CN100366640C - Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst - Google Patents
Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst Download PDFInfo
- Publication number
- CN100366640C CN100366640C CNB2004100862866A CN200410086286A CN100366640C CN 100366640 C CN100366640 C CN 100366640C CN B2004100862866 A CNB2004100862866 A CN B2004100862866A CN 200410086286 A CN200410086286 A CN 200410086286A CN 100366640 C CN100366640 C CN 100366640C
- Authority
- CN
- China
- Prior art keywords
- carrier
- olefin polymerization
- magnesium halide
- feed liquid
- polymerization catalysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a carrier for an olefin polymerization catalyst and a preparation method thereof, and the use of the carrier for preparing the olefin polymerization catalyst. The spherical carrier is characterized in that firstly, a spherical magnesium halide or magnesium halide-inorganic compound carrier is prepared by a conventional spray drying method; secondly, the carrier is complemented with alcohol; finally, the carrier with high magnesium alkoxide is obtained. Compared with a carrier prepared by the conventional spray drying method, the spherical carrier prepared by the method generates a polyphase magnesium alkoxide compound and has high alcohol content. The activity of the catalyst prepared by the method is greatly enhanced. Compared with the spray cooling method, the method is simple and easy. The alcohol content of the prepared carrier is lower than that of a carrier prepared by the spray cooling method, reaction is mild during catalyst preparation, and accordingly, the crushing of the catalyst is effectively reduced. The method is suitable for preparing the olefin polymerization catalyst.
Description
Technical field
The present invention relates to a kind of carrier that is used for olefin polymerization catalysis, relate to a kind of carrier and preparation method thereof and its application in the preparation olefin polymerization catalysis of the high magnesium alkoxide ratio that adopts spray drying method for preparation more specifically.
Technical background
In polyolefinic industrial production, the Ziegler-Natta catalyst of polyreaction use is made up of Primary Catalysts and promotor two portions mostly usually.Primary Catalysts is included in the transistion metal compound that is positioned at the 4th to the 8th main group in the periodictable, and promotor is then for being positioned at the organometallics of first to the 3rd main group in periodictable.Usually, Primary Catalysts can be divided into two parts again: the active constituent of inert support and load thereof.Character such as the form of carrier and size-grade distribution not only have extremely important influence to activity of such catalysts subsequently, and, because " duplicating " of existing in polymerization process effect, also determined the form of final polymeric articles.Though disclosed at present kind of carrier has a lot, have only and in carrier, contain MgCl
2The time, the catalyzer that obtains just shows advantages of high catalytic activity.
As everyone knows, MgCl
2Carrier or MgCl
2/ SiO
2The preparation method of carrier generally includes high-speed mixing method, tubule extrusion molding and spray method.Wherein high-speed mixing method such as Chinese patent 99103280 are with anhydrous MgCl
2Join by a certain percentage in the inert liquid medium immiscible with it with alcohol, under agitation heating makes EtOH/MgCl
2Form mixture and melt and be dispersed in the medium.In high speed agitator or mulser, carry out emulsification then and transfer in the cryogenic medium MgCl
2-pure mixture is the MgCl of rapid condensation cured globulate therein
2Carrier.Tubule extrusion molding such as U.S. Pat 4399054 are the EtOH/MgCl with certain proportioning
2With a kind of immiscible liquid mixing, under agitation heating makes MgCl
2The mixture fusing.Mixed solution is extruded with turbulent velocity by tubule.Mixed solution is emulsified in tubule, and emulsion enters in the heat-eliminating medium under the whipped state and solidify to form spheroidal particle rapidly.
