CN101225128A - Spherical complex carrier for olefin polymerization catalyst and preparation method thereof - Google Patents
Spherical complex carrier for olefin polymerization catalyst and preparation method thereof Download PDFInfo
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- CN101225128A CN101225128A CNA200710062874XA CN200710062874A CN101225128A CN 101225128 A CN101225128 A CN 101225128A CN A200710062874X A CNA200710062874X A CN A200710062874XA CN 200710062874 A CN200710062874 A CN 200710062874A CN 101225128 A CN101225128 A CN 101225128A
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Abstract
The invention discloses a spherical catalyst composite support and the preparation method, which is characterized in that: anhydrous magnesium chloride and alcohol are warmed up according to certain matching and reacted to produce magnesium chloride/alcohol adduct melt which is then mixed with solid support powder containing carbon, thereby preparing spherical catalyst support through spraying shaping. The preparation method for the spherical catalyst composite support has the advantages of more simply controllably preparing and directly being used for preparing spherical catalyst without needing working procedure such as dealcoholization.
Description
Technical field
The invention belongs to petrochemical complex polyolefin catalyst field, relate to a kind of preparation method who is used for alpha-olefin homopolymerization and copolymerization spherical catalyst complex carrier.In particular, relate to a kind of spherical magnesium chloride complex carrier and preparation method thereof.
Technical background
Adopting spherical magnesium chloride is carrier, can make the catalyzer of spheroidal particle, and then the catalyzer that adopts this spheroidal particle can synthesize similar to catalyst shape, have good fluidity and bulk density, need not the spheroidene hydrocarbon polymer of granulation, so this class catalyzer has very high industrial application value.And the key that obtains this type of spherical catalyst is to obtain spherical magnesium chloride support.Ball type carrier round how using fairly simple, controlled method processability excellence has many research units and company to explore both at home and abroad always.
Existing a large amount of comes the patent documentation report of load titanium tetrahalide as olefin polymerization catalysis with spherical magnesium halide, as USP4399054 (high pressure extrusion molding), USP4111835 (spray cooling), US4421674 (spray-drying process) CN1091748A (high-speed mixing method), CN1428489A (hypergravity bed method) etc.
The preparation method one who summarizes to get up present ball type carrier has above-mentioned five kinds, and high pressure is wherein extruded, three kinds of methods of high-speed stirring and hypergravity all be basically with Magnesium Chloride Anhydrous and alcohol join by a certain percentage with its inert liquid medium that does not hold mutually in, heating under agitation, make dissolved magnesium alkoxide mixture and dispersion medium form emulsion, and then this emulsion is transferred in the cryogenic media of precooling, make the rapid condensation cured of magnesium alkoxide mixture in the emulsion form the spheric magnesium chloride support, and then this carrier washed drying, the ball type carrier that obtains being suitable for.These two kinds of methods of spraying drying and spray cooling all need through an atomization process, different is: spray-dired method generally is with nitrogen the magnesium alkoxide mixed system to be entered kiln after nozzle atomization, and is dried to spherical magnesium chloride support in the rare gas element of preheating; And the spray cooling rule is the cooling that is cooled again after the magnesium alkoxide mixed system atomizing is solidified and to form ball type carrier.Two compare, and the exsiccant method atomizes easily, but need evaporate a large amount of solvents, and the pure content of gained carrier is wayward.The refrigerative method is owing to use high concentration material, saved solvent, and because the variation of alcohol can be ignored substantially in being shaped, the pure content ratio of products therefrom is easier to control, but because concentration is excessive, make its atomizing effect not as spray-dired method, the median size of gained carrier is than the control more complicated of big and corresponding technological conditions.
In each above-mentioned method, all be to adopt simple magnesium chloride alcohol adduct to prepare magnesium chloride support basically.Just in spray method, in order to obtain better ball type carrier, add some inert mineral compound sometimes as silicon oxide, aluminum oxide etc., but its effect only is to carry out the adjusting of spray effect, add the effect that compound does not play carrier, and in catalyst preparation process thereafter, also might reduce the efficient of catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of spherical catalyst complex carrier, and preparation method thereof, this method comparatively simply, comparatively effectively, more controllably obtains spherical carrier of catalyst.
