CN115926029A - Polymerization anti-scaling agent for polyolefin device and preparation method and application thereof - Google Patents
Polymerization anti-scaling agent for polyolefin device and preparation method and application thereof Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 80
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 alkyl sulfonic acid Chemical compound 0.000 claims abstract description 170
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- 239000003607 modifier Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 36
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 6
- 239000002519 antifouling agent Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- 230000003449 preventive effect Effects 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 claims description 3
- RSHHCURRBLAGFA-UHFFFAOYSA-M dimethyl-di(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCC RSHHCURRBLAGFA-UHFFFAOYSA-M 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 47
- 239000003054 catalyst Substances 0.000 abstract description 26
- 238000011156 evaluation Methods 0.000 description 67
- 230000037048 polymerization activity Effects 0.000 description 37
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002245 particle Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a polymerization anti-scaling agent for a polyolefin device, and a preparation method and application thereof. The polymerization anti-scaling agent comprises alkyl sulfonic acid, alkyl diethanol amine, modified alkyl quaternary ammonium salt compound modified by aromatic compound modifier containing hydroxyl and solvent. The preparation method comprises the following steps: modifying quaternary ammonium salt with modifier: mixing the modifier with alkyl quaternary ammonium salt, and stirring to form a uniform solution, namely a modified alkyl quaternary ammonium salt compound; and mixing the modified alkyl quaternary ammonium salt compound with alkyl sulfonic acid, alkyl diethanol amine and a solvent, and stirring to obtain the polymerization anti-scaling agent for the polyolefin device. The polymerization anti-scaling agent is applied to the anti-scaling of ethylene polymerization reaction. Compared with the prior art, the method has small influence on the activity of the catalyst, reduces the contact time of the anti-scaling agent and the catalyst by introducing the anti-scaling agent into a polymerization reaction device through a new method, is easy to implement and has good operability.
Description
Technical Field
The invention relates to the technical field of polymerization anti-scaling agents, in particular to a polymerization anti-scaling agent for a polyolefin device and a preparation method and application thereof.
Background
In polymerization processes for the polymerization of olefins carried out continuously, in particular in gas-phase processes, it is necessary to face polymer agglomerates in the polymerization reactor. See U.S. Pat. nos. 5,436,304 and 5,405,922. Sheeting is the adhesion of molten catalyst and resin particles to the reactor walls. The frost is the same as sheeting in that the molten catalyst and resin particles adhere to the reactor walls, except that the point of occurrence is the conical portion of the dome or the hemispherical head at the top of the reactor. Sheeting can be a problem in commercial gas phase polyolefin production reactors if not adequately mitigated. The problem is characterized by the formation of large solid masses of polymer on the reactor walls. These solid matter or polymer (sheets) are eventually removed from the walls and fall into the reaction chamber where they impede fluidization, block the product outlet and eventually force the reactor to shut down.
Some anti-scaling agents have been developed to solve the problem of polymer agglomeration generated in the continuous production process of olefin polymerization, wherein the alkyl diethanol amine can effectively eliminate the negative electricity generated by the system. Patent No. WO 97/46599 discloses a process for controlling static electricity generated during production by blending an anti-fouling agent containing an alkyl diethanol amine (e.g., atmer 163) with a catalyst and introducing the resulting mixture into an olefin polymerization apparatus.
The alkyl sulfonic acid substances can effectively eliminate positive electricity generated by the system. Patent No. US9303095B2 discloses a method for controlling fouling problems in polyolefin production using an anti-fouling agent (trade name Statsafe 6000) containing an alkyl sulfonic acid.
The above anti-fouling agent compounds can lead to a substantial reduction in catalyst activity due to the active and sensitive nature of the catalyst used in the polymerization reaction, possibly due to catalyst interaction with the anti-fouling agent, e.g. catalyst interaction with sulphonic acid species or anti-fouling agent reaction with the catalyst active sites, depending on the type of anti-fouling agent used and the amount of anti-fouling agent added required to inhibit agglomeration. Meanwhile, the anti-scaling agent is observed to have static elimination hysteresis phenomenon when being used alone, so that the required anti-scaling effect can be achieved only by increasing the using amount of the anti-scaling agent.