Spray method generally is divided into two kinds of spray-drying process and spray cooling.U.S. Pat 4421674, US4481342 and US4843049 disclose a kind of method that is used for the carrier of polyolefin catalyst with spray drying method for preparation: use N
2Gas is with MgCl
2-pure mixed system sprays into kiln by specially designed nozzle, and is dried to spherical MgCl in the rare gas element of preheating
2Carrier.Because the out temperature of spraying drying instrument is higher, causes the spherical MgCl that obtains
2Carrier alcohol content is lower, especially spherical MgCl
2Particle surface alcohol is very few, and in follow-up loading process, active constituent can not be with the carrier useful effect and in conjunction with from the teeth outwards, makes in the catalyzer active ingredient content low and influence final catalyzed polymerization activity; U.S. Pat 5215949, US5468698, US5476824, US5905050 and US6020279 also disclose a kind of method that is used for the carrier of polyolefin catalyst with the spray cooling preparation: use N
2Gas is with MgCl
2-pure mixed system sprays into kiln by specially designed nozzle, and condensation forms spherical MgCl in heat-eliminating medium
2Carrier.The spherical MgCl of this method preparation
2In the nEtOH carrier, because median size is bigger, n is greater than 3, and pure content is higher, at carrier and TiCl
4During reaction,, often make the carrier fragmentation, cause that final fine powder increases because reaction is too violent.
Summary of the invention
In order to overcome the spherical MgCl of conventional spray drying method for preparation
2Alcohol contains quantity not sufficient in the carrier, and spray cooling prepares spherical MgCl
2The carrier process is comparatively complicated, plant and instrument is had relatively high expectations, be difficult for making the little shortcomings such as ball type carrier of particle diameter, the invention provides a kind of ball type carrier that is used for olefin polymerization catalysis and preparation method thereof and of the utilization of this ball type carrier at the preparation olefin polymerization catalysis.
A kind of ball type carrier that is used for olefin polymerization catalysis, it at first utilizes conventional spray-drying process, makes spherical magnesium halide or magnesium halide-mineral compound carrier, after handle through " mend alcohol " again, finally obtain magnesium alkoxide than higher carrier.
The carrier that is used for olefin polymerization catalysis of the present invention, it is by containing the method preparation of following steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in fully obtains even magnesium halide feed liquid in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl.
Suitable magnesium halide comprises the alcohol adduct of magnesium dihalide, magnesium dihalide, or any can with alcohol reaction after, generate the magnesium-containing compound of magnesium dihalide and the mixture of these compounds.Object lesson such as magnesium dichloride, dibrominated magnesium, two magnesium iodides are preferably magnesium dichloride;
Suitable R OH Fatty Alcohol(C12-C14 and C12-C18) be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, ethylene glycol, propylene glycol, chloroethanol or ethapon one or more, ethanol preferably.
Generally, every mole of magnesium halide needs 3～50 moles Fatty Alcohol(C12-C14 and C12-C18) dissolving, is preferably 6～30 moles; Simultaneously, the preparation of magnesium halide feed liquid can be carried out in one or more inert organic solvents, inert organic solvents such as alkane, haloalkane and carbon atom number are 6～12 aromatic hydrocarbons, concrete as hexane, heptane, ethylene dichloride, toluene, dimethylbenzene, ethylbenzene etc., the volume ratio of the consumption of described inert solvent and magnesium halide feed liquid is approximately 0.1～10 times.
In order to obtain the better ball type carrier of pattern, also can add a certain amount of inert inorganic compounds, mineral compound commonly used is silicon oxide, aluminum oxide, diatomite, molecular sieve etc., preferably uses SiO
2Used SiO
2The particulate granularity has material impact to the carrier size that obtains, used silica gel particle median size should be less than 30um, the preferred silicon oxide particle that uses less than 10um most preferably uses the smoke-like silica gel of median size below 1um, and the specific surface area of this silica gel is generally 200m
2About/g.The consumption of mineral compound and the mass ratio of magnesium halide should be in 0.1～10 scopes.
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
Spray drying process of the present invention can adopt the conventional spraying drying of prior art, in the spraying drying instrument, with rare gas element such as N
2Gas is with the magnesium halide feed liquid (MgCl that obtains of step a)
2-alcohol or MgCl
2-alcohol-SiO
2) spray into kiln by nozzle, and in the rare gas element of preheating, be dried to ball type carrier.
