CN100400553C - Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization - Google Patents
Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization Download PDFInfo
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- CN100400553C CN100400553C CNB2006100496248A CN200610049624A CN100400553C CN 100400553 C CN100400553 C CN 100400553C CN B2006100496248 A CNB2006100496248 A CN B2006100496248A CN 200610049624 A CN200610049624 A CN 200610049624A CN 100400553 C CN100400553 C CN 100400553C
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- catalyst
- loaded catalyst
- chromium
- chromic oxide
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Abstract
The present invention discloses an improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization. The present invention is characterized in that the catalyst system comprises a chromous loaded catalyst or a mixture system of the chromous loaded catalyst and a chrome oxide loaded catalyst, and a dispersion solvent. The dispersion solvent can be mineral oil. The catalyst system of the present invention can prevent catalyst granules at a reaction initial stage from being agglomerated due to overheating, can eliminate the electrostatic problem of the chromous loaded catalyst and can be operated in a fluidized bed condensing state schema of a vapour phase process.
Description
Technical field
The present invention relates to a kind of catalyzer, in particular for the improved catalyst system of vinyl polymerization or ethene and alpha-olefin copolymer.
Background technology
United States Patent (USP) 2825721 disclosed chromic oxide (the logical CrO that refers to
3) loaded catalyst, also being referred to as the Phillips catalyzer is the polyethylene field catalyst type of exploitation early.Utilize the aqueous solution or the organic solvent solution impregnated carrier of the compound of chromium such as chromium trioxide, through super-dry, roasting chromium cpd is converted into chromium trioxide, thereby finally forms the chromic oxide loaded catalyst.Chromic oxide loaded catalyst synthetic molecular weight of polyethylene height, molecular weight distribution is wide, and a spot of long-chain branch is arranged on the molecular chain, so resin has good processing properties again when having good physicals.But because the chromic oxide loaded catalyst has a process that is reduced into divalence chromium active centre in polymerization process, the inductive phase that has a very long almost non-activity when making the catalyst vinyl polymerization, make the chromic oxide loaded catalyst drive or trade mark handoff procedure in operational difficulty, even may cause the reactor temperature runaway because having added too much catalyzer.And because the existence of the inductive phase of very long almost non-activity, the chromic oxide loaded catalyst can not shorten the residence time, therefore can not adopt United States Patent (USP) 4543399,4588790 and the condensation mode of 5352749,5405922 gas-phase polyethylenes of announcing and the operating method that supercool coagulates pattern.United States Patent (USP) 3780011,3887494,4806513,4877763 by add other components for example the method for the compound of aluminium, titanium, zinc, boron, phosphorus etc. shorten inductive phase, and improve catalyst performance, but can not eliminate inductive phase by the compound that adds these elements.
Fubini etc. (Fubini B, Ghiotti G, Stradella L, et al.[J] .J.Catal.1980,66:200～213) find, contain Cr (the VI)/SiO of chromium 1%
2, with after the CO reduction, chromous content is up to 98% under 623K.Chromium-based catalysts after the CO reduction and very fast formation active centre after ethene contacts.McDaniel (McDanie M P.[J] .Adv.Catal.1985,33:47～98) discovers, through the vinyl polymerization behavior of CO reductive chromium-based catalysts with unreduced be very much similar, and the performance of product is about the same.
United States Patent (USP) 4247421,4735931,4966951,5208309,5274056,5284926,6255413 have announced different divalence chromium loaded catalysts, are used to produce the polymkeric substance of different performance.But this catalyzer initial reaction rate is too fast, and initial activity is too high behind the adding reactor, and reaction is difficult to control.
The investigator utilizes the chromium and the chromic oxide load altogether of other types, and perhaps other chrome catalysts and chromic oxide mix, and reach the purpose of improving kinetics or improving polymer performance.United States Patent (USP) 4325839,4369295 on activatory chromic oxide loaded catalyst basis the luxuriant chromium cpd of load with quick starting characteristic again, United States Patent (USP) 5034364 usefulness silane chromate esters and chromic oxide load on identical carrier together, obtain a kind of mixing chrome catalysts, above-mentioned two patents all are to utilize to mix two kinds of different dynamic characteristic chrome catalysts, reach and improve dynamic (dynamical) purpose.United States Patent (USP) 5198400 and continuity patent 5310834 thereof have been announced a kind of mixed catalyst, a kind of component is a chromic oxide, and contain the compound of aluminium, phosphorus etc., another component is a chromium acetate, United States Patent (USP) 5169816 has been announced a kind of organic chromium mixed catalyst, and above-mentioned three patents all are to utilize the different polymerization properties of two kinds of components to produce high performance polymer.
Too high in order to solve the metallocene catalyst initial activity, reactor is the problem of caking easily, and United States Patent (USP) 5317036 and 5693727 has been announced the not process and the method for the metallocene catalyst introducing polymerization reactor of load.United States Patent (USP) 6069213 has been announced the mixed system that the metallocene catalyst of the metallocene of load and not load is formed.
United States Patent (USP) 6846886 announced a kind of in polymerization process, prepare continuously carried catalyst and not supported catalyst solution composition mixed system introduce the method for polymerization reactor then.
International Application No. WO 2004094489 has been announced two types slurry catalyst, a kind of is single slurry catalyst system of planting supported chrome catalysts (chromic oxide or silane chrome catalysts) and mineral oil composition, and another kind is the slurry catalyst system that chromic oxide loaded catalyst and silane type chrome catalysts are formed dual catalyst and mineral oil composition.In the slurry catalyst system of above-mentioned patent, all do not relate to divalence chromium loading type slurry system, and the slurry system of chromic oxide loading type and divalence chromium loading type mixed catalyst.
Summary of the invention
The present invention is directed to being difficult to that divalence chromium loaded catalyst or chromic oxide and divalence chromium loaded catalyst mixed catalyst exist preserve, static is many, initial activity is high and shortcoming such as easy caking, has developed divalence chromium loaded catalyst or the chromic oxide and the divalence chromium loaded catalyst mixed catalyst slurry system of vinyl polymerization and ethene and a-olefin-copolymerization.
The invention provides the improved catalyst system of vinyl polymerization or ethene and a-olefin-copolymerization, comprise
A) mixed system of divalence chromium loaded catalyst or divalence chromium loaded catalyst and chromic oxide loaded catalyst; B) dispersion solvent.
Described dispersion solvent can be a mineral oil.
Solid content is 0.1～5.5% in the described catalyst system.
Catalyst system of the present invention can polymerising ethylene, also can be ethene and other a-olefin-copolymerizations, and a-alkene is specially propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, one or several in 1-nonene and the 1-decene.
In the mixed system of described divalence chromium loaded catalyst and chromic oxide loaded catalyst, the chromic oxide loaded catalyst with and divalence chromium loaded catalyst weight ratio be 0.01～10, be preferably 0.02～1.
The chromic oxide loaded catalyst can adopt United States Patent (USP) 2825721 disclosed chromic oxide loaded catalysts, also can adopt United States Patent (USP) 3780011,3887494,4806513,4877763 announce pass through for example chromic oxide loaded catalyst of the compound of aluminium, titanium, zinc, boron, phosphorus, fluorine etc. of other components of interpolation.The weight content that the interpolation element accounts for the chromic oxide loaded catalyst is 0.2～5%.
Divalence chromium loaded catalyst can adopt United States Patent (USP) 4247421,4735931,4966951,5208309,5274056,5284926, the 6255413 various divalence chromium loaded catalysts of being announced.
In the catalyst system, chromic oxide loaded catalyst and divalence chromium loaded catalyst can be same vehicle, also can be different carriers, for example, all are with a kind of silica gel (SiO
2), perhaps different model silica gel, perhaps a kind of is silica gel (SiO
2), a kind of is aluminum phosphate (AlPO
4).
In the catalyst system, the content of chromium is 0.1～5% in the chromic oxide loaded catalyst, and the content of chromium is 0.1～2% in the divalence chromium loaded catalyst.
Catalyst system of the present invention can prevent that the initial reaction stage granules of catalyst from luming because of overheated, and can eliminate the electrostatic problem of chromium loaded catalyst, and can be at United States Patent (USP) 4543399,4588790 and 5352749, the condensation mode of 5405922 gas-phase polyethylenes of announcing and supercool coagulate under the pattern to be operated, and improves the space-time yield of production equipment greatly
Embodiment
Embodiment 1
1. the preparation of divalence chromium supported catalyst
1. the preparation of chromic oxide loaded catalyst:
1) silica gel is predrying.With N
2Be fluidized gas, in activator, Davison957 silica gel (chromium that contains 0.18～0.30wt%) is heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N
2, silica gel transferred to after being cooled to 100 ℃ and blows jar;
2) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO
2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C
3H
7O)
4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5～4.5%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation;
3) silica gel activating.Titanizing silica gel is delivered to activator from Preparation tank, and use N
2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃ then, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N
2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr;
4) CO reduction.Fluidized gas is switched to N from air
2, wait catalyzer to be cooled to 350 ℃, with fluidized gas from N
2Switch to CO and N
2Gas mixture, and at 350 ℃ of constant temperature 2hr;
5) catalyzer cooling.Stop heating, fluidized gas is switched to N from gas mixture
2, be cooled to 100 ℃ always, obtain divalence chromium loaded catalyst.
2. catalyst preparation
Catalyzer dispersion solvent mineral oil, solid content are 4.5%.
3. polymerization
In the gas-phase fluidized-bed reactor of a pilot scale level, produce the multipolymer of ethene and 1-butylene.The reactor controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 25kg/hr, and the space-time yield of reactor is 74.5kgPE/hrm
3Polymerizing condition and polyethylene product characteristic see Table 1.
Embodiment 2
The preparation of divalence chromium supported catalyst and catalyst formulation are with embodiment 1.
In the gas-phase fluidized-bed reactor of a pilot scale level, under the frozen state pattern, produce the multipolymer of ethene and 1-butylene, reactor device controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 35kg/hr, and the space-time yield of reactor is 104kg PE/hrm3.
Polymerizing condition and polyethylene product characteristic see Table 1
Embodiment 3
1. the preparation of chromic oxide loaded catalyst:
1) silica gel dipping.Chromium trioxide aqueous solution dip loading Davison955 silica gel, the concentration of chromium make that the weight content of chromium is 0.3% after the load;
2) silica gel is predrying.With N
2Be fluidized gas, the silica gel after in activator, will flooding be heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N
2, silica gel transferred to after being cooled to 100 ℃ and blows jar;
3) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO
2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C
3H
7O)
4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5～4.5%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation;
4) silica gel is fluoridized and is activated.Be lower than in the activator temperature under 100 ℃ the situation, titanizing silica gel is delivered to activator from Preparation tank, add hexafluorosilicic acid amine salt ((NH
4)
2SiF
6) (3g hexafluorosilicic acid amine salt/kg SiO
2) to activator, use N
2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N
2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr;
5) catalyzer cooling.Stop heating, continue blowing air, wait catalyzer to be cooled to 325 ℃, air is switched to N
2, be cooled to 100 ℃ always, obtain the chromic oxide loaded catalyst.
2. the preparation of divalence chromium loaded catalyst
1) silica gel is predrying.With N
2Be fluidized gas, in activator, Davison957 silica gel (chromium that contains 0.18～0.30wt%) is heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N
2, silica gel transferred to after being cooled to 100 ℃ and blows jar.
2) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO
2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C
3H
7O)
4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5～4.5wt%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation.
3) silica gel is fluoridized and is activated.Be lower than in the activator temperature under 100 ℃ the situation, titanizing silica gel is delivered to activator from Preparation tank, add hexafluorosilicic acid amine salt ((NH
4)
2SiF
6) (3g hexafluorosilicic acid amine salt/kg SiO
2) to activator, use N
2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N
2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr.
4) CO reduction.Fluidized gas is switched to N from air
2, wait catalyzer to be cooled to 350 ℃, with fluidized gas from N
2Switch to CO and N
2Gas mixture, and at 350 ℃ of constant temperature 2hr.
