CN108250330A - Preparation method of spherical catalyst carrier and olefin polymerization catalyst - Google Patents
Preparation method of spherical catalyst carrier and olefin polymerization catalyst Download PDFInfo
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- CN108250330A CN108250330A CN201611247055.8A CN201611247055A CN108250330A CN 108250330 A CN108250330 A CN 108250330A CN 201611247055 A CN201611247055 A CN 201611247055A CN 108250330 A CN108250330 A CN 108250330A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000002685 polymerization catalyst Substances 0.000 title abstract 3
- 239000011777 magnesium Substances 0.000 claims abstract description 59
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 59
- -1 magnesium halide Chemical class 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 150000007527 lewis bases Chemical class 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000037048 polymerization activity Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 230000000707 stereoselective effect Effects 0.000 abstract 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 235000011147 magnesium chloride Nutrition 0.000 description 24
- 229910001629 magnesium chloride Inorganic materials 0.000 description 21
- 238000005660 chlorination reaction Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000033912 thigmotaxis Effects 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- CEVFCYUJPROJPK-UHFFFAOYSA-N 1,2-dimethoxy-9h-fluorene Chemical class C1=CC=C2C3=CC=C(OC)C(OC)=C3CC2=C1 CEVFCYUJPROJPK-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 1
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl 2-methoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 1
- XLXGCFTYXICXJF-UHFFFAOYSA-N ethylsilicon Chemical compound CC[Si] XLXGCFTYXICXJF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a preparation method of a spherical catalyst carrier and application of the spherical catalyst carrier in preparation of an olefin polymerization catalyst. The method comprises the following steps: the spherical catalyst carrier is obtained by emulsifying and dispersing magnesium halide adduct melt in an inert liquid medium by using a multi-stage high-shear reactor and then quenching. The particle size of the spherical catalyst carrier particles can be adjusted and is uniformly distributed. The olefin polymerization catalyst prepared by the spherical catalyst carrier has higher polymerization activity, good stereospecific capacity, low polymer fine powder content and high melt mass flow rate when being used for olefin polymerization.
Description
Technical field
The present invention relates to a kind of preparation method and applications of olefin polymerization spherical carrier of catalyst.More specifically, it relates to
And a kind of the method for spherical magnesium halide/alcohol adducts catalyst carrier is prepared using multi-stage high shear reactor and alkene gathers
Close catalyst.
Background technology
In published catalyst system, the preparation method of the chlorination magnesium alcoholate particle as spherical carrier of catalyst
Mainly there are spray drying process, spray cooling, high pressure extrusion methods, high-speed mixing method and gravity Method.
US4469648 discloses a kind of method for preparing magnesium halide ball type carrier：(1) magnesium chloride/alcohol of molten is prepared
Adduct；(2) adduct with inert liquid medium is mixed, and makes mixture (Reynolds number is more than 3000) under turbulent-flow conditions
By the tubule of draw ratio 50~100, to form lotion；(3) lotion is quickly cooled down, obtains solid adduct particle.This method
The form of the chlorination magnesium alcoholate particle of gained is not good enough.
The patents such as WO 8707620, WO 9311166, US 5100849, US 5468698 and US 6020279 all describe
A kind of method for being used to prepare chlorination magnesium alcoholate particle, this method are to melt the chlorination magnesium alcoholate that magnesium alkoxide molar ratio is 3~6
Spray body cools down, and obtains spherical chlorination magnesium alcoholate particle.The disadvantages of this method is that technological process is more complicated, and prepared urges
Agent diameter of carrier is bigger than normal.
The patents such as US 4399054, EP 395383, US 6127304 and US 6323152 describe a kind of using at a high speed
The method that paddling process prepares chlorination magnesium alcoholate particle.This method is that magnesium chloride alcohol is closed using high-speed stirred in inert media
Object is dispersed into droplet, then mixed liquor is discharged into in the cooling medium that stirred solidified forming to get to spherical magnesium chloride alcohol
Polymer beads.This method technics comparing is simple, but chlorination magnesium alcoholate grain diameter obtained is larger, broad particle distribution.
