CN102399324B - Preparation method of olefin polymerization catalyst slurry - Google Patents
Preparation method of olefin polymerization catalyst slurry Download PDFInfo
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- CN102399324B CN102399324B CN 201010283016 CN201010283016A CN102399324B CN 102399324 B CN102399324 B CN 102399324B CN 201010283016 CN201010283016 CN 201010283016 CN 201010283016 A CN201010283016 A CN 201010283016A CN 102399324 B CN102399324 B CN 102399324B
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- polymerization catalyst
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- catalyst components
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Abstract
The invention relates to a preparation method of olefin polymerization catalyst slurry. The preparation method of the olefin polymerization catalyst slurry is characterized in that in olefin polymerization catalyst component preparation, after low-boiling point alkane washing, catalyst suspension is formed and then is directly mixed with mineral oil; and the mixture is subjected to vacuum drying with stirring. The olefin polymerization catalyst slurry obtained by the preparation method has a slow sedimentation rate and good stability, and is suitable for continuous production adopting a vapor phase method-based polypropylene production device.
Description
Technical field
The present invention relates to a kind of preparation method of olefin polymerization catalysis slurries, belong to field of olefin polymerisation.
Background technology
Normally known for the preparation of polyolefinic olefin polymerization catalyst components, in general, in the intermittence type polymerization production process, olefin polymerization catalyst components enters reactor with the powder form by inert gas purge or solvent washing; In the continous way polymerization production process, olefin polymerization catalyst components generally enters reactor with the slurries form.
In the continuous flow procedure of gas-phase polymerization polypropylene device, olefin polymerization catalyst components generally continuously adds reactor by volume pump with the slurries form under whipped state, this feed way has accurate measurement, safety advantage such as controlled, and slurries mainly are made up of catalyst component dry powder and liquid dispersion medium.In order to ensure slurries catalyst component steady concentration in reinforced process, dispersion medium adopts usually and has the chemically inert mineral oil of having of certain viscosity in the slurries, makes olefin polymerization catalyst components sedimentation in mineral oil slower, disperses more even.If the concentration instability of slurries or olefin polymerization catalyst components disperse inhomogeneous in mineral oil, the fluctuation of polyreaction actuator temperature will be caused, can make local superheating produce caking when serious, normal operation to device produces great effect, so olefin polymerization catalysis slurries stability and dispersed significant to the continuous production of gas-phase polymerization polypropylene device.
Solid particulate disperses the preparation slurries normally known in liquid, can realize by churned mechanically mode, but because olefin polymerization catalyst components is the fine particle in 0.1～100 micrometer range, specific surface area is big, surface energy is very big, olefin polymerization catalyst components takes place to assemble or reunite in being dried to the process of dry powder easily, simply olefin polymerization catalyst components dry powder is added in the mineral oil and stir, the dry powder particle that gathering takes place or reunite is difficult to stir is uniformly dispersed it, therefore the slurries settling velocity of preparation is fast, less stable.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of olefin polymerization catalyst components slurries, the olefin polymerization catalyst components slurries of this method preparation are uniformly dispersed, and settling velocity is slower, and the slurries good stability is applicable to the continuous production of gas-phase polymerization polypropylene device.
The preparation method of a kind of olefin polymerization catalyst components slurries of the present invention comprises the steps:
(a) in the preparation process of olefin polymerization catalyst components, making the finished product is suspension; This suspension no longer carries out the vacuum-drying operation and becomes catalyzer dry powder;
(b) with the suspension of gained with the washing of lower boiling alkane again with mineral oil, under agitation condition, carry out the vacuum-drying operation then, vacuum drying service temperature is 20～120 ℃, the relative vacuum degree is-0.1Mpa;
Described olefin polymerization catalyst components refers to that main ingredient is the catalyst component particle of particle size range in 0.1～100 micron of titanium, magnesium, chlorine and electron donor;
Described lower boiling alkane is the aliphatic hydrocarbon of 1～7 carbon atom;
Described mineral oil is white oil, and it is 10～100mm 40 ℃ of following kinematic viscosity
2/ s;
Olefin polymerization catalyst components refers to the granules of catalyst in 0.1～100 micrometer range among the present invention, its main ingredient is titanium, magnesium, chlorine and electron donor, for example Chinese patent CN85100997, CN1453298A, the disclosed catalyst component of ZL200410062290.9.
