CN112724284B - Solid catalyst component, preparation method, olefin polymerization catalyst and application - Google Patents

Solid catalyst component, preparation method, olefin polymerization catalyst and application Download PDF

Info

Publication number
CN112724284B
CN112724284B CN201911032146.3A CN201911032146A CN112724284B CN 112724284 B CN112724284 B CN 112724284B CN 201911032146 A CN201911032146 A CN 201911032146A CN 112724284 B CN112724284 B CN 112724284B
Authority
CN
China
Prior art keywords
titanium
compound
catalyst component
solid catalyst
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911032146.3A
Other languages
Chinese (zh)
Other versions
CN112724284A (en
Inventor
郭正阳
周俊领
刘萃莲
王迎
唐璐
雷世龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201911032146.3A priority Critical patent/CN112724284B/en
Publication of CN112724284A publication Critical patent/CN112724284A/en
Application granted granted Critical
Publication of CN112724284B publication Critical patent/CN112724284B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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 invention belongs to the field of catalysts, and relates to a solid catalyst component, a preparation method, an olefin polymerization catalyst and application. The solid catalyst component comprises titanium element, magnesium element, alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1-15 wt%, the content of the magnesium element is 10-30 wt%, the content of the phosphorus element is 0.01-1 wt%, the content of the alkoxy compound is 1-10 wt%, and the content of the halogen is 40-70 wt%, based on the total weight of the solid catalyst component; the solid catalyst component has an angle of repose of 20 to 40 °. The solid catalyst component and the catalyst of the invention have good particle shape, good fluidity, high bulk density, high catalyst activity, concentrated particle size distribution of the prepared polymer, high bulk density, simple production process and relatively low production cost.