C) mending alcohol handles: in inert organic solvents, the Fatty Alcohol(C12-C14 and C12-C18) that spheroidal particle that step b is obtained and general formula are ROH mixes, and keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
In the step c) suitable Fatty Alcohol(C12-C14 and C12-C18) be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, ethylene glycol, propylene glycol, chloroethanol or ethapon one or more, preferably identical with used Fatty Alcohol(C12-C14 and C12-C18) among the step a.
Suitable volatility inert organic solvents in the step c) should not react with carrier, can be selected from the aromatic hydrocarbons of alkane, halohydrocarbon and 6～12 carbon atoms, and is concrete as hexane, heptane, ethylene dichloride, toluene, dimethylbenzene and ethylbenzene etc.Ball type carrier quality and inert organic solvents volume ratio can be at 1～30g/100mL, preferably between 3～5g/100mL.The add-on of mending alcohol should be, and after the alcohol of metering adds, makes magnesium alkoxide molar ratio total in the system below 6, preferably between 2.5～3.0.Mend pure temperature of reaction and should be lower than the boiling temperature of reaction system, preferred temperature of reaction is lower than temperature of reaction system 2-10 ℃.
So obtain the carrier median size less than 70 μ m, more preferably 10-60 μ m.
The present invention also provides a kind of preparation method who is used for the carrier of olefin polymerization catalysis, and it may further comprise the steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in fully obtains even magnesium halide feed liquid in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl;
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
C) mending alcohol handles: in inert organic solvents, it is that the Fatty Alcohol(C12-C14 and C12-C18) of ROH mixes that step b is obtained spheroidal particle and general formula, keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
In addition, the carrier that is used for olefin polymerization catalysis of the present invention can also adopt the method preparation that may further comprise the steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH fully, and to wherein add median size less than 30um and with the mol ratio of magnesium halide consumption be 0.1～10: 1 silica gel particle, obtain even magnesium halide feed liquid, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl;
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
C) mending alcohol handles: in inert organic solvents, it is that the Fatty Alcohol(C12-C14 and C12-C18) of ROH mixes that step b is obtained spheroidal particle and general formula, keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
In addition, the invention still further relates to the application of a kind of above-mentioned carrier in the preparation olefin polymerization catalysis.Carrier of the present invention can be widely used in the preparation olefin polymerization catalyst.
Embodiment
The invention is further illustrated by the following examples, to deepen the understanding of the present invention.Invention itself is not subjected to the restriction of these embodiment.
The x-ray diffraction pattern of Fig. 1 embodiment of the invention and Comparative Examples carrier
In Fig. 1, curve 1 is not for adding the X-ray diffraction curve of the pure support samples of processing, and curve 2 is the X-ray diffraction curve of the embodiment of the invention 3 carriers, and curve 3 is the X-ray diffraction curve of Comparative Examples 3 carriers (spray condensation method).
The test condition of X-ray: carry out on the Rigaku D/max-rA type X-ray diffractometer, condition of work is pressed 40kV for pipe, pipe stream 100mA, CuKa radiation, graphite monochromator.
A) preparation of magnesium chloride solution: at process N
2Fully add the ethanol of 200mL in the 350mL reactor that the metathetical band stirs through processed, under room temperature, add the 20g Magnesium Chloride Anhydrous while stirring, the adding speed of control magnesium chloride, system temperature is remained on below 40 ℃, after the magnesium chloride adding finishes, the mixed system temperature is risen to 70 ℃, and, obtain even MgCl this temperature constant temperature 4 hours
2Ethanolic soln.
B) spraying drying: this experiment is undertaken by (Buchi Mini B-290spray-drier).Use peristaltic pump with the MgCl that obtains in a) step
2Solution is incorporated into two-fluid spray nozzle by pipeline, and atomizing enters kiln.Control feed liquid and spray gas N
2Flow is respectively 8mL/min and 1400L/h, and spraying temperature degree is a room temperature.Carrier gas N
2Flow control is at the 11000L/min place, and the instrument inlet port temperature is 170 ℃, and correspondingly the instrument temperature out is stabilized near 105 ℃.Obtain spherical carrier particle in the collection of the exit, below of cyclonic separator, wherein alcohol/magnesium ratio is 1.0.
