CN100422223C - Ball shape catalyst for ethylene polymerization and preparation process thereof - Google Patents
Ball shape catalyst for ethylene polymerization and preparation process thereof Download PDFInfo
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- CN100422223C CN100422223C CNB2005100690760A CN200510069076A CN100422223C CN 100422223 C CN100422223 C CN 100422223C CN B2005100690760 A CNB2005100690760 A CN B2005100690760A CN 200510069076 A CN200510069076 A CN 200510069076A CN 100422223 C CN100422223 C CN 100422223C
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Abstract
The present invention discloses a spherical Ziegler. Natta catalyst for ethene slurry and a gas-phase polymerization technology and a preparation method thereof. The method achieves the goal of controlling the form of an ethene polymer by preparing the spherical catalyst with a controllable form. The prepared catalyst particle has the particle diameter between 20 mu m to 50 mu m, the specific surface area is larger than 100m<2>/g, and the aperture distribution curve has a peak with a large area at the position of 30 A. The present invention has the advantages that the catalyst and an organic aluminium cocatalyst are used for obtaining the spherical ethene polymer in ethene homopolymerization and the copolymerization of ethene and alpha-olefin, the polymerization activity is high, the hydrogen sensitivity and the copolymerization performance are excellent, polymer particles are mainly in 10 to 20 meshes, and the stacking density is larger than 0.33 g/ml. The present invention is favorable to industrial production.
Description
Technical field
The present invention relates to a kind of ball-type ziegler natta catalyst that can be used for ethene slurries, gas-phase polymerization process and preparation method thereof.
Background technology
Along with the development of olefin polymetiation process, people recognize the ideal olefin polymerization catalysis gradually except that should having higher activity, and the catalyzer form comprises that catalyst particle size, shape etc. are too as the accurately control of important indicator needs.Especially in recent years along with the continually developing of gas-phase polymerization process, cause reactor plugs for avoiding abnormal fluidized state and fine powder, the meaning that adopts the controlled morphologies catalyzer to implement polymer morphology control has seemed more and more important.The prepared globular polymer of ball shape catalyst has characteristics such as greater particle size, narrower size-grade distribution, higher tap density, good mobility, fine powder content are few, can improve the polymerizing power and the operability of device greatly, further optimize the character of resin material and widen product scope, reduce the running cost of polymerization process, increase the polymeric articles added value.
CN1330086A, CN1109067A, CN1034736C all provide the method for preparing ball shape catalyst, and have accumulated the preparation experience of a large amount of ball-type carriers.But the catalyzer of preparation only is applicable to propylene polymerization, and it is less to be used for the research of ethylene polymerization catalysts.
Summary of the invention
For a change at present ethene slurries, gas-phase polymerization process, broad particle distribution little with catalyst particle size, tap density is low, flowability is poor, the shortcoming more than the fine powder content.The invention provides a kind of ball-type ziegler natta catalyst that can be used for ethene slurries, gas-phase polymerization process and preparation method thereof, particularly in catalyst preparation process, add one or more silicoorganic compound as the dealcoholysis solvent.The granules of catalyst particle diameter of this method preparation is between 20-50 μ m, and specific surface area is greater than 100m
2/ g, pore size distribution curve exists
There is larger area point cutting edge of a knife or a sword in the place, and the Ti weight percentage is 4.5～5.5%.This catalyzer is used for ethene slurries, gas-phase polymerization process, the reactor plugs that can avoid abnormal fluidized state and fine powder to cause.
Method for preparing catalyst provided by the invention is as follows:
A. prepare the magnesium chloride homogeneous phase solution
Under nitrogen protection, open and stir, in reactor, add 3～10ml/g.MgCl under the normal temperature successively
2Inertia dispersion agent and emulsifying agent, inertia dispersion agent and emulsifying agent be preferred white oil and methyl-silicone oil respectively, is 2.0～5.0: 1 ratio adding in molar ratio with organic alcohol and magnesium chloride, is preferably 2.5～3.5: 1.Described organic alcohol is C
1～C
4Low-carbon alcohol, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol etc.
