CN102952221A - Preparation method of chromium polyethylene catalyst - Google Patents
Preparation method of chromium polyethylene catalyst Download PDFInfo
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- CN102952221A CN102952221A CN2011102519404A CN201110251940A CN102952221A CN 102952221 A CN102952221 A CN 102952221A CN 2011102519404 A CN2011102519404 A CN 2011102519404A CN 201110251940 A CN201110251940 A CN 201110251940A CN 102952221 A CN102952221 A CN 102952221A
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Abstract
The invention relates to a preparation method of a catalyst, and particularly relates to a preparation method of a chromium polyethylene catalyst. The method mainly comprises the steps of impregnation, drying, activation and reduction. Through the invention, a chromium catalyst with relatively high activity is prepared by the catalyst preparation method, and the catalyst preparation technology is simple and easy to implement industrially. The polymerization activity of the catalyst prepared by the preparation method is higher than that of the industrial chromium catalyst applied to the existing production device; by applying the catalyst to vinyl polymerization, high-density polyethylene resin with a relatively wide melt index range can be obtained; and the performance of the resin meets the index requirements for high-density polyethylene products.
Description
Technical field
The present invention relates to a kind of preparation method of catalyzer, be specifically related to a kind of for the Cr-polyethylene method for preparing catalyst.
Background technology
Polyethylene (PE) is with the honest and clean advantage of its property favorable rates, become the kind of output maximum in the general synthetic resin, (LDPE, linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), medium-density polyethylene (MDPE) and some have the PP Pipe Compound resin of property mainly to comprise Low Density Polyethylene.Catalyst technology is the core of polyethylene industry, and the catalyzer of research and development property or excellent properties polyvinyl resin is the focus that present polyethylene Application Areas is paid close attention to.The present composite catalyst etc. that comprises Ziegler-Natta catalyst, chrome catalysts, metallocene catalyst, transition-metal catalyst and prepare bimodal or broad peak distribution polyolefin of the Catalytic processes in the research and development.At present industrial catalyzer for polyvinyl resin production main still Ziegler-Natta catalyst and chrome catalysts.
Ziegler-Natta catalyst is with titanium chloride load preparation, and the large catalyzer that generally uses, and main carriers is magnesium chloride and silica gel, and preparation becomes spherical supported catalyst.These solid catalysts need to carry out compositely with aluminum alkyl catalyst, form the catalyst system with catalytic activity.Ziegler-Natta catalyst presents excellent polymerization catalyzed performance, and partially modified catalyzer has the copolymerization catalytic performance, can control comonomer distribution.The normally used preparation technology of Ziegler-Natta catalyst adopts the whole bag of tricks at first the magnesium compound (magnesium chloride, alkyl magnesium compound, alkoxyl magnesium compound) of solubility to be dissolved into homogeneous phase solution, then it is separated out to prepare again efficient olefin polymerization catalysis.Also the magnesium compound solution of solubility at first can be impregnated on the micro-spherical silica gel carrier in addition, then prepare form, well-distributed efficient olefin polymerization catalysis.
Korea S Samsung synthetic chemistry company develops the solid-state ligand catalyst of a kind of titanium, it is that magnesium halogenide is formed solution in ethanol, add ester compound and boride, add again titanium compound and a kind of silicon compound after the reaction, make it form high-activity magnesium-supported titanium solid catalyst.U.S. Engelhard company develops a kind of have high reactivity and the desirable load catalyst system of hydrogen response value, and carrier is made of a kind of magnesium compound, a kind of silicic acid alkyl fat and a kind of monoesters, the preparation supported titanium catalyst.Mitsui chemical company develops a kind of supported titanium catalyst, utilize liquid magnesium compound and liquid titanium compound to react, add simultaneously a kind of silicoorganic compound that do not contain active hydrogen, this catalyzer has high reactivity, the gained polyethylene particle is even, and ash content is few.The Italian branch office of Basell company realizes that with the magnesium chloride load titanium catalyst ethene and alpha-olefin carry out copolymerization, and more special is to have used 1,3-diether as internal electron donor, and the copolymerization catalytic activity is good, and polymer performance is good.