Description

Solid catalyst component, preparation method, olefin polymerization catalyst and application
Technical Field
The invention belongs to the field of catalysts, and in particular relates to a solid catalyst component, a preparation method of the solid catalyst component, the solid catalyst component prepared by the preparation method, an olefin polymerization catalyst containing the solid catalyst component, and applications of the solid catalyst component and the olefin polymerization catalyst.
Background
In the polymerization of olefins, in particular in the homopolymerization of ethylene or in the copolymerization of ethylene with alpha-olefins, catalyst components based on magnesium, titanium, halogen and electron donors are mostly used.
In practice, the above catalyst component is mainly composed of magnesium chloride, titanium chloride and an electron donor. The early catalyst component is prepared by mixing and grinding magnesium chloride, titanium tetrachloride and an electron donor together, the catalyst has low activity, the prepared polymer has wide particle size distribution, and coarse powder and fine powder are more, so that the catalyst is basically eliminated. The morphology of the catalyst component has a decisive influence on the morphology of the polymer produced during the polymerization of olefins, and so there has been a search for improving the morphology of the catalyst particles for many years in order to obtain polymers with better particle morphology.
There are two main approaches to improving the morphology of the catalyst component particles.
One is to support the catalyst component on porous spherical silica in a fixed form, as disclosed in chinese patent application CN1158136a as a main catalyst for producing ethylene polymers, which comprises an inorganic carrier (preferably an active silica carrier), a chlorine compound supported on the carrier, a magnesium compound supported on the carrier, and a titanium compound supported on the carrier. The catalyst is characterized in that: the catalyst particles are spherical, have better fluidity and good hydrogen regulation sensitivity, and the polymerization activity is less reduced along with the increase of the addition amount of the chain transfer agent (hydrogen), so that the catalyst is suitable for producing polyethylene resin with wide molecular weight distribution. However, the silica gel in the catalyst occupies a large part, and the content of active catalyst components is not high, so that the catalyst has low activity, is suitable for gas phase process, is not suitable for slurry polyethylene process device, and has complex catalyst production process and high production cost.
The other is to dissolve magnesium compound into homogeneous solution, then react with titanium compound to separate out magnesium chloride particles and load titanium chloride and electron donor, as disclosed in Chinese patent ZL85100997.2 (N), chinese patent application CN1112373A (RZ), CN1229092A (CT), CN1958620A (BCE) and the like. The method generally dissolves the magnesium compound in the polar solvent, and separates out the catalyst component particles containing titanium magnesium and electron donor through the contact reaction of the dissolution liquid and titanium tetrachloride, the method is simple and easy to implement, the performance of the catalyst component is better than that of the catalyst mixed and ground, but the method has a plurality of defects.
For example, in chinese patent ZL85100997.2, it is prepared by dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution, and then reacting with at least one precipitation aid and a halide of transition metal titanium and its derivatives. Because the organic epoxy compound and the organic phosphorus compound which do not contain active hydrogen are adopted as solvents, the dissolution of magnesium chloride is slower, the reaction of the magnesium chloride and titanium tetrachloride is convenient to control, so that the precipitated particles are better in particle shape and are similar to spheres, and the prepared polymer is better in particle shape and higher in bulk density. However, the catalyst has low activity when used for slurry polymerization of ethylene, and the hydrogen regulation performance is insensitive.
For example, in chinese patent application CN1112373a, magnesium chloride is dissolved in isooctanol using decane as a dispersant, and silane is added as a precipitation agent, and catalyst component particles are precipitated by reaction with titanium tetrachloride. The solvent used in the system is isooctyl alcohol, the raw material is simple, the catalyst component has higher activity and better hydrogen regulation performance in ethylene polymerization, but the catalyst needs high temperature for dissolution, the prepared solution has high viscosity, the consumption of titanium tetrachloride is more, and the post-treatment process of the solvent is complex.
For example, chinese patent application CN1229092a discloses a catalyst for ethylene polymerization or copolymerization, which is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, adding a low carbon alcohol as an electron donor activator to form a uniform solution, and reacting with at least one anhydride-type precipitation aid, a halide of transition metal titanium and its derivatives, wherein the catalyst exhibits high activity when used for slurry polymerization of ethylene, but the catalyst has a less regular particle shape, poor catalyst flowability, relatively dispersed particle size distribution of the prepared polymer, and low bulk density of the polymer.
