CN1129617C - Linear polyethylene catalyst of gas-phase fluidized-bed method and its preparing process - Google Patents

Linear polyethylene catalyst of gas-phase fluidized-bed method and its preparing process Download PDF

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CN1129617C
CN1129617C CN 00121076 CN00121076A CN1129617C CN 1129617 C CN1129617 C CN 1129617C CN 00121076 CN00121076 CN 00121076 CN 00121076 A CN00121076 A CN 00121076A CN 1129617 C CN1129617 C CN 1129617C
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catalyst
ticl
linear polyethylene
base catalyst
catalyzer
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CN1334276A (en
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张汉倬
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Abstract

The present invention relates to a linear polyethylene catalyst for a gas phase fluidized bed method and a preparation method thereof. The linear polyethylene catalyst is composed of silica gel as a carrier, TiCl3 or as a main catalyst, MgCl2 as a cocatalyst, tetrahydrofuran (THF) as an electron donor and RX as a modifier. The linear polyethylene catalyst is prepared by an immersion method, the TiCl3 is used for substituting TiCl4 required by the quantity of Mg for restoring the catalyst, the linear polyethylene catalyst has the chemical equation that Mg+ 2 Ti <4 +> is converted into Mg<2+> + 2Ti<3+>, sufficient MgCl2 is supplemented, a parent matrix obtained from the prepared mother liquid dipping silica gel is processed by chloro diethyl aluminum, and an obtained basal body catalyst is modified by the RX. The activity of the catalyst of the present invention is increased by 78%, polyreaction is stable, the granularity distribution of products is narrow, and stacking density is increased by 20 %.

