CN102050898B - Method for pretreating polyethylene catalyst - Google Patents
Method for pretreating polyethylene catalyst Download PDFInfo
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- CN102050898B CN102050898B CN2009102366651A CN200910236665A CN102050898B CN 102050898 B CN102050898 B CN 102050898B CN 2009102366651 A CN2009102366651 A CN 2009102366651A CN 200910236665 A CN200910236665 A CN 200910236665A CN 102050898 B CN102050898 B CN 102050898B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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 provides a method for pretreating a polyethylene catalyst. In the method, an active ingredient of the catalyst is contacted with an active agent for pretreatment by an intermittent method before polymerization reaction is performed, so that the performance of the active ingredient of the catalyst is improved, the active ingredient of the catalyst has higher activity and copolymerization performance than the unpretreated active ingredient of the catalyst, and the content of produced resin fine powder is lower; and the pretreated catalyst can be stored at room temperature for a long time and has unchanged performance.
Description
Technical field
The present invention relates to a kind of pretreated method of polyethylene catalysts, belong to field of olefin polymerisation.
Technical background
The catalyzer that uses on the gas-phase polyethylene device can according to the difference of transition metal in its active constituent, be divided into Ti series catalysts, Cr series catalysts.Wherein the Ti series catalysts is suitable for the production of LLDPE product, and the Cr series catalysts is mainly used in the production of HDPE product.Catalyst activity component normally directly joins in polymerization reactor.The method that adds can adopt dry-coal feeding, can also adopt the form charging of the slurries that are made into by inert solvent.Compare with the charging of dry powder solid catalyst, adopt the catalyzer of slurry feeding that higher polymerization activity can be arranged, but the higher space-time yield of realization response device; And the appliance arrangement of the existing dry-coal feeding that generally uses of the device of catalyst slurry feeding is simple, construction investment is low, running is reliable, has become the mainstream technology of gas-phase polythene apparatus catalyst charge.
The online prereduction technology of a kind of catalyzer is disclosed in Chinese patent CN1484655A, adopt the slurry form charging, the catalyst activity component successively in the reactor that two bands stir with a certain proportion of tri-n-hexyl aluminum and aluminium diethyl monochloride reaction after, then enter fluidized-bed reactor and carry out polyreaction.The method is incorporated into the multiple aluminum alkyls that has danger on full scale plant, processes through complicated process procedure, just makes catalyzer that performance is preferably arranged, thereby on industrial application, investment is high, and difficulty is large, difficult enforcement.
The invention provides a kind of pretreated method of polyethylene catalysts, avoided using online prereduction stirring tank, saved the online reaction of the activator such as tri-n-hexyl aluminum and aluminium diethyl monochloride and catalyst activity component.The performance of catalyzer can utilize simple tractable method to transfer to optimum in Catalyst Production enterprise, avoids on device non-specialised staff's operation to cause the reduction of catalyst performance.
Summary of the invention
The invention provides a kind of pretreated method of polyethylene catalysts, before carrying out polyreaction, adopt method intermittently, catalyst activity component is contacted with activator, carry out pre-treatment, make the performance of catalyst activity component be improved, without pretreated catalyst activity component, higher activity is arranged, better copolymerization performance, the resin fine powder content of production is still less; And pretreated catalyzer can at room temperature be preserved for a long time, and its performance is constant.
The catalyst activity component that uses in the present invention can be by Chinese patent CN1405191, CN1463991, CN1463991A, CN1463992, CN1213082C, the described method preparation of CN101134790.
The pretreatment process of catalyzer of the present invention is to carry out in the tank reactor that can settle whipping device, at nitrogen or helium or neon or argon gas etc., catalyst component is to carry out under the gas shield of inertia.The purpose that stirs is to obtain good liquid-solid mixed effect.Thereby all kinds of technique means such as oblique oar of knowing altogether in the industry, ribbon oar, outer circulation all can be used for the present invention.Tank reactor can have jacket water (J.W.) to carry out temperature control, also can not have.This tank reactor can arrange the Level Detection facility of the various types such as glass, pressure reduction, magnetic float, ultrasonic wave, electric capacity, also can not establish the Level Detection facility.
The activator that uses in the present invention is nonrestrictive, comprise aikyiaiurnirsoxan beta, aluminum alkyls, ionization activator (can be neutrality or ion) and general type promotor, preferred alkyl aluminium activator comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride etc.The present invention preferably uses tri-n-hexyl aluminum and/or aluminium diethyl monochloride as activator.Catalyst activity component of the present invention randomly adds the pre-treatment still with form of suspension or solution form.The solvent of formulated suspension is randomly for containing 3～60 carbon atoms, the alkane of preferred 5～20 carbon atoms, and naphthenic hydrocarbon, aromatic hydrocarbon, or for polymerization being mineral oil or the silicone oil of inertia.
