CN114409832A - Electrostatic control method for olefin polymerization process - Google Patents
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- CN114409832A CN114409832A CN202210092023.4A CN202210092023A CN114409832A CN 114409832 A CN114409832 A CN 114409832A CN 202210092023 A CN202210092023 A CN 202210092023A CN 114409832 A CN114409832 A CN 114409832A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 48
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 55
- 229920000098 polyolefin Polymers 0.000 claims abstract description 45
- 230000003068 static effect Effects 0.000 claims abstract description 24
- 230000005611 electricity Effects 0.000 claims abstract description 16
- -1 hydroxyl ester Chemical class 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002216 antistatic agent Substances 0.000 abstract description 7
- 238000012685 gas phase polymerization Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 230000005587 bubbling Effects 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000013065 commercial product Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- QHZLMUACJMDIAE-SFHVURJKSA-N 1-hexadecanoyl-sn-glycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)CO QHZLMUACJMDIAE-SFHVURJKSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a static control method for an olefin polymerization process, which comprises the steps of mixing nascent state polyolefin powder with an antistatic compound at the temperature of 30-60 ℃, standing for 24-72 hours to obtain nascent state polyolefin powder loaded with the antistatic compound; when the electrostatic voltage is increased to the electrostatic voltage threshold value in the olefin polymerization process, introducing the nascent state polyolefin powder loaded with the antistatic compound into a polymerization reactor filled with polyolefin powder through cascade control so as to control the electrostatic voltage in the olefin polymerization process. The method can reduce the dispersion time of the antistatic agent in the gas-phase polymerization reactor, and has less loss, thereby having higher electricity eliminating effect and stability.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization, and particularly relates to a static control method for an olefin polymerization process.
Background
In the industrial production of polyolefins, the dry reaction environment in the gas phase polymerization reactor and the high insulation of polyolefins result in frequent triboelectrification and slow static dissipation, providing natural conditions for the generation and accumulation of static electricity. The existence of static electricity in the production process can cause potential hazards such as wall sticking, caking and the like, and even cause the occurrence of reactor failure and explosion accidents. Therefore, antistatic agents are widely used in industrial fluidized bed reactors to control static electricity.
U.S. Pat. No. 5, 5034480A discloses a process for preparing ultra high molecular weight ethylene polymers using antistatic agents such as chromium salts of alkyl salicylic acids in titanium based catalyst systems, resulting in products that are free of fouling in the polymerization reactor. EP0560035 discloses a polymerization process using an alkyldiethanolamine to selectively inhibit polymerization on polymer particles smaller than 850 μm, thereby eliminating or reducing the build-up of polymer particles on the inner wall of a gas phase polymerization reactor caused by static electricity. U.S. Pat. No. 5, 6894127, 2 discloses a process for preventing reactor fouling and reducing temperature discontinuities around walls in the gas phase polymerization of olefins using an adjuvant comprising a polysulfone copolymer, a polymeric polyamine and an oil-soluble sulfonic acid.
The antistatic agents are introduced directly into the polymerization reactor in the above-mentioned patent documents. In addition to direct introduction, there are also processes in which the antistatic compound is premixed with other substances (catalysts) and then introduced into the polymerization reactor. WO2012041810a1 discloses a process for preparing a catalyst suspension comprising a surfactant-type antistatic compound and transferring said catalyst suspension to a polymerization reactor, reducing the risk of fouling inside the polymerization reactor.
The direct or indirect addition of the antistatic compound to the polymerization reactor in the continuous polymerization of olefins using the above method, although effective in reducing the production static electricity during the reaction, has a disadvantage in that the addition of the liquid-phase antistatic compound affects the flow pattern of the fluid in the polymerization reactor and is easily carried out or left on the wall surface of the reactor during the polymerization reaction, resulting in some loss of the liquid-phase antistatic compound. In addition, the high boiling point of liquid antistatic agents makes them generally incapable of vaporizing in a polymerization environment, and the poor flowability also makes them incapable of atomizing, and antistatic effects are severely restricted by antistatic agents that are not sufficiently dispersed.