For example, in chinese patent application CN1958620a, a magnesium halide is dissolved in an organic epoxy compound, an organic phosphorus compound and a low carbon alcohol to form a homogeneous solution, and then reacted with at least one silane compound and a halide of transition metal titanium and its derivative to prepare the catalyst, which has high activity when used for slurry polymerization of ethylene, improved particle shape of the catalyst, but still has problems of less regular catalyst particle shape, poor flowability, relatively dispersed particle size distribution of the prepared polymer, low bulk density, and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a solid catalyst component, a preparation method and an olefin polymerization catalyst.
The first aspect of the present invention provides a solid catalyst component comprising titanium element, magnesium element, an alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1 to 15wt%, the content of the magnesium element is 10 to 30wt%, the content of the phosphorus element is 0.01 to 1wt%, the content of the alkoxy compound is 1 to 10wt%, and the content of the halogen is 40 to 70wt%, based on the total weight of the solid catalyst component; the solid catalyst component has an angle of repose of 20 to 40 °.
The second aspect of the present invention provides a method for preparing a solid catalyst component, comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the system temperature and adding a titanium compound to obtain a suspension system containing a solid component, then increasing the system temperature, filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system in multiple times.
A third aspect of the present invention provides a solid catalyst component produced by the above-described production method.
In a fourth aspect, the present invention provides an olefin polymerization catalyst comprising the following components:
A. the above solid catalyst component;
B. an organoaluminum compound.
A fifth aspect of the present invention provides the use of the above solid catalyst component and/or an olefin polymerization catalyst in ethylene polymerization reactions.
The solid catalyst component and the catalyst of the invention have good particle shape, good fluidity, high bulk density, high catalyst activity, concentrated particle size distribution of the prepared polymer, high bulk density, simple production process and relatively low production cost. The solid catalyst component and catalyst are particularly useful in slurry polymerization of ethylene.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a solid catalyst component comprising titanium element, magnesium element, an alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1 to 15wt%, the content of the magnesium element is 10 to 30wt%, the content of the phosphorus element is 0.01 to 1wt%, the content of the alkoxy compound is 1 to 10wt%, and the content of the halogen is 40 to 70wt%, based on the total weight of the solid catalyst component; the solid catalyst component has an angle of repose of 20 to 40 °.
According to the present invention, preferably, the content of the titanium element is 2 to 10wt%, the content of the magnesium element is 15 to 25wt%, the content of the phosphorus element is 0.1 to 0.8wt%, the content of the alkoxy compound is 2 to 8wt%, and the content of the halogen element is 50 to 65wt%, based on the total weight of the solid catalyst component.
According to the present invention, preferably, the solid catalyst component has an angle of repose of 25 to 35 °.
According to the present invention, preferably, the solid catalyst component has an average particle diameter of 2 to 10 micrometers, preferably 3 to 8 micrometers; the bulk density is 0.30 to 0.50 g/ml, preferably 0.35 to 0.45 g/ml.
In the present invention, the catalyst particle size distribution was measured by a Mastersizer 2000 instrument (Malvern, england). The bulk density of the catalyst solids is determined with reference to ASTM D1895-96; the angle of repose of the solid component of the catalyst was determined with reference to GB-T11986-98.
The second aspect of the present invention provides a method for preparing a solid catalyst component, comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the system temperature and adding a titanium compound to obtain a suspension system containing a solid component, then increasing the system temperature, filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system in multiple times.
Compared with the prior art, the method optimizes the adding mode of the titanium compound, and in the prior art, the titanium compound is added into the system at one time. The inventors of the present invention have found in the study that adding a titanium compound in portions can improve the morphology and performance parameters of the resulting solid catalyst component.
The number of addition times of the titanium compound is not particularly limited in the present invention, and may be two, three, or more times.
According to the method of the present invention, preferably, the amount of the titanium compound added for the first time is 5 to 20%, more preferably 8 to 20%, still more preferably 9 to 15% of the total amount of the total titanium compound added; the time interval between the first addition of the titanium compound and the immediately next addition of the titanium compound is 20 to 80%, preferably 40 to 70%, of the total time required for the addition of all titanium compounds to the system. The morphology and performance parameters of the resulting solid catalyst component can be further improved by further refining the manner in which the titanium compound is added.
In the method of the invention, the titanium compound can be added at the initial stage, the middle stage or after the end of the cooling of the system. Preferably, part of the titanium compound is added during the system cooling process, and the rest of the titanium compound is added after the system cooling process.