C) the support samples 2.25g that step b is obtained adds in the 100ml hexane, after disperseing 30 minutes under the room temperature, slowly drips 1mL exsiccant ethanol.After dripping end, continue stirring 5 hours, stop to stir, crossing cleaner liquid, at last through normal temperature N
2Purge more than 5 hours, obtaining exsiccant alcohol/magnesium ratio is 1.7 ball type carrier.Sample alcohol Mg content and particle size distribution analysis branch as a result see Table 1 and 2.
Embodiment 2-3
Step a is all identical with embodiment 1 with b, and just the alcoholic acid add-on changes 2mL and 3mL in step c, and other are with embodiment 1.Obtain alcohol/magnesium ratio and be respectively 2.4 and 2.5 ball type carrier.Sample alcohol Mg content and particle size distribution analysis branch as a result see Table 1 and 2.
The ball type carrier of embodiment 3 has been carried out the test of X-diffraction, and its XRD spectrum is composed shown in 2 as Fig. 1.
Embodiment 4
A) the magnesium chloride spraying preparation of mother liquor: at process N
2Fully add the ethanol of 200mL in the 350mL reactor that the metathetical band stirs through processed, under room temperature, add the 17g Magnesium Chloride Anhydrous while stirring, the adding speed of control magnesium chloride, system temperature is remained on below 40 ℃, after the magnesium chloride adding finishes, the mixed system temperature is risen to 70 ℃, and, obtain even MgCl this temperature constant temperature 4 hours
2Ethanolic soln.17g smoke-like silica gel is being joined in the above-mentioned solution under the stirring condition fast, continuing to maintain original temperature and stir more than 1.5 hours fast, it is standby with mother liquor to obtain spraying.
B) spraying drying prepares MgCl
2/ SiO
2Carrier: use peristaltic pump that the mother liquor that obtains in a) step is incorporated into two-fluid spray nozzle by pipeline, atomizing enters kiln.Control feed liquid and spray gas N
2Flow is respectively 18mL/min and 350L/h, and spraying temperature degree is a room temperature.Carrier gas N
2Flow control is at the 7200L/min place, and the instrument inlet port temperature is 190 ℃, and correspondingly the instrument temperature out is stabilized near 97 ℃.Obtain spherical MgCl in the collection of the exit, below of cyclonic separator
2/ SiO
2Carrier granule.
C) the carrier 7g that step b is obtained adds in the 100ml hexane,, after disperseing 30 minutes under the room temperature, slowly drip 1.5mL exsiccant ethanol.After dripping end, continue stirring 5 hours, stop to stir, crossing cleaner liquid, at last through normal temperature N
2Purge more than 5 hours, obtain exsiccant alcohol/magnesium ratio and be 2.4 spherical MgCl
2/ SiO
2Carrier.Sample alcohol Mg content and particle size distribution analysis branch as a result see Table 1 and 2.
Comparative Examples 1
Step a is all identical with embodiment 1 with b, does not just have embodiment 1 described step c (mending pure step).Carrier granule alcohol Mg content and results of grain size analysis are shown in table 1 and 2.
The ball type carrier of Comparative Examples 1 has been carried out the test of X-diffraction, and its XRD spectrum is composed shown in 1 as Fig. 1.
Comparative Examples 2
As described in embodiment 4, except that not mending pure step c, other are all identical.Carrier granule alcohol Mg content and results of grain size analysis are shown in table 1 and 2.
Comparative Examples 3 (adopting the high-speed stirring condensation method)
In the abundant metathetical glass reactor of nitrogen, add dehydrated alcohol 36.5mL, anhydrous MgCl
221.3g, stir down and heat up, treat MgCl
2The dissolving back adds white oil 75mL, silicone oil 75mL fully, maintains 120 ℃ of certain hours, obtains mixture.This mixture is pressed into the silicone oil that 112.5mL white oil and equal volume are housed rapidly and is preheating in 120 ℃ the reactor, with the 3500rpm high-speed stirring after 3 minutes, under agitation material is introduced in the hexane that is pre-chilled to-25 ℃, shift to material and to finish, outlet temperature is no more than 0 ℃, and suction filtration, the magnesium alkoxide that obtains using condensation technology to make with hexane flush away silicone oil and white oil, vacuum-drying are 2.4 carrier.