Then slowly heat up and make the magnesium chloride dissolving,, under pressure 0.1～0.5MPa, reacted 1.0～6.0 hours, obtain the magnesium chloride homogeneous phase solution 120～140 ℃ of temperature.
B. emulsification shaping legal system is equipped with magnesium chloride ball-type carrier
Open mulser, keep reactor pressure more than 0.05MPa, preferred 0.05MPa～0.2Mpa, be transferred in the inert solvent that is chilled to-30～-15 ℃ in advance after the magnesium chloride homogeneous phase solution that obtains sheared by mulser, the preferred hexane of inert solvent, preferred-22 ℃ of temperature, the inert solvent consumption is 3～20 times of magnesium chloride homogeneous phase solution volume, keeps low temperature and stirs 0.5～3.0 hour, then is warming up to room temperature naturally, liquid is wherein extruded, with the inert solvent washing repeatedly, the preferred hexane of inert solvent, then nitrogen drying, obtain magnesium chloride ball-type carrier, analyzing its magnesium alkoxide mol ratio is 2.2～3.0: 1.
C. the physics of magnesium chloride ball-type carrier and chemical treatment
At room temperature the magnesium chloride ball-type carrier that obtains is joined in the hot nitrogen fluidisation bed, elevated temperature to 80～130 ℃ gradually then, constant temperature 0.5～8 hour obtains the magnesium alkoxide mol ratio 1.2～2.0: 1 carrier; Then under nitrogen protection, again this carrier is joined in the reactor of an amount of inert solvent of pre-throwing that has stirring, the preferred hexane of inert solvent, inert solvent and carrier usage ratio are 3.0ml～20.0ml/g.MgCl
2, being added dropwise to one or more silicoorganic compound as the dealcoholysis solvent, consumption is 0.3～9.0 times of alcohol matter amount in the carrier, preferred 1～3 times.Described dealcoholysis solvent is silicoorganic compound, is selected from trichlorosilane, is specially METHYL TRICHLORO SILANE, ethyl trichlorosilane, phenyl-trichloro-silicane; Dichlorosilane is specially dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, dichloromethyl phenylsilane; One chlorosilane is specially trimethylchlorosilane; Silicon tetrachloride.Reacted 0.5～6 hour, preferred 1～3 hour, most preferably 2 hours.10～50 ℃ of temperature of reaction, preferred 20～30 ℃, the carrier magnesium alkoxide mol ratio that obtains is 0.2～1.2: between 1.
D. the load of titanium tetrachloride
With the carrier that obtains in the c step, under nitrogen protection, join in the reactor of an amount of-25～-5 ℃ of low temperature titanium tetrachlorides of pre-throwing that have stirring; magnesium consumption mol ratio is 10～30: 1 in titanium tetrachloride and the carrier; constant temperature 0.5～6 hour preferred 2 hours, progressively heats up; temperature of reaction is 110 ℃～130 ℃; pressure is 0.02～0.5MPa, reacts 1～6 hour, and reaction gained solids is handled 1～3 time with fresh titanium tetrachloride again; 100 ℃～140 ℃ of temperature of reaction, 1～4 hour time.Wherein liquid is extruded, with the inert solvent washing repeatedly, the preferred hexane of inert solvent, nitrogen drying then, obtaining with the magnesium chloride is the ball shape catalyst of carrier.
Pass through the magnesium chloride ball-type carrier that the hot nitrogen drying obtains handling well again.
By the catalyzer of above method preparation, it is characterized by: the granules of catalyst particle diameter is between 20-50 μ m, and specific surface area is greater than 100m
2/ g is specially 100m
2/ g～300m
2/ g, pore size distribution curve exists
There is larger area point cutting edge of a knife or a sword in the place, and analyze its pore size distribution: the aperture is
Hole account for 70%～90% of total pore volume; The Ti weight percentage is 4.5～5.5%.
