CN106632759B - Solid catalyst component for ethylene polymerization, preparation and application thereof - Google Patents
Solid catalyst component for ethylene polymerization, preparation and application thereof Download PDFInfo
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- CN106632759B CN106632759B CN201510718809.2A CN201510718809A CN106632759B CN 106632759 B CN106632759 B CN 106632759B CN 201510718809 A CN201510718809 A CN 201510718809A CN 106632759 B CN106632759 B CN 106632759B
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Abstract
The invention relates to a solid catalyst component for ethylene polymerization, comprising: inorganic oxide is used as a carrier to load reaction products of magnesium halide, titanium halide and phosphate ester compounds. The application also relates to a preparation method of the solid catalyst component and a catalyst for ethylene polymerization. When the solid catalyst component is used for ethylene polymerization reaction, the polymerization activity is high, and the melt index and the hydrogen regulation sensitivity are high.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for ethylene polymerization and a preparation method thereof.
Background
In the polymerization of ethylene or the copolymerization of ethylene with alpha-olefins, Z-N catalysts are widely used. In the disclosed patent, most of magnesium halide is used as carrier, and different methods are adopted, so that the catalyst has high activity and good particle state, but the hydrogen regulation performance is not ideal.
In the publication of patent ZL02146016, there is provided an ethylene polymerization catalyst which has high activity and excellent hydrogen response by adding an alkyl group-containing silicon compound during the preparation of the catalyst.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a supported solid catalyst component which takes an inorganic oxide as a carrier and is used for ethylene polymerization reaction. The catalyst prepared by using the solid catalyst component is used as a main catalyst for ethylene polymerization reaction, and has high catalytic activity, high melt index and high hydrogen regulation sensitivity.
According to one aspect of the present invention, there is provided a solid catalyst component for ethylene polymerization comprising: inorganic oxide is used as a carrier to load reaction products of magnesium halide, titanium halide and phosphate ester compounds.
According to the invention, the phosphate compound is used as an electron donor and acts with an active center, so that the hydrogen regulation performance of the catalyst is improved.
According to a particular embodiment of the invention, the phosphate compound is selected from the group consisting of diethyl salicylate, triethyl phosphate and tributyl phosphate.
According to a particular embodiment of the invention, the magnesium halide is selected from magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride.
According to a particular embodiment of the invention, the titanium halide is chosen from titanium chloride and titanium bromide, preferably titanium trichloride and/or titanium tetrachloride.
According to one embodiment of the invention, the molar ratio of the magnesium halide to the titanium halide, in Mg/Ti, is 1: (0.1-10). The titanium halide and the phosphate ester compound are 1: (0.05-5), preferably 1: (0.1-2), more preferably 1: (0.4-1.5).
According to the invention, the inorganic oxide support can be an oxide of silicon and/or aluminium, having an oxide particle size of 0.01 to 10 μm, preferably 0.01 to 2 μm, more preferably 0.1 to 2 μm. Most preferred are silica supports having an inorganic oxide of 0.1 to 1 μm. The catalyst generated by the silica gel with the particle size has good particle shape and high strength and is not easy to break.
According to another aspect of the present invention, there is provided a method for preparing a solid catalyst component for ethylene polymerization, comprising: in an organic solvent, mixing magnesium halide, titanium halide and a phosphate compound for reaction to obtain mother liquor, then mixing the mother liquor with an inorganic oxide carrier to obtain slurry liquid, and finally carrying out spray drying on the slurry liquid to obtain the solid catalyst component.
According to one embodiment of the invention, the inorganic oxide support should be dry, i.e. free of adsorbed water, at the time of use. A sufficient amount of carrier should be mixed with the mother liquor to form a slurry suitable for spray drying. The inorganic oxide support is present in an amount of 5 to 50 wt%, preferably 5 to 30 wt%, based on the total weight of the slurry.
According to the method, the reaction temperature is 65-95 ℃, the reaction pressure is 0.8-2MPa, the reaction time is 0.5-3 hours, and the blending temperature is 10-70 ℃.
According to the method of the present invention, the spray drying conditions are: the inlet temperature of the spray drying equipment is 80-240 ℃, preferably 120-.
According to a particular embodiment of the invention, the organic solvent is selected from C1-C4Alkyl esters of saturated fatty carboxylic acids, C7-C8Alkyl esters of aromatic carboxylic acids, C2-C6Fatty ethers, C3-C4Cyclic ethers and C3-C6Saturated aliphatic ketones, preferably selected from methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone, most preferably tetrahydrofuran.
According to a specific embodiment of the present invention, the amount of the organic solvent is 1 to 600 moles, preferably 20 to 200 moles, per mole of Ti.
According to another aspect of the present invention, there is provided a catalyst for ethylene polymerization comprising the reaction product of:
A. the above solid catalyst component for ethylene polymerization;
B. an organic aluminum compound with the general formula of AlR'nX3-nWherein R' is hydrogen or C1-C20X is halogen, n is an integer of 1 to 3.
According to the present invention, in order to make the solid catalyst component obtained after spray-drying suitable for the production of ethylene polymers, it is necessary to reduce the titanium atom in the solid catalyst component to a state capable of efficiently polymerizing ethylene using an organoaluminum compound as an activator. Generally, the solid catalyst component is reacted with an activator in a hydrocarbon solvent to obtain the catalyst; the solid catalyst component may also be reacted with an activator component during the polymerization to initiate olefin polymerization. The hydrocarbon solvent is selected from isopentane, hexane, heptane, toluene, xylene, naphtha and mineral oil.
According to a particular embodiment of the invention, the organoaluminium compound comprises at least one of triethylaluminium, triisobutylaluminium, tri-n-hexylaluminium, tri-n-octylaluminium or diethylaluminium monochloride. Wherein the ratio between the organoaluminum compound and the solid catalyst component is (20-500) in terms of Al/Ti molar ratio: 1, preferably (50-200): 1.
according to the invention, the catalyst is suitable for the homopolymerization of ethylene or the copolymerization of ethylene and other alpha-olefins selected from propylene, butene, pentene, hexene, octene and 4-methylpentene-1. The polymerization process adopts a gas phase method, a slurry method or a solution method, and is more suitable for gas phase fluidized bed polymerization.
The invention adopts inorganic oxide as carrier, reaction product of loading magnesium halide, titanium halide and phosphate compound as solid catalyst component, and prepares high-performance solid catalyst by spray drying forming mode, and the catalyst has high catalytic activity, hydrogen regulation sensitivity and melt index.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but do not limit the present invention.
The analysis in the present invention is characterized as follows:
(1) melt index was determined using ASTM D1238-99.
The synthesis of the catalyst compositions used was carried out under a nitrogen atmosphere.
Example 1
(1) Preparation of the catalyst
Into a 250ml three-necked flask purged with nitrogen, 1.5g of TiCl were added successively44.4g of anhydrous MgCl22.6g of salicylic acid diethyl phosphate and 100ml of tetrahydrofuran, and the temperature was raised to 65 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at a constant temperature. The temperature is reduced to 35 ℃.
To a 250ml three-necked flask purged with nitrogen gas was added 6g of silica gel (Cabot Corporation TS-610, 0.02-0.1 μm), and the mother liquor after cooling was added, maintained at 35 ℃ and stirred for 1 hour, and then the mother liquor after blending the silica gel was spray-dried using a spray dryer under spray conditions: the inlet temperature was 190 ℃ and the outlet temperature was 105 ℃ to obtain a solid catalyst having a titanium content of 2.3 wt%.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen, simultaneously adding 1mmol of triethyl aluminum and 0.02g of solid catalyst, heating to 75 ℃, adding 0.18Mpa of hydrogen, adding 0.75Mpa of ethylene after hydrogenation, heating to 85 ℃, reacting for 2 hours, cooling and discharging, wherein the polymerization result is shown in Table 1.
Example 2
The same as example 1 except that the amount of salicylic acid diethyl phosphate was 3.9g, and the spraying conditions were: the inlet temperature was 190 ℃ and the outlet temperature was 100 ℃ and the polymerization results are shown in Table 1.
Example 3
The same as example 1 except that the amount of salicylic acid diethyl phosphate was 5.2g, and the spraying conditions were: the inlet temperature was 190 ℃ and the outlet temperature was 101 ℃ and the polymerization results are shown in Table 1.
Comparative example 1
(1) Preparation of the catalyst
Into a 250ml three-necked flask purged with nitrogen, 1.5g of TiCl were successively charged44.0g of anhydrous MgCl2And 100ml of tetrahydrofuran, and the temperature was raised to 65 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at a constant temperature. The temperature is reduced to 35 ℃.
To a 250ml three-necked flask purged with nitrogen gas was added 6g of silica gel (Cabot Corporation TS-610, 0.02-0.1 μm), and the mother liquor after cooling was added, maintained at 35 ℃ and stirred for 1 hour, and then the mother liquor after blending the silica gel was spray-dried using a spray dryer under spray conditions: the inlet temperature was 195 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the titanium content was 2.4 wt%.
(2) Ethylene slurry polymerization as in example 1. The polymerization results are shown in Table 1.
TABLE 1
As can be seen from the polymerization data in table 1, under the same polymerization conditions, the solid catalyst component supporting the reaction product of magnesium halide, titanium halide and phosphate compound using an inorganic oxide as a carrier was used as a main catalyst, and the polymerization activity was higher and the melt index was high, compared to comparative example 1. The higher the melt index of the polymer product under the same conditions, the better the hydrogen control performance. Therefore, it was revealed that the solid catalyst component according to the present invention is high in hydrogen response when used as a main catalyst.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (15)
1. A solid catalyst component for ethylene polymerization comprising: taking an inorganic oxide as a carrier, and loading a reaction product of magnesium halide, titanium halide and a phosphate compound, wherein the phosphate compound is salicylic acid diethyl phosphate, and the molar ratio of the magnesium halide to the titanium halide is 1 in terms of Mg/Ti: (0.1-10); the molar ratio of the titanium halide to the phosphate ester compound is 1: (0.05-5).
2. The solid catalyst component according to claim 1, characterized in that the molar ratio of the titanium halide to the phosphate compound is 1: (0.1-2).
3. The solid catalyst component according to claim 2, characterized in that the molar ratio of the titanium halide to the phosphate compound, expressed as Ti/P, is 1: (0.4-1.5).
4. The solid catalyst component according to any one of claims 1 to 3, characterized in that the particle size of the inorganic oxide is 0.01 to 10 μm; and/or the inorganic oxide is silica and/or alumina.
5. The solid catalyst component according to claim 4, characterized in that the particle size of the inorganic oxide is 0.01-2 μm.
6. The solid catalyst component according to claim 5, characterized in that the particle size of the inorganic oxide is 0.1-1 μm.
7. A process for preparing the solid catalyst component of any one of claims 1 to 6, comprising: in an organic solvent, magnesium halide, titanium halide and a phosphate compound are mixed and reacted to obtain mother liquor, then the mother liquor and an inorganic oxide are mixed to obtain slurry liquid, and finally the slurry liquid is subjected to spray drying to obtain the solid catalyst.
8. The method according to claim 7, wherein the temperature of the reaction is 65-95 ℃, the pressure of the reaction is 0.8-2MPa, and the time of the reaction is 0.5-3 hours; and/or
The temperature during mixing is 10-70 ℃; and/or
The conditions of the spray drying are as follows: the inlet temperature of the spray drying equipment is 80-240 ℃, and the outlet temperature of the spray drying equipment is 60-130 ℃.
9. The method of claim 8, wherein the spray drying conditions are: the inlet temperature of the spray drying equipment is 120-190 ℃, and the outlet temperature of the spray drying equipment is 90-105 ℃.
10. The process according to claim 9, wherein the magnesium halide is selected from the group consisting of magnesium dichloride, magnesium dibromide and magnesium diiodide; and/or the titanium halide is selected from titanium chloride and titanium bromide; and/or the organic solvent is selected from C1-C4Alkyl esters of saturated fatty carboxylic acids, C7-C8Alkyl esters of aromatic carboxylic acids, C2-C6Fatty ethers, C3-C4Cyclic ethers and C3-C6A saturated aliphatic ketone.
11. The method of claim 10, wherein the organic solvent is selected from the group consisting of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.
12. A catalyst for the polymerization of ethylene comprising the reaction product of:
A. a solid catalyst component according to any one of claims 1 to 6 or a solid catalyst component prepared by a process according to any one of claims 7 to 11;
B. an organic aluminum compound with the general formula of AlR'nX3-nWherein R' is hydrogen or C1-C20X is halogen, n is an integer of 1 to 3.
13. Catalyst according to claim 12, characterized in that the ratio between component B and component a is (20-500) in terms of Al/Ti molar ratio: 1.
14. catalyst according to claim 13, characterized in that the ratio between component B and component a is (50-200) in terms of Al/Ti molar ratio: 1.
15. use of the solid catalyst component according to any one of claims 1 to 6 or the solid catalyst component prepared by the process according to any one of claims 7 to 11 or the catalyst according to any one of claims 12 to 14 in the polymerization of ethylene.
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| CN102585057A (en) * | 2011-01-05 | 2012-07-18 | 中国石油化工股份有限公司 | Catalyst for vinyl polymerization reaction |
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| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
| CN101775086B (en) * | 2009-01-09 | 2012-05-23 | 中国石油天然气股份有限公司 | Preparation method for ethylene homopolymer and copolymer |
| CN101838352B (en) * | 2009-03-20 | 2013-11-06 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof |
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| 《聚丙烯酯类内给电子体化合物的合成与催化性能研究》;王月娜;《硕士毕业论文-中国石油大学（北京）》;20081231;全文 * |
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