The ball type carrier of Comparative Examples 3 has been carried out the test of X-diffraction, and its XRD spectrum is composed shown in 3 as Fig. 1.
Table 1
| Example | The chemical constitution of carrier | ||
| Mg content | EtOH content | EtOH/Mg molar Ratio | |
| 1234 contrasts, 1 contrast, 2 |
13.7％ 12.4％ 11.7％ 9.8％ 17.1％ 10.9％ 11.8％ | 44.3％ 54.6％ 54.9％ 45.0％ 31.0％ 35.0％ 53.7％ | 1.7 2.4 2.5 2.4 1.0 1.7 2.4 |
Table 2
| Example | The size distribution of carrier | |||
| D 0.5(um) | D 0.1(um) | D 0.9(um) | |
|
| 1 2 | 32.8 34.6 | 12.1 15.6 | 71.3 70.2 | 1.8 1.6 |
| 34 contrasts, 1 contrast, 2 |
36.9 55.5 24.0 49.5 43.0um | 12.3 19.4 9.7 17.6 26.0 | 79.7 120 47.1 109 70.1 | 1.8 1.8 1.6 1.8 1.03 |
In Fig. 1, the diffraction peak of spectrum shown in 1 (Comparative Examples 1) than disperse and intensity a little less than.Relative spectrum 1, the most significant variation in spectrum 2 (embodiment 3) is to add alcohol processing back sample diffraction peak intensity obvious reinforcement, the peak type is also more sharp-pointed, and has located to occur the strongest new diffraction peak at 24.2 °, and the obviously more contiguous diffraction peak halfwidth of this diffraction peak halfwidth is narrow.The contriver think these XRD test results show carrier structurally with do not add carrier that alcohol handles and have significantly differently, should constitute by heterogeneous through the carrier that adds after alcohol is handled, its newly-generated alcohol adduct should be positioned at the particulate skin.So more help reacting, improve catalytic activity with the active ingredient of alkene catalyst.
In Fig. 1, spectrum 2 and spectrum 3 diffraction peak intensity are very approaching, new diffraction peak do not occur but compose 3 near 24.2 ℃, and 2 θ are in the scope of 5～15 ° and 20～30 ° in spectrum 3, the halfwidth of diffraction peak is approaching in the co-extensive, can think that this carrier is phase structure substantially.
Vinyl polymerization is used:
1, adopts the preparing carriers catalyzer: get the carrier 5g of embodiment 3 and Comparative Examples 1 respectively, adopt following method to prepare catalyst component: in N
2Fully in the metathetical reaction flask, add 100mL hexane and heptane mixture.Slowly drip 15mL TiCl
4After, slowly be warming up to 100 ℃, constant temperature 2 hours, suction filtration, several times hexane wash, the dry ingredient of solid catalyst that gets.
2, polymerization: carry out in adding the 2L stainless steel cauldron that the 1L hexane is arranged in advance, temperature is 80 ℃, and the ingredient of solid catalyst consumption is 10mg, and triethyl aluminum concentration is 8mmol/L, and hydrogen-ethylene pressure ratio is 0.28: 0.45, and reaction continues two hours.The result shows that Comparative Examples 1 and embodiment 3 carrier gained catalyzer have obtained 120g and 250g polymkeric substance respectively, and the polymer stacks ratio is respectively 0.27g/cm
3And 0.28g/cm
3
Propylene polymerization is used:
1, adopts the preparing carriers catalyzer: get spherical embodiment 4 of 7g and Comparative Examples 2 complex carriers in N
2Fully in the metathetical reactor, add the 100mL hexane, be cooled to-20 ℃, slow Dropwise 5 0mLTiCl
4After.Slowly be warming up to 40 ℃, suction filtration.Add 100mLTiCl again
4, be warming up to 40 ℃, add diisobutyl phthalate (DIBP) 1mL, be warming up to 100 ℃ of reactions 1 hour, suction filtration.Add 50mLTiCl
4, be warming up to 80 ℃, reaction 1 hour, suction filtration.Add 100mLTiCl
4, be warming up to 120 ℃, reaction two hours, suction filtration, after washing, five hexane heat obtain solid catalyst again.
