CN1071339C - Ethylene polymerization composite load titanium catalyst - Google Patents

Ethylene polymerization composite load titanium catalyst Download PDF

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Publication number
CN1071339C
CN1071339C CN98113183A CN98113183A CN1071339C CN 1071339 C CN1071339 C CN 1071339C CN 98113183 A CN98113183 A CN 98113183A CN 98113183 A CN98113183 A CN 98113183A CN 1071339 C CN1071339 C CN 1071339C
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China
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catalyzer
magnesium
ticl
promotor
hours
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CN98113183A
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CN1195668A (en
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林尚安
欧阳巍
王海华
李悦
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Sun Yat Sen University
National Sun Yat Sen University
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National Sun Yat Sen University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a catalytic system which is formed by that: composite carrier organic magnesium-AlEt3-n-butyl ether-SiO2 is used for loading a titanium compound TiCl4; CCl4 is used as accelerant; alkylaluminium is used as a cocatalyst. The catalytic system is formed by adopting an impregnation-reaction method; the present invention has the advantages of simple method, short technical processes and low cost. The obtained catalyst has the advantages of good flowing dispersancy and good particle shape; when the catalyst is used for the gas-phase polymerization of ethylene, the catalytic activity is high; high-density polyethylene and linear low-density polyethylene with good particle shape, narrow particle size distribution and high bulk density can be prepared.