The add-on of pre-treatment of the present invention activator used is by the ratio-dependent of the tetrahydrofuran (THF) in activator and catalyst activity component.Can adopt a kind of activator also can adopt two or more activators to carry out catalyst pretreatment, preferred two kinds of different activators carry out catalyst pretreatment.In formula, in activator and catalyst activity component, the molar ratio range of tetrahydrofuran (THF) can be between 0.01～1, preferably between 0.01～0.5.The time of catalyst pretreatment in the present invention, when using a kind of activator to carry out catalyst pretreatment, pretreatment time can be 1～10 hour, preferred 1～5 hour, and more preferably 2～4 hours; When using two kinds of activators to carry out catalyst pretreatment, the first activator pretreatment time can be 1～10 hour, preferred 1～5 hour, and more preferably 2～4 hours.The second activator pretreatment time can be 1～5 hour, preferred 1～3 hour.Two kinds of activators also can add simultaneously, select the identical time to carry out pre-treatment.
The present invention can be used for polyreaction immediately through pretreated catalyzer, also can preserve under certain condition, and the shelf time can be greater than 360 days, and is constant in this retention period inner catalyst property retention.Storage temperature is-30～100 ℃, preferred-10～50 ℃, and in being the gas atmosphere of inertia to catalyst component, nitrogen or helium or neon or argon gas etc. seal up for safekeeping, preferably use nitrogen.
To achieve these goals, the technical scheme taked of the present invention is: the preprocessing process of catalyzer is completed under nitrogen protection.Pre-treatment step: the quantitative catalyzer dry powder that 1. will measure adds in the container that contains hexane of band stirring.This container is furnished with agitator, reaches later pretreatment stage before adding catalyzer, and the even mixing of material in container is kept in this stirring; 2. after calculating, a certain amount of activator of accurate-metering adds the fs pretreatment reaction that carries out catalyzer in aforementioned container, and the time is 2～4 hours, preferred 2.5 hours; 3. after calculating, the another kind of activator of accurate-metering adds the subordinate phase pretreatment reaction that carries out catalyzer in aforementioned container, 0.5～2 hour time, preferred 1.0 hours.After the time, the off-line preprocessing process of catalyzer namely comes to an end.The catalyzer of completing the prereduction processing is transferred to the slurry catalyst agent feeding device, be used for polyreaction.Polymeric kettle is a gas-phase polythene fluidized-bed, and temperature of reaction is 50～90 ℃, preferred 85～88 ℃; Reaction pressure is 1.8～2.0MPa; Comonomer is alpha-olefines; Ethylene partial pressure 0.5～0.8MPa; Reaction time is 2～3 hours;
Embodiment 1
Carry out on a gas-phase polythene pilot plant, its designed capacity is 5kg/h, and the working pressure of polymerization reactor is 1.90MPa, and temperature of reaction is 86 ℃.Produce a kind of ethylene/butylene-1 multipolymer (density 0.918g/cm3; Melt flow index 2.0g/10min).Ethylene partial pressure is 0.76MPa, and reaction time is 2.5 hours, and it is 5.5kg that bed is held the material amount.The catalyzer that uses is for pressing the Ziegler-Natta catalyst of Chinese patent CN1213082C preparation, and promotor is triethyl aluminum.Adding two kinds of activators to carry out prereduction this catalyzer processes, namely first add tri-n-hexyl aluminum to carry out the prereduction reaction of catalyzer fs, add-on is tetrahydrofuran (THF) in tri-n-hexyl aluminum/catalyzer=0.20 (mol/mol), and pretreatment time is 2.5 hours; Add subsequently aluminium diethyl monochloride to carry out catalyzer subordinate phase prereduction reaction, add-on is tetrahydrofuran (THF) in aluminium diethyl monochloride/catalyzer=0.45 (mol/mol), and pretreatment time is 1.0 hours.After the time, catalyzer off-line preprocessing process namely comes to an end, and will complete pretreated catalyzer and transfer to the slurry catalyst agent feeding device, is used for polyreaction.Catalyst performance and the resin property of producing see Table 1 and 2.