Description

Linear polyethylene catalyst of gas-phase fluidized-bed and preparation method thereof
The present invention relates to a kind of linear polyethylene catalyst of gas-phase fluidized-bed and preparation method thereof.
At present, the catalyzer that production polyethylene (PE) generally uses is the Ti series that belongs to Ziegler-Natta, and its main active constituent is TiCl 4And TiCl 3, more generally use metallic aluminium (Al) reduction TiCl and use in the industry 4The TiCl that makes 3AlCl 3As everyone knows, AlCl 4Existence, not only influence activity of such catalysts, influence simultaneously the performance of PE resin again.In gas-phase fluidized bed PE produces,, require the fluidisation resin to have higher tap density (BD) for guaranteeing the reactor long-period stable operation.Yet the method that tradition improves tap density is in catalyst preparation process, introduces a certain amount of three basic just aluminium (TnHAL), and the result causes the decline of activity of such catalysts.
U.S. UCC (union carbide corporation) has announced a kind of gas-phase fluidized-bed polyethylene Ti series catalysts and preparation method thereof for patent US5290745 number.Its catalyzer composition formula is: MgCl 2TiCl 3(THF) 4.5NSiO 2It is to pass through the silica gel of high temperature dehydration and surface treatment 10-80 μ m as carrier, with Primary Catalysts TiCl 3, promotor MgCl 2, electron donor THF (tetrahydrofuran (THF)) is mixed with mother liquor and is carried on the silica gel, make parent with aluminium diethyl monochloride (DC) reduction after, handle with TnHAL again, remove thinner, collect purpose product gas-phase polyethylene finely grained catalyst.This catalyzer truly has and improves and raising, but its activity is not high, and poly bulk density is not high yet, is unfavorable for fluidized-bed steady running.
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, and a kind of gas fluidized bed method linear polyethylene high performance catalyst is provided, make that poly bulk density is improved, stable polymerization reaction, fluidized-bed long-term operation, polymerization product distribution granularity narrow down.
A kind of linear polyethylene catalyst of gas-phase fluidized-bed comprises silica-gel carrier, Primary Catalysts TiCl 3, promotor MgCl 2Base catalyst with electron donor THF forms is characterized in that halohydrocarbon is the properties-correcting agent of base catalyst, and this catalyzer adopts immersion process for preparing:
A. with the TiCl of base catalyst requirement 4With being enough to be reduced to TiCl 3Mg, mix with tetrahydrofuran (THF), add TiCl again 4, its chemical reaction is:
Add the MgCl of capacity 2, make Mg/Ti=3.0～4.0 (wt), make mother liquor,
B. will be with the above-mentioned mother liquor that makes, dipping silica-gel carrier and the parent that obtains is dispersed in the iso-pentane is handled with aluminium diethyl monochloride, makes base catalyst,
C. with properties-correcting agent halohydrocarbon RX the above-mentioned base catalyst that makes is handled, obtained comprising by base catalyst and halohydrocarbon RX and form catalyst prod of the present invention, halohydrocarbon is C 6H 5X, wherein X can be Cl or F.。
In the above-mentioned catalyzer, Ti content is 1.4～1.5% (wt), and tetrahydrofuran THF content is 15～16% (wt), wherein Mg/Ti=3.0～4.0 (wt); Ti/RX=1.0～0.5/0.5～1.0 (mol), all the other are carrier.
Preparation method to linear polyethylene catalyst of gas-phase fluidized-bed of the present invention is described further below:
1. at pure N 2Protection is added to anhydrous fresh tetrahydrofuran THF in the mother liquor tank down, stirs and heats up 40～45 ℃, under nitrogen protection, with the TiCl of base catalyst aequum 4With being enough to be reduced to TiCl 3Mg, add in the mother liquor tank, thorough mixing, in 2 hours with TiCl 4Add in the mother liquor tank, controlled temperature is 70 ℃, restir 30 minutes.Make its reaction.Its chemical equation is:
Add capacity MgCl 2, making Mg/Ti is 3.0～4.0 (wt), the constant temperature continuously stirring made mother liquor after 8 hours.
2. the above-mentioned mother liquor temperature that makes is reduced to 60～70 ℃, behind the deep bed filter by one 100 μ m, with nitrogen it is delivered in the mixing tank, silica gel with 10～80 μ m that wherein handled through high temperature dehydration with triethyl aluminum, 65 ± 5 ℃ of temperature controls, continuously stirring 4 hours makes its TiCl 3And MgCl 2More be uniformly impregnated within the silica gel micropore, under this temperature, steam THF, make parent.Add iso-pentane, controlled temperature is 40～50 ℃, adds aluminium diethyl monochloride and continuously stirring under the continuously stirring after 1 hour, makes base catalyst.
3. add properties-correcting agent halohydrocarbon RX in the above-mentioned mixing tank that base catalyst is housed, restir 30min handles base catalyst, steams iso-pentane, collects purpose product linear polyethylene catalyst of gas-phase fluidized-bed.Above-mentioned halohydrocarbon RX is C 6H 5X, wherein X can be Cl or F.
In the catalyzer, Ti content is 1.4～1.5% (wt), and content of tetrahydrofuran is 15～16% (wt), wherein Mg/Ti=3.0～4.0 (wt); Ti/RX=1.0～0.5/0.5～1.0 (mol), all the other are carrier.
Catalyzer of the present invention is owing to adopt the TiCl of Mg reduction base catalyst requirement 4Be TiCl 3And MgCl 2, and add MgCl 2, make that Mg/Ti is increased to 3.0-4.0 (wt) in the base catalyst, avoid the disadvantage brought with the AL reduction and TiCl 3And MgCl 2More be evenly distributed in the silica gel micropore of 10-80 μ m, Ti content has improved 28% (wt) simultaneously, and can make catalyst activity (is catalytic efficiency: KgPE/Kgcat) be significantly improved; Particularly make improvements agent, promptly improve catalyst activity, also make the polyethylene tap density improve 40KgPE/m with halohydrocarbon RX 3Catalyst activity--catalyst efficiency improves more than 50%.
4. catalyzer of the present invention is used for gas-phase fluidized bed polymerization, and pressure is 2360Kpa, and temperature is 88 ℃, and AL/Ti is 36-40, H 2Be the molecular regulation agent, other polymerizing condition sees Table 1.Inject catalyzer of the present invention, ethene and comonomer successively continuously, the catalyzer injection rate is 1.0Kgcat/h, and polyethylene production is 8260kg/h, operate continuously 72 hours, its catalyst activity--catalyst efficiency is 8260kgPE/kgcat, and the tap density of PE is 380-400kg/m 3
Now the present invention is further described as follows by embodiment and comparative example:
One. embodiment
1. Preparation of Catalyst:
(1), preparing carriers (utilization transfers the known UCC technology that chemical company limited is united in Tianjin)
The silica gel 150kg of the 10-80 μ m that will purchase from U.S. Grice company is in 600 ℃ of high temperature dehydrations, delivering to temperature after water content is less than 5ppm closes in the jar, the iso-pentane that then adds 72kg, continuously stirring is warming up to 40-50 ℃, be made into slurries, be metered into the triethyl aluminum of 9.35kg, continue to stir 30min silica gel treatment, iso-pentane is removed in the degree evaporation under this temperature then, and the carrier that makes is stand-by.