Description

Ethylene polymerization composite load titanium catalyst and application thereof
The present invention relates to a kind of ethylene polymerization composite load titanium catalyst and application thereof.
The CN1037157A patent application discloses a kind of ethene gas-phase polymerization catalyzer, adopts organic-magnesium and halo uncle butane to prepare spherical magnesium chloride support in the presence of ether, uses TiCl again 4Dip treating, good, the easy flow dispersion of the granules of catalyst form that makes has high reactivity and good copolymerization performance, can make good high density polyethylene(HDPE) of particle form (HDPE) and linear low density polyethylene (LLDPE).But this catalyzer adopts preparation magnesium chloride supports such as the high organic-magnesium of a large amount of valencys, and complicated process of preparation, and step is many, thereby catalyzer cost height.
The purpose of this invention is to provide the composite load Titanium series catalyst that is applicable to vinyl polymerization that a kind of preparation method is simple and cost is low, i.e. complex carrier organic-magnesium-AlEt 3-n-butyl ether-SiO 2Load TiCl 4, with accelerant C Cl 4And promotor AlR 3The catalyzer of forming.
Catalyzer of the present invention comprises the Primary Catalysts titanium compound, complex carrier organic-magnesium-AlEt 3-n-butyl ether-SiO 2, accelerant C Cl 4, and promotor aluminum alkyls AlR 3, wherein titanium compound is TiCl 4, organic-magnesium is C 4H 9MgCl, AlR 3In R be C 2～C 8Alkyl.The composition proportioning of catalyzer is as follows:
SiO 2: TiCl 4(weight)=4～8: 1
With TiCl 4Mole number calculate, the mol ratio of all the other each components is:
TiCl 4 1
Organic-magnesium 3～6
N-butyl ether 0.5～1.0
CCl 4 0.8～1.5
AlEt 3 0.2～0.5
Above-mentioned catalyzer adopts the preparation of dipping-reaction method, and the concrete step is poly-as follows:
1. at N 2In the air-flow, 600 ℃ of temperature lower calcination microspheroidal SiO 26 hours, the cooling back added organic-magnesium n-heptane solution, AlEt 3Hexane solution and quantitative n-butyl ether, 45～55 ℃ of following stirring reactions 45 minutes, organic-magnesium C wherein 4H 9MgCl n-heptane solution concentration is 0.5～1.0mol/L;
2. at N 2Protection continues to add TiCl down 4, CCl 4, be warming up to 70 ℃ of stirring reactions 2 hours, be cooled to 50 ℃ again and continued stirring reaction 3 hours, leave standstill, be cooled to room temperature, filter, use hexane wash 3 times, temperature is lower than 60 ℃ of vacuum-dryings, then gets complex carrier organic-magnesium-AlEt 3-n-butyl ether-SiO 2Load TiCl 4Primary Catalysts.It and promotor aluminum alkyls AlR 3Form ethylene polymerization composite load titanium catalyst, for gaseous ethylene polymerization, the Ti of Primary Catalysts and promotor: Al (mol ratio)=1: (50～200).
Catalyzer of the present invention can be used for the normal pressure ethene gas-phase polymerization, the polyreactions such as agitated bed ethene gas-phase polymerization, and φ-100 fluidized-bed ethene gas phase copolymerization of pressurizeing.For the normal pressure ethene gas-phase polymerization, be dispersion medium with the PE powder, add Primary Catalysts and promotor AlEt 3Wherein the Al/Ti mol ratio is (50～200)/1, is 106.7KPa at ethylene pressure, and reaction is 2 hours under 70～90 ℃ of temperature, catalytic efficiency is 8600～11000g PE/gTi, stable polymerization reaction, product 20～200 order particle 〉=98% have good particle form; For pressurization agitated bed ethene gas-phase polymerization, the Al/Ti mol ratio of Primary Catalysts and promotor is (50～200)/l, in the ethene total pressure is 0.6Mpa, polyreaction is 3 hours under 70～90C temperature, catalytic efficiency is 124～160KgPE/gTi, the product particle form is good, and 10～200 order particle 〉=98%, product bulk density are 0.35～0.38g/cm 3For adopting Φ-100 fluidized-bed ethene gas phase copolymerization, as with the 1-butylene polymerization, the Al/Ti mol ratio of Primary Catalysts and promotor is (50～200)/1, at ethylene pressure 1.0Mpa, under 80～90 ℃ of temperature, H 2Dividing potential drop 0.15～0.2Mpa, 1-butylene dividing potential drop 0.12～0.20MPa, copolymerization 3 hours, catalytic efficiency are 230～550KgLLDPE/gTi, and the product particle form is good, and 10～120 order particles account for 96～98.7%, and bulk density is 0.32～0.36g/cm 3, product density is 0.912～0.926 LLDPE, the MI value is 0.5～2.3.
The present invention adopts a spot of organic-magnesium (C 4H 9MgCl) handle the good micro-spherical silica gel SiO of flow dispersion 2, making complex carrier load titanium compound again, the gained catalyzer had both had microspheroidal SiO 2Flow dispersion, even particle distribution has organic-magnesium treatment S iO again 2Make the catalyst activity height; With butyl ether, CCl 4Modifying function, it is good that catalyst activity can be regulated with copolymerization performance, can improve the particle shape and the product bulk density of copolymerized product.The method of catalyzer is simple, technical process short, the organic-magnesium that is consumed, TiCl owing to make 4Few Deng raw material, therefore have the low advantage of cost.
It below is the specific embodiment of the invention
Embodiment one