From the standpoint of considering both the performance of the obtained solid catalyst component and the convenience of operation, the titanium compound is added into the system in two times, the first part of the titanium compound is added in the cooling process of the system, and the rest part of the titanium compound is added after the cooling process of the system. More specifically, when the system is cooled to a first target temperature, a first portion of the titanium compound is added, then the system is continuously cooled to a final target temperature, and then the rest of the titanium compound is added.
Typically, during the preparation of the solid catalyst component, the temperature of the system (i.e., the final target temperature) is reduced to-30 ℃ to 30 ℃, preferably-30 ℃ to 10 ℃.
According to one embodiment of the invention, when the system is cooled to-15 ℃ to 0 ℃, adding a first part of titanium compound, then continuously cooling the system to-30 ℃ to-20 ℃, and then adding the rest part of titanium compound.
Similar to the manner of adding the titanium compound in the prior art, each addition of the titanium compound was slowly dropped.
According to one embodiment of the invention, the temperature of the system is raised to 60℃to 110℃and the process further comprises stirring the suspension at this temperature for 0.5 to 8 hours, and then filtering, washing and drying the suspension.
According to the invention, the formation of a homogeneous solution may be achieved using conditions conventional in the art, such as by heating, for example at a temperature of 50-60 ℃, to promote dissolution of the components.
In the present invention, the titanium compound may be various titanium compounds commonly used in the preparation of solid components of olefin polymerization catalysts, for example, titanium compounds having the general formula Ti (OR) a X b Wherein R is C 1 ～C 14 X is a halogen atom, a is an integer from 0 to 2, b is an integer from 0 to 4, a+b=3 or 4; preferably selected from titanium tetrachloride, titanium tetrabromide, tetraAt least one of titanium iodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium monochloroethoxide and titanium trichloride, more preferably at least one selected from titanium tetrachloride, titanium monochloroethoxide and titanium trichloride. The titanium compound may be added in the form of a halide of titanium alone or in the form of a mixed solution of a halide of titanium and an inert diluent.
In the present invention, the specific type of each component used may be a matter of routine choice in the art.
The magnesium compound may be at least one of a halide of magnesium, an alkoxide of magnesium, and a halogenated alkoxide of magnesium; specific examples include, but are not limited to: magnesium chloride.
The organic epoxy compound may be selected from C 2 ～C 8 At least one of an aliphatic olefin, a diene or a halogenated aliphatic olefin or an oxide of a diene, a glycidyl ether and a internal ether; specific examples include, but are not limited to: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, or mixtures thereof.
The organophosphorus compound is selected from hydrocarbyl esters and/or halogenated hydrocarbyl esters of orthophosphoric acid and/or phosphorous acid; specific examples include, but are not limited to: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, or mixtures thereof.
The organic alcohol compound is selected from C 2 ～C 10 Fatty alcohols of (a); specific examples include, but are not limited to: methanol, ethanol, propanol, butanol, hexanol, diethyl hexanol, or mixtures thereof.
The precipitation aid is at least one selected from organic acid, organic anhydride, organic ether and organic ketone; specific examples include, but are not limited to: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, or mixtures thereof.
The inert diluent is selected from C 6 ～C 10 Alkane and/or C of (C) 6 ～C 8 Is a hydrocarbon aromatic hydrocarbon. Specific examples include, but are not limited to: hexane, heptane, octane, decane, benzene, toluene, xylene, or mixtures thereof, or derivatives thereof.
The amounts of the above components may also be selected as is conventional in the art. Specifically, the organic epoxy compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 4 moles, per mole of magnesium halide; the amount of the organic phosphorus compound is 0.1 to 3 moles, preferably 0.3 to 1 mole; the amount of the organic alcohol compound is 0.1 to 10 moles, preferably 0.5 to 5 moles; the dosage of the inert diluent is 0.5-5L; the amount of the titanium compound is 1 to 15 moles, preferably 2 to 10 moles.
A third aspect of the present invention provides a solid catalyst component produced by the above-described production method. The solid catalyst component of the present invention is in the form of particles.
In a fourth aspect, the present invention provides an olefin polymerization catalyst comprising the following components:
A. the above solid catalyst component;
B. an organoaluminum compound.
The general formula of the organic aluminum compound is AlR' n X’ 3-n Wherein R' may be hydrogen, C 1 ～C 20 In particular alkyl, aralkyl, aryl; x' is halogen, in particular chlorine and bromine; 0<n is less than or equal to 3. Specific compounds are as follows: alkyl aluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, and ethylaluminum dichloride are preferable, and triethylaluminum and triisobutylaluminum are preferable.
In the catalyst of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 5 to 5000:1, preferably 20 to 500:1.
a fifth aspect of the present invention provides the use of the above solid catalyst component and/or an olefin polymerization catalyst in ethylene polymerization reactions. The solid catalyst component and the olefin polymerization catalyst of the present invention are particularly suitable for slurry polymerization of ethylene.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
In the following examples:
the catalyst particle size distribution was determined using a Mastersizer 2000 instrument (Malvern, england).