Therefore, it is desirable to design a new method for reducing static electricity in a polyolefin fluidized bed reactor, which is easy to implement, has good operability, and not only prevents the antistatic from being dispersed in a gas phase polymerization reactor for a long time, but also does not affect the flow pattern of the fluid in the polymerization reactor to prevent large loss and residue.
Disclosure of Invention
The invention provides a static control method for an olefin polymerization process, which can reduce the dispersion time of an antistatic agent in a gas-phase polymerization reactor and reduce loss, thereby having higher electricity eliminating effect and stability.
A method for electrostatic control of an olefin polymerization process, comprising:
(1) mixing the nascent polyolefin powder with an antistatic compound at 30-60 ℃, and standing for 24-72h to obtain the nascent polyolefin powder loaded with the antistatic compound;
(2) when the electrostatic voltage is increased to the electrostatic voltage threshold value in the olefin polymerization process, introducing the nascent state polyolefin powder loaded with the antistatic compound into a polymerization reactor filled with polyolefin powder through cascade control so as to control the electrostatic voltage in the olefin polymerization process.
Because the surface of the nascent state polyolefin powder has higher roughness and pore channels, the antistatic compound can be attached to the interior of the pore channels of the nascent state polyolefin powder, and then the nascent state polyolefin powder loaded with the antistatic compound participates in the powder mixing process in the olefin polymerization reactor in a solid state. The particles move violently and are mixed under the fluidization effect of high-speed gas in the reactor, the antistatic compound can slowly seep out from the inside of the pore channel, and the phenomenon that the antistatic compound is blown away due to the fact that the antistatic compound is attached to the surface of powder in a shallow layer when the antistatic compound is directly added is avoided, so that the antistatic effect is achieved for a long time, and the purposes of high electricity eliminating effect and high stability are achieved.
Further, the mixing temperature of the nascent state polyolefin powder and the antistatic compound is 50-60 ℃, and the standing time is 60-72 h.
Higher mixing temperature can destroy the surface appearance of nascent state polyolefin, influences the ability of adsorbing antistatic compound, and lower mixing temperature makes antistatic compound mobility worsen to influence antistatic compound's inflow pore, under suitable mixing temperature and the time of stewing, antistatic compound can get into inside the pore of nascent state polyolefin powder, thereby avoids in olefin polymerization process, and the too fast seepage of antistatic compound influences antistatic effect and stability.
The antistatic compounds comprise hydroxy esters having at least two free hydroxyl groups, alcohols and ketones containing up to 7 carbon atoms, polyepoxide oils, R-N (CH)2CH2OH2)2Alkyl diethanolamines of (1), amides of R-CONR 'R'.
Further, the hydroxy ester having at least two free hydroxy groups is glyceryl monostearate and glyceryl monopalmitate;
the polyepoxide oil is epoxidized soybean oil or epoxidized linseed oil, preferably the polyepoxide oil is a commercial product under the trademarks Edenol D82 and Edenol B316.
The R-N (CH)2CH2OH2)2Wherein R is an alkyl group containing 10 to 20 carbon atoms.
The amide of said R-CONR 'R ", wherein R, R' and R" may be the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
Further preferably, the antistatic compound is R-N (CH)2CH2OH2)2Wherein R is an alkyl group containing from 13 to 15 carbon atoms, as sold under the trademark Atmer163, or a natural alkyldiethanolamine, such as Armostat 410M.
Based on the weight of the nascent state polyolefin powder, the dosage of the antistatic compound is 0.1-10.0%, preferably 1.0-5.0%.
The amount of the nascent polyolefin powder loaded with the antistatic compound is 0.05 to 5.0 percent, preferably 0.1 to 1 percent, based on the weight of the polyolefin powder in the reactor.
The particle size selection range of the nascent polyolefin powder is 100-.
Further, the nascent state polyolefin powder is introduced into the bottom of a bubbling fluidized bed of the polymerization reactor, or the middle and the bottom of a descending section of a circulating fluidized bed of the polymerization reactor.