Chinese patent ZL 03153152.0, ZL 200410062291.3 disclose a kind of side for preparing olefin polymer
Method.This method is first to premix the mixture of chlorination magnesium alcoholate melt and inert media by blender, then disposable fast
Speed is uniformly dispersed chlorination magnesium alcoholate melt by the shear action of wire packing in rotary packed bed by rotary packed bed
Solidified forming is passed through in cooling medium to get to spherical chlorination magnesium alcoholate particle into inert media, then by mixture.The party
Method effectively improves the form of carrier, but easily rotates the problem of packed bed is insufficient to emulsifying materials.
Invention content
The object of the present invention is to provide a kind of preparation methods and olefin polymerization catalysis of spherical carrier of catalyst, should
Method prepare carrier have it is simple for process efficiently, diameter of carrier size is adjusted and is evenly distributed, the excellent advantage of carrier property.
For this purpose, the present invention provides a kind of preparation method of spherical carrier of catalyst, include the following steps：
S1, magnesium halide is reacted with lewis base, reaction temperature be 100 DEG C~140 DEG C, preferably 110~130 DEG C, instead
It is 20~300min, preferably 60~120min between seasonable, forms adduct of magnesium halides melt；
S2, the adduct of magnesium halides melt with inert liquid medium is mixed, obtains adduct of magnesium halides melt blend,
Then emulsion dispersion is carried out, obtains adduct of magnesium halides melt dispersion；
S3, by the adduct of magnesium halides melt dispersion rapid cooling, the washed liquid washing of spherical solid particles of formation,
And after drying, adduct of magnesium halides particle, that is, spherical carrier of catalyst is formed.
The preparation method of spherical carrier of catalyst of the present invention, in step S1, it is preferred that the magnesium halide meets
Formula M gX1X2, in formula, X1For fluorine, chlorine or bromine, X2With X1It is identical or different, X2For fluorine, chlorine, bromine, the alkyl of C1~C14, aryl,
Alkoxy or aryloxy group, the magnesium halide are more preferably magnesium dichloride, dibrominated magnesium or chlorination butoxy magnesium.
The preparation method of spherical carrier of catalyst of the present invention, in step S1, the lewis base be preferably selected from alcohol,
At least one of phenol, ether, ketone, ester, carboxylic acid, amine and silane.
The preparation method of spherical carrier of catalyst of the present invention, in step S1, it is preferred that the lewis base is extremely
A kind of rare general formula that is selected from is R (OH)nAlcohol, in formula, R is alkyl, cycloalkyl or aralkyl, and n is positive integer；Above-mentioned alcohol is into one
Step is preferably methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2- ethyls
Hexanol, ethylene glycol or propylene glycol.
The preparation method of spherical carrier of catalyst of the present invention, usually, the usage amount of alcohol should ensure that magnesium halide adds
It is solid at normal temperatures to close object.Magnesium alkoxide molar ratio changes as the alcohol used is different with the type of magnesium halide.Wherein, preferably
It is that in terms of every mole of magnesium in the magnesium halide of the adduct of magnesium halides melt, the lewis base includes 2~6 moles of alcohol,
When the alcohol used is methanol, ethyl alcohol, propyl alcohol, butanol and magnesium chloride, preferably 2.5~4 moles of the dosage of alcohol, which causes
Adduct of magnesium halides is at room temperature solid, but is molten condition at a temperature of 100-140 DEG C；And 0~1 mole be selected from
The compound of at least one of phenol, ether, ketone, ester, carboxylic acid, amine and silane；The dosage of the inert liquid medium is 0.5~10
It rises.
The compound of at least one of above-mentioned phenol, ether, ketone, ester, carboxylic acid, amine and silane, further preferred molecular structure
In at least one of the phenol containing aromatic ring, ether, ketone, ester, carboxylic acid, amine and silane, more preferably 2- isopropyls 2- isopentyl 1,3-
Bis- (benzoyloxy methyl) fluorenes of dimethoxy propane, 9,9-, bis- (methoxy) fluorenes of 9,9-, ethyl benzoate, o-hydroxy
Ethyl formate, o-methoxybenzoic acid ethyl ester, 2,4-PD dibenzoate, 4- ethyl -3,4- heptandiols dibenzoate,
N-butyl phthalate, diisobutyl phthalate, Cyclohexyl Methyl Dimethoxysilane or bicyclopentyl dimethoxy
Base silane.