The apparent Bulk Density (BD) of the catalyst and polymer was measured with reference to ASTM D1895-96.
The angle of repose is determined with reference to GB-T11986-98.
The contents of titanium, magnesium and chlorine in the catalyst are determined by adopting a chemical analysis method, the alkoxy content is determined by adopting a gas chromatography, and the phosphorus content is determined by adopting an X-ray energy spectrum analysis method.
Catalyst component ethylene polymerization evaluation method: the 2-liter polymerizer was alternately purged with nitrogen and evacuated with three times, and 1.0 liter of n-hexane, 2mmol of triethylaluminum and 10 mg of the above-mentioned solid catalyst component were added. The reaction kettle is heated to 60 ℃, then ethylene is introduced to the kettle pressure of 0.7MPa, and the reaction is carried out for 2 hours. And after the reaction is finished, cooling, separating and collecting the polymer.
Example 1
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour under the condition of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to minus 10 ℃, 30 ml of a mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 30min, the temperature is reduced to minus 30 ℃ after 90min, and the rest of the mixed solution is added dropwise, and the time is 90min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Example 2
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour under the condition of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to minus 10 ℃, 50 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 45min, the temperature is reduced to minus 30 ℃ after 120min, and the rest of mixed solution is added dropwise, and the time is 120min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Example 3
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour under the condition of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to-20 ℃, 55 ml of a mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 60min, the temperature is reduced to-30 ℃ after 120min, and the rest of the mixed solution is added dropwise, and the time is 90min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Example 4
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour at the temperature of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to minus 10 ℃, 30 ml of a mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 30min, the time is then kept for 90min, and the rest of the mixed solution is added dropwise, and the time is 90min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Example 5
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour under the condition of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to minus 10 ℃, 30 ml of a mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 30min, the temperature is reduced to minus 30 ℃ after 60min, and the rest of the mixed solution is added dropwise, and the time is 120min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Example 6
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour under the condition of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to minus 10 ℃, 80 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene is slowly added dropwise, the time is 60min, the temperature is reduced to minus 30 ℃ after 60min, and the rest of mixed solution is added dropwise, and the time is 90min. The temperature was raised to 90℃over 4 hours, the mother liquor was filtered off after keeping the temperature for 1.5 hours, washed twice with toluene and then 3 times with hexane, and the remaining solid product was dried to obtain a solid titanium catalyst component.
Comparative example 1
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour at the temperature of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to-10 ℃, 80 ml of titanium tetrachloride is dropwise added at the temperature, then the temperature is raised to 90 ℃ within 4 hours, the mother solution is filtered after the temperature is kept for 1.5 hours, the mother solution is washed twice by toluene, the washing is carried out for 3 times by hexane, and the residual solid product is dried to obtain the solid titanium catalyst component.
Comparative example 2
In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the reaction is carried out for 1 hour at the temperature of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to-30 ℃, 80 ml of titanium tetrachloride is dropwise added at the temperature, then the temperature is raised to 90 ℃ within 4 hours, the mother solution is filtered after the temperature is kept for 1.5 hours, the mother solution is washed twice by toluene, the washing is carried out for 3 times by hexane, and the residual solid product is dried to obtain the solid titanium catalyst component.
Comparative example 3
The catalyst component was prepared according to the method of example 4 in chinese patent application CN1958620 a.
Comparative example 4
The catalyst component was prepared according to the method of example 1 in chinese patent ZL 85100997.2.
Comparative example 5
The catalyst component was prepared according to the method of example 1 in chinese patent application CN 1091748A.
Test case
The catalyst components prepared in the above examples and comparative examples were tested in the following table 1 and the ethylene polymerization evaluation data were as follows table 2.
Table 1 catalyst test data
Figure BDA0002250463050000121
Table 2 ethylene polymerization evaluation data
Figure BDA0002250463050000131
As can be seen from the data in Table 1, the catalyst component particles of the present invention have higher bulk density, smaller angle of repose and better flowability. The data in Table 2 shows that the catalyst component of the present invention has high activity, the prepared polymer has high bulk density, concentrated particle size distribution and less coarse powder and fine powder.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