(2). the mother liquor preparation:
At nitrogen (H 2O content＜5ppm; as follows) protection is down; fresh electron donor tetrahydrofuran (THF) 156.7kg less than 5ppm is added in the mother liquor tank with water-content; the starting agitator; and when it being warming up to 40-50 ℃ with temperature adjustment water; be that the cylindrical Mg0.735kg of Φ 5 * 6mm is added in the mother liquor tank with diameter under nitrogen protection, stir about is after 30 minutes, in 2 hours with the TiCl of catalyzer requirement 411.466kg, slowly being pressed in the mother liquor tank with nitrogen, controlled temperature is 70 ℃, restir 4 hours, the Mg that makes the front add 0.735kg is enough to the TiCl of the 11.466kg that catalyzer is required 4Be reduced to TiCl 3, its chemical equation is:
Add the MgCl of 16.802kg then 2, to improve Mg/Ti=3.0～4.0 (wt).Constant temperature continuously stirring 8 hours makes mother liquor.
(3) base catalyst preparation:
When the mother liquor that above-mentioned (2) are made is cooled to 60～70 ℃, with nitrogen it is delivered in the mixing tank, and wherein passed through high temperature dehydration, handle silica gel described in the back stand-by (1) together with triethyl aluminum, 65 ± 5 ℃ of controlled temperature make TiCl through continuously stirring 4 hours 3And MgCl 2More even dipping is distributed in the silica gel micropore.Evaporation removes tetrahydrofuran (THF) under this temperature, makes parent.Add the iso-pentane of 422Kg in the above-mentioned mixing tank that parent is housed, make itself and parent be the slurries shape, continuously stirring and controlled temperature are metered into the aluminium diethyl monochloride of 22kg at 40～50 ℃, and continuously stirring 1 hour makes base catalyst, and its composition formula is:
MgCl 3·TiCl 3·(THF) 4.5·nSiO 2。
(4) base catalyst modification:
Add the halohydrocarbon of 10Kg in the above-mentioned mixing tank that base catalyst is housed, wherein halohydrocarbon RX is C 6H 5Cl or C 6H 5F stirred 30～40 minutes, and (40～50 ℃) iso-pentane is removed in evaporation, collected the gas-phase fluidized bed linear full density polythene catalyzer 288kg of purpose product
The catalyzer composition formula is: MgCl 2TiCl 3(THF) 4.5(RX) 1.5NSiO 2Wherein RX is C 6H 5X, X can be Cl or F.
Ti content is 1.4～1.5% (wt), and THF content is 15～16% (wt), wherein Mg/Ti=3.0～4.0 (wt); Ti/RX=1.0～0.5/0.5～1.0 (mol), all the other are carrier silica gel.
2. gas-phase fluidized bed polymerization (catalyzer application of the present invention):
Diameter is 3 meters, high 12 meters gas-phase fluidized-bed, dry up according to a conventional method with nitrogen replacement qualified after, be that 2360Kpa, 88 ℃ of temperature, Al/Ti are 36～40 at pressure, H 2Be the molecular regulation agent, other polymerizing condition sees Table 1.Inject catalyzer of the present invention successively continuously, ethene and comonomer butene-1, the catalyzer injection rate is 1.0kg/h, polyethylene production is 8260kg/h, operate continuously 72 hours, stopped reaction, the reactant calculating catalyst efficiency of weighing, distribute with the weight granularity (%) of obtaining product after the standard screening, its catalyst efficiency (being catalyst activity) is 8260kgPE/kgcat, and poly bulk density is 380～400kg/m 3Other characteristic of polyethylene: melting index (MI), density (DE), melt flow ratio (MFR) and size-grade distribution situation are shown in Table 1.Specificity of catalyst such as Ti content and catalyst activity also see Table 1.As seen from the table, narrow with the prepared product size distribution of catalyzer of the present invention, mainly between the 20-100 order, (account for 98.5%), few dust particle.
Two, comparative example (the UCC patent that chemical company limited uses is united in Tianjin):
1. Preparation of Catalyst:
(1), preparing carriers: with 1 it (1) among the embodiment one.
(2), mother liquor preparation:
Under nitrogen protection, the fresh electron donor tetrahydrofuran (THF) 156.7kg less than 5ppm is added in the mother liquor tank with water-content, starts to stir, when with temperature adjustment water its temperature being risen to 40～50 ℃, under nitrogen protection, with the MgCl of 15.685kg 2, 10.85kg TiCl 3Be added to successively in the mother liquor tank, be warming up to 70 ℃, continuously stirring 8 hours makes mother liquor.
(3) parent preparation:
The above-mentioned mother liquor temperature for preparing is reduced to 60～70 ℃, with nitrogen with it by behind the deep bed filter of one 100 μ m, deliver in the mixing tank, with wherein passed through high temperature dehydration, handle silica gel described in the back stand-by (1) together with triethyl aluminum, 65 ± 5 ℃ of continuously stirring of controlled temperature 4 hours make TiCl 3And MgCl 2Evenly dipping is distributed in the silica gel micropore.Tetrahydrofuran (THF) is removed in evaporation under this temperature, makes parent.
(4) parent is handled:
The iso-pentane that in the above-mentioned mixing tank that parent is housed, adds 422kg, make itself and parent be the slurries shape, continuously stirring and controlled temperature are 40～50 ℃, be metered into the aluminium diethyl monochloride of 22kg, continuously stirring adds 51.7kg tri-n-hexyl aluminum TnHAL about 30 minutes more again, stirs 30 minutes, iso-pentane is removed in evaporation under this temperature, collects the gas-phase fluidized bed linear full density polythene catalyzer 290kg of purpose product.
(5) catalyzer application example:
Diameter is 3 meters, high 12 meters gas-phase fluidized-bed, dry up according to a conventional method with nitrogen replacement qualified after, be that 2400Kpa, 88 ℃ of temperature, Al/Ti are 30～40 at pressure, H 2Be the molecular regulation agent, other condition sees Table 1.Injecting catalyst successively, ethene and comonomer butene-1, the catalyzer injection rate is 1.8kg/h, polyethylene production 8280kg/h, operate continuously 72 hours, stopped reaction, the reactant calculating catalyst efficiency of weighing.Distribute with the weight granularity (%) of obtaining product after the standard sieve screening, its catalyst activity is 4600kg.PE/kg.cat, and poly melting index, density, melt flow ratio and size-grade distribution situation are shown in Table 1.
Table 1. catalyzer of the present invention and UCC catalyzer application result
The contrast project Comparative example The embodiment of the invention
1. specificity of catalyst Ti content wt% activity (catalytic efficiency) kgPE/kgcat 0.96 4600 1.40 8260
2. polymerizing condition temperature ℃ pressure kpa AL/Ti is than ethylene concentration mol% butylene concentration mol% density of hydrogen mol% nitrogen gas concn mol% time of staying hr 88 2400 36-40 30.5 12.2 5.9 51.4 3.8 88 2360 38-40 30.1 11.9 5.8 52.2 4.0
3. product performance melting index g/10min density g/co bulk density kg/m 2Melt-flow index 1.1 0.919 325-360 28 0.2 0.918 380-400 29
Size distribution less than 20 orders (wt) % 20--40 orders (wt) % 40--100 orders (wt) % 100--200 orders (wt) % greater than 200 orders (wt) % 10 30 50 8 2 1.5 77 20 1.0 0.5