In terms of every mole of magnesium, one or more total dosages in phenol, ether, ketone, ester, carboxylic acid, amine and silane are rubbed for 0~1
You, inert liquid medium dosage is 0.5~10 liter.
The preparation method of spherical carrier of catalyst of the present invention, in step S2, it is preferred that the inert fluid is situated between
Matter be it is unmixing with the adduct of magnesium halides melt and in chemically inert aliphatic hydrocarbon and organo-silicon compound extremely
Few one kind.It is described in chemically inert aliphatic hydrocarbon can be kerosene, paraffin oil, vaseline oil, white oil etc.；Described is in chemistry
Inert organo-silicon compound can be methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil, methyl phenyl silicone oil
Deng；The inert liquid medium is more preferably the mixture of methyl-silicone oil or methyl-silicone oil and white oil.
The preparation method of spherical carrier of catalyst of the present invention, in step S2, it is preferred that the emulsion dispersion makes
With multi-stage high shear reactor.
The preparation method of spherical carrier of catalyst of the present invention, these, it is preferred to, the multi-stage high shear reaction
Device, series be 1 grade or more, preferably 3 grades or more, to ensure being sufficiently mixed for material；Every grade of mixing section is by staggered more
Layer stationary ring and rotating ring composition with one heart, stationary ring is made of circumferentially spaced column spoiler, and rotating ring is by annular packing layer, porous
At least one of plate or column composition drive reactor rotation to make to generate opposite fortune between stationary ring and rotating ring by motor
It is dynamic.Further preferably, the section of stationary ring or the column on rotating ring is circle, ellipse, square, rectangle, diamond shape or three
It is angular；Rotating ring can further preferably at least one of concentric annular packing layer, porous plate and column, more preferable annular packing
Layer and its combination with porous plate or column.Filler can further preferably stainless steel cloth, plastic silk screen, bead etc., more
It is preferred that stainless steel cloth filler.
Preparation in accordance with the present invention after adduct of magnesium halides melt blend is mixed with inert liquid medium, is drawn
Enter above-mentioned multi-stage high shear reactor, and disposably quickly through the reactor, material is by stationary ring and rotating ring during this
Intensive shear acts on, and so as to which adduct of magnesium halides melt be made to be dispersed in inert media in the form of fine droplet, forms halogenation
The dispersion of magnesium adduct melt mixture.
The preparation method of spherical carrier of catalyst of the present invention, these, it is preferred to, the multi-stage high shear reaction
The operating temperature of device is room temperature to 200 DEG C, and operating pressure is normal pressure to 1.5MPa；Further preferably, operating temperature for 100~
140 DEG C, operating pressure is more than 0.2MPa.
The preparation method of spherical carrier of catalyst of the present invention, in step S3, it is preferred that the rapid cooling makes
It is carried out with low-temperature cooling media.The cooling medium using the relatively low inertia hydrocarbon compound of boiling point, as pentane, hexane, heptane,
Gasoline or petrol ether etc..Before being contacted with adduct of magnesium halides melt dispersion, the temperature for cooling down medium is controlled at -50 DEG C
~-10 DEG C, preferably -40 DEG C~-20 DEG C.
The preparation method of spherical carrier of catalyst of the present invention, in step S3, it is preferred that the magnesium halide adduction
The grain size D50 of composition granule is 10~150 μm, and size distribution Span values are (D90-D10)/D50≤1.2.Its average grain diameter can lead to
Rotating speed, the material for crossing change multi-stage high shear reactor are regulated and controled by means such as the proportionings of time and material.Wherein, D90 is
The diameter value that 90% particle diameter of whole particles is less than, D10 are that 10% particle diameter of whole particles is less than
Diameter value, D50 are the diameter values that 50% particle diameter of whole particles is less than.
