CN113248639A - Silica gel supported polyolefin catalyst and preparation method and application thereof - Google Patents
Silica gel supported polyolefin catalyst and preparation method and application thereof Download PDFInfo
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- CN113248639A CN113248639A CN202110609517.0A CN202110609517A CN113248639A CN 113248639 A CN113248639 A CN 113248639A CN 202110609517 A CN202110609517 A CN 202110609517A CN 113248639 A CN113248639 A CN 113248639A
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- silica gel
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- acetate
- chromium
- nitrate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000741 silica gel Substances 0.000 title claims abstract description 49
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- -1 transition metal salt Chemical class 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000010355 oscillation Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 7
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 5
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 claims abstract description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 5
- RHPIJWYTYJJCFU-UHFFFAOYSA-L diacetyloxyaluminum;hydrate Chemical compound O.CC(=O)O[Al]OC(C)=O RHPIJWYTYJJCFU-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 5
- 239000011565 manganese chloride Substances 0.000 claims abstract description 5
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 5
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 15
- 238000001514 detection method Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 239000011651 chromium Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 230000037048 polymerization activity Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- FOJJCOHOLNJIHE-UHFFFAOYSA-N aluminum;azane Chemical compound N.[Al+3] FOJJCOHOLNJIHE-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
Classifications
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a silica gel loaded polyolefin catalyst: the catalyst takes silica gel as a carrier, transition metal salt as an active metal and aluminum salt and a boron compound as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method and a soft-hard template method, the transition metal salt is selected from one of chromium acetate, chromium nitrate, chromium chloride, manganese acetate, manganese nitrate, manganese chloride, nickel acetate, nickel nitrate or nickel chloride, and the aluminum salt is one of basic aluminum acetate, basic aluminum magnesium carbonate or basic aluminum ammonium carbonate. The invention also discloses a preparation method of the silica gel loaded polyolefin catalyst, which comprises the following steps: soaking the silica gel carrier into a solution composed of transition metal salt, aluminum salt and boron compound, performing ultrasonic oscillation, filtering, and drying to obtain a solid. The catalyst provided by the invention can be used for olefin polymerization reaction, and not only can improve the production efficiency of polymerization reaction, but also can improve the melting point of the obtained polymer.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a silica gel-loaded polyolefin catalyst, and a preparation method and application thereof.
Background
Since the past fifties, Ziegler-Natta catalysts and silica gel supported chromium-based catalysts were discovered and commercialized, catalyst technology became one of the key core technologies in the polyolefin industry (wangwei. research progress in single-site catalyst polyolefin materials [ J ] petrochemical, 2013, 42 (1): 95-103.). Catalysts for olefin polymerization can be classified into homogeneous catalysts and homogeneous catalysts; the homogeneous catalyst has the advantages of mild reaction conditions, high catalytic activity, good selectivity and the like, but the problems of difficult separation of the catalyst in the polymerization reaction, adhesion of the polymer and the catalyst, poor particle morphology of the obtained polymer, difficult regulation and control and the like still exist. Therefore, in order to effectively improve the above problems, especially to meet the production requirements of industrial gas-phase fluidized beds, active catalysts used in olefin polymerization reactions generally require that active metal catalysts be supported on inorganic supports. The active metal catalyst loading is to load the metal catalyst on a carrier by a physical or chemical method, and the most common inorganic carrier comprises silica gel, alumina, montmorillonite, magnesium chloride, a molecular sieve, clay and the like; a commonly used organic support is polystyrene based polymerization. The metal catalyst is generally provided with the following advantages after being loaded: the metal active center is fixed on the carrier, so that the stability of the catalyst is improved, and meanwhile, the probability of bimolecular inactivation and beta hydrogen elimination in the polymerization reaction process can be reduced, so that the molecular weight of the obtained polymer is improved, and the polyolefin powder with regular shape and high apparent density can be obtained. However, the activity of the catalyst is reduced by loading the metal catalyst, and the types of active sites are increased. Therefore, how to increase the activity of the supported metal catalyst is one of the challenging problems at present.
Disclosure of Invention
The invention aims to provide a silica gel supported polyolefin catalyst, and a preparation method and application thereof.
In order to achieve the above purpose, the solution of the invention is:
the catalyst takes silica gel as a carrier, transition metal salt as active metal and aluminum salt and boron compound as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method and a soft and hard template method: adding the carbon microspheres into an acid solution to prepare an acid solution containing the carbon microspheres, and then sequentially and slowly adding organosilicate and adding a sodium silicate aqueous solution to prepare a silicon source solution; adding a template agent into the silicon source solution, uniformly stirring, performing microwave reaction to obtain silica gel, and drying to obtain powder; and carrying out low-temperature plasma treatment on the obtained powder to remove the template agent, thus generating the silica gel carrier in situ.
Preferably, the silica gel-supported polyolefin catalyst according to claim 1, wherein the transition metal salt is selected from one of chromium acetate, chromium nitrate, chromium chloride, manganese acetate, manganese nitrate, manganese chloride, nickel acetate, nickel nitrate or nickel chloride.
Preferably, the aluminum salt is one of basic aluminum acetate, basic aluminum magnesium carbonate or basic aluminum ammonium carbonate.
Preferably, the boron compound is boric acid.
Preferably, the specific surface area of the silica gel carrier is 200-550 m2The pore volume is between 1.2 and 3.8mL/g, and the particle diameter is between 30 and 120 mu m.
The preparation method of the silica gel supported polyolefin catalyst comprises the following steps: soaking the silica gel carrier into a solution composed of transition metal salt, aluminum salt and boron compound, performing ultrasonic oscillation, filtering, and drying to obtain a solid.
Preferably, the transition metal salt is selected from one of chromium acetate, chromium nitrate, chromium chloride, manganese acetate, manganese nitrate, manganese chloride, nickel acetate, nickel nitrate or nickel chloride; the aluminum salt is one of basic aluminum acetate, basic aluminum magnesium carbonate or basic aluminum ammonium carbonate; the boron compound is boric acid.
Preferably, the temperature of the ultrasonic oscillation is 30-50 ℃, and the time of the ultrasonic oscillation is 15-30 min.
The application of the silica gel supported metal catalyst for olefin polymerization or the silica gel supported metal catalyst for olefin polymerization prepared by the preparation method in olefin polymerization.
The silica gel supported metal catalyst for olefin polymerization is applied to olefin polymerization.
Compared with the prior art, the principle and the gain effect of the invention are as follows:
1. the preparation of the olefin polymerization catalyst is to prepare the silica gel carrier by combining a sol-gel method with a double template agent, wherein the selected carbon microspheres are hard template agents, the pore size of the synthesized silica gel carrier can be regulated by regulating the particle size of the used carbon microspheres, the selected soft template agent PVP can regulate the particle size and the morphology of the synthesized silica gel carrier, and the porous silica gel carrier particles with larger specific surface area, more uniform pore size and more uniform particle size distribution can be prepared by the double template agent method. .
2. The catalyst prepared by the silica gel carrier loaded catalyst has higher metal loading capacity, because compared with the traditional stirring reaction impregnation method, the ultrasonic oscillation impregnation method adopted by the catalyst preparation method provided by the invention not only improves the metal loading capacity, but also greatly shortens the impregnation time, and the catalyst preparation method also has the advantages of simple operation and mild conditions.
3. The catalyst prepared by the invention can be used for olefin polymerization, and not only can improve the production efficiency of polymerization reaction, but also can improve the melting point of the obtained polymer or copolymer.
Detailed Description
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention.
All reagents were commercial reagents unless otherwise indicated and were not further purified prior to use. The specific surface area and pore volume test uses a 3H-2000PS2 model specific surface aperture detector of Bechard instruments; the particle size test uses a Beckmann Coulter LS 13320 XR laser diffraction particle size analyzer; the ICP-OES test used an ICP-OES plasmaQuant 9100 inductively coupled plasma spectrometer from Jena, Germany.
Example 1
The preparation steps of the silica gel carrier are as follows: adding 10g of carbon microspheres (the particle size range is 10-40 mu m) into 400ml of hydrochloric acid solution with the molar concentration of 1mol/L, and uniformly stirring to obtain hydrochloric acid solution containing the carbon microspheres; slowly adding 2.4g of methyl orthosilicate into the hydrochloric acid solution containing the carbon microspheres prepared in the previous step under stirring, continuously stirring, and then adding 50g of sodium silicate aqueous solution with the mass concentration of 40% to prepare a silicon source solution; adding 10g of template agent PVP (polyvinylpyrrolidone, K12) into the silicon source solution, uniformly stirring to obtain hydrated silicon gel, transferring the obtained gel into a microwave reaction tank for thermal ageing, and carrying out microwave reaction for 5 hours at the microwave power of 300W and the temperature of 90 ℃; and cooling and filtering the obtained product, washing the obtained solid with ethanol/water (the volume ratio of the ethanol to the water is 1:1, 100ml each time) until the solid is neutral (detected by a silver nitrate solution until no chloride ions exist), drying, preparing the dried solid into powder, transferring the powder into a Dielectric Barrier Discharge (DBD) device for low-temperature plasma treatment to remove a template agent, treating the powder for 6 hours in an oxygen atmosphere at the temperature of 200 ℃, under the voltage of 220V and under the current of 3.5A, and naturally cooling to room temperature to obtain the silica gel carrier for the olefin polymerization catalyst. Specific surface area and pore volume tests of the prepared silica gel carrier show that the specific surface area is 485cm2The pore volume is 1.82 ml/g; the prepared silica gel carrier was subjected to a particle size analysis test, and the result showed that the average particle size was 106.3. mu.m.
The silica gel carrier with different specific surface area and particle size distribution can be prepared by adjusting the particle size range of the used carbon microspheres.
Example 2:
the procedure for the preparation of the olefin polymerization catalyst was as follows (all operations were carried out under nitrogen protection):
(1) 4g of the silica gel prepared in example 1 was put into an oven at 110 ℃ to be dried for 5 hours, and then added into a flask for drying reaction;
(2) adding 0.230g of chromium acetate and 0.568g of basic aluminum acetate (stabilized by 1% boric acid) into 25ml of methanol, and uniformly stirring to obtain a Cr/Al-B composite solution;
(3) and (3) adding the Cr/Al-B composite solution prepared in the step (2) into the silica gel prepared in the step (1), transferring the obtained mixture into an ultrasonic reactor, carrying out ultrasonic oscillation at 30 ℃ for 30min, filtering, drying the obtained solid in a vacuum drying oven at 110 ℃ for 12 hours to obtain the catalyst for olefin polymerization, and marking the obtained catalyst as Cr/Al-B/SG-1. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the loading capacity of metal Cr in the catalyst prepared by the ultrasonic impregnation method is 3.25%, and the loading capacity of metal Al is 9.06%.
Example 3
The catalytic ethylene polymerization steps were as follows (all operations were carried out under nitrogen protection):
in a fluidized-bed reactor, 20g of the catalyst Cr/Al-B/SG-1 from example 2 were activated at 600 ℃ for 8 hours using dry air as fluidizing gas and cooled to room temperature in a nitrogen atmosphere. 1.05g of activated catalyst was transferred to a 30L isobutane slurry polymerization reactor and polymerization runs were carried out with ethylene as monomer: the total pressure of the reactor is 4MPa, the ethylene partial pressure is 1.6MPa, the reactor is kept at 100 ℃, the flow rate of slurry is 2.5m/s, the polymerization reaction is maintained for 1 hour, then the temperature is reduced, then the reaction liquid is poured into 150ml of acidified ethanol solution (hydrochloric acid/ethanol is 1/10) with the mass concentration of 10 percent to terminate the reaction, the polymer obtained by washing the product with 30ml of deionized water and 30ml of absolute ethanol in sequence after filtration, finally the polymer is placed in a vacuum drying oven to be dried to constant weight at 60 ℃, and the weight and the activity are weighed and calculated. The specific conditions for the polyethylene obtained were characterized as follows: the molecular weight of the polyethylene was measured by a viscometry with a Ubbelohde viscometer using a solvent ofDecalin at a temperature of 135 ℃; the melting point of the polyethylene was determined using an XT-4 binocular microscopy melting point apparatus. The reaction result is: the polymerization activity was 105.82(gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 18.23 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 150.4 ℃.
Example 4
Preparation of silica gel Carrier As in example 1, catalyst preparation with reference to example 2 was carried out except that in step (2), chromium acetate was changed to nickel acetate, the amount of nickel acetate was 0.178g, and the conditions were otherwise the same, and the catalyst obtained was designated as Ni/Al-B/SG-2. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the loading capacity of metal Ni in the catalyst prepared by the ultrasonic impregnation method is 3.16%, and the loading capacity of metal Al is 8.94%.
The conditions for the catalytic ethylene polymerization were the same as in example 3, and the results were: the polymerization activity was 43.61 (gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 8.05 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 115.4 ℃.
Example 5
Preparation of silica gel support As in example 1, catalyst was prepared by referring to example 2 except that the ultrasonic oscillation condition in step (3) was adjusted to 50 ℃ for 15 min. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the loading capacity of metal Cr in the catalyst prepared by the ultrasonic impregnation method is 3.21%, and the loading capacity of metal Al is 9.03%. The conditions for the catalytic ethylene polymerization were the same as in example 3, and the results were: the polymerization activity was 103.97(gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 18.17 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 149.6 ℃.
Example 6
Preparation of silica gel support As in example 1, the catalyst was prepared by reference to example 2, except that the basic aluminum acetate (stabilized with 1% boric acid) in step (2) was replaced by basic ammonium aluminum carbonateThe amount of basic ammonium aluminum carbonate used was 0.547g, and the other conditions were the same. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection results are as follows: the loading capacity of metal Cr in the catalyst prepared by the ultrasonic impregnation method is 3.16%, and the loading capacity of metal Al is 8.91%. The conditions for the catalytic ethylene polymerization were the same as in example 3, and the results were: the polymerization activity was 102.51(gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 18.14 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 148.7 ℃.
Comparative example 1
Preparation of silica gel support As in example 1, catalyst preparation refers to example 2 except that the ultrasonic vibration in step (3) is adjusted to conventional mechanical stirring, i.e., stirring at 30 ℃ for reaction for 6 hours, and other conditions are the same. ICP-OES detection is carried out on the prepared catalyst, active metal components loaded on the catalyst are inspected, and the detection result is as follows: the amount of Cr supported was 2.65% and the amount of metallic Al supported was 7.13%. The conditions for the catalytic ethylene polymerization were the same as in example 3, and the results were: the polymerization activity was 95.07(gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 17.04 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 139.6 ℃. .
Comparative example 2
The catalyst was prepared by referring to example 2 except that the silica gel carrier used in the step (1) was changed to ordinary commercially available 955 silica gel powder and the other conditions were the same. ICP-OES detection is carried out on the prepared catalyst, and the detection results of active metal components loaded on the catalyst are examined as follows: the amount of Cr supported was 2.03% and the amount of metallic Al supported was 5.86%. The conditions for the catalytic ethylene polymerization were the same as in example 3, and the results were: the polymerization activity was 79.61(gPE: gcat)-1h-1) (ii) a The polyethylene obtained had a molecular weight of 12.71 (10)4g/mol); the melting point Tm of the resulting polyethylene product was 135.1 ℃.
Claims (9)
1. A silica gel supported polyolefin catalyst characterized by: the catalyst takes silica gel as a carrier, transition metal salt as active metal and aluminum salt and boron compound as a cocatalyst, wherein the silica gel carrier is prepared by combining a sol-gel method with a soft and hard template method: adding the carbon microspheres into an acid solution to prepare an acid solution containing the carbon microspheres, and then sequentially and slowly adding organosilicate and adding a sodium silicate aqueous solution to prepare a silicon source solution; adding a template agent into the silicon source solution, uniformly stirring, performing microwave reaction to obtain silica gel, and drying to obtain powder; and carrying out low-temperature plasma treatment on the obtained powder to remove the template agent, thus generating the silica gel carrier in situ.
2. The silica gel-supported polyolefin catalyst of claim 1 wherein the transition metal salt is selected from one of chromium acetate, chromium nitrate, chromium chloride, manganese acetate, manganese nitrate, manganese chloride, nickel acetate, nickel nitrate or nickel chloride.
3. The silica gel supported polyolefin catalyst of claim 1, characterized in that: the aluminum salt is one of basic aluminum acetate, basic aluminum magnesium carbonate or basic aluminum ammonium carbonate.
4. The silica gel supported polyolefin catalyst of claim 1, characterized in that: the boron compound is boric acid.
5. The silica gel supported polyolefin catalyst of claim 1, characterized in that: the specific surface area of the silica gel carrier is 200-550 m2The pore volume is between 1.2 and 3.8mL/g, and the particle diameter is between 30 and 120 mu m.
6. The method of preparing the silica gel-supported polyolefin catalyst of claim 1, comprising the steps of: soaking the silica gel carrier into a solution composed of transition metal salt, aluminum salt and boron compound, performing ultrasonic oscillation, filtering, and drying to obtain a solid.
7. The method for preparing a silica gel-supported polyolefin catalyst according to claim 6, wherein the transition metal salt is one selected from chromium acetate, chromium nitrate, chromium chloride, manganese acetate, manganese nitrate, manganese chloride, nickel acetate, nickel nitrate or nickel chloride; the aluminum salt is one of basic aluminum acetate, basic aluminum magnesium carbonate or basic aluminum ammonium carbonate; the boron compound is boric acid.
8. The preparation method of the silica gel-supported polyolefin catalyst according to claim 7, wherein the temperature of the ultrasonic oscillation is 30 to 50 ℃ and the time of the ultrasonic oscillation is 15 to 30 min.
9. Use of the silica gel-supported metal catalyst for olefin polymerization according to claim 1 or the silica gel-supported metal catalyst for olefin polymerization prepared by the preparation method according to any one of claims 6 in olefin polymerization.
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