The present invention is used for the spherical complex carrier of olefin polymerization catalysis, its be by Magnesium Chloride Anhydrous with after alcohol mixes by a certain percentage, temperature reaction generates magnesium chloride alcohol adduct melt, mixes with carbonaceous solid carrier powder again, obtains through spray shaping; Wherein with MgCl
2Mole number be 1, with a represent alcohol mole number, b represents carbonaceous solid carrier M and MgCl
2Weight ratio, MgCl
2The chemical constitution of-alcohol-carrier M is: MgCl2-a alcohol-bM, and wherein a value is 1.0～6.0, preferred 1.5～3.5; The value of b is 0.001～1.0, preferred 0.005～0.5; Wherein carbonaceous solid carrier powder be median size at 0.06～350 μ m, the gac of preferred 0.2～40 μ m, CNT (carbon nano-tube), carbon black, graphite or carbon dust, preferred activated carbon, alcohol is the Fatty Alcohol(C12-C14 and C12-C18) of general formula R OH, 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.Specifically can be selected from a kind of of methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, n-Octanol, 2-Ethylhexyl Alcohol or their mixture, be best with ethanol wherein.Wherein used carrier M both can be that commercial product directly uses, also can join again in the alcohol adduct system through after the pre-treatment earlier, can in system, add suitable pure soluble gum stick in addition, require this tackiness agent can not be dissolved in the nonpolar alkane, nonpolar alkane such as toluene, hexane, heptane etc., optionally tackiness agent is polyethylene glycol, methylcellulose gum, polyvinyl alcohol or polyvinyl acetate (PVA) etc., preferably polyethylene alcohol; The weight ratio of tackiness agent and magnesium chloride is 0～0.5, preferred 0～0.05.Can also contain a spot of moisture in the gained complex carrier system in addition, the weight ratio that water accounts for carrier is 0～3.0%, preferred 0～1.0%.
Complex spherical carrier of the present invention can prepare according to following method:
(1) preparation magnesium chloride solution
In the reactor of stirring is housed, add pure and mild magnesium chloride, make that the alcohol and the mol ratio of magnesium chloride are 3～50: 1, rising temperature for dissolving gets homogeneous solution then.
(2) preparation spherical complex carrier
In the alcoholic solution of above-mentioned magnesium chloride, add described carrier M, stir, make slurries, then these slurries are carried out spraying drying, obtain the spherical complex carrier that median size is 5～60 μ m.
Consisting of of complex carrier: magnesium chloride: 20～60% weight, carrier M:0.1～30% weight, alcohol: 30～60% (weight).
Embodiment
Embodiment 1:
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the gac that adds 0.9 gram 2500 orders (5 μ m); continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 2
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the gac that adds 1.8 gram 6250 orders (2 μ m); continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 3
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the gac that adds 3.6 gram 12500 orders (1 μ m); continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 4
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the gac that adds 5.4 gram 200nm; continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 5
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the graphite that adds 3.6 gram 8000 orders (1.3 μ m); continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 6
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; the graphite that adds 10.8 gram 400nm; continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Embodiment 7
The glass there-necked flask of 500mL is equipped with agitator and thermometer, under the nitrogen protection; the dehydrated alcohol that adds 200mL, the 18.4g Magnesium Chloride Anhydrous stirs and heats up; 70 ℃ of temperature are bathed in control; after magnesium chloride dissolves fully, add the 0.2g polyvinyl alcohol, stir treat to dissolve fully after; the gac that adds 3.6 gram 12500 orders (1 μ m); continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Comparative example 1
The glass there-necked flask of 500mL is equipped with agitator and thermometer, under the nitrogen protection; the dehydrated alcohol that adds 200mL, the 18.4g Magnesium Chloride Anhydrous stirs and heats up; 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Comparative example 2
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; adding 10.8 gram median sizes is the silica gel of 0.02～0.1 μ m; continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Comparative example 3
The glass there-necked flask of 500mL; agitator and thermometer are housed, under the nitrogen protection, add the dehydrated alcohol of 200mL; 18.4g Magnesium Chloride Anhydrous; stir to heat up, 70 ℃ of temperature are bathed in control, wait magnesium chloride to dissolve fully after; adding 3.6 gram median sizes is the silica gel of 0.02～0.1 μ m; continue to stir, make to be uniformly dispersed, under agitation aforesaid liquid is used for spraying drying then.Test-results sees Table 1.
Table 1: test-results:
| Numbering | Median size Mm | MgCl2 content (%wt) | Oxyethyl group content (%wt) | Electron microscopic observation |
| Embodiment 1 | 22 | 38 | 50 | Spherical |
| Embodiment 2 | 23 | 37 | 57 | Spherical |
| Embodiment 3 | 18 | 36 | 52 | Spherical |
| Embodiment 4 | 18 | 35 | 49 | Spherical |
| Embodiment 5 | 25 | 35 | 33 | Spherical |
| Embodiment 6 | 18 | 38 | 37 | Spherical |
| Embodiment 7 | 38 | 34 | 41 | Spherical |
| Comparative example 1 | 25 | 45 | 57 | Fragmentation, irregular |
| Comparative example 2 | 25 | 35 | 41 | Spherical |
| Comparative example 3 | 25 | 39 | 48 | Fragmentation, irregular |
Claims (8)
1. spherical complex carrier that is used for olefin polymerization catalysis, its be by Magnesium Chloride Anhydrous with after alcohol mixes by a certain percentage, generate magnesium chloride alcohol adduct melt, mix with carbonaceous solid carrier powder again, obtain through spray shaping; Wherein with MgCl
2Mole number be 1, with a represent alcohol mole number, b represents carbonaceous solid carrier M and MgCl
2Weight ratio, MgCl
2The chemical constitution of-alcohol-carrier M is: MgCl
2-a alcohol-bM, wherein a value is 1.0～6.0; The value of b is 0.001～1.0; Wherein carbonaceous solid carrier powder is that median size is gac, CNT (carbon nano-tube), carbon black, graphite or the carbon dust of 0.06～350 μ m; Alcohol is the Fatty Alcohol(C12-C14 and C12-C18) of general formula R OH, and 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.
