CN100523017C - Preparing process of slurry catalyst for gaseous ethylene polymerization - Google Patents
Preparing process of slurry catalyst for gaseous ethylene polymerization Download PDFInfo
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- CN100523017C CN100523017C CNB2005101319693A CN200510131969A CN100523017C CN 100523017 C CN100523017 C CN 100523017C CN B2005101319693 A CNB2005101319693 A CN B2005101319693A CN 200510131969 A CN200510131969 A CN 200510131969A CN 100523017 C CN100523017 C CN 100523017C
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Abstract
The present invention is preparation process of slurry catalyst for gaseous ethylene polymerization. The preparation process of the slurry catalyst includes the following steps: modifying magnesium chloride to raise the homogeneity of components, and high speed shearing and pelletizing with an emulsifying reactor to obtain the catalyst. The catalyst includes one solid component containing active Mg and Ti, at least one electron donor and at least one activator, and is supported on nanometer inert silica gel. It has high polymerization activity, and is suitable for Unipol gaseous polymerization.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the slurry catalyst of olefin polymetiation process, particularly the preparation method of the slurry catalyst of gaseous ethylene polymerization technology.
Technical background
Ethene gas-phase polymerization technology, the most typical with the Unipol gas fluidized-bed process, catalyst system therefor is that active ingredient, macrobead silica gel are carrier with titanium magnesium normally, and the former is carried on to make on the latter forms, catalyst form is decided by the form of silica gel particle fully, wherein, concern the closest with the particle diameter of used silica gel and the polymerization of catalyzer.For example: US4,302,565, US4,302, the 565 disclosed catalyzer that are used for gas-phase fluidized bed polymerization process.The median size of its used silica gel is generally 40～150 microns.
This catalyst preparation process is simple relatively, but used silica gel particle median size is bigger, simultaneously, in order to improve the dispersion effect of titanium-magnesium catalyst active ingredient on silica gel particle, reaches the purpose that improves polymerization activity, must use a large amount of silica gel.Therefore the polymerization catalyst activity of the type is relatively low, and form and size distribution are also not fully up to expectations, and it is many unfavorable that the ordinary production of full scale plant is brought.
Summary of the invention
At the problems referred to above,, improve the polymerization catalyst activity for improving the final form and the size distribution of catalyzer.The present invention is set out by magnesium chloride, the catalyzer synthesis route is carried out bold innovation, at first magnesium chloride is carried out modification, then introduce inertia nano level silica gel, with the active ingredient even blend, realize the high dispersing of active ingredient, adopt novel granules of catalyst forming technique simultaneously, it is the technology of emulsion reactor high speed shear granulating and forming, make that the dispersion of catalyst activity component is even more ideal, the gained catalyzer is improved at aspects such as polymerization activity, particle size distribution, thereby has improved the bulk polymerization performance of catalyzer.
To describe in detail below according to a kind of slurry catalyst preparation method who can be used for ethene gas-phase polymerization technology of the present invention.
Step a. open to stir under nitrogen protection, in reactor, add successively 10～50m methylene dichloride, with the magnesium chloride mol ratio be properties-correcting agent, the 1.2g magnesium chloride of 0.01～2.0:1, reacted under the room temperature 0.5～3 hour.
Wherein, described properties-correcting agent is that general formula is Ti (OR)
4Alkoxy titanium compound or C
2～C
8Organic alcohol, wherein R is the alkyl of 2～6 carbonatomss.
Step b. adds 30～70ml tetrahydrofuran (THF), 0.3～0.7ml titanium tetrachloride successively in reactor, then slowly be warming up to 50～70 ℃, preferred 60 ℃; In 0.5～8 hour reaction times, preferred 1～4 hour, most preferably 2 hours, obtain magnesium titanium active component solution.