Olefin gas is used to introduce nascent state polyolefin powder loaded with antistatic compound into the polymerization reactor filled with polyolefin powder. The raw material gas is adopted for transmission, so that impurities can be prevented from being introduced, and the antistatic compound can well participate in the antistatic reaction in the olefin polymerization process.
In addition, the static electricity generated during the polymerization process can be monitored, and the antistatic compound-supporting nascent polyolefin powder can be intermittently added by cascade control when the static voltage rises, or can be continuously added, preferably the antistatic compound-supporting nascent polyolefin powder is intermittently added by cascade control when the static voltage rises.
The catalyst used in the polymerization process in the step (2) is a Ziegler-Natta catalyst or a metallocene catalyst.
The Ziegler-Natta catalyst comprises a magnesium halide, a titanium compound having at least one Ti-halogen bond, and an electron donor compound.
Further, the magnesium halide is MgCl2。
Further, the titanium compound is TiCl4、TiCl3Or Ti (OR)n-yXyThe above-mentioned Ti (OR)n-yXyWherein n is the valence of titanium, y is a number from 1 to n-1, X is a halogen and R is a hydrocarbon group having 1 to 10 carbon atoms.
The metallocene catalyst comprises at least one transition metal compound comprising at least one bond II, and at least one cocatalyst selected from an aluminoxane or a compound capable of forming an alkyl metallocene cation.
The olefins are CH ═ CHR α -olefins, where R is hydrogen or a hydrocarbyl group having 1 to 12 carbon atoms.
The olefin comprises ethylene, propylene, 1-butene, 1-hexene and 1-octene.
The olefins are polymerized either individually to form homopolymers or in combination with each other to produce copolymers.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a large amount of antistatic compounds can be loaded in nascent polyolefin by loading the antistatic compounds on the nascent polyolefin, and then the nascent polyolefin powder loaded with the antistatic compounds is introduced into a polymerization reactor filled with polyolefin powder, so that the antistatic compounds can slowly seep out of the surface from the interior of the polyolefin to continuously generate an antistatic effect, thereby reducing the surface resistance, guiding positive and negative charges to freely flow and/or dissipate to gas, and further having lower electrostatic voltage on the surface.
Detailed Description
Comparative example 1
In comparative example 1, the polymerization was carried out in a bubbling fluidized bed of polyethylene using a metallocene catalyst system, the antistatic compound used being the commercial product sold under the trademark Atmer163 (formula R-N (CH)2CH2OH2)2Wherein R is an alkyl group containing from 13 to 15 carbon atoms), introducing an antistatic compound in the bottom of the bubbling fluidized bed by direct injection, in a proportion of 0.02% (200ppm) with respect to the mass of the polyethylene powder inside the bed.
Dissipation of the static electricity was observed by sampling and measuring the particle charge to mass ratio in a faraday cage after the antistatic compound was introduced into the reactor. The charge to mass ratio of the polyethylene particles at the sampling point of the bubbling fluidized bed after 5min of injection of the antistatic compound rapidly decreased from-3.65. mu.C/kg to 0.25. mu.C/kg and remained between 0.22. mu.C/kg and-0.24. mu.C/kg for a duration of 60min, indicating that the bubbling fluidized bed is at a lower static level. However, after 60min, the static started to rise gradually and returned to-2.34. mu.C/kg at 240 min.
The electrostatic data of the polyolefins in the fluidized bed detected during the polymerization are shown in Table 1.
Example 1
In example 1, the polymerization was carried out in a bubbling fluidized bed of polyethylene using a metallocene catalyst system, the antistatic compound used being the commercial product sold under the trademark Atmer163 (formula R-N (CH)2CH2OH2)2Wherein R is an alkyl group having 13 to 15 carbon atoms), a nascent polyethylene powder having a particle size in the range of 850-1000 μm and loaded with an antistatic compound at 60 ℃ was conveyed by means of pneumatic ethylene transport at the bottom of the bubbling fluidized bed and allowed to stand for 60 hours at the same mass ratio of the antistatic compound to the ethylene powder in the bed as in comparative example 1, which was 0.02% (200 ppm). Wherein the amount of the antistatic compound is 4.0% by weight of the nascent polyethylene powder for loading, and the amount of the nascent polyethylene powder for loading the antistatic compound is 0.5% by weight of the polyethylene powder in the bed.