The preparation method of spherical carrier of catalyst of the present invention, in step S3, it is preferred that the cleaning solution uses
The relatively low inertia hydrocarbon compound of boiling point, such as pentane, hexane, heptane, gasoline or petrol ether, wash temperature be using room temperature
It can.
In the preparation method of the present invention, when preparing adduct of magnesium halides melt blend, the charging sequence of each raw material can
Arbitrary selection.
The present invention also provides a kind of olefin polymerization catalysis, using spherical carrier of catalyst obtained by above-mentioned preparation method as
Carrier.Well known synthetic method can be used in the synthesis of the component of catalyst in addition to carriers, generally according to the needs of practical application
It can be optionally added some internal electron donor compounds commonly understood in the industry.
Present invention discover that chlorination magnesium alcoholate particle is prepared using multi-stage high shear reactor, and it is simple for process efficient, it prepares
Chlorination magnesium alcoholate grain diameter size be adjusted and be evenly distributed.With the chlorination magnesium alcoholate particle for preparing of the present invention as
Olefin polymerization catalysis prepared by catalyst carrier, higher for polymerization activity during olefinic polymerization, stereotaxis ability is good, polymerization
Object fine powder content is low, and melt mass flow rate is high.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
The grain size of adduct of magnesium halides particle is measured with 2000 type laser particle analyzers of Mastersizer；
The molar ratio of alcohol and magnesium halide is measured using thermogravimetry in adduct of magnesium halides, the model of thermal gravimetric analyzer
TG 209F1；
Melt index (MI) is measured according to ASTM D1238-99；
Polymer isotactic index (II) is measured (heptane boiling extracting 6 hours) using heptane extraction process.
Embodiment 1
Magnesium chloride adduct particles are prepared using following steps：
(1) preparation of magnesium chloride adduct melt：With stirring 5L reactors in, add in 200g anhydrous magnesium chlorides and
370ml ethyl alcohol.120 DEG C are warming up under the mixture is stirred, magnesium chloride forms magnesium chloride adduct melt after all dissolving.It will
The melt is heated in 125 DEG C of 3000ml white oils and 1000ml methyl-silicone oils, is turned at 125 DEG C with 1000 revs/min
Fast high-speed stirred 10min forms the mixture of magnesium chloride adduct melt and inert liquid medium.
(2) multi-stage high shear reactor decentralized processing：Said mixture is introduced into multi-stage high shear reactor, specific series
It is 3, and is disposably discharged quickly through the multi-stage high shear reactor through discharge port.The rotating speed of rotating ring is 1000 revs/min.
(3) chilling curing molding：The material drawn from discharge port feeding 20L is cooled in -40 DEG C of hexane, is separated into
The magnesium chloride adduct melt of droplet cools and solidifies rapidly, becomes spherical solid particles.
(4) it is filtered, washed and dried：After chilling solid particulate matter is isolated in the suspension of gained.With hexane in room
The particulate matter is washed under temperature, is washed five times altogether, is then dried in vacuo up to magnesium chloride adduct particles.
Embodiment 2
The adjustment of rotational speed of multi-stage high shear reactor is only 500 revs/min with embodiment 1 by operation.
Embodiment 3
The adjustment of rotational speed of multi-stage high shear reactor is only 2000 revs/min with embodiment 1 by operation.
Embodiment 4
White oil additive amount is only adjusted to 1000ml, methyl-silicone oil additive amount is adjusted to by operation with embodiment 1
3000ml。
Embodiment 5
Operation only adds in 20ml n-butyl phthalates with embodiment 3 when preparing magnesium chloride adduct melt.
Embodiment 6
Operation only adds in 20ml diisobutyl phthalates with embodiment 3 when preparing magnesium chloride adduct melt.
Comparative example 1
Magnesium chloride adduct particles are prepared using following steps：
(1) preparation of magnesium chloride adduct melt：With stirring 5L reactors in, add in 200g anhydrous magnesium chlorides and
370ml ethyl alcohol.120 DEG C are warming up under the mixture is stirred, magnesium chloride forms magnesium chloride adduct melt after all dissolving.It will
The melt is heated in 125 DEG C of 3000ml white oils and 1000ml methyl-silicone oils, is turned at 125 DEG C with 1000 revs/min
Fast high-speed stirred 20min forms the mixture of magnesium chloride adduct melt and inert liquid medium.