2, bulk propylene polymerization: in the 2L stainless steel cauldron, carry out, the liquid third that adds the hydrogen of hexane solution, 4NL of the triethyl aluminum of 10mg solid catalyst, 2mL 0.5M, cyclohexyl methyl dimethoxy silane (CHMMS) that 1mL concentration is 0.1M and 1NL respectively is rare, temperature of reaction is 70 ℃, and the time length is 2h.The result shows, uses the catalyst activity of Comparative Examples 2 and embodiment 4 carriers to be respectively 44600 times and 52000 times, and bulk density is 0.41g/cm
3And 0.42g/cm
3, degree of isotacticity is 96% and 97%.
Test-results shows, uses " mending alcohol " to handle back MgCl
2Carrier can prepare and has more highly active olefin polymerization catalysis.
Claims (12)
1. carrier that is used for olefin polymerization catalysis, it is by containing the method preparation of following steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in fully obtains even magnesium halide feed liquid in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl;
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
C) mending alcohol handles: in inert organic solvents, it is that the Fatty Alcohol(C12-C14 and C12-C18) of ROH mixes that step b is obtained spheroidal particle and general formula, keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
2. the carrier that is used for olefin polymerization catalysis according to claim 1 is characterized in that the mol ratio of described Fatty Alcohol(C12-C14 and C12-C18) and magnesium halide is 3～50: 1 when preparation magnesium halide feed liquid.
3. the carrier that is used for olefin polymerization catalysis according to claim 1 is characterized in that the mol ratio of described Fatty Alcohol(C12-C14 and C12-C18) and magnesium halide is 6～30: 1 when preparation magnesium halide feed liquid.
4. the carrier that is used for olefin polymerization catalysis according to claim 1, its described magnesium halide is a magnesium chloride, and general formula is that the Fatty Alcohol(C12-C14 and C12-C18) of ROH is an ethanol, and the magnesium alkoxide mol ratio of the ball type carrier that step c) obtains is 1.7～2.5: 1.
5. the carrier that is used for olefin polymerization catalysis according to claim 1, the mean diameter that it is characterized in that described ball type carrier is less than 70 μ m.
6. the carrier that is used for olefin polymerization catalysis according to claim 1, the mean diameter that it is characterized in that described ball type carrier are 10-60 μ m.
7. according to the described carrier that is used for olefin polymerization catalysis of one of claim 1-6, it is characterized in that can also adding in the described step a) median size less than 30um and with the mass ratio of magnesium halide be 0.1～10: 1 silica gel particle, obtain even magnesium halide feed liquid.
8. the carrier that is used for olefin polymerization catalysis according to claim 7, the median size of its described silica gel particle is less than 10um.
9. the carrier that is used for olefin polymerization catalysis according to claim 7, the median size of its described silica gel particle is less than 1 μ m.
10. according to the described preparing carriers method that is used for olefin polymerization catalysis of one of claim 1-6, may further comprise the steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in fully obtains even magnesium halide feed liquid in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl;
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
C) mending alcohol handles: in inert organic solvents, the Fatty Alcohol(C12-C14 and C12-C18) that spheroidal particle that step b is obtained and general formula are ROH mixes, and keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
11. the preparing carriers method that is used for olefin polymerization catalysis according to claim 7 may further comprise the steps:
A) preparation of magnesium halide feed liquid: magnesium halide is dissolved in the Fatty Alcohol(C12-C14 and C12-C18) that general formula is ROH fully, and to wherein adding the silica gel particle of median size less than 30um, obtains even magnesium halide feed liquid, wherein R is C
1-C
10The alkyl of straight or branched, and the one or more hydrogen on the described alkyl can be replaced by halogen or hydroxyl;
B) spraying drying: with the spray-dried spheroidal particle that obtains of step a gained feed liquid;
C) mending alcohol handles: in inert organic solvents, the Fatty Alcohol(C12-C14 and C12-C18) that spheroidal particle that step b is obtained and general formula are ROH mixes, and keeps reaction certain hour, solid-liquid separation, obtains the magnesium alkoxide mol ratio and be 0.6～3.0: 1 ball type carrier.