Embodiment 2
Testing apparatus and reaction conditions are with embodiment 1, institute's difference is that catalyzer uses a kind of activator to carry out pre-treatment, namely only add tri-n-hexyl aluminum to carry out catalyst pretreatment, add-on is tetrahydrofuran (THF) in tri-n-hexyl aluminum/catalyzer=0.20 (mol/mol), and pretreatment time is 2.5 hours.Catalyst performance and the resin property of producing the results are shown in Table 1 and 2.
Embodiment 3
Testing apparatus and reaction conditions are with embodiment 1, institute's difference is that catalyzer uses another kind of activator to carry out pre-treatment, namely only add aluminium diethyl monochloride to carry out catalyst pretreatment, add-on is tetrahydrofuran (THF) in aluminium diethyl monochloride/catalyzer=0.20 (mol/mol), and pretreatment time is 1.0 hours.Catalyst performance and the resin property of producing the results are shown in Table 1 and 2.
Comparative Examples 1
Testing apparatus and reaction conditions are with embodiment 1, and institute's difference is that catalyzer directly is made into slurries without the activator pre-treatment and carries out polyreaction.Catalyst performance and the resin property of producing the results are shown in Table 1 and 2.
Can find out that from table than increasing without the pretreatment catalyst activity, under the different pretreatments formula, the hydrogen regulation performance of catalyzer is basically identical through after catalyst preconditioning process processing of the present invention.Pretreatment condition also there is no any impact to the copolymerization performance of catalyzer.Although the pre-treatment formula has carried out large variation, under same butene-1 concentration, still can obtain the product of same density.
Table 2 data show have the resin fine powder of pretreated Catalyst Production content than without pretreated will be still less.
Embodiment 4
Testing apparatus is identical with embodiment 1 with reaction conditions, and catalyst preconditioning process is identical with embodiment 1, different be that the catalyzer that uses is the Ziegler-Natta catalyst by Chinese patent CN1463991A preparation.Catalyst performance and the resin property of producing the results are shown in Table 3 and 4.
Embodiment 5
Testing apparatus is identical with embodiment 1 with reaction conditions, and catalyst preconditioning process is identical with embodiment 2, different be that the catalyzer that uses is the Ziegler-Natta catalyst by Chinese patent CN1463991A preparation.Catalyst performance and the resin property of producing the results are shown in Table 3 and 4.
Embodiment 6
Testing apparatus is identical with embodiment 1 with reaction conditions, and catalyst preconditioning process is identical with embodiment 3, different be that the catalyzer that uses is the Ziegler-Natta catalyst by Chinese patent CN1463991A preparation.Catalyst performance and the resin property of producing the results are shown in Table 3 and 4.
Comparative Examples 2
Testing apparatus is identical with embodiment 1 with reaction conditions, and catalyzer directly is made into slurries without the activator pre-treatment and carries out polyreaction.Different be that the catalyzer that uses is the Ziegler-Natta catalyst by Chinese patent CN1463991A preparation.Catalyst performance and the resin property of producing the results are shown in Table 3 and 4.
In table 3, data show through pre-treatment of the present invention, and catalyst activity is than high without pre-treatment, and along with the increase of activator level, the content that reaches butylene in the required gas phase composition of same resin density reduces gradually.The copolymerized ability that catalyzer is described is that the increase with the total consumption of activator strengthens, and continues to improve the activator total amount, and the trend that the copolymerized ability of catalyzer improves dies down.Without pretreated catalyzer, its copolymerization performance is the poorest.This shows, activator plays very important effect to the performance of slurry catalyst copolymerized ability.The variation of pre-treatment formula, little on the hydrogen regulation performance impact of catalyzer, in the scope of test, should say that hydrogen regulation performance is on all four.
Table 4 data show have resin fine powder content that pretreatment catalyst produces than without pretreated will be still less.
Embodiment 7
Testing apparatus is identical with embodiment 1 with reaction conditions, and the catalyzer of use is for pressing the Ziegler-Natta catalyst of Chinese patent CN1213082C preparation, and catalyst preconditioning process is also identical with embodiment 1.Pretreated catalyzer is stored in respectively the Brown Glass Brown glass bottles and jars only interior (lucifuge) of a plurality of nitrogen envelopes, at room temperature stores.Respectively after the same day, 7 days of catalyst preparation, after 47, after 150 days, 360 days laggard promoting the circulation of qi phase-polymerization pilot evaluations.The catalyzer of different retention periods is transferred to a kind of slurries or liquid catalyst feeding device (Chinese patent CN1927440), be used for polyreaction.Catalyst performance and the resin property of producing the results are shown in Table 5.
