CN110964141B - Chromium-zirconium-molybdenum-loaded trimetal catalyst and preparation method and application thereof - Google Patents
Chromium-zirconium-molybdenum-loaded trimetal catalyst and preparation method and application thereof Download PDFInfo
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- CN110964141B CN110964141B CN201911247309.XA CN201911247309A CN110964141B CN 110964141 B CN110964141 B CN 110964141B CN 201911247309 A CN201911247309 A CN 201911247309A CN 110964141 B CN110964141 B CN 110964141B
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- 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
- C08F10/02—Ethene
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- 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
- C08F110/02—Ethene
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a chromium-zirconium-molybdenum loaded trimetallic catalyst, and a preparation method and application thereof. The catalyst comprises a porous inorganic carrier and three loaded active components, wherein the three active components comprise chromium oxide, zirconium oxide and molybdenum oxide, and the preparation method comprises the following steps: the solution containing chromium, zirconium and molybdenum is jointly dipped into an inorganic carrier, and then dried and roasted to obtain the trimetal catalyst for ethylene polymerization. The catalyst of the invention has the advantages of high catalytic activity, short polymerization time, simple preparation, high hydrogen regulation sensitivity, wide molecular weight distribution and the like, and can produce ethylene polymers with wide molecular weight distribution and multimodal distribution.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a trimetal-loaded catalyst, and a preparation method and application thereof.
Background
Polyethylene is one of the most productive general plastics in the world, and is widely applied to various fields such as industry, agriculture, automobiles, communication, daily life and the like due to excellent mechanical property, electrical insulation property and chemical corrosion resistance, the excellent properties mainly depend on the production process, catalyst technology, post-processing technology and the like of polyethylene, wherein the catalyst technology is the core technology of polyolefin industry, and the modification of the catalyst can effectively improve the production capacity of polyethylene, optimize the production process, save the cost, avoid the waste of raw materials and reduce the environmental pollution, so the polyethylene is widely concerned and researched by the industrial and academic fields.
The polyethylene catalysts known at present mainly comprise Ziegler-Natta catalysts, metallocene catalysts, non-metallocene catalysts and chromium catalysts, and researchers develop new catalysts such as composite catalysts, i.e. two catalysts are blended, such as various bimetallic composite catalysts, including Ziegler-Natta/Ziegler-Natta composite catalysts, Ziegler-Natta/metallocene composite catalysts, dual metallocene composite catalysts, chromium/metallocene composite catalysts and metallocene/late transition metal composite catalysts.
Patent 201210118427.2 discloses a new supported chromium vanadium metal oxide dual active center ethylene polymerization catalyst as a Phillips catalyst with Cr-V dual active center, which introduces a supported vanadium active component on the Phillips chromium catalyst to make it into a chromium polyethylene catalyst with Cr-V dual active center. Patent 201610741054.2 discloses a supported chromium zirconium bimetallic active center polyethylene catalyst, which is a chromium based polyethylene catalyst with two active centers of Cr-Mn by introducing a supported zirconium active component into the chromium based catalyst. Patent 201610742122.7 discloses a supported chromium-tungsten bimetallic active center polyethylene catalyst, which is a chromium-based polyethylene catalyst with two active centers of Cr-W by introducing a supported tungsten active component into the chromium-based catalyst. However, the bimetallic chromium catalyst still has the disadvantages of low catalytic activity and long polymerization time.
Few in the prior art have used a single reactor to synthesize high performance multimodal broad molecular weight distribution polyethylene by three metal supported olefin catalysts.
Disclosure of Invention
The invention aims to provide a supported chromium-zirconium-molybdenum trimetal catalyst for polyethylene, which has the advantages of high catalytic activity, short polymerization time, high hydrogen regulation sensitivity and excellent copolymerization performance and can produce multimodal polyethylene products with wide molecular weight distribution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a supported chromium-zirconium-molybdenum trimetal catalyst is characterized in that: the catalyst comprises a porous inorganic carrier and three loaded active components, wherein the three active components comprise chromium oxide, zirconium oxide and molybdenum oxide, and the total loading amount of chromium is 0.1-5 wt% of the total weight of the catalyst, based on the weight of Cr; the total loading of zirconium is 0.1-5 wt% of the total weight of the catalyst, based on the weight of Zr; the total loading of molybdenum is 0.1-5 wt% of the total weight of the catalyst, based on the weight of Mo.
The porous inorganic carrier is silicon oxide, aluminosilicate, titanium oxide and oxygenAt least one of magnesium oxide and calcium oxide; the specific surface area of the porous inorganic carrier is 300-500 m2Per g, pore volume of 4.0-6.0 cm3(ii)/g, the average pore diameter is 4-10 nm.
The raw material of the chromium oxide is at least one selected from chromium nitrate, chromium acetate, chromium chloride and chromium sulfate, the raw material of the zirconium oxide is at least one selected from zirconium nitrate, zirconium acetate, zirconium oxychloride and zirconium sulfate, and the raw material of the molybdenum oxide is at least one selected from molybdenum nitrate, molybdenum acetate, molybdenum sulfate and molybdenum phosphate.
The invention also aims to provide a preparation method of the supported chromium-zirconium-molybdenum trimetallic catalyst for polyethylene, which has the characteristics of simple preparation process and easy industrial implementation.
The preparation method of the supported chromium-zirconium-molybdenum trimetal catalyst comprises the following steps:
(1) preparing a chromium source, a zirconium source and a molybdenum source into an active component solution by using deionized water, then adding a porous inorganic carrier into the active component solution, uniformly stirring, standing and soaking for 3-8 hours;
(2) drying at 60-150 ℃ for 10-20h to obtain a catalyst loading substance;
(3) and (3) carrying out high-temperature roasting activation on the catalyst load in air or oxygen atmosphere, wherein the roasting temperature is 300-600 ℃, and the time is 2-8h, and cooling to obtain the chromium-zirconium-molybdenum loaded trimetal catalyst.
The chromium source is selected from at least one of chromium nitrate, chromium acetate, chromium chloride and chromium sulfate, the zirconium source is selected from at least one of zirconium nitrate, zirconium acetate, zirconium oxychloride and zirconium sulfate, and the molybdenum source is selected from at least one of molybdenum nitrate, molybdenum acetate, molybdenum sulfate and molybdenum phosphate.
The invention also provides the use of the supported chromium zirconium molybdenum trimetallic catalyst in the production of ethylene polymers for the production of ethylene homopolymers or copolymers. Contacting an olefin under polymerization conditions with the supported chromium zirconium molybdenum trimetallic catalyst, at least one cocatalyst; a molecular weight regulator is also added during the polymerization reaction; the cocatalyst is aluminum alkyl.
The invention has the beneficial effects that:
(1) the supported chromium-zirconium-molybdenum trimetal catalyst has the advantages of high catalytic activity, short polymerization time, high hydrogen regulation sensitivity and excellent copolymerization performance, can produce multimodal polyethylene products with wide molecular weight distribution, and has polymerization activity obviously superior to that of the supported bimetallic catalyst and polymerization time obviously shortened.
(2) The invention can conveniently adjust the molecular weight and molecular weight distribution of the ethylene homopolymer or copolymer by loading three different metal sources, namely a chromium source, a zirconium source and a molybdenum source on the same catalyst carrier and changing the factors such as the using amount of a cocatalyst, the polymerization temperature, a molecular weight regulator and the like, thereby easily obtaining the polymer with required performance.
(3) The preparation method can obtain the polyethylene catalyst with multiple active centers, has simple preparation process and is easy for industrial implementation.
Detailed Description
Preparation of the catalyst:
example 1: 15g of porous silica was impregnated with an aqueous solution of chromium nitrate, zirconium nitrate, and molybdenum nitrate at a concentration where the chromium loading (by mass) was 2.5% Cr, the zirconium loading (by mass) was 1.2% Zr, and the molybdenum loading (by mass) was 0.9% Mo. After the immersion was continued for 6.5 hours with stirring, the resultant was taken out and dried by heating at 100 ℃ for 14 hours. And (3) roasting the loaded porous silicon dioxide carrier at high temperature in a high-temperature furnace, wherein the roasting temperature is 500 ℃, and the roasting time is 4 hours, and cooling to obtain the loaded trimetallic catalyst. Wherein the pore volume of the porous silica carrier is 4.2cm3Per g, surface area 373m2In terms of/g, the mean pore diameter is 4.5 nm.
Comparative example 1: 15g of porous silica was impregnated with an aqueous solution of chromium nitrate and molybdenum nitrate at a concentration where the chromium loading (by mass) was 2.5% Cr and the molybdenum loading (by mass) was 2.1% Mo. After the immersion was continued for 6.5 hours with stirring, the resultant was taken out and dried by heating at 100 ℃ for 14 hours. The loaded porous silicon dioxide carrier is roasted at high temperature in a high-temperature furnace, the roasting temperature is 500 ℃, the roasting time is 4 hours, and the chromium-molybdenum-loaded porous silicon dioxide carrier is obtained after coolingA catalyst. Wherein the pore volume of the porous silica carrier is 4.2cm3Per g, surface area 373m2In terms of/g, the mean pore diameter is 4.5 nm.
Comparative example 2: 15g of porous silica was impregnated with an aqueous solution of chromium nitrate and zirconium nitrate at a concentration where the chromium loading (by mass) was 2.5% Cr and the zirconium loading (by mass) was 2.1% Zr. After the immersion was continued for 6.5 hours with stirring, the resultant was taken out and dried by heating at 100 ℃ for 14 hours. And (3) roasting the loaded porous silicon dioxide carrier at high temperature in a high-temperature furnace, wherein the roasting temperature is 500 ℃, and the roasting time is 4 hours, and cooling to obtain the chromium-zirconium two-metal loaded catalyst. Wherein the pore volume of the porous silica carrier is 4.2cm3Per g, surface area 373m2In terms of/g, the mean pore diameter is 4.5 nm.
Polymerization test:
the polymerization experiment was carried out by weighing 200mg each of the supported trimetallic catalyst of example 1, the supported chromium molybdenum trimetallic catalyst of comparative example 1 and the supported chromium zirconium trimetallic catalyst of comparative example 2. Replacing a stainless steel polymerization kettle with high-purity nitrogen for at least three times, adding normal hexane into the polymerization kettle, adding triethyl aluminum and the solid catalyst with certain concentration, filling ethylene into the reaction kettle to 0.6MPa, continuously introducing ethylene and keeping the pressure, reacting at 80 ℃ for 1 hour, adding a hydrochloric acid/ethanol mixed solution to terminate the reaction, drying the polymer in vacuum, weighing and analyzing.
TABLE 1 ethylene homopolymerization Activity of example 1 and comparative examples 1 and 2
| Catalysts for polymerization experiments | Activity (g)pE·gcat-1·h-1) |
| Catalyst of example 1 | 460.54 |
| Catalyst of comparative example 1 | 330.6 |
| Catalyst of comparative example 2 | 286.45 |
As can be seen from Table 1, the polymerization activity of the supported chromium-zirconium-molybdenum trimetallic catalyst in the polymerization test is obviously higher than that of the supported chromium-zirconium two-metal catalyst and the supported chromium-molybdenum two-metal catalyst, which indicates that the polymerization time of the supported chromium-zirconium-molybdenum trimetallic catalyst is obviously shortened and the production efficiency is improved.
In addition, the present invention can conveniently adjust the molecular weight and molecular weight distribution of ethylene homopolymer or copolymer by loading three different metal sources, i.e., chromium source, zirconium source and molybdenum source, on the same catalyst carrier, and also by changing the amount of cocatalyst used, polymerization temperature, molecular weight regulator and other factors, thereby easily obtaining a polymer having desired properties. The preparation method can obtain the polyethylene catalyst with multiple active centers, has simple preparation process and is easy for industrial implementation.
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A supported chromium zirconium molybdenum trimetallic catalyst for the production of ethylene homopolymers or copolymers characterized by: the catalyst comprises a porous inorganic carrier and three loaded active components, wherein the three active components comprise chromium oxide, zirconium oxide and molybdenum oxide, and the total loading amount of chromium is 2.5wt% of the total weight of the catalyst, based on the weight of Cr; the total loading of zirconium was 1.2wt% based on the total weight of the catalyst, based on the weight of Zr; the total loading of molybdenum is 0.9wt% of the total weight of the catalyst, based on the weight of Mo;
the porous inorganic carrier is at least one of silicon oxide, aluminosilicate, titanium oxide, magnesium oxide and calcium oxide; the specific surface area of the porous inorganic carrier is 300-500 m2Per g, pore volume of 4.0-6.0 cm3(ii)/g, the average pore diameter is 4-10 nm;
the preparation method of the catalyst comprises the following steps:
(1) preparing a chromium source, a zirconium source and a molybdenum source into an active component solution by using deionized water, then adding a porous inorganic carrier into the active component solution, uniformly stirring, standing and soaking for 3-8 hours;
(2) drying at 60-150 ℃ for 10-20h to obtain a catalyst loading substance;
(3) and (3) carrying out high-temperature roasting activation on the catalyst load in air or oxygen, wherein the roasting temperature is 300-600 ℃, and the time is 2-8h, and cooling to obtain the chromium-zirconium-molybdenum loaded trimetal catalyst.
2. The supported chromium zirconium molybdenum trimetallic catalyst of claim 1, wherein: the raw material of the chromium oxide is at least one selected from chromium nitrate, chromium acetate, chromium chloride and chromium sulfate, the raw material of the zirconium oxide is at least one selected from zirconium nitrate, zirconium acetate, zirconium oxychloride and zirconium sulfate, and the raw material of the molybdenum oxide is at least one selected from molybdenum nitrate, molybdenum acetate, molybdenum sulfate and molybdenum phosphate.
3. The supported chromium zirconium molybdenum trimetallic catalyst of claim 1, wherein: the chromium source is selected from at least one of chromium nitrate, chromium acetate, chromium chloride and chromium sulfate, the zirconium source is selected from at least one of zirconium nitrate, zirconium acetate, zirconium oxychloride and zirconium sulfate, and the molybdenum source is selected from at least one of molybdenum nitrate, molybdenum acetate, molybdenum sulfate and molybdenum phosphate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| NL8103703A (en) * | 1981-08-06 | 1983-03-01 | Stamicarbon | PROCESS FOR PREPARING A POLYMERIZATION CATALYST AND PREPARING ETHENE POLYMERS THEREOF |
| FI98916C (en) * | 1994-03-24 | 1997-09-10 | Borealis Polymers Oy | Process for copolymerizing ethylene and olefins |
| GB0300821D0 (en) * | 2003-01-14 | 2003-02-12 | Bp Chem Int Ltd | Polymerisation catalysts |
| DE102004020525A1 (en) * | 2004-04-26 | 2005-11-10 | Basell Polyolefine Gmbh | Production of catalyst system for the polymerization or copolymerization of olefins, by impregnating a dry porous support component with a mixture of organic transition metal compounds, hydrolyzed organo-aluminum compound(s), and solvent |
| DE102004028777A1 (en) * | 2004-06-16 | 2006-01-19 | Basell Polyolefine Gmbh | Preparation of supported catalyst to polymerize and/or copolymerize of olefins for, e.g. fibers, involves contacting homogeneous solution having chromium compound and other elements with inorganic support, and calcining catalyst precursor |
| WO2009045215A1 (en) * | 2007-10-03 | 2009-04-09 | Chevron Phillips Chemical Company Lp | Methods of preparing a polymerization catalyst |
| CN102443082B (en) * | 2010-10-15 | 2014-11-05 | 中国科学院上海有机化学研究所 | Novel chromium catalyst and application thereof in catalysis of olefin oligomerization and polymerization |
| US8703886B1 (en) * | 2013-02-27 | 2014-04-22 | Chevron Phillips Chemical Company Lp | Dual activator-support catalyst systems |
| CN105418812B (en) * | 2015-11-19 | 2018-08-21 | 华东理工大学 | A kind of load-type vanadium catalyst for olefine polymerization and its preparation method and application |
| CN107778390A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method and application of supported chrome tungsten bimetallic catalyst |
| CN108203478B (en) * | 2016-12-20 | 2021-04-30 | 中国石油天然气股份有限公司 | Preparation method of supported molybdenum-containing polyethylene catalyst |
| CN110204636B (en) * | 2019-05-09 | 2020-07-31 | 华南农业大学 | Supported three-center catalyst and preparation method and application thereof |
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