Claims (23)

1. The solid catalyst component is characterized by comprising titanium element, magnesium element, alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1-15 wt%, the content of the magnesium element is 10-30 wt%, the content of the phosphorus element is 0.01-1 wt%, the content of the alkoxy compound is 1-10 wt%, and the content of the halogen is 40-70 wt%, based on the total weight of the solid catalyst component; the repose angle of the solid catalyst component is 20-40 degrees;
the preparation method of the solid catalyst component comprises the following steps: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the system temperature and adding a titanium compound to obtain a suspension system containing a solid component, then increasing the system temperature, filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system in two times;
wherein the amount of the titanium compound added for the first time accounts for 5-30% of the total amount of all titanium compounds added; the time interval between the first time of adding the titanium compound and the next time of adding the titanium compound is 20-80% of the total time required by adding all the titanium compounds into the system;
the first part of titanium compound is added in the system cooling process, and the rest of titanium compound is added after the system cooling process;
wherein, the temperature of the system is reduced to minus 30 ℃ to minus 20 ℃.
2. The solid catalyst component according to claim 1, wherein the content of the titanium element is 2 to 10wt%, the content of the magnesium element is 15 to 25wt%, the content of the phosphorus element is 0.1 to 0.8wt%, the content of the alkoxy compound is 2 to 8wt%, and the content of the halogen is 50 to 65wt%, based on the total weight of the solid catalyst component; the repose angle of the solid catalyst component is 25-35 degrees.
3. The solid catalyst component according to claim 1 or 2, wherein the solid catalyst component has an average particle diameter of 2 to 10 μm; the bulk density is 0.30-0.50 g/ml.
4. The solid catalyst component according to claim 3, wherein the solid catalyst component has an average particle diameter of 3 to 8 μm.
5. The solid catalyst component according to claim 3, wherein the bulk density of the solid catalyst component is 0.35 to 0.45 g/ml.
6. A method of preparing a solid catalyst component comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the system temperature and adding a titanium compound to obtain a suspension system containing a solid component, then increasing the system temperature, filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system in two times;
wherein the amount of the titanium compound added for the first time accounts for 5-30% of the total amount of all titanium compounds added; the time interval between the first time of adding the titanium compound and the next time of adding the titanium compound is 20-80% of the total time required by adding all the titanium compounds into the system;
the first part of titanium compound is added in the system cooling process, and the rest of titanium compound is added after the system cooling process;
wherein, the temperature of the system is reduced to minus 30 ℃ to minus 20 ℃.
7. The production method according to claim 6, wherein the amount of the titanium compound added for the first time is 8 to 20% of the total amount of all titanium compounds added; the time interval between the first titanium compound addition and the next immediately subsequent titanium compound addition is 40-70% of the total time required for adding all titanium compounds into the system.
8. The preparation method according to claim 7, wherein the amount of the titanium compound added for the first time is 9 to 15% of the total amount of all titanium compounds added.
9. The process of claim 6 wherein a first portion of the titanium compound is added as the system is cooled to a first target temperature, then the system is cooled to a final target temperature and the remainder of the titanium compound is added.
10. The preparation method according to claim 6, wherein the temperature of the system is increased to 60-110 ℃, the method further comprises stirring the suspension system at the temperature for 0.5-8 hours, and then filtering, washing and drying the suspension system.
11. The production method according to any one of claims 6 to 10, whereinThe general formula of the titanium compound is Ti (OR) a X b Wherein R is C 1 ~C 14 X is a halogen atom, a is an integer from 0 to 2, b is an integer from 0 to 4, a+b=3 or 4;
the titanium compound is added in the form of a titanium halide or a mixture of titanium halide and an inert diluent.
12. The production method according to claim 11, wherein the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy and titanium trichloride.
13. The production method according to claim 12, wherein the titanium compound is at least one selected from titanium tetrachloride, titanium trichloro-monoethoxy and titanium trichloride.
14. The preparation method according to any one of claims 6 to 10, wherein,
the magnesium compound is at least one of a halide of magnesium, an alkoxide of magnesium and a halogenated alkoxide of magnesium;
the organic epoxy compound is selected from C 2 ~C 8 At least one of an aliphatic olefin, a diene or a halogenated aliphatic olefin or an oxide of a diene, a glycidyl ether and a internal ether;
the organophosphorus compound is selected from hydrocarbyl esters and/or halogenated hydrocarbyl esters of orthophosphoric acid and/or phosphorous acid;
the organic alcohol compound is selected from C 2 ~C 10 Fatty alcohols of (a);
the precipitation aid is at least one selected from organic acid, organic anhydride, organic ether and organic ketone;
the inert diluent is selected from C 6 ~C 10 Alkane and/or C of (C) 6 ~C 8 Is a hydrocarbon aromatic hydrocarbon.
15. The production method according to any one of claims 6 to 10, wherein the organic epoxy compound is used in an amount of 0.2 to 10 mol per mol of magnesium halide; the using amount of the organic phosphorus compound is 0.1-3 mol; the dosage of the organic alcohol compound is 0.1-10 mol; the dosage of the inert diluent is 0.5-5L; the amount of the titanium compound is 1 to 15 moles.
16. The production method according to claim 15, wherein the organic epoxy compound is used in an amount of 0.5 to 4 mol.
17. The production method according to claim 15, wherein the amount of the organic phosphorus compound is 0.3 to 1 mol.
18. The production method according to claim 15, wherein the organic alcohol compound is used in an amount of 0.5 to 5 mol.
19. The production method according to claim 15, wherein the amount of the titanium compound is 2 to 10 mol.
20. A solid catalyst component produced by the production process according to any one of claims 6 to 19.
21. An olefin polymerization catalyst comprising the following components:
A. a solid catalyst component according to any one of claims 1 to 5, 20;
B. an organoaluminum compound.
22. Use of the solid catalyst component according to any one of claims 1 to 5, 20 and/or the olefin polymerization catalyst according to claim 21 in ethylene polymerization.
23. The use according to claim 22 in ethylene slurry polymerization.
CN201911032146.3A 2019-10-28 2019-10-28 Solid catalyst component, preparation method, olefin polymerization catalyst and application Active CN112724284B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911032146.3A CN112724284B (en) 2019-10-28 2019-10-28 Solid catalyst component, preparation method, olefin polymerization catalyst and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911032146.3A CN112724284B (en) 2019-10-28 2019-10-28 Solid catalyst component, preparation method, olefin polymerization catalyst and application