Saudi Aribian Basic Industry Company develops a kind of heterogeneous catalyst, and it comprises at least a transistion metal compound, uses magnesium compound and a kind of internal electron donor.Preparation is based on a kind of polypropylene of producing with the waste liquid of Ziegler-Natta catalyst, adds pure magnesium compound, and the weight that contains for Recycling of waste liquid is the transistion metal compound of 10%-20%, cleans subsequently and drying, consists of supported catalyst.
Chrome catalysts is called again the Phillips catalyzer, even be that chromic oxide and so on is compound loaded on the inorganic oxide of single or complex carrier such as silicon-dioxide, aluminum oxide, zirconium white Thorotrast and so on.Be mainly used at first the polyethylene production technique of Phillips company and Univation technology company, production homopolymerization HDPE also can be used for the copolymerization of ethene and alpha-olefin after the improvement, and the characteristics of polyolefin resin product are the molecular weight distribution with non-constant width.
Germany Basell polyolefins company is developed a kind of titanium and chromium composite catalyst, but the polyethylene catalysts that production machinery performance and processing characteristics have both, carrier is a kind of spray-dired oxide compound of sphere, utilize titanium compound that carrier is processed in suspension, then add a kind of chromium salt solution, calcine in the rare gas element under 280 ℃ again, at last, the polyolefin resin that activation obtains in the oxygen-containing gas under 500 ℃ to 800 ℃ has good mechanical property and processing characteristics, and the spot incidence in the film product reduces.
Titanium and the chromium composite catalyst of the development of Exxon Mobil company, that the chromium impregnated carrier is dewatered, then join in the inertia solution of titanium-containing compound and stir, generate titanium-containing compound solution, then desolventizing, and under 427 ℃, activate and can be made into the polyethylene with wide molecular weight distribution, the melting index of product and environmental stress crack resistance (ESCR) are all even more ideal.U.S. Univation technology company develops the bimodal or poly chromium oxide catalyst of broad peak molecular weight distribution of a kind of production, is a kind of chromium cpd to be loaded on the silica supports activate, and then adds a kind of alkylsilanol and a kind of tetraisonpropoxide.The silica supports component can have three kinds, is respectively that pore volume is 1.1-1.8cm
3/ g, surface-area are 245-375m
2/ g, pore volume are 2.4-3.7cm
3/ g, surface-area are 410-620m
2/ g, and pore volume is 0.9-1.4cm
3/ g, surface-area are 390-590m
2/ g can regulate and control catalyzer and polyolefine quality by control alkylsilanol addition, improves catalyst activity, molecular weight distribution and density polymer.
A kind of microgranular modified oxidized chrome catalysts has been invented by Finland Borealis company, it is the catalyzer that chromium oxide compounds is combined with inorganic carrier, under 400-950 ℃, carry out oxidation, again the chrome catalysts of gained and a kind of catalyst activator and a kind of transistion metal compound are flooded, obtain at last microgranular catalyzer.In steeping process, at least a cyclopentadienyl rings and described transition metal binding, part is alkoxyl group or amino, and select in the alkyl.In the situation that halogen and hybrid and described transition metal bonding can also contain heteroatoms or substituting group on the cyclopentadienyl rings.Such Dan Mao and dual metallocene catalysts can prepare bimodal or broad peak molecular weight distribution polyethylene.
A kind of novel process that is made of the prepolymer active particle catalyzer has been invented by Britain BP chemical company, utilize the fluidized-bed vapor phase process, employing loads on the chromium compound catalyst that contains refractory oxide particle shape carrier, carries out activating under 250 ℃ of conditions in non-reduced gas, makes the granular carrier clinkering.The prepolymer that generates in the catalytic reaction process contains 4 * 10 in every gram catalyzer
-5To the chromium atom of 3mg, can be used in and produce HDPE and LLDPE.
Exxon Mobil company develops a kind of couple of 2-three fragrant silicon base chromic salt catalyzer, but the HDPE at the end falls in production ultra-high molecular weight component concentration.By to fluidized-bed combined reactor and recycle gas line in introduce the generation that at least a catalysis deactivator reduces ultra-high molecular weight component in the high density polyethylene(HDPE).