After feeding the nascent polyethylene powder loaded with the antistatic compound into the reactor, dissipation of the static electricity was observed by sampling and measuring the particle charge to mass ratio in a faraday cage. The charge-to-mass ratio of the polyethylene particles at the sampling point of the bubbling fluidized bed after 5min of injection of the nascent polyethylene powder loaded with the antistatic compound is rapidly reduced from-3.60 mu C/kg to 0.25 mu C/kg, and can be maintained between 0.18 mu C/kg and-0.17 mu C/kg within the duration of 240 min. It is shown that the efficiency and stability of the transport of nascent polyethylene powder loaded with antistatic compound is better than the direct injection of antistatic compound under the given process compared to comparative example 1.
The electrostatic data of the polyolefins in the fluidized bed detected during the polymerization are shown in Table 1.
Comparative example 2
In comparative example 2, the polymerization was carried out in a circulating fluidized bed of polypropylene using a Ziegler-Natta catalyst system, the antistatic compound used being the commercial product sold under the trademark Atmer163 (of formula R-N (CH)2CH2OH2)2Wherein R is an alkyl group containing from 13 to 15 carbon atoms), introducing an antistatic compound in the middle of the descending section of the circulating fluidized bed by direct injection, in an amount of 0.025% by weight (250ppm) with respect to the weight of the polyethylene powder in the bed.
When the antistatic compound was fed into the reactor, dissipation of the static electricity was observed by sampling and measuring the particle charge to mass ratio in a faraday cage. The charge/mass ratio of the polypropylene particles at the sampling point of the circulating fluidized bed after 5min of injection of the antistatic compound was reduced from-4.47. mu.C/kg to 0.21. mu.C/kg and was maintained between 0.32. mu.C/kg and-0.11. mu.C/kg for a duration of 60min, indicating that the circulating fluidized bed was at a lower static level. However, after 90min, the static started to rise gradually and returned to-3.24. mu.C/kg at 240 min.
The electrostatic data of the polyolefins in the fluidized bed detected during the polymerization are shown in Table 1.
Example 2
In comparative example 2, the polymerization was carried out in a circulating fluidized bed of polypropylene using a Ziegler-Natta catalyst system, the antistatic compound used being the commercial product sold under the trademark Atmer163 (of formula R-N (CH)2CH2OH2)2Wherein R is an alkyl group having 13 to 15 carbon atoms), a nascent polypropylene powder having a particle size in the range of 850-1000 μm and loaded with an antistatic compound at 60 ℃ is conveyed in the middle of the descending section of the circulating fluidized bed by means of pneumatic conveying of propylene, and left for 72 hours, the amount of the antistatic compound used is 0.025% (250ppm) relative to the weight of the propylene powder in the bed, which is the same as that in comparative example 2. Wherein, the dosage of the antistatic compound is 2.5 percent relative to the weight of the nascent polypropylene powder for loading, and the adding amount of the nascent polypropylene powder for loading the antistatic compound is 1 percent relative to the weight of the polypropylene powder in the bed.
After feeding the nascent polypropylene powder loaded with antistatic compound into the reactor, dissipation of the static electricity was observed by sampling and measuring the particle charge to mass ratio in a faraday cage. After 5min of injection of the antistatic compound-loaded nascent polypropylene powder, the charge-to-mass ratio of polypropylene particles at the sampling point of the circulating fluidized bed is rapidly reduced from minus 5.04 mu C/kg to 0.28 mu C/kg, and the charge-to-mass ratio of the polypropylene particles can be maintained between 0.27 mu C/kg and minus 0.94 mu C/kg within the duration of 240 min. It is shown that the static electricity eliminating effect and stability of the nascent polypropylene powder carrying the antistatic compound are superior to those of the nascent polypropylene powder directly injected with the antistatic compound in the given process compared with the comparative example 2.