Disclosure of Invention
The present invention is directed to overcoming at least one of the above-mentioned drawbacks of the prior art, and providing a polymeric anti-fouling agent for polyolefin plants, which has a small effect on the activity of the catalyst, reduces the contact time between the anti-fouling agent and the catalyst, is easy to implement, and has good operability, and a preparation method and applications thereof.
The purpose of the invention can be realized by the following technical scheme:
a polymerization anti-scaling agent for polyolefin devices comprises alkyl sulfonic acid, alkyl diethanol amine, a modified alkyl quaternary ammonium salt compound modified by a hydroxyl-containing aromatic compound modifier and a solvent.
Further, the weight ratio of the alkyl sulfonic acid to the alkyl diethanol amine is (0.01-100) 1; the weight ratio of the sum of the mass of the alkyl sulfonic acid and the alkyl diethanol amine to the modified alkyl quaternary ammonium salt compound is (0.01-100): 1; the weight ratio of the modifier to the alkyl quaternary ammonium salt is (0.01-100) to 1; the content of the solvent is 1-99%.
Further, the weight ratio of the alkyl sulfonic acid to the alkyl diethanol amine is (0.1-10): 1; the weight ratio of the sum of the mass of the alkyl sulfonic acid and the alkyl diethanol amine to the modified alkyl quaternary ammonium salt compound is (0.1-10) to 1; the weight ratio of the modifier to the alkyl quaternary ammonium salt is (0.1-10) to 1.
Further, the weight ratio of the alkyl sulfonic acid to the alkyl diethanol amine is (0.5-2) 1; the weight ratio of the sum of the mass of the alkyl sulfonic acid and the alkyl diethanol amine to the modified alkyl quaternary ammonium salt compound is (0.1-1): 1; the weight ratio of the modifier to the alkyl quaternary ammonium salt is (0.5-2) to 1.
Further, the alkyl sulfonic acid is benzene sulfonic acid or a general formula R-C 6 H 4 -SO 3 H, wherein R is an alkyl group containing 1 to 18 carbon atoms;
the general formula of the alkyl diethanol amine is R1-N (CH) 2 CH 2 OH) 2 Wherein R1 is alkyl containing 1-18 carbon atoms;
the general formula of the alkyl quaternary ammonium salt is R1 (R3) 3-n NR2X n Wherein R1 and R2 may be the same or different, R1 and R2 are alkyl containing 1-18 carbon atoms, R3 is alkyl containing 1-7 carbon atoms, and X is fluorine, chlorine, bromine, iodine, RCOO, SO 3 Or NO 3 N is 1 to 3;
the aromatic compound modifier containing hydroxyl comprises one or more of the following compounds:
the solvent comprises one or more of hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, mineral oil, polyol, polybasic acid or polyol ester.
Further, the alkyl sulfonic acid is alkyl benzene sulfonic acid containing 6 to 16 carbon atoms, preferably dodecyl benzene sulfonic acid;
the alkyl diethanol amine comprises alkoxy propyl dihydroxy ethyl amine, stearyl bis (2-hydroxyethyl) amine, bis (beta-hydroxyethyl) cocoamine, bis (beta-hydroxyethyl) stearyl amine or bis (beta-hydroxyethyl) tallow amine; preferably alkoxypropyldihydroxyethylamine or stearylbis (2-hydroxyethyl) amine;
the modifier comprises
The alkyl quaternary ammonium salt comprises dicocoyl dimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium chloride or dilauryl dimethyl ammonium bromide; dicocodimethylammonium chloride or didodecyldimethylammonium chloride is preferred.
A method for preparing a polymeric anti-fouling agent for polyolefin devices as described above, comprising the steps of:
modifying quaternary ammonium salt with modifier: mixing the modifier with alkyl quaternary ammonium salt, and stirring to form a uniform solution, namely a modified alkyl quaternary ammonium salt compound;
and mixing the modified alkyl quaternary ammonium salt compound with alkyl sulfonic acid, alkyl diethanol amine and a solvent, and stirring to obtain the polymerization anti-scaling agent for the polyolefin device.