Publications (2)

Publication Number Publication Date
CN112724284A CN112724284A (en) 2021-04-30
CN112724284B true CN112724284B (en) 2023-05-12

Family

ID=75588844

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911032146.3A Active CN112724284B (en) 2019-10-28 2019-10-28 Solid catalyst component, preparation method, olefin polymerization catalyst and application

Country Status (1)

Country Link
CN (1) CN112724284B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1086191C (en) * 1998-03-17 2002-06-12 中国石油化工集团公司 Catalyst used for vinyl polymerizing or copolymerizing and its making method
CN1279069C (en) * 2003-12-03 2006-10-11 中国石油化工股份有限公司 Polyethylene catalyst and its preparation method
KR101433174B1 (en) * 2005-10-31 2014-08-22 차이나 페트로리움 앤드 케미컬 코포레이션 Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same
CN103772537B (en) * 2012-10-19 2016-04-27 中国石油化工股份有限公司 A kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE)
CN105777953B (en) * 2014-12-24 2018-10-16 中国石油天然气股份有限公司 The main catalyst component and preparation method of propylene polymerization
CN106317275B (en) * 2015-06-18 2018-12-28 中国石油化工股份有限公司 Prepare catalytic component of fiber polyolefin and its preparation method and application and catalyst system and application and olefine polymerizing process

Also Published As

Publication number Publication date
CN112724284A (en) 2021-04-30

Similar Documents

Publication Publication Date Title
CN1955195B (en) Catalyst, preparation method and application for olefin polymerization or copolymerization
CN104558276A (en) Olefin polymerization catalyst, and preparation method and application thereof
CN105622798A (en) Catalyst component for olefin polymerization, preparation method and applications thereof
CN1931885B (en) Catalyst for polymerizing olefin and its preparation process
CN109694423B (en) Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization
CN104974283A (en) Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN112724290B (en) Ultra-high molecular weight polyethylene powder and preparation method thereof
CN107129549A (en) Ingredient of solid catalyst, catalyst and application for olefinic polymerization
CN112724284B (en) Solid catalyst component, preparation method, olefin polymerization catalyst and application
CN100363389C (en) Catalyst used for ethylene polymerization or copolymerization and its preparation method
CN114426605B (en) Catalyst component for olefin polymerization and preparation method and application thereof
CN105622789A (en) Small pore size catalyst component for olefin polymerization, preparation method and applications thereof
CN110862472A (en) Olefin polymerization reaction catalyst, preparation method and composite catalyst
CN101565476B (en) Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof
CN104974279A (en) Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN111057168B (en) Catalyst for olefin polymerization and preparation method and application thereof
CN112661885B (en) Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application
CN103772550A (en) Catalyst ingredient used for ethylene polymerization, and catalyst thereof
CN115490789B (en) Micron-sized catalyst component for olefin polymerization, preparation method thereof and olefin polymerization method
CN117946298A (en) Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof
JP2006233063A (en) Olefin polymerization catalyst and method for polymerizing olefin
CN111057169B (en) Catalyst for olefin polymerization and preparation method and application thereof
CN115975083A (en) Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method
CN107936153B (en) Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application thereof
CN103087229B (en) Catalyst component and catalyst used in ethylene polymerization

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant