CN109627363A - A kind of method of one kettle way preparation small particle polyolefin catalyst - Google Patents
A kind of method of one kettle way preparation small particle polyolefin catalyst Download PDFInfo
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- CN109627363A CN109627363A CN201710933845.XA CN201710933845A CN109627363A CN 109627363 A CN109627363 A CN 109627363A CN 201710933845 A CN201710933845 A CN 201710933845A CN 109627363 A CN109627363 A CN 109627363A
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- catalyst
- small particle
- polyolefin catalyst
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- 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
- C08F10/02—Ethene
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of methods of one kettle way preparation small particle polyolefin catalyst, belong to material engineering field.The present invention specifically provides the reaction kettle that a kind of utilization is mounted with high-shear emulsion machine, implements one kettle way and prepares small particle polyolefin catalyst.For technology of the invention for manufacturing polyolefin catalyst particle of the partial size less than 5 microns, process units change is small, at low cost, and it is applied to the polymerization of alkene, obtained polyethylene powders partial size can satisfy user's needs less than 120 microns, enhance the competitiveness of product in market.
Description
Technical field
The present invention relates to a kind of methods of one kettle way preparation small particle polyolefin catalyst, belong to material engineering field.
Background technique
Magnesium ethylate is a kind of raw material for preparing polyolefin catalyst, is widely used in polyethylene and polypropylene catalyst
In preparation.By the catalyst particle size of magnesium ethylate preparation generally in 5~10 microns, polyethylene product granularity produced exists
150~300 microns, it is mainly used for the products such as downstream user manufacture injection molding, extrusion molding.And the smaller polyethylene powders of partial size also have extensively
The wealthy market space, and the catalyst particle size of produced in conventional processes is bigger than normal at present, causes the granularity of polymer powder bigger than normal, it cannot
Meet market needs.Therefore it needs to develop a kind of new catalyst manufacturing technology, can reduce catalyst and polymer powder
Partial size.Inventor has found at work, by magnesium ethylate particulate abrasive at small size particle or emulsion before catalyst preparation,
Foregoing problems can be solved, the catalyst particle size of preparation is small, can be used for producing the polyethylene powders of small particle.
Summary of the invention
Present invention aim to address the deficiencies in the prior art, manufacture catalyst granules of the partial size less than 5 microns, production dress
It is small to set change, it is at low cost；It by the polyethylene powders partial size of this method preparation less than 120 microns, can satisfy user's needs, enhance
The competitiveness of product in market.
Present invention firstly provides a kind of method for preparing small particle polyolefin catalyst, the method is comprised the steps of:
(1) it disperses magnesium ethylate in the linear paraffin of organic solvent C6~C13, transistion metal compound tetrachloro is added
Change titanium (TiCl4), be placed in reaction kettle, at a temperature of 50~180 DEG C stir 2~for 24 hours, obtain emulsion；
(2) emulsion in step (1) is filtered, washed, obtain small particle polyolefin catalyst.
High-shear emulsion machine is installed, magnesium ethylate is 0.1- with compounding for titanium tetrachloride by weight inside the reaction kettle
99.0%.
The present invention also provides a kind of methods for carrying out olefinic polymerization using the small particle polyolefin catalyst: with described small
Partial size polyolefin catalyst is major catalyst, and a kind of co-catalyst is added, makes olefinic polymerization.The co-catalyst be aikyiaiurnirsoxan beta,
One of alkyl aluminum, halogenated alkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt are a variety of.
In existing technology, catalyst particle size obtained is urged at 7 microns or more using what method of the invention was prepared
Agent particle size reduction is to 2-4 microns.
The utility model has the advantages that
(1) present invention is not necessarily to the preparation method of catalyst granules to carry out big transformation to preparing kettle；
(2) present invention reduces reaction raw materials partial size substantially using high-shear emulsion machine, the catalyst pellets not only prepared
Spend small, and catalyst preparation speed greatly improves；
(3) to be reduced to 120 from 200 microns of traditional handicraft using the polyethylene product granularity produced of the present invention micro-
Rice or so, more meets market needs.
Specific embodiment
Embodiment 1:
The magnesium ethylate of 150L octane solvent and 5Kg is added in 300L reaction kettle, speed of agitator 200rpm is warming up to
100 DEG C and at this temperature be added dropwise 21Kg titanium tetrachloride, 4h complete be added dropwise.Then the reaction was continued at 100 DEG C 2h.Reaction knot
Unlatching high-shear emulsion machine grinds 6h after beam, then cools down, standing sedimentation, is washed after suction filtration with 100L hexane, repeated washing 3
It is secondary to get to the supported catalyst prepared.
3.8 microns of catalyst average grain diameter, Ti constituent content is 6.22%, and polymerization catalyst activity is 32.0KgPE/
Gcat, polyethylene powders average grain diameter produced are 125 microns, and heap density is 0.35g/cm3。
Embodiment 2:
150L octane solvent, the magnesium ethylate and 2L tetraethoxysilane of 5Kg, speed of agitator are added in 300L reaction kettle
For 200rpm, it is warming up to 100 DEG C and the titanium tetrachloride of 21Kg is added dropwise at this temperature, 4h completes to be added dropwise.Then at 100 DEG C after
Continuous reaction 2h.Unlatching high-shear emulsion machine grinds 4h after reaction, then cools down, standing sedimentation, uses 100L hexane after suction filtration
Washing washes repeatedly 3 times to get to the supported catalyst prepared.
3.9 microns of catalyst average grain diameter, Ti constituent content is 4.08%, and polymerization catalyst activity is 27.4KgPE/
Gcat, polyethylene powders average grain diameter produced are 123 microns, and heap density is 0.36g/cm3。
Comparative example 1:
The magnesium ethylate of 150L octane solvent and 5Kg is added in 300L reaction kettle, speed of agitator 200rpm is warming up to
After 100 DEG C, the titanium tetrachloride of 21Kg is then added dropwise at this temperature, 4h completes to be added dropwise.Then the reaction was continued at 100 DEG C 2h.
Cool down after reaction, standing sedimentation is washed with 100L hexane after suction filtration, is urged to get to the load prepared for repeated washing 3 times
Agent.
7.6 microns of catalyst average grain diameter, Ti constituent content is 6.25%, and polymerization catalyst activity is 30.4KgPE/
Gcat, polyethylene powders average grain diameter produced are 225 microns, and heap density is 0.35g/cm3。
Comparative example 2:
150L octane solvent, the magnesium ethylate and 2L tetraethoxysilane of 5Kg, speed of agitator are added in 300L reaction kettle
For 200rpm, 100 DEG C are warming up to, the titanium tetrachloride of 21Kg is then added dropwise at this temperature, 4h completes to be added dropwise.Then at 100 DEG C
Lower the reaction was continued 2h.Cool down after reaction, standing sedimentation is washed with 100L hexane after suction filtration, washes repeatedly 3 times to get arriving
The supported catalyst prepared.
8.2 microns of catalyst average grain diameter, Ti constituent content is 3.95%, and polymerization catalyst activity is 28.5KgPE/
Gcat, polyethylene powders average grain diameter produced are 260 microns, and heap density is 0.35g/cm3。
Claims (5)
1. a kind of method of one kettle way preparation small particle polyolefin catalyst, which is characterized in that the method comprises the steps of:
(1) it disperses magnesium ethylate in the linear paraffin of organic solvent C6~C13, four chlorination of transistion metal compound is added
Titanium is placed in reaction kettle, at a temperature of 50~180 DEG C stir 2~for 24 hours, obtain emulsion；
(2) emulsion in step (1) is filtered, washed, obtain small particle polyolefin catalyst.
2. the method according to claim 1, wherein installing high-shear emulsion machine inside the reaction kettle.
3. the method according to claim 1, wherein magnesium ethylate is by weight with compounding for titanium tetrachloride
0.1-99.0%.
4. a kind of method for carrying out olefinic polymerization using the small particle polyolefin catalyst, which is characterized in that with the granule
Diameter polyolefin catalyst is major catalyst, and a kind of co-catalyst is added, makes olefinic polymerization.
5. according to the method described in claim 4, it is characterized in that, the co-catalyst is aikyiaiurnirsoxan beta, alkyl aluminum, halogenated alkyl
One of aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt are a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710933845.XA CN109627363A (en) | 2017-10-09 | 2017-10-09 | A kind of method of one kettle way preparation small particle polyolefin catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710933845.XA CN109627363A (en) | 2017-10-09 | 2017-10-09 | A kind of method of one kettle way preparation small particle polyolefin catalyst |
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| CN109627363A true CN109627363A (en) | 2019-04-16 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60262802A (en) * | 1984-06-11 | 1985-12-26 | Toyo Soda Mfg Co Ltd | Production of polyolefin |
| CN1656131A (en) * | 2002-05-29 | 2005-08-17 | 巴塞尔聚烯烃有限公司 | Method for producing a poly-1olefin in the presence of a ziegler catalyst |
| CN1986575A (en) * | 2005-12-22 | 2007-06-27 | 北京燕化高新催化剂有限公司 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
| CN101659715A (en) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | Preparation method of high-activity high-efficiency polyethylene catalyst |
| CN101712732A (en) * | 2009-12-02 | 2010-05-26 | 营口鼎际得石化有限公司 | Method for preparing spherical catalyst for propylene polymerization |
-
2017
- 2017-10-09 CN CN201710933845.XA patent/CN109627363A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60262802A (en) * | 1984-06-11 | 1985-12-26 | Toyo Soda Mfg Co Ltd | Production of polyolefin |
| CN1656131A (en) * | 2002-05-29 | 2005-08-17 | 巴塞尔聚烯烃有限公司 | Method for producing a poly-1olefin in the presence of a ziegler catalyst |
| CN1986575A (en) * | 2005-12-22 | 2007-06-27 | 北京燕化高新催化剂有限公司 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
| CN101659715A (en) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | Preparation method of high-activity high-efficiency polyethylene catalyst |
| CN101712732A (en) * | 2009-12-02 | 2010-05-26 | 营口鼎际得石化有限公司 | Method for preparing spherical catalyst for propylene polymerization |
Non-Patent Citations (2)
| Title |
|---|
| 刘俊泉 等: "《石油化工应用技术》", 31 May 2001, 中国石化出版社 * |
| 蒋智清 等: "《物理化学实验指导》", 3 March 2014, 厦门大学出版社 * |
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Application publication date: 20190416 |