2. the spherical complex carrier that is used for olefin polymerization catalysis according to claim 1, wherein Chun mole number a is 1.5～3.5, carbonaceous solid carrier M and MgCl
2Weight ratio b be 0.005～0.5.
3. the spherical complex carrier that is used for olefin polymerization catalysis according to claim 1, wherein carbonaceous solid carrier powder is an activated carbon.
4. the spherical complex carrier that is used for olefin polymerization catalysis according to claim 1, wherein said alcohol are a kind of of methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, n-Octanol, 2-Ethylhexyl Alcohol or their mixture.
5. the spherical complex carrier that is used for olefin polymerization catalysis according to claim 1, wherein said alcohol are ethanol.
6. any one described preparation method who is used for the spherical complex carrier of olefin polymerization catalysis of claim 1～5 is:
A. prepare magnesium chloride solution
In the reactor of stirring is housed, add pure and mild magnesium chloride, make that the alcohol and the mol ratio of magnesium chloride are 3～50: 1, rising temperature for dissolving gets homogeneous solution then;
B. prepare spherical complex carrier
In above-mentioned magnesium chloride solution, add described carrier M, stir, make slurries, then these slurries are carried out spraying drying, obtain spherical complex carrier.
7. the preparation method who is used for the spherical complex carrier of olefin polymerization catalysis according to claim 6, it is characterized in that, can also in the slurries system, add pure soluble gum stick, described tackiness agent is polyethylene glycol, methylcellulose gum, polyvinyl alcohol or polyvinyl acetate (PVA), and the weight ratio of tackiness agent and magnesium chloride is 0～0.5: 1.
8. the preparation method who is used for the spherical complex carrier of olefin polymerization catalysis according to claim 7 is characterized in that, described tackiness agent is a polyvinyl alcohol.
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| CNA200710062874XA CN101225128A (en) | 2007-01-19 | 2007-01-19 | Spherical complex carrier for olefin polymerization catalyst and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010133081A1 (en) * | 2009-05-18 | 2010-11-25 | 中国石油化工股份有限公司 | Catalyst support used for olefinic polymerization and preparing method and application thereof |
| CN104926969A (en) * | 2015-03-27 | 2015-09-23 | 青岛科技大学 | Preparation method for polyisoprene resin |
| CN104926968A (en) * | 2015-03-27 | 2015-09-23 | 青岛科技大学 | Novel carbon material/polyisoprene nano-grade composite material preparation method |
| CN108219040A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component of spherical alkoxyl magnesium particle, preparation method and application |
| CN114426604A (en) * | 2021-12-23 | 2022-05-03 | 广东石油化工学院 | MgCl2@ modified activated carbon composite carrier supported titanium compound catalyst and preparation method thereof |
-
2007
- 2007-01-19 CN CNA200710062874XA patent/CN101225128A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010133081A1 (en) * | 2009-05-18 | 2010-11-25 | 中国石油化工股份有限公司 | Catalyst support used for olefinic polymerization and preparing method and application thereof |
| US9120089B2 (en) | 2009-05-18 | 2015-09-01 | China Petroleum & Chemical Corporation | Catalyst support used for olefin polymerization and preparing method and application thereof |
| CN104926969A (en) * | 2015-03-27 | 2015-09-23 | 青岛科技大学 | Preparation method for polyisoprene resin |
| CN104926968A (en) * | 2015-03-27 | 2015-09-23 | 青岛科技大学 | Novel carbon material/polyisoprene nano-grade composite material preparation method |
| CN104926968B (en) * | 2015-03-27 | 2018-11-27 | 青岛科技大学 | A kind of preparation method of carbon material/polyisoprene nanocomposite |
| CN108219040A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component of spherical alkoxyl magnesium particle, preparation method and application |
| CN114426604A (en) * | 2021-12-23 | 2022-05-03 | 广东石油化工学院 | MgCl2@ modified activated carbon composite carrier supported titanium compound catalyst and preparation method thereof |
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Open date: 20080723 |