Summary of the invention
The purpose of this invention is to provide a kind of for the Cr-polyethylene method for preparing catalyst, can greatly reduce the energy consumption in the Catalyst Production process, reduce simultaneously the granules of catalyst degree of crushing, improve the particle form of catalyzer, the catalyzer for preparing of technique has higher polymerization activity thus, can be used for producing the polyvinyl resin in certain molten finger and the density range, polymerization product has preferably particle shape.
Of the present invention for the Cr-polyethylene method for preparing catalyst, may further comprise the steps:
(1) dipping: in the double-cone type rotary drum dryer, add silica-gel carrier, start running program, allow silica-gel carrier be in the rolling state, at the uniform velocity spray into simultaneously mass concentration in the double-cone type rotary drum dryer and be 1 ‰～20% the steeping fluid that contains active ingredient, steeping fluid and silica gel mass ratio are 1: 2.5～3: 1;
(2) drying: the silica-gel carrier after will flooding carries out vacuum-drying in the double-cone type rotary drum dryer, drying temperature is 20～150 ℃, vacuum tightness is-0.001～-0.1MPa, 3～40 hours time of drying, in whole drying process, keep the double-cone type rotary drum dryer and be in running condition;
(3) activation: material is transferred to activation furnace carries out high-temperature activation, at first in 100～400 ℃ of lower High Purity Nitrogen atmosphere, activate 2～8 hours and remove whole physical absorption waters, then switch to dry air, under 300～1000 ℃, carry out high-temperature activation, activate 2～8 hours, form catalyst precursor;
(4) reduction: will under nitrogen protection, be transferred in the catalyst make up tank through the catalyzer precursor behind the high-temperature activation; pressed the solid-liquid mass ratio 1: 4～1: 20; adding C5～C9 varsol mixes; the organo-aluminium compound promotor is joined the reduction of carrying out catalyzer in the Preparation tank; the add-on of organo-aluminium compound is 0.5～15 according to aluminium, chromium element mol ratio; reduced 0.5～4 hour; be warming up to 20～100 ℃ after reduction process finishes and carry out solvent removal; dry 4～72 hours, obtain finished catalyst.
Preparation method's preferred version of the present invention is as follows:
(1) dipping: in the double-cone type rotary drum dryer, add silica-gel carrier, start running program, allow silica-gel carrier be in the rolling state, at the uniform velocity spray into simultaneously mass concentration in the double-cone type rotary drum dryer and be 5 ‰～10% the steeping fluid that contains active ingredient, steeping fluid and silica gel mass ratio are 1: 1.8～2: 1, allow steeping fluid fully contact with silica-gel carrier, and quick adsorption is finished the absorption dipping of active ingredient on carrier in the micropore of silica-gel carrier;
(2) drying: the silica-gel carrier after will flooding carries out vacuum-drying in the double-cone type rotary drum dryer, drying temperature is 30～100 ℃, vacuum tightness-0.01～-0.08MPa, 5～30 hours time of drying, in whole drying process, keep the double-cone type rotary drum dryer and be in running condition;
(3) activation: material is transferred to activation furnace carries out high-temperature activation, at first in 200～300 ℃ of lower High Purity Nitrogen atmosphere, activate 2～8 hours and remove whole physical absorption waters, then switch to dry air, under 600～800 ℃, carry out high-temperature activation, activate 2～8 hours, form catalyst precursor, in this process variation of valence has occured, the chromium of lower valency is oxidized to sexavalent chrome;
(4) reduction: will under nitrogen protection, be transferred in the catalyst make up tank through the catalyzer precursor behind the high-temperature activation, pressed the solid-liquid mass ratio 1: 5～1: 12, add C
5～C
9Varsol mixes, the organo-aluminium compound promotor is joined the reduction of carrying out catalyzer in the Preparation tank, the add-on of organo-aluminium compound is 1～10 according to aluminium, chromium element mol ratio, reduced 0.5～4 hour, be warming up to 30～80 ℃ after reduction process finishes and carry out solvent removal, dry 10～48 hours, obtain finished catalyst.
Wherein, active ingredient of the present invention is preferably the chromium compounds, can be the chromic salts compounds such as chromium nitrate, chromium acetate or chromium trioxide.Chromium element mass content is controlled at 0.1%-10% in the catalyzer, preferred 0.1%-5%.
Described organo-aluminium compound is preferably R (3-n)-Al-Ln, and the R in the formula is C
2～C
12Alkyl, L is C
1～C
8Alkoxyl group or phenoxy group, n is the rational number between 0～1.
Described C
5～C
9Varsol is preferably iso-pentane, normal hexane or normal heptane.
The invention has the advantages that: make the chromium-based catalysts with greater activity by this kind method for preparing catalyst, catalyst preparation process is simple, is easy to industrial implementation.The polymerization catalyst activity that adopts this preparation method to obtain is higher than the industrial chromium-based catalysts that uses on the present production equipment, this catalyzer carries out the high-density polyethylene resin that vinyl polymerization can obtain wider molten how, and resin property satisfies the requirement of high density polyethylene(HDPE) product index.
Embodiment
The present invention will be further described below in conjunction with embodiment.
As follows for the measuring method among the embodiment:
1) viscosity average molecular weight determination: adopt viscosimetry to measure, make solvent with perhydronaphthalene, 135 ℃ of temperature, Ubbelohde viscometer records intrinsic viscosity.Calculate molecular weight according to formula.
Mn＝5.37×10
4×[η]
1.37
2) melt mass flow rate is measured (MFR): carry out 190 ℃ of temperature by GB/T 3682-2000.
3) weight-average molecular weight (Mw) and molecular weight distribution (PDI): adopt gpc analysis, take the orthodichlorobenzene of 0.025g/L BHT as eluent, flow velocity 1.0ml/min, 135 ℃ of test temperatures.
Embodiment 1:
Take by weighing 40 grams, 955 silica gel and be transferred in the double-cone type rotary drum dryer in the beaker of 1 1000ml drying, starting the machine makes silica gel be in the rolling state.The massfraction that takes by weighing 0.4497 gram in the dry beaker of 100ml is 50% chromium acetate solution, adds the 60ml deionized water and is made into dipping solution, and dipping solution is at the uniform velocity sprayed into the double-cone type rotary drum dryer, and silica gel is fully contacted with chromium acetate solution, mixes.The double-cone type rotary drum dryer is warming up to 80 ℃, carries out 4 hours dryings in vacuum tightness under-the 0.08MPa.The silica-gel carrier that drying is good moves in the silica tube, and the bottom passes into high pure nitrogen, 200 ℃ of lower constant temperature activation 2 hours, then rises to 300 ℃ of activated gas and switches to dry air by high pure nitrogen, is warming up to 600 ℃ of activation 4 hours again.Stopped heating slow cooling after activation finishes; taking by weighing 10 grams after material is down to room temperature is transferred under nitrogen protection by in the catalyst arrangement bottle of processing through vacuum nitrogen; add 100ml through the normal hexane of deoxidation dehydration; open magnetic agitation; adding 2.2ml massfraction is 25% oxyethyl group 2 aluminium triethyl solution, reduces 30 minutes.Temperature of charge is risen to 70 ℃, keep this temperature to remove normal hexane, catalyzer is cooled to room temperature after being dried to the dry powder that can flow, and under nitrogen protection catalyzer is transferred in the catalyzer receiving bottle.