5) catalyzer cooling.Stop heating, fluidized gas is switched to N from gas mixture
2, be cooled to 100 ℃ always, obtain divalence chromium loaded catalyst.
3. catalyst preparation
The proportioning of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 1: 2.5.
Catalyzer dispersion solvent mineral oil, solid content are 5.5%.
4. polymerization
In the gas-phase fluidized-bed reactor of a pilot scale level, produce the multipolymer of ethene and 1-hexene.The reactor controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 25kg/hr, and the space-time yield of reactor is 74.5kg PE/hrm
3Polymerizing condition and polyethylene product performance see Table 1.
Table 1
Claims (6)
1. improved catalyst system that is used for vinyl polymerization or ethene and alpha-olefin copolymer is characterized in that: described catalyst system comprises a) mixed system of divalence chromium loaded catalyst and chromic oxide loaded catalyst; B) dispersion solvent;
Described dispersion solvent is a mineral oil;
The solid weight content is 0.1～5.5% in the described catalyst system.
2. according to the described catalyst system of claim 1, it is characterized in that: divalence chromium loaded catalyst or the used carrier of chromic oxide loaded catalyst are silica gel or aluminum phosphate.
3. according to the described catalyst system of claim 1, it is characterized in that: in the mixed system of described divalence chromium loaded catalyst and chromic oxide loaded catalyst, the weight ratio of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 0.01～10.
4. according to the described catalyst system of claim 3, it is characterized in that: in the catalyst system, the weight ratio of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 0.02～1.
5. according to claim 1,2,3,4 arbitrary described catalyst systems, it is characterized in that: in the catalyst system, the weight content of chromium is 0.1～5% in the chromic oxide loaded catalyst, and the weight content of chromium is 0.1～2% in the divalence chromium loaded catalyst.
6. according to the described catalyst system of claim 1, it is characterized in that: contain in the catalyst system and add in element aluminum, titanium, zinc, boron, phosphorus, the fluorine one or more, the weight content that adds element is 0.2～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100496248A CN100400553C (en) | 2006-02-25 | 2006-02-25 | Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100496248A CN100400553C (en) | 2006-02-25 | 2006-02-25 | Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization |
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| CN100400553C true CN100400553C (en) | 2008-07-09 |
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| CNB2006100496248A Expired - Fee Related CN100400553C (en) | 2006-02-25 | 2006-02-25 | Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2740755C (en) | 2011-05-25 | 2019-01-15 | Nova Chemicals Corporation | Chromium catalysts for olefin polymerization |
| CN104817752B (en) * | 2015-05-06 | 2017-05-10 | 无锡耀汇科技有限公司 | Polyethylene thin film and preparation method thereof |
| CN108976326B (en) * | 2017-05-31 | 2021-04-13 | 中国石油化工股份有限公司 | Metallocene polyethylene catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4820785A (en) * | 1986-06-16 | 1989-04-11 | Phillips Petroleum Company | In situ comonomer generation in olefin polymerization |
| US5310834A (en) * | 1987-05-20 | 1994-05-10 | Quantum Chemical Corporation | Mixed chromium catalysts and polymerizations utilizing same |
| WO2004094489A1 (en) * | 2003-03-28 | 2004-11-04 | Union Carbide Chemicals & Plastics Technology Corporation | Chromium-based catalysts in mineral oil for production of polyethylene |
-
2006
- 2006-02-25 CN CNB2006100496248A patent/CN100400553C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4820785A (en) * | 1986-06-16 | 1989-04-11 | Phillips Petroleum Company | In situ comonomer generation in olefin polymerization |
| US5310834A (en) * | 1987-05-20 | 1994-05-10 | Quantum Chemical Corporation | Mixed chromium catalysts and polymerizations utilizing same |
| WO2004094489A1 (en) * | 2003-03-28 | 2004-11-04 | Union Carbide Chemicals & Plastics Technology Corporation | Chromium-based catalysts in mineral oil for production of polyethylene |
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| CN1814628A (en) | 2006-08-09 |
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