In table 5, data show that in shelf-time about 360 days, the polymerization of catalyzer is basically identical.Under similarity condition, activity, density, melting index are suitable.Explanation can adopt off-line pre-treatment pattern to carry out directly using on device after pre-treatment for catalyzer, and the retention period of the pretreated catalyzer of off-line is not less than 360 days.
Table 1 different off-line pretreatment catalyst formula with without the pre-treatment correlation data
Table 2 off-line pretreatment catalyst with without pre-treatment size distribution correlation data
Table 3 different off-line pretreatment catalyst formula with without the pre-treatment correlation data
Table 4 off-line pretreatment catalyst with without pre-treatment size distribution correlation data
The impact of the different retention periods of table 5 off-line pre-treatment on catalyst performance
Claims (7)
1. pretreated method of polyethylene catalysts, it is characterized in that, before carrying out polyreaction, adopt method intermittently, catalyst activity component is contacted with activator, carry out pre-treatment, make the performance of catalyst activity component be improved, without pretreated catalyst activity component, higher activity is arranged, better copolymerization performance, the resin fine powder content of production is still less; And pretreated catalyzer can at room temperature be preserved for a long time, and its performance is constant;
Described activator is tri-n-hexyl aluminum and/or aluminium diethyl monochloride alkylaluminium cpd;
Pre-treatment step: first add tri-n-hexyl aluminum to carry out the prereduction reaction of catalyzer fs, add-on is tetrahydrofuran (THF) in tri-n-hexyl aluminum/catalyzer=0.20 (mol/mol), and pretreatment time is 2.5 hours; Add subsequently aluminium diethyl monochloride to carry out catalyzer subordinate phase prereduction reaction, add-on is tetrahydrofuran (THF) in aluminium diethyl monochloride/catalyzer=0.45 (mol/mol), and pretreatment time is 1.0 hours.
2. the pretreated method of polyethylene catalysts according to claim 1, is characterized in that, described catalyst activity component is CN1405191, CN1463991, CN1463991A, CN1463992, method preparation described in CN1213082C, CN101134790.
3. the pretreated method of polyethylene catalysts according to claim 1; it is characterized in that, described method is to carry out nitrogen or helium or neon or argon gas are the gas shield of inertia to catalyst component under in the tank reactor of whipping device at one.
4. the pretreated method of polyethylene catalysts according to claim 1, it is characterized in that, catalyst activity component randomly adds the pre-treatment still with form of suspension or solution form, the solvent of formulated suspension is randomly the alkane of 5～20 carbon atoms, naphthenic hydrocarbon, aromatic hydrocarbon, or for polymerization being mineral oil or the silicone oil of inertia.
5. the pretreated method of polyethylene catalysts according to claim 1, is characterized in that, catalyst activity component after pretreatment randomly is directly used in vinyl polymerization or stores.
6. want the 5 pretreated methods of described polyethylene catalysts according to right, it is characterized in that, catalyst activity component period of storage scope after pretreatment is 1～360 day, storage requirement is at-30～100 ℃, and nitrogen or helium or neon or argon gas are catalyst component in the gas atmosphere of inertia to be sealed up for safekeeping.
7. the pretreated method of polyethylene catalysts according to claim 6, is characterized in that, storage requirement is at-10～50 ℃.
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| CN2009102366651A CN102050898B (en) | 2009-10-27 | 2009-10-27 | Method for pretreating polyethylene catalyst |
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| CN2009102366651A CN102050898B (en) | 2009-10-27 | 2009-10-27 | Method for pretreating polyethylene catalyst |
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| CN102050898B true CN102050898B (en) | 2013-11-06 |
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| WO2018147931A1 (en) * | 2017-02-07 | 2018-08-16 | Exxonmobil Chemical Patents Inc. | Processes for reducing the loss of catalyst activity of a ziegler-natta catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405191A (en) * | 2001-09-19 | 2003-03-26 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof |
| CN1463991A (en) * | 2002-06-06 | 2003-12-31 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization and catalyst therefor |
| CN1490342A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | Gas phase ethene polymerization catalyst component and catalyst thereof |
| CN1213082C (en) * | 2002-10-31 | 2005-08-03 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405191A (en) * | 2001-09-19 | 2003-03-26 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof |
| CN1463991A (en) * | 2002-06-06 | 2003-12-31 | 中国石油化工股份有限公司 | Solid catalyst component for ethylene polymerization and catalyst therefor |
| CN1490342A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | Gas phase ethene polymerization catalyst component and catalyst thereof |
| CN1213082C (en) * | 2002-10-31 | 2005-08-03 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
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