Adopt above-mentioned preparation method to carry out the preparation of catalyzer, and carried out the polymerization evaluation test at the 1L polymerization reactor, the activity that obtains catalyzer is higher than 170gPE.gcat
-1h
-1
Embodiment 2:
Take by weighing 40 grams, 955 silica gel and be transferred in the double-cone type rotary drum dryer in the beaker of 1 1000ml drying, starting the machine makes silica gel be in the rolling state.The massfraction that takes by weighing 0.4497 gram in the dry beaker of 100ml is 50% chromium acetate solution, adds the 80ml deionized water and is made into dipping solution, and dipping solution is at the uniform velocity sprayed into the double-cone type rotary drum dryer, and silica gel and chromium acetate solution are mixed.The double-cone type rotary drum dryer is warming up to 70 ℃, in vacuum tightness be-0.03MPa under dry 4 hours.The loaded article that drying is good moves in the silica tube, and the bottom passes into high pure nitrogen, 200 ℃ of lower constant temperature activation 3 hours, then rises to 300 ℃ of activated gas and switches to dry air by high pure nitrogen, is warming up to 600 ℃ of activation 6 hours again.Taking by weighing 10 grams after material is down to room temperature is transferred under nitrogen protection by in the catalyst arrangement bottle of processing through vacuum nitrogen; add 100ml through the normal hexane of deoxidation dehydration; open magnetic agitation, adding 2.2ml massfraction is 25% oxyethyl group 2 aluminium triethyl solution, reduces 30 minutes.Temperature of charge is risen to 70 ℃, keep this temperature to remove normal hexane, catalyzer is cooled to room temperature after being dried to the dry powder that can flow, and under nitrogen protection catalyzer is transferred in the catalyzer receiving bottle, and the polymerization catalyst that obtains is active to be 210gPE.gcat
-1h
-1
Embodiment 3:
Take by weighing 40 grams, 955 silica gel and be transferred in the double-cone type rotary drum dryer in the beaker of 1 1000ml drying, starting the machine makes silica gel be in the rolling state.The massfraction that takes by weighing 0.4497 gram in the dry beaker of 100ml is 50% chromium acetate solution, adds the 60ml deionized water and is made into dipping solution, and dipping solution is at the uniform velocity sprayed into the double-cone type rotary drum dryer, and silica gel is fully contacted with chromium acetate solution, mixes.The double-cone type rotary drum dryer is warming up to 60 ℃, in vacuum tightness be-0.07MPa under dry 10 hours.The loaded article that drying is good moves in the silica tube, and the bottom passes into high pure nitrogen, 200 ℃ of lower constant temperature activation 6 hours, then rises to 300 ℃ of activated gas and switches to dry air by high pure nitrogen, is warming up to 600 ℃ of activation 5 hours again.The catalyzer that takes by weighing after 10 grams activate is transferred under nitrogen protection by in the catalyst arrangement bottle of processing through vacuum nitrogen; add 120ml through the normal hexane of deoxidation dehydration; open magnetic agitation, adding 2.2ml massfraction is 25% oxyethyl group 2 aluminium triethyl solution, reduces 30 minutes.Remove normal hexane under 70 ℃, catalyzer is cooled to room temperature after being dried to the dry powder that can flow, and under nitrogen protection catalyzer is transferred in the catalyzer receiving bottle, and the polymerization catalyst that obtains is active to be 187gPE.gcat
-1h
-1
Embodiment 4:
Catalyst preparation process is identical with embodiment 1, just the activation temperature under the dry air is transferred to 500 ℃.
Embodiment 5:
Catalyst preparation process is identical with embodiment 1, just the activation temperature under the dry air is transferred to 700 ℃.
Embodiment 6:
Catalyst preparation process is identical with embodiment 1, just the activation temperature under the dry air is transferred to 800 ℃.
Embodiment 7:
Catalyst preparation process is identical with embodiment 2, has just changed the activity component load quantity of catalyzer, and namely chromium element mass content transfers to 0.20% in the catalyzer.
Embodiment 8:
Catalyst preparation process is identical with embodiment 2, has just changed the activity component load quantity of catalyzer, and namely chromium element mass content transfers to 0.30% in the catalyzer.
Embodiment 9:
Catalyst preparation process is identical with embodiment 2, has just changed the activity component load quantity of catalyzer, and namely chromium element mass content transfers to 0.50% in the catalyzer.