The invention provides a kind of ethene slurries that can be used for, ball-type ziegler natta catalyst of gas-phase polymerization process and preparation method thereof, this catalyzer and organoaluminum promotor one are used from ethylene homo and close, the ethene polymers of gained is a ball-type when ethene and alpha-olefin copolymer, the polymerization activity height, hydrogen susceptibility and copolymerization excellent performance, polymer beads mainly concentrates between 10～20 orders, tap density is greater than 0.33g/ml, than conventional ethylene rolymerization catalyst, especially with respect to gaseous ethylene polymerization silica gel load type catalyzer remarkable advantages is arranged more, be very beneficial for industrial production.
The catalyst A polymerization evaluation result that following table makes for this method.From the result, catalyst A than conventional ethylene rolymerization catalyst, especially more has remarkable advantages with respect to gaseous ethylene polymerization silica gel load type catalyst B (activity generally has only 4000～6000 times) at aspects such as activity, particle shape, size-grade distribution.
Annotate: slurry polymerization, 80 ℃, 2.0hr, H
2/ C
==0.28MPa/0.45Mpa
Embodiment
The present invention is further described with reference to the following example.
Embodiment 1
The preparation ingredient of solid catalyst
Under nitrogen protection, open and stir, in reactor, add 54ml white oil, 70ml methyl-silicone oil, 10g magnesium chloride, 17ml ethanol successively, then slowly be warming up to 130 ℃, isothermal reaction obtained the magnesium chloride homogeneous phase solution in 3 hours under the pressure 0.2MPa.Open mulser, keep reactor pressure at 0.05MPa, the magnesium chloride homogeneous phase solution that obtains is transferred to by mulser in the hexane solution of the 1000ml that is chilled to-22 ℃ in advance in advance, keep low temperature and stirred 1 hour, then be warming up to room temperature naturally, with liquid extrusion wherein, with hexane wash four times, each 100ml, and after 60 ℃ of nitrogen dryings obtain magnesium chloride ball-type carrier, sampling analysis is magnesium alkoxide mol ratio 2.47 wherein.
The magnesium chloride ball-type carrier that obtains is transferred in advance in the gas fluidized bed of fully replacing with nitrogen, slowly is warming up to 110 ℃, nitrogen flow 0.25m
3/ h, fluidisation 2 hours.
Further carrier is taken off the reaction of alkoxyl group kind solvent with 35ml silicon tetrachloride etc. in reactor, 20 ℃-30 ℃ of temperature, 2.0 hours time, the magnesium chloride ball-type carrier that obtains handling well through 60 ℃ of nitrogen dryings again, sampling analysis magnesium alkoxide mol ratio 0.75.
The 200ml titanium tetrachloride is joined in the catalyzer synthesis reactor, be cooled to-22 ℃, will add wherein, in 4 hours, slowly be warming up to 113 ℃, constant temperature 2 hours through physics and chemically treated magnesium chloride ball-type carrier 10g.Constant temperature in returnable bottle, then adds the filtrate press filtration in the reactor the fresher titanium tetrachloride of 200ml and is warming up to 115 ℃ rapidly, constant temperature 1 hour after finishing.
After constant temperature finishes, the filtrate press filtration in the reactor in returnable bottle, is used the interior solid of hexane wash reactor four times, each hexane consumption 100ml; After the hot nitrogen drying obtains catalyzer dry powder.
Ti (weight %) is 4.99%.
Catalyzer adopts slurry method to carry out the polyreaction evaluation
The 2L autoclave is opened and is stirred to 150 rev/mins with pure hydrogen vacuum pump drainage three times.In polymeric kettle, advance quantitative hexane and triethyl aluminum and catalyst slurry then, 450 rev/mins of mixing speed.80 ± 0.5 ℃ of polymerization temperatures, hydrogen alkene be than 0.28/0.45Mpa, take out behind the polymerization time 2h polymkeric substance air-dry after, weigh, calculate catalyst activity, in PEg/gTi; And the bulk density and the size-grade distribution of mensuration polymkeric substance.Concrete data see Table 1 and table 2.
Embodiment 2
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silicon tetrachloride consumption becomes 50ml by 35ml with embodiment 1.Ti (weight %) is 4.61%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 3
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silicon tetrachloride consumption becomes 17ml by 35ml with embodiment 1.Ti (weight %) is 5.11%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 4
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride changes trimethylchlorosilane into, consumption is changed into 9 times of alcohol matter amount in the carrier by 35ml.Ti (weight %) is 4.86%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 5
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride changes trimethylchlorosilane into, consumption changes 6 times of alcohol matter amount in the carrier into by 35ml, and the dealcoholysis time changed 3 hours into by 2 hours.Ti (weight %) is 5.01%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 6
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride changes dimethyldichlorosilane(DMCS) into, consumption changes 0.5 times of alcohol matter amount in the carrier into by 35ml, and hexane solution is chilled to-22 ℃ in advance and changes-30 ℃ into.Ti (weight %) is 5.39%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 7
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride changes dichloromethyl phenylsilane into, consumption changes 5 times of alcohol matter amount in the carrier into by 35ml, and 17ml ethanol changes the 21ml Virahol into.Ti (weight %) is 4.91%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 8
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride changes ethyl trichlorosilane into, consumption changes 1 times of alcohol matter amount in the carrier into by 35ml, and 17ml ethanol changes the 10ml propyl carbinol into.Ti (weight %) is 4.56%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Embodiment 9
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, silicon tetrachloride such as changes at the phenyl-trichloro-silicane of amount, and the dealcoholysis time changed 1 hour into by 2 hours.Ti (weight %) is 5.27%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Comparative example 1
Prepare catalyst component with the method identical, but when the preparation catalyst component, do not add dealcoholysis solvent silicon tetrachloride with embodiment 1.Ti (weight %) is 5.42%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1 and table 2.
Table 1 polyethylene performance
Annotate: slurry polymerization, 80 ℃, 2.0hr, H
2/ C
==0.28MPa/0.45Mpa
Table 2 catalyst performance table
Claims (6)
1. the preparation method of a ball shape catalyst for ethylene polymerization, this method may further comprise the steps:
A. under nitrogen protection, open and stir, in reactor, add 3～10ml/g.MgCl under the normal temperature successively
2White oil and methyl-silicone oil, be that 2.0～5.0: 1 ratio adds in molar ratio with organic alcohol and magnesium chloride, then slowly heating up makes the magnesium chloride dissolving, 120～140 ℃ of temperature, under pressure 0.1～0.5MPa, reacted 1.0～6.0 hours, obtain the magnesium chloride homogeneous phase solution;
B. open mulser, keep reactor pressure at 0.05MPa～0.2MPa, be transferred in the inert solvent that is chilled to-30～-15 ℃ in advance after the magnesium chloride homogeneous phase solution that obtains sheared by mulser, the inert solvent consumption is 3～20 times of magnesium chloride homogeneous phase solution volume, keeping low temperature stirred 0.5～3.0 hour, then be warming up to room temperature naturally, liquid is wherein extruded, wash with inert solvent, nitrogen drying then, obtain magnesium chloride ball-type carrier, analyzing its magnesium alkoxide mol ratio is 2.2～3.0: 1;
C. at room temperature the magnesium chloride ball-type carrier that obtains is joined in the hot nitrogen fluidisation bed, then be warming up to 80～130 ℃ gradually, constant temperature 0.5～8 hour obtains the magnesium alkoxide mol ratio 1.2～2.0: 1 carrier; Then under nitrogen protection, this carrier is joined in the reactor of an amount of inert solvent of pre-throwing that has stirring, inert solvent and carrier usage ratio are 3.0ml～20.0ml/g.MgCl again
2, being added dropwise to one or more silicoorganic compound as the dealcoholysis solvent, consumption is 0.3～9.0 times of alcohol matter amount in the carrier, reacts 10～50 ℃ of temperature of reaction 0.5～6 hour; The carrier magnesium alkoxide mol ratio that obtains is 0.2～1.2: 1;
D. with the carrier that obtains in the c step, under nitrogen protection, join in the reactor of an amount of low temperature titanium tetrachloride of pre-throwing that has stirring; magnesium consumption mol ratio is 10～30: 1 in titanium tetrachloride and the carrier, and low temperature is-25～-5 ℃, constant temperature 0.5～6 hour; progressively heat up; temperature of reaction is 110 ℃～130 ℃, and pressure is 0.02～0.5MPa, reacts 1～6 hour; liquid is wherein extruded; with inert solvent washing, nitrogen drying then, obtaining with the magnesium chloride is the ball shape catalyst of carrier.