(2) chilling curing molding：Said mixture is drawn feeding 20L from discharge port to be cooled in -40 DEG C of hexane.Point
It dissipates and is cooled and solidified rapidly for the magnesium chloride adduct melt of droplet, become spherical solid particles.
(3) it is filtered, washed and dried：After chilling solid particulate matter is isolated in the suspension of gained.With hexane in room
The particulate matter is washed under temperature, is washed five times altogether, is then dried in vacuo up to magnesium chloride adduct particles.
Embodiment 7
The preparation of catalytic component
In the 500ml glass reaction bottles of band stirring being sufficiently displaced from high pure nitrogen, 300ml titanium tetrachlorides, cooling are added in
To -25 DEG C, the magnesium chloride adduct particles that 15.0g is prepared respectively by embodiment 1-6 and comparative example 1-3 are added in, -25 DEG C is maintained and stirs
Mix 30min.Then 110 DEG C are to slowly warm up to, n-butyl phthalate 3.0ml is added in temperature-rise period, in 110 DEG C of constant temperature
Liquid is filtered after reaction 2h.300ml titanium tetrachlorides are added in, are warming up to 110 DEG C, liquid is filtered after maintaining 1h at 110 DEG C.Finally use
Then 60 DEG C of hexane hot wash 6 times is dried in vacuo solids to get to catalytic component.
Propylene polymerization
In a 5L in the stainless steel autoclave of stirring, after being replaced with nitrogen, the hexane solution of triethyl aluminum is added in
Hexane solution (the CHMMS of (a concentration of 2.4mol/L of triethyl aluminum) 10mL, Cyclohexyl Methyl Dimethoxysilane (CHMMS)
A concentration of 0.18mol/L) 6mL, above-mentioned catalytic component 20mg；It closes autoclave, introduces hydrogen 4.5L (under standard state)
With liquid propene 2L；Temperature is risen to 70 DEG C under stiring, after 1 hour, cooling stops stirring polymerisation, removes at 70 DEG C
Remaining propylene monomer, obtains polymer.
Table 1 is listed respectively by the size distribution of the embodiment 1-6 and comparative example 1-3 magnesium chloride adduct particles prepared；
Table 2 lists the magnesium chloride adduct particles prepared respectively by embodiment 1-6 and comparative example 1-3 by 7 the method system of embodiment
The performance indicator of standby gained catalytic component.
Table 1
Table 2
By table 1 and 2 it is found that chlorination magnesium alcoholate grain diameter size prepared by the present invention is adjusted and is evenly distributed, i.e.,
Make when grain size is less than or equal to 20 μm, Span values can still be less than 1.2.It is done with chlorination magnesium alcoholate particle prepared by the present invention
For olefin polymerization catalysis prepared by catalyst carrier, higher for polymerization activity during olefinic polymerization, stereotaxis ability is good, gathers
It is low to close object fine powder content, melt mass flow rate is high.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (12)
1. a kind of preparation method of spherical carrier of catalyst, which is characterized in that include the following steps：
S1, magnesium halide with lewis base is reacted, forms adduct of magnesium halides melt；
S2, the adduct of magnesium halides melt with inert liquid medium is mixed, obtains adduct of magnesium halides melt blend, then
Emulsion dispersion is carried out, obtains adduct of magnesium halides melt dispersion；
S3, by the adduct of magnesium halides melt dispersion rapid cooling, the washed liquid washing of spherical solid particles of formation, and doing
After dry, adduct of magnesium halides particle, that is, spherical carrier of catalyst is formed.
2. the preparation method of spherical carrier of catalyst according to claim 1, which is characterized in that in step S1, the halogen
Change magnesium and meet formula M gX1X2, in formula, X1For fluorine, chlorine or bromine, X2With X1It is identical or different, X2For fluorine, chlorine, bromine, C1~C14 alkane
Base, aryl, alkoxy or aryloxy group.