In the preparation process of olefin polymerization catalyst components, generally through the washing of inertia alkane, obtain solid powder th-1 catalyst component product through vacuum-drying again.Vacuum-drying is a kind of of lock out operation, be to detach after being adsorbed on the alkane gasification on granules of catalyst surface, because olefin polymerization catalyst components is the fine particle in 0.1～100 micrometer range, specific surface area is big, surface energy is very big, therefore olefin polymerization catalyst components inevitably can take place to assemble or reunite in being dried to the process of dry powder, this agglomeration of particles or reunion influence the homogeneity of catalyst component particle, the dispersing property of catalyst component in gas phase, liquid-phase system reduced greatly, and this is that we do not wish situation about occurring aborning.
The present invention finds unexpectedly, in the preparation process of olefin polymerization catalyst components, after adopting the washing of lower boiling alkane, no longer carry out the vacuum-drying operation and become catalyzer dry powder, employing makes catalyst suspension directly and mineral oil, carries out vacuum-drying under agitation condition again, and the catalyst slurry settling velocity that obtains is slow, stability better is applicable to the continuous production of gas-phase polymerization polypropylene device.
The method according to this invention, lower boiling alkane generally adopt the aliphatic hydrocarbon of 1～7 carbon atom, are preferably the aliphatic hydrocarbon of 5～7 carbon atoms, for example, and Skellysolve A, iso-pentane, normal hexane, heptane etc., more preferably iso-pentane, hexane.
The method according to this invention, mineral oil are white oil, and it is the mixture of liquid type hydro carbons, main component is the mixture of the positive isoparaffin of C16～C31, the molecular weight of white oil all within the 250-450 scope, has good oxidative stability, chemical stability usually.The trade mark of white oil is divided and is divided with the size of 40 ℃ of kinematic viscosity usually.40 ℃ of following kinematic viscosity of white oil that method of the present invention adopts are 10～100mm
2/ s is preferably 20～80mm
2/ s, No. 68 white oils more preferably, 40 ℃ of following kinematic viscosity are 68mm
2/ s.
The method according to this invention, drying process can be carried out at normal temperature, also can carry out in certain temperature, preferably at 20～120 ℃, more preferably at 40～80 ℃.
The method according to this invention, vacuum tightness adopt the relative vacuum kilsyth basalt to show that the relative vacuum degree is preferably-0.1Mpa in the drying process, and the time is more than 2 hours.
The method according to this invention, drying process are preferably carried out under agitation condition, and mixing speed per minute 20～500 changes, and being preferably 50～300 changes, and more preferably 70～200 change.
Embodiment
Embodiment 1
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 60 milliliters of iso-pentane and washs 3 times, adds 30 milliliters of iso-pentane again and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension.
In the 250ml of drying round-bottomed flask, add 28 gram white oils, add 90 milliliters of above-mentioned suspension again, under agitation condition, carry out vacuum-drying, temperature is 60 ℃, after 2 hours, gets 20 milliliters of catalyst slurries and injects 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Embodiment 2
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 60 milliliters of iso-pentane and washs 3 times, adds 30 milliliters of iso-pentane again and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension.
In the 250ml of drying round-bottomed flask, add 28 gram white oils, add 90 milliliters of above-mentioned suspension again, under agitation condition, carry out vacuum-drying, temperature is 40 ℃, after 2 hours, gets 20 milliliters of catalyst slurries and injects 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Embodiment 3
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 30 milliliters of hexanes and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension.
In the 250ml of drying round-bottomed flask, add 28 gram white oils, add 90 milliliters of above-mentioned suspension again, under agitation condition, carry out vacuum-drying, temperature is 60 ℃, after 2 hours, gets 20 milliliters of catalyst slurries and injects 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Embodiment 4
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 30 milliliters of hexanes and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension.