Further, the stirring temperature is-50 to 150 ℃, preferably 0 to 80 ℃.
Further, the temperature of the stirring is 0 to 100 ℃, preferably 10 to 50 ℃.
The application of the polymerization anti-scaling agent for the polyolefin device is applied to the anti-scaling of ethylene polymerization reaction, and comprises the following specific operation steps: feeding the polymerization anti-scaling agent through an independent feeding pipeline, atomizing the polymerization anti-scaling agent by an atomizing device, introducing the atomized polymerization anti-scaling agent into a seed bed of a reaction device for direct reaction, or fluidizing the atomized polymerization anti-scaling agent in the reaction device after the atomized polymerization anti-scaling agent is fully contacted with resin of the seed bed in advance.
Furthermore, the addition amount of the polymerization anti-scaling agent is 0.1-5000ppm of the weight of the polyolefin powder in the polymerization reactor, and the time for which the polymerization anti-scaling agent is in contact with the inside of the seed bed in advance is 0.1-24h.
Furthermore, the addition amount of the polymerization anti-scaling agent is 0.1-5000ppm of the weight of the polyolefin powder in the polymerization reactor, and the time for which the polymerization anti-scaling agent is in contact with the inside of the seed bed in advance is 1-24h.
Further, the addition amount of the polymerization anti-scaling agent is 1-1000ppm, and the contact time is 0.5-5h.
Further, the addition amount of the polymerization anti-scaling agent is 1-1000ppm, and the contact time is 3-5h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The modified alkyl quaternary ammonium salt is introduced into the anti-scaling agent, so that the conductivity of the system can be improved, the descaling efficiency of the anti-scaling agent is increased, and the integral dosage of the anti-scaling agent is reduced. Also, such composite anti-fouling agents can reduce their impact on catalyst activity;
(2) The invention feeds the anti-scaling agent composition into the seedbed independently of the catalyst through a separate feed line, thereby shortening the contact time of the catalyst and the anti-scaling agent. The anti-scaling agent atomized by the atomizing device can be contacted with resin materials in the reaction device more uniformly, the anti-scaling effect is improved better, and the using amount of the anti-scaling agent is reduced.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
A polymerization anti-scaling agent for polyolefin devices and a preparation method and application thereof, wherein the polymerization anti-scaling agent composition comprises the following components: the first component is an alkyl sulfonic acid compound; the second component is an alkyl diethanol amine compound; the third component is alkyl quaternary ammonium salt compound modified by aromatic compound modifier containing hydroxyl; the fourth component is a solvent. The preparation method comprises the following steps:
(1) Modifying the alkyl quaternary ammonium salt by using a modifier. The modifier and alkyl quaternary ammonium salt are mixed according to a certain proportion and stirred to form a uniform solution. The stirring temperature is-50 to 150 ℃, preferably 0 to 80 ℃; the weight ratio of the first component to the second component is (0.01-100): 1, preferably (0.5-2): 1. The weight ratio of the sum of the weight of the first component and the second component to the third component is (0.01-100): 1, preferably (0.1-1): 1. The weight ratio of the sum of the first component, the second component and the third component to the fourth component is (0.01-100): 1, preferably (0.05-0.5): 1. The weight ratio of the modifier to the quaternary ammonium salt is (0.01-100): 1, preferably (0.5-2): 1.
(2) Mixing the obtained modified alkyl quaternary ammonium salt with other components in proportion, stirring to form uniform solutionThe stirring temperature is-50 to 150 ℃, preferably 0 to 80 ℃. The alkyl sulfonic acid is benzenesulfonic acid or has a general formula of R-C 6 H 4 -SO 3 H, wherein R is an alkyl group containing from 1 to 18 carbon atoms, preferably an alkylbenzene sulfonic acid containing from 6 to 16 carbons. The general formula of the alkyl diethanol amine is R1-N (CH) 2 CH 2 OH) 2 Wherein R1 is an alkyl group containing 1 to 18 carbon atoms, preferably alkoxypropyldihydroxyethylamine, stearylbis (2-hydroxyethyl) amine, bis (. Beta. -hydroxyethyl) cocoamine, bis (. Beta. -hydroxyethyl) stearylamine, bis (. Beta. -hydroxyethyl) tallowamine. Further preferred are alkoxypropyldihydroxyethylamine and stearylbis (2-hydroxyethyl) amine. The quaternary alkyl ammonium salt is represented by the general formula R1 (R3) 3- n NR2X n Wherein R1 and R2 may be the same or different, R1 and R2 are alkyl groups containing 1 to 18 carbon atoms, R3 is an alkyl group containing 1 to 7 carbon atoms, and X is fluorine, chlorine, bromine, iodine, RCOO, SO 3 Or NO 3 And n is 1 to 3. Preferred are dicocodimethylammonium chloride, didodecyldimethylammonium bromide, ditetradecyldimethylammonium chloride, and dilauryldimethylammonium bromide. More preferably dicocodimethylammonium chloride or didodecyldimethylammonium chloride. The solvent is hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, mineral oil, polyol, polybasic acid, polyol ester or their mixture, preferably heptane, cyclohexane, castor oil.
The using method comprises the following steps: the anti-scaling agent composition is fed independently of the catalyst through an independent feeding pipeline, is atomized by an atomization device and then is introduced into a seed bed of a reaction device for direct reaction, or is fluidized in the reaction device after being fully contacted with resin of the seed bed in advance. The contact time is from 0.01 to 24 hours, preferably from 0.5 to 5 hours. The anti-fouling agent composition is added in an amount of 0.1 to 5000ppm, preferably 1 to 1000ppm, based on the weight of the polyolefin powder in the polymerization reactor.
Evaluating the anti-scaling effect of the device:
the method is characterized in that the method is independent of a catalyst, the prepared anti-scaling agent mixture is atomized in an atomization device through an independent pipeline and then added into a seed bed, and the anti-scaling agent mixture is contacted with polyethylene powder in the seed bed for 4 hours and then introduced into a metal fluidized bed. The mass ratio of the dosage of the anti-scaling agent to the polyethylene powder in the reactor is 200ppm.
After introducing the anti-fouling agent into the fluidized bed, the particle charge to mass ratio was measured by sampling and in an electrostatic analyzer. Samples were taken 5min, 10min, and 60min after the anti-kogation agent was injected, and the charge-to-mass ratio of the polyethylene particles was analyzed, and the results are shown in tables 1-4. The charge-to-mass ratio represents the amount of electrostatic charge per kg of polyethylene particles, a positive value representing a positive charge of the polyethylene particles and a negative value representing a negative charge of the polyethylene particles.
Evaluation of polymerization Activity:
the polymerization activity of the catalyst was evaluated by slurry polymerization of ethylene. The polymerization reactor had a volume of 2L and was previously replaced with nitrogen several times. Replacing the reaction bottle with nitrogen for several times, sequentially adding solvent hexane 1L, self-made metallocene polyethylene catalyst 10-100mg, alkyl aluminum (10 wt%) 1ml, and a certain amount of antiscaling agent. And introducing nitrogen to flush the solvent and the catalyst into the reaction kettle which is subjected to anhydrous and anaerobic treatment. And (3) introducing ethylene, wherein the reaction pressure of the ethylene is 0.8MPa, opening the stirrer, gradually heating, and keeping the reaction for 2 hours after the temperature is raised to the specified temperature. The temperature in the reaction kettle is controlled by water bath. Finally, ethylene is shut off, the polymerization product is taken out after cooling, dried and weighed, and the catalyst activity is calculated. The polymerization system was subjected to evaluation tests with concentrations of the fouling preventive agent of 50, 200 and 5000ppm, and the polymerization activity results are shown in tables 1 to 4.
Example 1a
The composition and the formulation of example 1a are shown in Table 1.
Step 1: modifying alkyl quaternary ammonium salt with modifier: mixing a modifier with alkyl quaternary ammonium salt, and stirring to form a uniform solution, namely a modified alkyl quaternary ammonium salt compound, wherein the mixing temperature is 30 ℃;
step 2: mixing and stirring the modified alkyl quaternary ammonium salt compound, alkyl sulfonic acid, alkyl diethanol amine and solvent hexane to obtain the polymerization anti-scaling agent K1 for the polyolefin device, wherein the mixing temperature is 30 ℃.
The results of the evaluation of the scale-preventing effect of the apparatus for K1 and the evaluation of the polymerization activity are shown in Table 1.
Example 1b
The components and the ratio of the components in the example 1b are shown in the table 1, the steps are the same as the step 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 10 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 10 ℃, and the polymerization anti-scaling agent K2 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K2 and the evaluation of the polymerization activity are shown in Table 1.
Example 1c
The components and the mixture ratio of the example 1c are shown in table 1, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 50 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 50 ℃, so as to obtain the polymerization anti-scaling agent K3 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K3 and the evaluation of the polymerization activity are shown in Table 1.
Example 1d
The components and the ratio of the components in example 1d are shown in Table 1, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 0 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 0 ℃, so as to obtain the polymerization anti-scaling agent K4 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K4 and the evaluation of the polymerization activity are shown in Table 1.
Example 1e
The components and the proportion of the component in example 1e are shown in Table 1, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 50 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 50 ℃, so as to obtain the polymerization anti-scaling agent K5 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K5 and the evaluation of the polymerization activity are shown in Table 1.
Example 1f
The components and the mixture ratio of the example 1f are shown in the table 1, the steps are the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 20 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 20 ℃, so that the polymerization anti-scaling agent K6 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K6 and the evaluation of the polymerization activity are shown in Table 1.
Example 1g
The components and the mixture ratio of the example 1g are shown in Table 1, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 60 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 60 ℃, so as to obtain the polymerization anti-scaling agent K7 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K7 and the evaluation of the polymerization activity are shown in Table 1.
Example 1h
The components and the mixture ratio of the example 1h are shown in the table 1, the steps are the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 80 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 80 ℃, so that the polymerization anti-scaling agent K8 for the polyolefin device is obtained. The results of the evaluation of the scale-preventing effect of the apparatus for K8 and the evaluation of the polymerization activity are shown in Table 1.
Example 1i
The components and the proportion of the components in example 1i are shown in Table 1, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 40 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 40 ℃, so that the polymerization anti-scaling agent K9 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K9 and the evaluation of the polymerization activity are shown in Table 1.
Example 1j
The components and the proportion of the example 1j are shown in the table 1, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 100 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 100 ℃, so as to obtain the polymerization anti-scaling agent K10 for the polyolefin device. The results of the evaluation of the fouling-preventing effect of the apparatus for K10 and the polymerization activity are shown in Table 1.
Comparative example 1
The components and the proportions of comparative example 1 are shown in Table 1. Stirring and blending the mixture and a solvent at the temperature of 30 ℃ to obtain the polymerization anti-fouling agent C1 for the polyolefin device. The results of the evaluation of the scale-preventing effect of the apparatus for C1 and the evaluation of the polymerization activity are shown in Table 1.
Compared with the comparative example 1, in all the examples in the table 1, the quaternary ammonium salt is modified by using different modifiers, so that the influence of the quaternary ammonium salt on the catalyst activity is reduced, and the polymerization activity is obviously improved compared with the comparative example 1.
TABLE 1 formulations and catalyst activity, charge to mass ratio results for examples and comparative examples using different modifiers
Example 2a
The components and the proportion of the component in example 2a are shown in Table 2, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 30 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 30 ℃, so that the polymerization anti-scaling agent K11 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K11 and the evaluation of the polymerization activity are shown in Table 2.
Example 2c
The components and the mixture ratio of the example 2c are shown in the table 2, the steps are the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 50 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 50 ℃, so that the polymerization anti-scaling agent K12 for the polyolefin device is obtained. The results of the evaluation of the scale-preventing effect of the apparatus for K12 and the evaluation of the polymerization activity are shown in Table 2.
Example 2d
The components and the proportion of the component in example 2d are shown in Table 2, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 10 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 10 ℃, so that the polymerization anti-scaling agent K12 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K12 and the evaluation of the polymerization activity are shown in Table 2.
Example 2e
The components and the proportion of the example 2e are shown in Table 2, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 0 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 0 ℃, so as to obtain the polymerization anti-scaling agent K13 for the polyolefin device. The results of the evaluation of the scale-preventing effect of the apparatus for K13 and the evaluation of the polymerization activity are shown in Table 2.
Example 2f
The components and the ratio of the components in example 2f are shown in table 2, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 100 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 100 ℃, so that the polymerization anti-scaling agent K14 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K14 and the evaluation of the polymerization activity are shown in Table 2.
Example 2g
The components and the ratio of example 2g are shown in table 2, the procedure is the same as example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 60 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 60 ℃, and the polymerization anti-scaling agent K16 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K16 and the evaluation of the polymerization activity are shown in Table 2.
Example 2h
The components and the ratio of the components in example 2h are shown in table 2, the steps are the same as those in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 20 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 20 ℃, so that the polymerization anti-scaling agent K17 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K17 and the evaluation of the polymerization activity are shown in Table 2.
Comparative example 2
The components and the proportions of comparative example 2 are shown in Table 2. Stirring and blending the mixture and a solvent at the temperature of 30 ℃ to obtain the polymerization anti-fouling agent C2 for the polyolefin device. The results of the evaluation of the anti-fouling effect of the apparatus for C2 and the evaluation of the polymerization activity are shown in Table 2.
All the examples in the table 2 adopt the sulfonic acid, the alkyl diethanol amine and the alkyl quaternary ammonium salt to be compounded together, while the comparative example 2 only adopts the single alkyl quaternary ammonium salt, and the static elimination effect of the anti-scaling agent obtained in each example is better than that of the comparative example 2 in different degrees.
TABLE 2 formulation and catalyst activity, charge to mass ratio results for examples and comparative examples using different alkyl quaternary ammonium salts
Example 3a
The components and the ratio of the components in example 3a are shown in Table 3, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 30 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 30 ℃, so that the polymerization anti-scaling agent K18 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K18 and the evaluation of the polymerization activity are shown in Table 3.
Example 3b
The components and the ratio of the components in example 3b are shown in table 3, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt is 50 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 50 ℃, and the polymerization anti-scaling agent K19 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K19 and the evaluation of the polymerization activity are shown in Table 3.
Example 3c
The components and the ratio of the components in example 3c are shown in table 3, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt is 10 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 10 ℃, and the polymerization anti-scaling agent K20 for the polyolefin device is obtained. The results of the evaluation of the scale-preventing effect of the apparatus for K20 and the evaluation of the polymerization activity are shown in Table 3.
Example 3d
The components and proportions of example 3d are shown in Table 3, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 0 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 0 ℃, so as to obtain the polymeric anti-fouling agent K21 for polyolefin devices. The results of the evaluation of the scale-preventive effect of the apparatus for K21 and the evaluation of the polymerization activity are shown in Table 3.
Example 3e
The components and the ratio of the components in example 3e are shown in table 3, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt is 100 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 100 ℃, and the polymerization anti-fouling agent K22 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K22 and the evaluation of the polymerization activity are shown in Table 3.
Example 3f
The components and the mixture ratio of the example 3f are shown in Table 3, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 20 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 20 ℃, so that the polymerization anti-scaling agent K23 for the polyolefin device is obtained. The results of the evaluation of the scale-preventive effect of the apparatus for K23 and the evaluation of the polymerization activity are shown in Table 3.
Comparative example 3
The components and the proportions of comparative example 3 are shown in Table 3. Stirring and blending with a solvent at 30 ℃ to obtain the polymerization anti-fouling agent C3 for the polyolefin device. The results of the evaluation of the anti-fouling effect of the apparatus for C3 and the evaluation of the polymerization activity are shown in Table 3.
