure of the polymerization kettle is reduced, propane in the polymerization kettle is recovered, unreacted ethylene, propylene and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into liquid phase materials through a recovery condenser, and the liquid phase materials enter a recovery tank. When the polymerization vessel pressure was reduced to 1.5MPa, recovery was stopped. Discharging the gas in the polymerization kettle and the polyethylene powder into a flash evaporation kettle for flash evaporation (gauge pressure is 0.01 MPa), discharging the gas after flash evaporation into a gas holder, and replacing the gas in the flash evaporation tank with nitrogen, specifically, discharging the flash evaporation kettle to 0.01MPa; and (3) filling nitrogen into the flash evaporation kettle to 0.4MPa, emptying to normal pressure, discharging the replaced gas into a gas holder, filling nitrogen for 3 times, and discharging and weighing the powder in the kettle to obtain 315g of polyethylene powder. The powder was tested and the results are shown in Table 1.
Example 3
The polymerization was carried out in a batch liquid phase polymerization vessel having a volume of 5 liters. Hydrogen was added to the polymerization vessel to raise the pressure of the vessel by 0.2MPa, and 25.3mg of BCE catalyst and 10mL of triethylaluminum solution were charged into the polymerization vessel with 2 liters of liquid propane at 20 ℃. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 65 ℃, the gauge pressure of the polymerization kettle is raised to 3MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.3MPa, adding n-butene, and controlling the molar ratio of n-butene to ethylene to be 0.04 according to the analysis value of gas chromatography (sampling analysis every 3 min). And (3) regulating the flow of cooling water to maintain the polymerization reaction temperature at 65 ℃, releasing pressure in the polymerization kettle to recover propane in the polymerization kettle after the polymerization reaction is carried out for 150 minutes, vaporizing unreacted ethylene, n-butene and propane in the polymerization kettle, condensing the obtained gas phase into a liquid phase material through a recovery condenser, and allowing the liquid phase material to enter a recovery tank. When the polymerization vessel pressure was reduced to 1.5MPa, recovery was stopped. Discharging the gas in the polymerization kettle and the polyethylene powder into a flash evaporation kettle for flash evaporation (gauge pressure is 0.01 MPa), discharging the gas after flash evaporation into a gas holder, and replacing the gas in the flash evaporation tank with nitrogen, specifically, discharging the flash evaporation kettle to 0.01MPa; and (3) filling nitrogen into the flash evaporation kettle to 0.4MPa, emptying to normal pressure, discharging the replaced gas into a gas holder, filling nitrogen for 3 times, and discharging and weighing powder in the kettle to obtain 367g of polyethylene powder. The powder was tested and the results are shown in Table 1.
Example 4
The polymerization was carried out in a batch liquid phase polymerization vessel having a volume of 5 liters. Hydrogen was added to the polymerization vessel to raise the pressure of the vessel by 0.8MPa, and 21.9mg of BCE catalyst and 10mL of triethylaluminum solution were charged into the polymerization vessel with 2 liters of liquid propane at 20 ℃. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 60 ℃, the gauge pressure of the polymerization kettle is raised to 3MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.5MPa, adding n-butene, and controlling the molar ratio of n-butene to ethylene to be 0.06 according to the analysis value of gas chromatography (sampling analysis every 3 min). And (3) regulating the flow of cooling water to maintain the polymerization temperature at 60 ℃, discharging pressure in the polymerization kettle to recover propane in the polymerization kettle after the polymerization reaction is carried out for 150 minutes, vaporizing unreacted ethylene, n-butene and propane in the polymerization kettle, condensing the obtained gas phase into a liquid phase material through a recovery condenser, and feeding the liquid phase material into a recovery tank. When the polymerization vessel pressure was reduced to 1.5MPa, recovery was stopped. Discharging the gas in the polymerization kettle and the polyethylene powder into a flash evaporation kettle for flash evaporation (gauge pressure is 0.01 MPa), discharging the gas after flash evaporation into a gas holder, and replacing the gas in the flash evaporation tank with nitrogen, specifically, discharging the flash evaporation kettle to 0.01MPa; and (3) filling nitrogen into the flash evaporation kettle to 0.4MPa, emptying to normal pressure, discharging the replaced gas into a gas holder, filling nitrogen for 3 times, and discharging and weighing the powder in the kettle to obtain 292g of polyethylene powder. The powder was tested and the results are shown in Table 1.
Example 5
The polymerization was carried out in a batch liquid phase polymerization vessel having a volume of 5 liters. Hydrogen was added to the polymerization vessel to raise the pressure of the vessel by 1MPa, and 24.5mg of BCE catalyst and 10mL of triethylaluminum solution were charged into the polymerization vessel with 2 liters of liquid propane at 20 ℃. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 55 ℃, the gauge pressure of the polymerization kettle is raised to 3MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.4MPa, adding n-butene, and controlling the molar ratio of n-butene to ethylene to be 0.05 according to the analysis value of gas chromatography (sampling analysis every 3 min). The flow rate of the cooling water was adjusted to maintain the polymerization temperature at 55 ℃. After the polymerization reaction is carried out for 150 minutes, the pressure of the polymerization kettle is reduced, propane in the polymerization kettle is recovered, unreacted ethylene, propylene and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into liquid phase materials through a recovery condenser, and the liquid phase materials enter a recovery tank. When the polymerization vessel pressure was reduced to 1.5MPa, recovery was stopped. Discharging the gas in the polymerization kettle and the polyethylene powder into a flash evaporation kettle for flash evaporation (gauge pressure is 0.01 MPa), discharging the gas after flash evaporation into a gas holder, and replacing the gas in the flash evaporation tank with nitrogen, specifically, discharging the flash evaporation kettle to 0.01MPa; and (3) filling nitrogen into the flash evaporation kettle to 0.4MPa, emptying to normal pressure, discharging the replaced gas into a gas holder, filling nitrogen for 3 times, and discharging and weighing powder in the kettle to obtain 306g of polyethylene powder. The powder was tested and the results are shown in Table 1.
Comparative example 1
Hydrogen was added to the polymerization vessel to raise the vessel pressure by 0.6MPa, and 2 liters of propane was used to charge 23.5mg of BCE catalyst and 10mL of triethylaluminum solution to the polymerization vessel. Heating the polymerization kettle by jacket hot water of the polymerization kettle, when the temperature of the polymerization kettle reaches 65 ℃, rising the gauge pressure of the polymerization kettle to 3MPa, adding ethylene to raise the pressure of the polymerization kettle to 3.3MPa, and starting to perform polymerization reaction; the flow rate of the cooling water was adjusted according to the polymerization pot temperature, thereby maintaining the polymerization temperature. After the polymerization reaction is carried out for 150 minutes, a valve connecting the polymerization kettle and a recovery system is opened, the pressure of the polymerization kettle is released, unreacted ethylene and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into a liquid phase material through a recovery condenser, and the liquid phase material enters a recovery tank; when the autoclave pressure was reduced to 1.5MPa, recovery was stopped. And discharging the gas in the kettle and the polyethylene powder into a flash tank (gauge pressure is 0.01 MPa), opening a valve between the flash tank and gas storage equipment to discharge the gas in the flash tank into the gas storage equipment, reducing the pressure of the flash tank to 0.01MPa, then charging nitrogen to 0.4MPa, discharging the gas after nitrogen replacement into the gas storage equipment, discharging and weighing the powder in the tank after the nitrogen replacement is performed for 3 times, and obtaining 272g of polyethylene powder. The powder was tested and the results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the polyethylene density in examples 1-5 can be obtained by adopting the technical scheme of the present application, which shows that the polyethylene density has a remarkable effect by adopting the method of the present invention, thereby effectively improving the utilization rate and economic benefit of the production device.
In addition, the invention adopts propane as suspending solvent to produce polyethylene, compared with the traditional slurry process which uses hexane, solvent oil and other traditional solvents, the invention does not need the process steps of centrifugation, filtration, drying and the like, does not need the equipment of a centrifuge, a dryer and the like, and reduces the production cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for producing polyethylene using batch production equipment, the process comprising:
in the presence of propane and a catalyst, ethylene and a comonomer are contacted in a polymerization kettle to carry out polymerization reaction;
in the polymerization reaction process, sampling and analyzing are carried out from a polymerization kettle at regular intervals to obtain the content ratio of ethylene and comonomer in the polymerization kettle, and the content ratio is transmitted to a comonomer feeding system; the comonomer feeding system adjusts the feeding amount of the comonomer according to the content ratio, so that the content ratio of the ethylene to the comonomer in the polymerization kettle is maintained within a preset range.
2. The method of claim 1, wherein the comonomer is an alpha-olefin;
preferably, the alpha-olefin is selected from at least one of butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof, more preferably propylene and/or n-butene.
3. The process according to claim 1 or 2, wherein the contacting is performed in the presence of hydrogen in an amount such that the pressure within the system increases by 0.01-1.5MPa;
and/or, the hydrogen is fed into the polymerizer before feeding the propane and the catalyst into the polymerizer, or is fed into the polymerizer after feeding the propane and the catalyst into the polymerizer and before feeding the ethylene gas.
4. The method of claim 1 or 2, wherein the polymerization conditions include: the temperature is 50-90 ℃, preferably 60-80 ℃; the pressure is 2.3-3.8MPa, preferably 2.8-3.6MPa.
5. The method of claim 1, wherein the method further comprises:
(a) After the polymerization reaction is finished, the pressure of the polymerization kettle is reduced, unreacted ethylene, comonomer and propane are vaporized in the polymerization kettle, the obtained gas phase is condensed into a liquid phase material through a recovery condenser, and the liquid phase material enters a recovery tank.
6. The method according to claim 5, wherein the vaporisation pressure is 0.8-1.8MPa, preferably 1-1.5MPa.
7. The method according to claim 5 or 6, wherein the method further comprises:
after the step (a) is finished, utilizing residual pressure in the polymerization kettle to spray materials in the kettle into a flash tank for flash evaporation, so as to obtain flash evaporation gas and polyethylene powder;
preferably, the conditions of the flash evaporation include: the pressure is 0-0.1MPa.
8. The method according to any one of claims 1 to 7, wherein the apparatus for sampling analysis from the polymerizer is a gas chromatograph.
9. A method according to claim 1 or 8, wherein the time between sampling analysis intervals is less than 30 minutes, preferably less than 10 minutes.
10. The process according to any one of claims 1-9, wherein the catalyst is a Ziegler-Natta catalyst comprising: (1) A titanium-containing solid catalyst active component containing magnesium, titanium, halogen and an internal electron donor; (2) an organoaluminum compound cocatalyst component; and (3) optionally an external electron donor component.
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| CN1817919A (en) * | 2006-03-08 | 2006-08-16 | 南京金陵塑胶化工有限公司 | Production and reactor for polypropylene |
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