Step c is with 2.0～8.0g inertia nano level silica gel (Cabot Corporation TS-610,0.2～0.3 micron of median size) joins in the magnesium titanium active component solution, preferred inertia nano level silica gel consumption is 4.0～6.0g, keeps 50～70 ℃ of temperature, preferred 60 ℃; Stirred 0.5～5 hour, preferred 1～3 hour, most preferably 2 hours.
Steps d. above-mentioned solution is carried out the high speed shear moulding with emulsion reactor, and the reactor of filter screen, rotating speed 10000～28000rpm are equipped with in the terminal connection one of emulsion reactor, preferred 14000～20000rpm, keep 65～85 ℃ of still temperature, preferred 70 ℃～80 ℃, obtain ingredient of solid catalyst.
Step e. mixes the ingredient of solid catalyst of drying with the purified white oil, the white oil add-on is 2.0～4.0ml/g. solid catalyst.Then add alkylaluminium cpd, the content of tetrahydrofuran mol ratio is 0.2～2.0:1 in consumption and the catalyzer, and preferred 0.4～1.0:1 stirred preferred 2 hours 1～3 hour; 0～50 ℃ of temperature of reaction, makes the ethene gas-phase polymerization slurry catalyst by preferred 20～30 ℃.
Wherein, described aluminum alkyls is triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3In one or more.
The slurry catalyst that can be used for gaseous ethylene polymerization technology that preparation method provided by the invention makes.It comprises a kind of magnesium titanium active solid component, at least a electron donor and at least a activator of containing, and is carried on the inertia nano level silica gel; At first magnesium chloride is carried out modification to improve the homogeneity of active constituent in this catalyst preparation process, adopt the method for emulsion reactor high speed shear granulating and forming simultaneously, the granules of catalyst size-grade distribution of gained is concentrated, has high polymerization activity, fine powder content is lower, is suitable for the Unipol gas-phase polymerization process of catalyzer with the charging of slurries form.
When the resulting catalyzer of the present invention was used for gaseous ethylene polymerization, Yin Ben can directly join in the reactor as the slurries form.In reactor, need add activator in addition and activate, to carry out final ethylene polymerization.The activator of selecting for use is an aluminum alkyls, is preferably triethyl aluminum or triisobutyl aluminium or the mixture of the two.
The polymerization catalyst evaluation result that following table makes for this method.From the result, the polymerization catalyst excellent performance more has remarkable advantages with respect to gaseous ethylene polymerization silica gel load type catalyzer (activity generally has only 5000～8000 times).
Annotate: slurry polymerization, 85 ℃, 2.0hr, H
2/ C
2=0.28MPa/0.75MPa
A: this catalyzer; B: traditional ethene gas-phase polymerization catalyzer
Embodiment
Embodiment 1
(Preparation of catalysts)
Under nitrogen protection, open and stir, in reactor, add 30ml methylene dichloride, 0.64ml tetrabutyl titanate, 1.2g magnesium chloride successively, reaction is 1 hour under the room temperature.
Add 50ml tetrahydrofuran (THF), 0.5ml titanium tetrachloride successively in reactor, then slowly be warming up to 60 ℃, isothermal reaction 2 hours obtains magnesium titanium active component solution.
5.0g inertia nano level silica gel (Cabot Corporation TS-610,0.2～0.3 micron of median size) is joined in the magnesium titanium active component solution, keep 60 ℃ of temperature, stirred 2 hours.
Above-mentioned solution is carried out the high speed shear moulding with emulsion reactor, and the reactor of filter screen is equipped with in the terminal connection one of emulsion reactor, and rotating speed 17000rpm keeps 73 ℃ of still temperature, obtains ingredient of solid catalyst.THF in the ingredient of solid catalyst that obtains (weight) 12.5%, Ti (weight) 1.78%.
The ingredient of solid catalyst of drying is mixed with the refining white oil of 30ml, and then adding 12ml concentration is the aluminium diethyl monochloride hexane solution of 2.2mol/L, and 25 ℃ were stirred 2.0 hours, and made the ethene gas-phase polymerization slurry catalyst.
(polymerization)
Nitrogen pump drainage three times of 2L stainless steel autoclave are pressed into the 0.5L hexane then in polymeric kettle, add certain density triethyl aluminum hexane solution.Open stirring then and add a certain amount of catalyzer, add the 1L hexane at last.Begin to heat up, and feed a certain amount of hydrogen and ethene, hydrogen alkene compares 0.28/0.75Mpa.By the add-on of solenoid control ethene, it is constant that the stagnation pressure of reaction system is kept, and by temperature controller controlled chilling discharge, makes to be aggregated in 85 ℃ of reactions two hours down, closes ethene then, stopped reaction.Cooling also bleeds off the still internal pressure, takes out polymerisate and suction filtration drying.The dry good product of weighing calculates catalyst activity, in gPE/gcat. measure bulk density and size-grade distribution simultaneously.Polymerization catalyst the results are shown in Table 1.
Embodiment 2
Prepare catalyst component with the method identical, but when the preparation catalyst component, tetrabutyl titanate changes the tetraethyl titanate of equimolar amount into embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 11.6%, Ti (weight) 1.56%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 3
Prepare catalyst component with the method identical, but when the preparation catalyst component, tetrabutyl titanate changes the propyl carbinol of equimolar amount into embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 12.6%, Ti (weight) 1.81%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 4
Prepare catalyst component with the method identical, but when the preparation catalyst component, the consumption of tetrabutyl titanate reduces by half with embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 10.9%, Ti (weight) 1.50%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 5
Prepare catalyst component with the method identical, but when the preparation catalyst component, the consumption of tetrabutyl titanate doubles with embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 12.9%, Ti (weight) 1.83%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 6
Prepare catalyst component with the method identical, but when the preparation catalyst component, the emulsion reactor rotating speed transfers to 14000rpm by 17000rpm with embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 11.4%, Ti (weight) 1.52%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 7
Prepare catalyst component with the method identical, but when the preparation catalyst component, the emulsion reactor rotating speed transfers to 20000rpm by 17000rpm with embodiment 1.THF in the ingredient of solid catalyst that obtains (weight) 13.0%, Ti (weight) 1.84%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 8
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel consumption changes 4g into by 5g with embodiment 1, add silica gel simultaneously after churning time changed 1 hour into by 2 hours.THF in the ingredient of solid catalyst that obtains (weight) 11.6%, Ti (weight) 1.92%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 9
Prepare catalyst component with the method identical with embodiment 1, but when preparing final slurry catalyst, alkyl aluminum solutions changes the triethyl aluminum hexane solution (1.0mol/L) of equimolar amount into by the aluminium diethyl monochloride hexane solution, and temperature of reaction changes 0 ℃ into by 25 ℃ simultaneously.THF in the ingredient of solid catalyst that obtains (weight) 12.5%, Ti (weight) 1.78%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Embodiment 10
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, alkyl aluminum solutions changes aluminium diethyl monochloride and triethyl aluminum hexane solution into by the aluminium diethyl monochloride hexane solution, and amount of substance remains unchanged, and aluminium diethyl monochloride and triethyl aluminium solution respectively are half.Reaction times was respectively 1 hour, and order is that aluminium diethyl monochloride solution is preceding.THF in the ingredient of solid catalyst that obtains (weight) 12.5%, Ti (weight) 1.78%.Carry out polymerization with final slurry catalyst component with embodiment 1 identical method.Its polymerization result is listed in table 1.
Table 1
Annotate: slurry polymerization, 85 ℃, 2.0hr, H
2/ C
2=0.28MPa/0.75MPa
Claims (5)
1. preparation method who is used for the slurry catalyst of gaseous ethylene polymerization technology may further comprise the steps:
Step a. open to stir under nitrogen protection, in reactor, add successively 10～50ml methylene dichloride, with the magnesium chloride mol ratio be properties-correcting agent, the 1.2g magnesium chloride of 0.01～2.0:1, reacted under the room temperature 0.5～3 hour;
Wherein, properties-correcting agent is that general formula is Ti (OR)
4Alkoxy titanium compound or C
2～C
8Organic alcohol, wherein R is the alkyl of 2～6 carbonatomss;
Step b. adds 30～70ml tetrahydrofuran (THF) successively in reactor, 0.3～0.7ml titanium tetrachloride then slowly is warming up to 50～70 ℃, in 0.5～8 hour reaction times, obtains magnesium titanium active component solution;
Step c joins the inertia nano level silica gel of 0.2～0.3 micron of 2.0～8.0g median size in the magnesium titanium active component solution, keeps 50～70 ℃ of temperature, stirs 0.5～5 hour;
Steps d. above-mentioned solution is carried out the high speed shear moulding with emulsion reactor, and the reactor of filter screen is equipped with in the terminal connection one of emulsion reactor, and rotating speed 10000～28000rpm keeps 65～85 ℃ of still temperature, obtains ingredient of solid catalyst;
Step e. mixes the ingredient of solid catalyst of drying with the purified white oil, the white oil add-on is 2.0～4.0ml/g. solid catalyst, then add alkylaluminium cpd, the content of tetrahydrofuran mol ratio is 0.2～2.0:1 in consumption and the catalyzer, stirred 1～3 hour, 0～50 ℃ of temperature makes the gaseous ethylene polymerization slurry catalyst.
2. Preparation of catalysts method according to claim 1, wherein the silica gel consumption described in the step c is 4.0～6.0g; 60 ℃ of temperature of reaction, 1～3 hour reaction times.
3. Preparation of catalysts method according to claim 1, wherein 2 hours step c reaction times.
4. Preparation of catalysts method according to claim 1, wherein the rotating speed of emulsion reactor described in the steps d is 14000～20000rpm; Temperature is 70 ℃～80 ℃.
5. Preparation of catalysts method according to claim 1, wherein the aluminum alkyls described in the step e is triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3In one or more; Tetrahydrofuran (THF) amount mol ratio 0.4～1.0:1 in alkylaluminium cpd consumption and the catalyzer; 2 hours reaction times; 20～30 ℃ of temperature of reaction.
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|---|---|---|---|
| CNB2005101319693A CN100523017C (en) | 2005-12-22 | 2005-12-22 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
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|---|---|---|---|
| CNB2005101319693A CN100523017C (en) | 2005-12-22 | 2005-12-22 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
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| CN100523017C true CN100523017C (en) | 2009-08-05 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399325B (en) * | 2010-09-16 | 2013-06-05 | 中国石油化工股份有限公司 | Spherical catalyst component with narrow particle size distribution for olefin polymerization, catalyst thereof and application thereof |
| CN103509140B (en) * | 2012-06-27 | 2016-04-13 | 中国石油化工股份有限公司 | The preparation method of ultrahigh molecular weight polyethylene(UHMWPE) catalyst for synthesizing |
| CN104418960B (en) * | 2013-09-03 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of catalytic component and catalyst and its preparation method for ethylene polymerization |
| CN104974282B (en) * | 2014-04-11 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of catalytic component for ethylene polymerization, preparation method and catalyst |
| CN107759718B (en) * | 2016-08-22 | 2020-04-21 | 辽宁鼎际得石化股份有限公司 | Catalyst for ethylene homopolymerization or copolymerization and preparation method thereof |
| CN109627363A (en) * | 2017-10-09 | 2019-04-16 | 中国石化扬子石油化工有限公司 | A kind of method of one kettle way preparation small particle polyolefin catalyst |
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Non-Patent Citations (3)
| Title |
|---|
| US20020120078A 1 2002.08.29 |
| 球形乙烯聚合催化剂的制备及性能. 李维贞等.石化技术，第11卷第2期. 2004 |
| 球形乙烯聚合催化剂的制备及性能. 李维贞等.石化技术，第11卷第2期. 2004 * |
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