All the examples in the table 3 adopt the sulfonic acid, the alkyl diethanol amine and the alkyl quaternary ammonium salt to be compounded together, while the comparative example 3 only adopts the single sulfonic acid, and the static electricity elimination effect of the anti-scaling agent obtained by each example is better than that of the comparative example 3 in different degrees.
TABLE 3 formulations and catalyst activity, charge to mass ratio results for examples and comparative examples using different sulfonic acids
Example 4a
The components and the proportion of the component in example 4a are shown in Table 4, the procedure is the same as that in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 30 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 30 ℃, so as to obtain the polymerization anti-scaling agent K24 for the polyolefin device. The results of the evaluation of the scale-preventing effect of the apparatus for K24 and the evaluation of the polymerization activity are shown in Table 4.
Example 4b
The components and the mixture ratio of the example 4b are shown in Table 4, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 50 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 50 ℃, so as to obtain the polymerization anti-scaling agent K25 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K25 and the evaluation of the polymerization activity are shown in Table 4.
Example 4c
The components and the mixture ratio of the example 4c are shown in Table 4, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 10 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 10 ℃, so as to obtain the polymerization anti-scaling agent K26 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K26 and the evaluation of the polymerization activity are shown in Table 4.
Example 4d
The components and the ratio of the components in example 4d are shown in Table 4, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 0 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 0 ℃, so as to obtain the polymerization anti-scaling agent K27 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K27 and the evaluation of the polymerization activity are shown in Table 4.
Example 4e
The components and the ratio of the components in example 4e are shown in table 4, the procedure is the same as in example 1a, the temperature of the modified alkyl quaternary ammonium salt is 20 ℃, the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 20 ℃, and the polymerization anti-scaling agent K28 for the polyolefin device is obtained. The results of the evaluation of the scale-preventing effect of the apparatus for K28 and the evaluation of the polymerization activity are shown in Table 4.
Example 4f
The components and the mixture ratio of the example 4f are shown in Table 4, the procedure is the same as the example 1a, the temperature of the modified alkyl quaternary ammonium salt of the modifier is 60 ℃, and the mixing temperature of the modified alkyl quaternary ammonium salt and other components is 60 ℃, so as to obtain the polymerization anti-scaling agent K29 for the polyolefin device. The results of the evaluation of the scale-preventive effect of the apparatus for K29 and the evaluation of the polymerization activity are shown in Table 4.
Comparative example 4
The components and the proportions of comparative example 4 are shown in Table 4. Stirring and blending with a solvent at 30 ℃ to obtain the polymerization anti-scaling agent C4 for the polyolefin device. The results of the evaluation of the anti-fouling effect of the apparatus for C4 and the evaluation of the polymerization activity are shown in Table 4.
All the examples in the table 4 adopt the sulfonic acid, the alkyl diethanol amine and the alkyl quaternary ammonium salt to be compounded together, while the comparative example 4 only adopts the alkyl diethanol amine alone, and the static electricity elimination effect of the anti-scaling agent obtained in each example is better than that of the comparative example 4 in different degrees.
TABLE 4 formulations and catalyst activity, charge to mass ratio results for examples and comparative examples using different alkyl diethanolamines
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A polymeric anti-fouling agent for polyolefin devices, comprising:
alkyl sulfonic acid is used as a first component;
alkyl diethanol amine is used as a second component;
the alkyl quaternary ammonium salt modified by the aromatic compound containing hydroxyl is used as a third component;
the solvent is the fourth component.
2. The polymeric antiscaling agent for polyolefin plants according to claim 1, wherein the weight ratio of the alkyl sulfonic acid to the alkyl diethanol amine is (0.01-100): 1; the weight ratio of the sum of the mass of the alkyl sulfonic acid and the alkyl diethanol amine to the modified alkyl quaternary ammonium salt compound is (0.01-100) to 1; the weight ratio of the modifier to the alkyl quaternary ammonium salt is (0.01-100) to 1; the mass content of the solvent is 1-99%.
3. The polymeric antiscaling agent for polyolefin plants according to claim 2, wherein the weight ratio of the alkyl sulfonic acid to the alkyl diethanol amine is (0.1-10): 1; the weight ratio of the sum of the mass of the alkyl sulfonic acid and the alkyl diethanol amine to the modified alkyl quaternary ammonium salt compound is (0.1-10) to 1; the weight ratio of the modifier to the alkyl quaternary ammonium salt is (0.1-10): 1.