The electrostatic data of the polyolefins in the fluidized bed detected during the polymerization are shown in Table 1.
TABLE 1 static level
Claims (10)
1. A method for electrostatic control of an olefin polymerization process, comprising:
(1) mixing the nascent polyolefin powder with an antistatic compound at 30-60 ℃, and standing for 24-72h to obtain the nascent polyolefin powder loaded with the antistatic compound;
(2) when the electrostatic voltage is increased to the electrostatic voltage threshold value in the olefin polymerization process, introducing the nascent state polyolefin powder loaded with the antistatic compound into a polymerization reactor filled with polyolefin powder through cascade control so as to control the electrostatic voltage in the olefin polymerization process.
2. The method for controlling static electricity in the olefin polymerization process according to claim 1, wherein the mixing temperature of the nascent state polyolefin powder and the antistatic compound is 50-60 ℃, and the standing time is 60-72 h.
3. The method of claim 1, wherein the antistatic compound comprises at least two free hydroxyl groupsHydroxy esters of radicals, alcohols and ketones containing more than 7 carbon atoms, polyepoxide oils, R-N (CH)2CH2OH2)2Alkyl diethanolamines of (1), amides of R-CONR 'R'.
4. The method of claim 3, wherein the hydroxyl ester having at least two free hydroxyl groups is glycerol monostearate and glycerol monopalmitate;
the polyepoxide oil is epoxidized soybean oil or epoxidized linseed oil.
5. The method of claim 3, wherein the R-N (CH) is selected from the group consisting of2CH2OH2)2R in the alkyl diethanolamines of (a) is an alkyl group containing from 10 to 20 carbon atoms.
6. The method of claim 3, wherein R, R 'and R "in the amide of R-CONR' R" may be the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
7. The method of claim 1, wherein the antistatic compound is used in an amount of 0.1-10.0% by weight based on the nascent polyolefin powder.
8. The method of claim 1, wherein the antistatic compound-loaded nascent polyolefin powder is added in an amount of 0.05% to 5.0% based on the weight of the polyolefin powder in the reactor.
9. The method as claimed in claim 1, wherein the particle size of the nascent state polyolefin powder for loading the antistatic compound is 100-1200 μm.
10. The method of claim 1, wherein the antistatic compound-loaded nascent polyolefin powder is intermittently added by cascade control or continuously added by cascade control when the electrostatic voltage is raised to the electrostatic voltage threshold.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975255A (en) * | 2022-12-28 | 2023-04-18 | 浙江大学杭州国际科创中心 | Antistatic composition and olefin polymerization method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055742A (en) * | 1990-04-11 | 1991-10-30 | 英国石油化学品有限公司 | Gas phase olefin polymerization process |
| US20150087793A1 (en) * | 2013-09-25 | 2015-03-26 | Chevron Phillips Chemical Company Lp | System and method for deterring fouling in a polymerization reactor |
| CN105452166A (en) * | 2013-08-26 | 2016-03-30 | 巴塞尔聚烯烃意大利有限公司 | Process for improving the operability of an olefin polymerization reactor |
-
2022
- 2022-01-26 CN CN202210092023.4A patent/CN114409832A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055742A (en) * | 1990-04-11 | 1991-10-30 | 英国石油化学品有限公司 | Gas phase olefin polymerization process |
| CN105452166A (en) * | 2013-08-26 | 2016-03-30 | 巴塞尔聚烯烃意大利有限公司 | Process for improving the operability of an olefin polymerization reactor |
| US20150087793A1 (en) * | 2013-09-25 | 2015-03-26 | Chevron Phillips Chemical Company Lp | System and method for deterring fouling in a polymerization reactor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975255A (en) * | 2022-12-28 | 2023-04-18 | 浙江大学杭州国际科创中心 | Antistatic composition and olefin polymerization method |
| CN115975255B (en) * | 2022-12-28 | 2025-05-27 | 浙江大学杭州国际科创中心 | Antistatic composition and olefin polymerization method |
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