3. the preparation method of spherical carrier of catalyst according to claim 1, which is characterized in that in step S1, the road
This easy alkali is selected from least one of alcohol, phenol, ether, ketone, ester, carboxylic acid, amine and silane.
4. the preparation method of spherical carrier of catalyst according to claim 3, which is characterized in that in step S1, the road
At least a kind of general formula that is selected from of this easy alkali is R (OH)nAlcohol, in formula, R is alkyl, cycloalkyl or aralkyl, and n is positive integer.
5. the preparation method of spherical carrier of catalyst according to claim 4, which is characterized in that in step S1 and S2, with
Every mole of magnesium meter in the magnesium halide of adduct of magnesium halides melt, the lewis base include 2~6 moles of alcohol and 0~1
Mole the compound selected from least one of phenol, ether, ketone, ester, carboxylic acid, amine and silane；The use of the inert liquid medium
Measure is 0.5~10 liter.
6. the preparation method of spherical carrier of catalyst according to claim 1 or 5, which is characterized in that described in step S2
Inert liquid medium is unmixing with the adduct of magnesium halides melt and in chemically inert aliphatic hydrocarbon and siliconated
Close at least one of object.
7. the preparation method of spherical carrier of catalyst according to claim 1, which is characterized in that in step S2, the breast
Change dispersion and use multi-stage high shear reactor.
8. the preparation method of spherical carrier of catalyst according to claim 7, which is characterized in that the multi-stage high shear is anti-
Answer device, series is 1 grade or more, and every grade of mixing section is made of staggered multilayer concentric stationary ring and rotating ring, the stationary ring by
Circumferentially spaced column spoiler is formed, and the rotating ring is by least one of annular packing layer, porous plate or column
It forms, reactor rotation is driven to make to generate relative motion between the stationary ring and the rotating ring by motor.
9. the preparation method of spherical carrier of catalyst according to claim 8, which is characterized in that the multi-stage high shear is anti-
It is room temperature to 200 DEG C to answer the operating temperature of device, and operating pressure is normal pressure to 1.5MPa.
10. the preparation method of spherical carrier of catalyst according to claim 1, which is characterized in that in step S3, the urgency
Quickly cooling is but carried out using low-temperature cooling media.
11. the preparation method of spherical carrier of catalyst according to claim 1, which is characterized in that in step S3, the halogen
The grain size D50 for changing magnesium adduct particles is 10~150 μm, size distribution Span value≤1.2.
12. a kind of olefin polymerization catalysis, which is characterized in that with obtained by claim 1-11 any one of them preparation methods
Spherical carrier of catalyst is carrier.
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|---|---|---|---|---|
| US5632596A (en) * | 1995-07-19 | 1997-05-27 | Charles Ross & Son Co. | Low profile rotors and stators for mixers and emulsifiers |
| US6000840A (en) * | 1997-12-17 | 1999-12-14 | Charles Ross & Son Company | Rotors and stators for mixers and emulsifiers |
| WO2005039745A1 (en) * | 2003-10-16 | 2005-05-06 | Basell Poliolefine Italia S.R.L. | Process for the continuous production of emulsions |
| CN103012624A (en) * | 2011-09-20 | 2013-04-03 | 中国石油天然气股份有限公司 | Spherical magnesium halide catalyst carrier, and preparation and application thereof |
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2016
- 2016-12-29 CN CN201611247055.8A patent/CN108250330A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5632596A (en) * | 1995-07-19 | 1997-05-27 | Charles Ross & Son Co. | Low profile rotors and stators for mixers and emulsifiers |
| US6000840A (en) * | 1997-12-17 | 1999-12-14 | Charles Ross & Son Company | Rotors and stators for mixers and emulsifiers |
| WO2005039745A1 (en) * | 2003-10-16 | 2005-05-06 | Basell Poliolefine Italia S.R.L. | Process for the continuous production of emulsions |
| CN103012624A (en) * | 2011-09-20 | 2013-04-03 | 中国石油天然气股份有限公司 | Spherical magnesium halide catalyst carrier, and preparation and application thereof |
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