1. with 5.5 gram microspheroidal SiO 2(40 microns of median sizes, pore volume 1.5～2.0ml/g) is put in the tube furnace, logical N 2Following heating was warming up to 600 ℃ in 2 hours, and most of bonded hydroxyl is removed in constant temperature dehydration calcining, and 6 hours postcooling are at N 2The protection bottom discharge gets 5g SiO 2, place reaction flask, add the C that 40ml contains 20mmol 4H 9MgCl n-heptane solution and contain 1.25mmol AlEt 3Hexane solution and 2.5mmol n-butyl ether, stir and to be warming up to 50 ℃ of reactions 45 minutes;
2. in 1 reactant, add 1g TiCl 4With 0.5ml CCl 4Be warming up to 70 ℃ of stirring reactions 2 hours, be cooled to 50 ℃ of constant temperature ageing reactions 3 hours, cooling is left standstill to 30 ℃, suction strainer is removed mother liquor, adds the 30ml normal hexane, stirs to be warming up to 50 ℃ of reactions 5 minutes, leave standstill filtration, so repetitive scrubbing is 3 times, vacuumizes heating, removes hexane under 60 ℃ and gets the 6g Primary Catalysts being lower than.Primary Catalysts and promotor aluminum alkyls are formed complex catalyst system and are used for ethene gas-phase polymerization.
Embodiment two
The normal pressure ethene gas-phase polymerization
In reaction flask, add the 2gPE powder as dispersion medium, through 120 ℃ of dryings of vacuum 1 hour, N 2Replace 3 times, at N 2Protection adds the AlEt of just own institute of 10ml and Al/Ti (mol ratio)=85 down 3Under agitation add the catalyzer that the embodiment one contain 1mgTi makes again, stir made the catalyzer homodisperse in 2 minutes after, heating is taken out and is desolvated, to PE powder and the complete flow dispersion of catalyzer, logical ethene is under the 106.7KPa condition at pressure, is warming up to 80～86 ℃ of reactions 2 hours, catalytic efficiency is 8.9KgPE/gTi, and the product bulk density is 0.33g/cm 3
Embodiment three
Pressurization agitated bed ethene gas-phase polymerization
Adopt 2 liter stills, vacuumized thorough drying 2 hours through 100 ℃, use N 2Replace 3 times, at N 2Protection adds 30g 40～80 order PE powder down and makes dispersion medium; Stir and to add catalyzer that the embodiment that contains 0.8mg Ti one that mixes makes and the AlEt of 2g down 3-SiO 2(wherein contain AlEt 3Lg), lead to into ethylene reaction, when the ethene total pressure is 0.6MPa, Al/Ti (mole)=150/1, temperature is 85～90 ℃, reacts 2 hours, and catalytic efficiency is 146KgPE/gTi, and the product bulk density is 0.35g/cm 3, particle 10～120 order particles account for 98.2% of gross weight.
Embodiment four
φ-100mm fluidized-bed ethene gas phase copolymerization
In φ-100mm fluidized-bed, add the dry PE particulate material of 100g 20～80 purposes.Vacuumize and use rare gas element N 2After ethene metathesis reactor 3 times, through dehydration, device for deoxidizing dehydration and deoxidation 1 hour, make H in the reactor with cyclic ethylene 2O≤2PPm, O 2≤ 0.5ppm adds catalyzer and 2gAlEt that the embodiment one that contains 1.3mg Ti makes 3-SiO 2(wherein contain AlEt 30.8g) mixture, feed ethene, H 2, the 1-butylene mixed gas, its volume ratio is 6.5: 1.5: 2.0, the reaction total pressure is 1.0MPa, 80～90 ℃ of temperature were reacted 3 hours, catalytic efficiency is 550KgLLDPE/gTi, product MI value is 2.3, product density is 0.912g/cm 3Product particle form and distribution are good, and 10～120 order particles account for 99.3% of gross weight, and bulk density is 0.35g/cm 3
Embodiment five
2.5mmol n-butyl ether with the step among the embodiment one poly-1 uses changes 3.8mmol into, and other condition is identical with embodiment one with operation, and Primary Catalysts that makes and promotor aluminum alkyls are formed complex catalyst system and be used for ethene gas-phase polymerization.
Embodiment six
The normal pressure ethene gas-phase polymerization
Adopt under the reaction conditions identical with embodiment two, adding contains the catalyzer that the embodiment five of 1mg Ti makes, and the polyreaction catalytic efficiency is 8.6KgPE/gTi, and the product bulk density is 0.33g/cm 3
Embodiment seven
Pressurization agitated bed ethene gas-phase polymerization
Adopt the reaction conditions identical with embodiment three, adding contains the catalyzer that the embodiment five of 0.8mg Ti makes, and the polyreaction catalytic efficiency is 124KgPE/gTi, and the product bulk density is 0.36g/cm 310～120 order products account for 98.4% of gross weight.
Embodiment eight
φ-100 fluidized-bed ethene gas phase copolymerization
Adopt the reaction conditions identical with embodiment four, add the catalyzer that the embodiment five that contains 1.3mg Ti makes, its catalytic efficiency that gathers of φ-100 fluidized-bed ethene-1-butylene gas phase is 230Kg LLDPE/gTi, and the product bulk density is 0.36g/cm 3, 10～120 order particles account for 96.1% of gross weight, and product density is 0.926g LLDPE/cm 3
Embodiment nine
0.5ml CCl with poly-2 uses of step among the embodiment one 4Change 0.75ml into, other condition is identical with embodiment one with operation, and catalyzer that makes and promotor aluminum alkyls are formed complex catalyst system and be used for ethene gas-phase polymerization.
Embodiment ten
The normal pressure ethene gas-phase polymerization
Adopt the reaction conditions identical with embodiment two, adding contains the catalyzer that the embodiment nine of 1mg Ti makes, and the polyreaction catalytic efficiency is that 11.9KgPE/gTi, product bulk density are 0.31g/cm 3
Embodiment 11
Pressurization agitated bed ethene gas-phase polymerization
Adopt the reaction conditions identical with embodiment three, adding contains the catalyzer that the embodiment nine of 0.8mg Ti makes, and polyreaction efficient is 171KgPE/gTi, and the product bulk density is 0.35g/cm 3, 10～120 order products account for 96.3% of gross weight.