In the 250ml of drying round-bottomed flask, add 28 gram white oils, add 90 milliliters of above-mentioned suspension again, under stirring, 40 ℃ of conditions of temperature, carry out vacuum-drying, after 2 hours, get 20 milliliters of catalyst slurries and inject 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Comparative example 1
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 30 milliliters of hexanes and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension, with 90 milliliters of suspension vacuum-dryings, obtains 12 gram catalyzer dry powder.
Subsequently in the 100ml of drying round-bottomed flask, add 28 gram white oils, under agitation add 12 gram catalyzer dry powder, under stirring, 60 ℃ of conditions of temperature, carry out vacuum-drying, after 2 hours, get 20 milliliters of catalyst slurries and inject 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Comparative example 2
Catalyst component is prepared according to patent CN85100997 embodiment 1 method, and just catalyst component does not carry out vacuum-drying after with hexane wash, adds 30 milliliters of hexanes and is mixed with suspension.So repeatedly preparation obtains 500 milliliters of suspension, with 90 milliliters of suspension vacuum-dryings, obtains 12 gram catalyzer dry powder.
Subsequently in the 100ml of drying round-bottomed flask, add 28 gram white oils, under agitation add 12 gram catalyzer dry powder, under stirring, 40 ℃ of conditions of temperature, carry out vacuum-drying, after 2 hours, get 20 milliliters of catalyst slurries and inject 25 milliliters of band scale Glass tubings, leave standstill the height that reads supernatant liquid after 72 hours, calculate settling velocity.
Table 1
By the data in the table 1 as can be seen, adopt its settling velocity of catalyst slurry of the inventive method preparation obviously slower, illustrate that compared with the prior art the slurries of this method preparation disperse more even, stability is better.
Claims (7)
1. the preparation method of olefin polymerization catalyst components slurries is characterized in that, comprises the steps:
(a) in the preparation process of olefin polymerization catalyst components, making the finished product is suspension; This suspension no longer carries out the vacuum-drying operation and becomes catalyzer dry powder;
(b) with the suspension of gained with the washing of lower boiling alkane again with mineral oil, under agitation condition, carry out the vacuum-drying operation then, vacuum drying service temperature is 20～120 ℃, relative vacuum Du Wei ?0.1MPa;
Described olefin polymerization catalyst components refers to that main ingredient is the catalyst component particle of particle size range in 0.1～100 micron of titanium, magnesium, chlorine and electron donor;
Described lower boiling alkane is the aliphatic hydrocarbon of 1～7 carbon atom;
Described mineral oil is white oil, and it is 10～100mm 40 ℃ of following kinematic viscosity
2/ s.
2. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, described lower boiling alkane is the aliphatic hydrocarbon of 5～7 carbon atoms.
3. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, described lower boiling alkane is Skellysolve A, iso-pentane, normal hexane or normal heptane.
4. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, described lower boiling alkane is iso-pentane or hexane.
5. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, 40 ℃ of following kinematic viscosity of described white oil are 20～80mm
2/ s.
6. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, described mineral oil is No. 68 white oils, and 40 ℃ of following kinematic viscosity are 68mm
2/ s.
7. the preparation method of olefin polymerization catalyst components slurries according to claim 1 is characterized in that, (b) vacuum drying service temperature is 40～80 ℃ in the step.
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| CN 201010283016 CN102399324B (en) | 2010-09-16 | 2010-09-16 | Preparation method of olefin polymerization catalyst slurry |
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| CN 201010283016 CN102399324B (en) | 2010-09-16 | 2010-09-16 | Preparation method of olefin polymerization catalyst slurry |
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| CN102399324B true CN102399324B (en) | 2013-08-14 |
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| CN107141376B (en) * | 2016-03-01 | 2019-12-24 | 中国石油化工股份有限公司 | Olefin polymerization catalyst grading method, olefin polymerization catalyst suspension and olefin polymerization catalyst |
| CN114507304B (en) * | 2022-01-19 | 2023-11-24 | 国家能源集团宁夏煤业有限责任公司 | Dispersing agent, olefin polymerization catalyst slurry, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101407A (en) * | 1984-04-10 | 1987-01-17 | 国际壳牌研究有限公司 | Olefin Polymerization catalyst compositions |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101407A (en) * | 1984-04-10 | 1987-01-17 | 国际壳牌研究有限公司 | Olefin Polymerization catalyst compositions |
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