Claims (2)

1, a kind of linear polyethylene catalyst of gas-phase fluidized-bed comprises silica-gel carrier, Primary Catalysts TiCl 3, promotor MgCl 2Base catalyst with the electron donor tetrahydrofuran THF is formed is characterized in that C 6H 5Cl and C 6H 5Among the F any is the properties-correcting agent of base catalyst, and this catalyzer adopts immersion process for preparing:
A. with the TiCl of base catalyst requirement 4With being enough to be reduced to TiCl 3Mg, mix with tetrahydrofuran (THF), add TiCl again 4, its chemical reaction is:
Add the MgCl of capacity 2, make Mg/Ti=3.0～4.0 by weight, make mother liquor;
B. will be with the above-mentioned mother liquor that makes, dipping silica-gel carrier and the parent that obtains is dispersed in the iso-pentane is handled with aluminium diethyl monochloride, makes base catalyst;
C. with described properties-correcting agent the above-mentioned base catalyst that makes is handled, obtained comprising by base catalyst and described properties-correcting agent and form catalyst prod of the present invention.
2, catalyzer according to claim 1 is characterized in that in the catalyzer that Ti content is 1.4～1.5% by weight, and tetrahydrofuran THF content is 15～16%, wherein Mg/Ti=3.0～4.0; In mole Ti/ properties-correcting agent=1.0～0.5/0.5～1.0 mole, all the other are silica gel.
CN 00121076 2000-07-19 2000-07-19 Linear polyethylene catalyst of gas-phase fluidized-bed method and its preparing process Expired - Fee Related CN1129617C (en)

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EP1375528A1 (en) * 2002-06-18 2004-01-02 Borealis Polymers Oy Method for the preparation of olefin polymerisation catalysts
EP1799727A2 (en) 2004-06-21 2007-06-27 ExxonMobil Chemical Patents Inc. Low fouling and high activity polymerization process
EP1765892A2 (en) 2004-06-21 2007-03-28 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006025917A2 (en) 2004-06-21 2006-03-09 Exxonmobil Chemical Patents Inc. Polymerization process
CN113754813A (en) * 2020-06-05 2021-12-07 中国石油化工股份有限公司 Preparation method of olefin-olefin alcohol copolymer
CN113912756B (en) * 2020-07-08 2022-09-09 中国科学院化学研究所 Catalyst system for improving fluidity of polyethylene melt and application thereof

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