Claims (5)

1. an ethylene polymerization composite load titanium catalyst is characterized in that comprising the Primary Catalysts titanium compound, complex carrier organic-magnesium-AlEt 3-n-butyl ether-SiO 2, accelerant C Cl 1, and promotor aluminum alkyls AlR 3, wherein titanium compound is TiCl 4, organic-magnesium is C 4H 9MgCl, AlR 3In R be C 2～C 8Alkyl; The composition proportioning of this catalyzer is as follows:
By weight SiO 2: TiCl 4=4～8: 1
With TiCl 4Mole number calculate, the mol ratio of all the other each components is:
TiCl 4 1
Organic-magnesium 3～6
N-butyl ether 0.5～1.0
CCl 4 0.8～1.5
AlEt 3 0.2～0.5
2. according to the described catalyzer of claim 1, it is characterized in that this catalyzer is prepared from by following dipping-reaction method:
1. at N 2In the air-flow, 600 ℃ of temperature lower calcination microspheroidal SiO 26 hours, the cooling back added organic-magnesium n-heptane solution, AlEt 3Hexane solution and quantitative n-butyl ether, 45～55 ℃ of following stirring reactions 45 minutes, organic-magnesium C wherein 4H 9MgCl n-heptane solution concentration is 0.5～1.0mol/L;
2. at N 2Protection continues to add TiCl down 4, CCl 4, be warming up to 70 ℃ of stirring reactions 2 hours, be cooled to 50 ℃ again and continued stirring reaction 3 hours, leave standstill, be cooled to room temperature, to filter and use hexane wash 3 times, temperature is lower than 60 ℃, and vacuum-drying then gets complex carrier organic-magnesium-AlEt 3-n-butyl ether-SiO 2Load TiCl 4Primary Catalysts, it and promotor aluminum alkyls AlR 3Form ethylene polymerization composite load titanium catalyst, for gaseous ethylene polymerization, the mol ratio of Primary Catalysts and promotor is Ti: Al=1: (50～200).
3. a catalyzer as claimed in claim 1 is used for the normal pressure ethene gas-phase polymerization, it is characterized in that with the PE powder be dispersion medium, adds Primary Catalysts and promotor AlEt 3, wherein the Al/Ti mol ratio is (50～200)/1, and at ethylene pressure 106.7KPa, reaction is 2 hours under 70～90 ℃ of temperature, and catalytic efficiency is 8600～11000gPE/gTi.
4. a catalyzer as claimed in claim 1 agitated bed ethene gas-phase polymerization that is used to pressurize, the Al/Ti mol ratio that it is characterized in that Primary Catalysts and promotor is (50～200)/1, in the ethene total pressure is 0.6MPa, polyreaction is 3 hours under 70～90 ℃ of temperature, and catalytic efficiency is 124～160KgPE/gTi.
5. a catalyzer as claimed in claim 1 is used for Φ-100 fluidized-bed ethene gas phase copolymerization, it is characterized in that the Al/Ti mol ratio of Primary Catalysts and promotor is (50～200)/1, at ethylene pressure 1.0MPa, and 80～90 ℃, H 2Dividing potential drop 0.15～0.20MPa, under 1-butylene dividing potential drop 0.12～0.20MPa condition, copolymerization 3 hours, catalytic efficiency are 230～550KgLLDPE/gTi.
CN98113183A 1998-04-22 1998-04-22 Ethylene polymerization composite load titanium catalyst Expired - Fee Related CN1071339C (en)

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KR100377287B1 (en) * 2000-05-29 2003-03-26 삼성종합화학주식회사 Ethylene polymerization method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1053240A (en) * 1990-01-10 1991-07-24 希蒙特公司 The catalyst component of olefinic polymerization and catalyzer
CN1092080A (en) * 1994-01-08 1994-09-14 中山大学 Ethene gas-phase homopolymerization and alpha-olefin copolymer close composite catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1053240A (en) * 1990-01-10 1991-07-24 希蒙特公司 The catalyst component of olefinic polymerization and catalyzer
CN1092080A (en) * 1994-01-08 1994-09-14 中山大学 Ethene gas-phase homopolymerization and alpha-olefin copolymer close composite catalyst

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