Embodiment 4～6 has carried out the polymerization evaluation to these three catalyzer on the 1L polymerization reactor, obtain the result as shown in table 1:
Table 1
Embodiment 7～9 has carried out the polymerization evaluation to these three catalyzer in the 1L polymerization reactor, obtain the result as shown in table 2:
Table 2
Claims (5)
1. one kind is used for the Cr-polyethylene method for preparing catalyst, it is characterized in that may further comprise the steps:
(1) dipping: in the double-cone type rotary drum dryer, add silica-gel carrier, start running program, allow silica-gel carrier be in the rolling state, at the uniform velocity spray into simultaneously mass concentration in the double-cone type rotary drum dryer and be 1 ‰～20% the steeping fluid that contains active ingredient, steeping fluid and silica gel mass ratio are 1: 2.5～3: 1;
(2) drying: the silica-gel carrier after will flooding carries out vacuum-drying in the double-cone type rotary drum dryer, drying temperature is 20～150 ℃, vacuum tightness is-0.001～-0.1MPa, 3～40 hours time of drying, in whole drying process, keep the double-cone type rotary drum dryer and be in running condition;
(3) activation: material is transferred to activation furnace carries out high-temperature activation, at first in 100～400 ℃ of lower High Purity Nitrogen atmosphere, activate 2～8 hours and remove whole physical absorption waters, then switch to dry air, under 300～1000 ℃, carry out high-temperature activation, activate 2～8 hours, form catalyst precursor;
(4) reduction: will under nitrogen protection, be transferred in the catalyst make up tank through the catalyzer precursor behind the high-temperature activation, pressed the solid-liquid mass ratio 1: 4～1: 20, add C
5～C
9Varsol mixes, the organo-aluminium compound promotor is joined the reduction of carrying out catalyzer in the Preparation tank, the add-on of organo-aluminium compound is 0.5～15 according to aluminium, chromium element mol ratio, reduced 0.5～4 hour, be warming up to 20～100 ℃ after reduction process finishes and carry out solvent removal, dry 4～72 hours, obtain finished catalyst.
2. according to claim 1 for the Cr-polyethylene method for preparing catalyst, it is characterized in that active ingredient is the chromium compounds.
3. according to claim 1 for the Cr-polyethylene method for preparing catalyst, it is characterized in that the steeping fluid mass concentration is 5 ‰～10%.
4. according to claim 1 for the Cr-polyethylene method for preparing catalyst, it is characterized in that organo-aluminium compound is R (3-n)-Al-Ln, the R in the formula is C
2～C
12Alkyl, L is C
1～C
8Alkoxyl group or phenoxy group, n is the rational number between 0～1.
5. according to claim 1 for the Cr-polyethylene method for preparing catalyst, it is characterized in that C
5～C
9Varsol is iso-pentane, normal hexane or normal heptane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160963A (en) * | 2018-08-28 | 2019-01-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of magnesium-modified chromium-based catalysts of ethylene polymerization and preparation method thereof |
| CN112679641A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
| CN114621368A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Ethylene gas-phase polymerization grade switching agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175590A (en) * | 1996-08-31 | 1998-03-11 | 中国石化齐鲁石油化工公司 | Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof |
| CN1373685A (en) * | 1999-09-09 | 2002-10-09 | 巴塞尔聚烯烃有限公司 | Method for producing supported chrome catalysts and use thereof for polymerization of olefins |
| CN101896508A (en) * | 2007-10-26 | 2010-11-24 | Pq硅石英国有限公司 | Catalyst precursor particles, their preparation and use |
| CN101932617A (en) * | 2008-02-27 | 2010-12-29 | 尤尼威蒂恩技术有限责任公司 | The chromium-based catalysts of modification and the polymerization process that uses it |
-
2011
- 2011-08-30 CN CN2011102519404A patent/CN102952221A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175590A (en) * | 1996-08-31 | 1998-03-11 | 中国石化齐鲁石油化工公司 | Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof |
| CN1373685A (en) * | 1999-09-09 | 2002-10-09 | 巴塞尔聚烯烃有限公司 | Method for producing supported chrome catalysts and use thereof for polymerization of olefins |
| CN101896508A (en) * | 2007-10-26 | 2010-11-24 | Pq硅石英国有限公司 | Catalyst precursor particles, their preparation and use |
| CN101932617A (en) * | 2008-02-27 | 2010-12-29 | 尤尼威蒂恩技术有限责任公司 | The chromium-based catalysts of modification and the polymerization process that uses it |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160963A (en) * | 2018-08-28 | 2019-01-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of magnesium-modified chromium-based catalysts of ethylene polymerization and preparation method thereof |
| CN109160963B (en) * | 2018-08-28 | 2021-05-04 | 吉化集团吉林市天龙催化剂有限公司 | Magnesium modified chromium catalyst for ethylene polymerization and preparation method thereof |
| CN112679641A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
| CN112679641B (en) * | 2019-10-18 | 2023-01-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
| CN114621368A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Ethylene gas-phase polymerization grade switching agent and preparation method thereof |
| CN114621368B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | Ethylene gas phase polymerization grade switching agent and preparation method thereof |
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Application publication date: 20130306 |