2. Preparation of catalysts method according to claim 1, wherein the organic alcohol described in the step a is selected from C
1～C
4Low-carbon alcohol; Organic alcohol and magnesium chloride mol ratio are 2.5～3.5: 1.
3. Preparation of catalysts method according to claim 1, wherein the organic alcohol described in the step a is selected from: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
4. Preparation of catalysts method according to claim 1, wherein the dealcoholysis solvent silicoorganic compound described in the step c are selected from: silicon tetrachloride, trichlorosilane, dichlorosilane or a chlorosilane; The dealcoholysis solvent load is 1～3 times of alcohol matter amount in the carrier, 1～3 hour reaction times; 20～30 ℃ of temperature of reaction.
5. Preparation of catalysts method according to claim 1, wherein the dealcoholysis solvent silicoorganic compound described in the step c are: silicon tetrachloride, METHYL TRICHLORO SILANE, ethyl trichlorosilane, phenyl-trichloro-silicane, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, dichloromethyl phenylsilane or trimethylchlorosilane; Reaction times is 2 hours.
6. Preparation of catalysts method according to claim 1, wherein inert solvent is a hexane.
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| WO2015054758A1 (en) * | 2013-10-17 | 2015-04-23 | Petróleo Brasileiro S.A. - Petrobras | Method for preparing bisupported ziegler-natta catalysts |
| CN115584003A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气股份有限公司 | High-density polyethylene resin for lithium battery diaphragm and preparation method thereof, lithium battery diaphragm and preparation method thereof |
| CN116041593A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of spherical magnesium halide adduct and product and application thereof |
| CN116041580A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Silicon-containing spherical olefin polymerization catalyst component, preparation method and catalyst system |
| CN116041585A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN116041583A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization and application thereof |
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| EP0421525A2 (en) * | 1989-10-06 | 1991-04-10 | ENICHEM S.p.A. | Process for the preparation of ethylene-propylene copolymers |
| CN1330086A (en) * | 2000-06-15 | 2002-01-09 | 中国石油化工股份有限公司 | Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst |
| CN1528793A (en) * | 2003-10-20 | 2004-09-15 | 上海金海雅宝聚合物添加剂有限公司 | Spherical carrier catalyst for alpha olefinic polymerization |
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2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0421525A2 (en) * | 1989-10-06 | 1991-04-10 | ENICHEM S.p.A. | Process for the preparation of ethylene-propylene copolymers |
| CN1330086A (en) * | 2000-06-15 | 2002-01-09 | 中国石油化工股份有限公司 | Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst |
| CN1528793A (en) * | 2003-10-20 | 2004-09-15 | 上海金海雅宝聚合物添加剂有限公司 | Spherical carrier catalyst for alpha olefinic polymerization |
Non-Patent Citations (2)
| Title |
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| 球型乙烯聚合催化剂的制备及性能. 李维真，张文平，张新军.石化技术，第11卷第2期. 2004 |
| 球型乙烯聚合催化剂的制备及性能. 李维真，张文平，张新军.石化技术，第11卷第2期. 2004 * |
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