4. The polymeric anti-fouling agent for polyolefin devices as claimed in claim 1, wherein the alkyl sulfonic acid is benzenesulfonic acid or general formula R-C 6 H 4 -SO 3 H, wherein R is an alkyl group containing 1 to 18 carbon atoms;
the general formula of the alkyl diethanol amine is R1-N (CH) 2 CH 2 OH) 2 Wherein R1 is alkyl containing 1-18 carbon atoms;
the general formula of the alkyl quaternary ammonium salt is R1 (R3) 3-n NR2X n Wherein R1 and R2 may be the same or different, R1 and R2 are alkyl containing 1-18 carbon atoms, R3 is alkyl containing 1-7 carbon atoms, and X is fluorine, chlorine, bromine, iodine, RCOO, SO 3 Or NO 3 N is 1 to 3;
the aromatic compound modifier containing hydroxyl comprises one or more of the following compounds:
the solvent comprises one or more of hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, mineral oil, polyol, polybasic acid or polyol ester.
5. The polymeric fouling preventive agent for polyolefin equipment according to claim 4, wherein the alkyl sulfonic acid is an alkyl benzene sulfonic acid containing 6 to 16 carbon atoms, preferably dodecyl benzene sulfonic acid;
the alkyl diethanol amine comprises alkoxy propyl dihydroxy ethyl amine, stearyl bis (2-hydroxyethyl) amine, bis (beta-hydroxyethyl) cocoamine, bis (beta-hydroxyethyl) stearyl amine or bis (beta-hydroxyethyl) tallow amine; preferably alkoxypropyldihydroxyethylamine or stearylbis (2-hydroxyethyl) amine;
the modifier comprises
The alkyl quaternary ammonium salt comprises dicocoyldimethyl ammonium chloride, didodecyldimethyl ammonium bromide, ditetradecyl dimethylammonium chloride or dilauryldimethyl ammonium bromide; dicocodimethylammonium chloride or didodecyldimethylammonium chloride is preferred.
6. A process for preparing a polymeric fouling preventive agent for polyolefin plants according to any of claims 1 to 5, comprising the steps of:
modifying quaternary ammonium salt with modifier: mixing the modifier with alkyl quaternary ammonium salt, and stirring to form a uniform solution, namely a modified alkyl quaternary ammonium salt compound;
and mixing the modified alkyl quaternary ammonium salt compound with alkyl sulfonic acid, alkyl diethanol amine and a solvent, and stirring to obtain the polymerization anti-scaling agent for the polyolefin device.
7. The method for preparing a polymeric anti-fouling agent for polyolefin plants according to claim 6, wherein the stirring temperature is-50 to 150 ℃, preferably 0 to 80 ℃.
8. The use of the polymeric anti-fouling agent for polyolefin plants according to any of claims 1 to 5, wherein the polymeric anti-fouling agent is used for preventing fouling in ethylene polymerization, and the method comprises the following steps: feeding the polymerization anti-scaling agent through an independent feeding pipeline, atomizing the polymerization anti-scaling agent by an atomizing device, introducing the atomized polymerization anti-scaling agent into a seed bed of a reaction device for direct reaction, or fluidizing the atomized polymerization anti-scaling agent in the reaction device after the atomized polymerization anti-scaling agent is fully contacted with resin of the seed bed in advance.
9. The use of the polymeric anti-fouling agent for polyolefin devices according to claim 8, wherein the amount of the polymeric anti-fouling agent added is 0.1-5000ppm of the weight of the polyolefin powder in the polymerization reactor, and the time for which the polymeric anti-fouling agent is previously contacted with the inside of the seed bed is 0.1-24h.
10. The use of the polymeric fouling preventive agent for polyolefin plants according to claim 9, wherein the polymeric fouling preventive agent is added in an amount of 1 to 1000ppm and the contact time is 0.5 to 5 hours.
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