12. the described application that is used for the carrier of olefin polymerization catalysis at the preparation olefin polymerization catalysis of one of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100862866A CN100366640C (en) | 2004-10-29 | 2004-10-29 | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100862866A CN100366640C (en) | 2004-10-29 | 2004-10-29 | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1765940A CN1765940A (en) | 2006-05-03 |
| CN100366640C true CN100366640C (en) | 2008-02-06 |
Family
ID=36742075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100862866A Active CN100366640C (en) | 2004-10-29 | 2004-10-29 | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100366640C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955556B (en) * | 2010-09-10 | 2012-05-23 | 北京化工大学 | Preparation method and application of spherical magnesium halide carrier |
| CN109337000A (en) * | 2018-09-13 | 2019-02-15 | 朱博源 | A kind of ingredient of solid catalyst and its catalyst system for olefinic polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59145204A (en) * | 1982-11-11 | 1984-08-20 | エニキミカ・セコンダラリア・エス・ピ−・エ− | Manufacture of carried ziegler catalyst useful for alpha-olefin polymerization |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
-
2004
- 2004-10-29 CN CNB2004100862866A patent/CN100366640C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59145204A (en) * | 1982-11-11 | 1984-08-20 | エニキミカ・セコンダラリア・エス・ピ−・エ− | Manufacture of carried ziegler catalyst useful for alpha-olefin polymerization |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1765940A (en) | 2006-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7361621B2 (en) | Magnesium halide/alcohol adduct, its preparation and use | |
| CN100513438C (en) | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application | |
| CN1289542C (en) | Globular catalyst component used for olefine polymerization and its catalyst | |
| CN105622807B (en) | The preparation method of polypropylene wax | |
| CN106830007A (en) | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application | |
| CN102040683A (en) | Spherical carriers for olefin polymerization catalyst and preparation method | |
| CN105502433A (en) | Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 | |
| CN104907103A (en) | Preparation method of spherical alumina carrier | |
| CN101215344B (en) | Olefin polymerization catalyst composition and preparing method thereof | |
| CN107949587A (en) | It is used to prepare the technique of catalyst component for olefin | |
| CN102558398B (en) | Method for preparing spherical magnesium chloride carrier | |
| CN106032282A (en) | Preparation method and applications of mordenite having mesopores and micropores | |
| CN105712378A (en) | Synthetic method for nanometer ZSM-5 molecular sieve | |
| CN100366640C (en) | Carrier for olefin polymerization catalyst and its preparation method and its uses in preparing olefin polymerization catalyst | |
| CN104177523A (en) | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof | |
| CN104588074A (en) | Hydro-dearomatization catalyst preparation method | |
| CN100400554C (en) | Catalyst components for propylene polymerization and catalyst thereof | |
| CN1986575A (en) | Preparing process of slurry catalyst for gaseous ethylene polymerization | |
| JP6837462B2 (en) | Alkoxymagnesium catalyst carrier and its manufacturing method and application | |
| CN104828839B (en) | The method for preparing small crystal grain Y-shaped molecular sieve | |
| CN109400763A (en) | Carrier for olefin polymerization catalyst and its preparation method and application | |
| CN1771266B (en) | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom | |
| CN104826647A (en) | Preparation method for hydrogenation dearomatization catalyst | |
| CN102698814A (en) | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof | |
| CN106698467A (en) | Synthetic method of nano SAPO-34 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |