CN117843838A - Preparation method of chromium-based catalyst for gas-phase polyethylene induced condensation process - Google Patents
Preparation method of chromium-based catalyst for gas-phase polyethylene induced condensation process Download PDFInfo
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- CN117843838A CN117843838A CN202410020787.1A CN202410020787A CN117843838A CN 117843838 A CN117843838 A CN 117843838A CN 202410020787 A CN202410020787 A CN 202410020787A CN 117843838 A CN117843838 A CN 117843838A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000011651 chromium Substances 0.000 title claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 50
- -1 polyethylene Polymers 0.000 title claims abstract description 45
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000009833 condensation Methods 0.000 title claims abstract description 17
- 230000005494 condensation Effects 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000741 silica gel Substances 0.000 claims abstract description 25
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 150000001844 chromium Chemical class 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000012808 vapor phase Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 5
- 229940009827 aluminum acetate Drugs 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 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 description 3
- 230000032683 aging Effects 0.000 claims description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000000499 gel Substances 0.000 abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 2
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 16
- 238000011068 loading method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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 preparation method of a chromium catalyst for a gas-phase polyethylene induced condensation state process, which comprises the following specific steps: (1) Adding organic silicate into an acid solution containing carbon microspheres, and then adding a sodium silicate aqueous solution to prepare a silicon source solution; adding a template agent into the silicon source solution to prepare silica gel sol; preparing silica gel sol into gel, and grinding into powder; roasting the obtained powder to obtain a silica gel carrier; (2) Adding the silica gel carrier into a mixed salt solution composed of sodium chloride, ammonium chloride and potassium chloride, and heating for reaction to obtain a modified silica gel carrier; (3) Adding the modified silica gel carrier into aqua regia, soaking to reduce the content of sodium ions contained in the modified silica gel carrier, and preparing the sodium-removed modified silica gel carrier; (4) Impregnating the sodium-removed modified silica gel carrier, chromium salt and a cocatalyst, filtering and drying the obtained solid. The catalyst prepared by the invention can be successfully applied to ethylene polymerization reaction in a gas-phase fluidized bed reactor under a condensation state for a long period.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a preparation method of a chromium catalyst for a gas-phase polyethylene induced condensation state process.
Background
The gas-phase fluidized bed process is a commonly used polyethylene synthesis process; the process mainly utilizes fluidization technology to realize the reaction process of high-efficiency catalytic ethylene polymerization (Wang Rong, edge steel month. Gas phase method polyethylene device energy expanding technology shallow analysis [ J ]. Modern petroleum petrochemical, 2001,9 (6): 33-36.). Specifically, the basic principle of the gas phase fluidized bed process used in ethylene polymerization is: firstly, placing solid catalyst particle materials in a reactor, and then introducing reaction gas ethylene from the bottom of the reactor; as the gas continues to flow, the catalyst particles become fluidized, forming a liquid-like state; in this state, the gas and the solid catalyst particles can be sufficiently contacted, thereby greatly improving the reaction efficiency of the catalyst. However, the ethylene polymerization reaction is an exothermic reaction, and the higher the reaction efficiency, the more reaction heat will be generated during the polymerization; if the reaction heat cannot be removed in time, the reaction temperature increases to cause a series of problems: for example, high temperatures may lead to catalyst deactivation or decomposition, reducing catalytic efficiency; in addition, high temperatures may also lead to thermal decomposition or thermal oxidation of the polymer, producing large amounts of undesirable byproducts; again, high temperatures may induce thermal instability within the reactor leading to non-uniformities in the reaction process, affecting product quality and yield. Therefore, the heat removal capacity is one of the main factors affecting the space-time yield of the gas-phase fluidized-bed reactor.
In addition, the design of the catalyst is also one of the key technologies affecting the gas phase fluidized bed process for ethylene polymerization (Ezeminum cyminum, michelia, high performance single site catalyst research for the preparation of full range polyolefin materials, development [ J ]. Chemical development, 2016,35 (1): 110-124.). Chromium-based catalysts are widely used in gas-phase fluidized bed processes for the production of high molecular polymer materials such as polyethylene and polypropylene because of their widest molecular weight distribution (Wang Jun, li Yun, li Cuiqin, etc.. Chromium-based polyethylene catalysts have been developed with new advances [ J ]. Chemical advances, 2012,31 (1): 91-97/22.). The relatively low efficiency of the conventional chromium-based catalysts currently available for use in gas phase fluidized bed polyethylene processes is often insufficient to meet the high throughput requirements, resulting in inefficient polymer production. Therefore, it is also necessary to design a high molecular chromium-based catalyst which has higher catalytic efficiency and is suitable for the vapor phase polyethylene induced condensation process.
Disclosure of Invention
The invention aims to provide a chromium catalyst for a gas-phase polyethylene induced condensation state process, and a preparation method and application thereof.
In order to achieve the above object, the solution of the present invention is:
the preparation method of the chromium-based catalyst for the vapor-phase polyethylene induced condensation process comprises the following steps:
(1) Slowly adding organic silicate into the acid solution containing the carbon microspheres, continuously stirring, and then adding sodium silicate aqueous solution to prepare silicon source solution; adding a template agent into the obtained silicon source solution and uniformly stirring to obtain silica gel sol; aging the obtained silica gel sol to obtain silica gel; drying the obtained silica gel and preparing into powder; roasting the obtained powder to obtain a silica gel carrier;
(2) Adding the silica gel carrier prepared in the step (1) into a mixed salt solution composed of sodium chloride, ammonium carbonate and potassium chloride to react to prepare a modified silica gel carrier;
(3) Adding the modified silica gel carrier prepared in the step (2) into aqua regia, and soaking to reduce the content of sodium ions contained in the aqueous solution to prepare a sodium-removed modified silica gel carrier;
(4) Adding the sodium-removed modified silica gel carrier prepared in the step (3), chromium salt and a cocatalyst into an organic solvent, soaking for a period of time, filtering, and drying the obtained solid to obtain the chromium catalyst for the gas-phase polyethylene induced condensation state process.
Preferably, the organosilicate in step (1) is one of ethyl orthosilicate or isopropyl orthosilicate.
Preferably, the firing conditions described in step (1) are: the roasting temperature is 650-800 ℃; the roasting time is 7-10h.
Preferably, the average particle size (D50) of the carbon microspheres described in step (1) is 70-90. Mu.m.
Preferably, the reduction in step (3) comprises a sodium ion content of less than 100ppm.
Preferably, the organic solvent in the step (4) is one of methanol, ethanol or isopropanol.
Preferably, the chromium salt in step (4) is selected from one of chromium acetate, chromium trichloride hexahydrate or chromium sulfate.
Preferably, the cocatalyst in step (4) consists of aluminum acetate and boric acid.
The catalyst prepared by the preparation method of the chromium-based catalyst for the vapor-phase polyethylene induced condensation state process takes sodium-removed modified silica gel as a carrier, chromium salt as active metal and aluminum acetate and boric acid as cocatalysts; wherein the specific surface area of the catalyst is 450-520m 2 Per gram, the pore volume is 2.1-2.6 ml/g; the content of metal aluminum in the catalyst is 1.0-4.0%, the content of metal chromium is 0.8-1.1%, and the molar ratio of metal aluminum to metal chromium is 2:1-4:1.
The chromium-based catalyst for the gas-phase polyethylene induced condensing process can be applied to long-period operation of gas-phase fluidized bed ethylene polymerization in a condensing state.
Compared with the existing method, the principle and gain effect of the invention are as follows:
1. according to the preparation method of the chromium-based catalyst for the gas-phase polyethylene induced condensation state process, the prepared silica gel is modified by using mixed salt, so that the silica gel carrier particles with larger specific surface area are prepared.
2. The catalyst prepared by the preparation method of the chromium-based catalyst for the gas-phase polyethylene induced condensation state process has higher metal loading capacity, and one of the main reasons is that the sodium-removed modified silica gel carrier particles with larger specific surface area are used.
3. The chromium-based catalyst for the gas-phase polyethylene induced condensation state process, which is prepared by the invention, can be successfully applied to catalyzing ethylene polymerization reaction; the heat removal capacity of the reactor can be effectively improved by using the isopentane-containing induced condensing agent in the catalytic reaction process, so that the space-time yield of the reactor is further improved; the results show that: the maximum activity of the catalyst used can reach 6.68kg PE/gcat; the melting point Tm of the obtained polyethylene product is 120.9 ℃; the space-time yield STY of the gas-phase fluidized bed reactor after running for 1 hour can reach 125 kg/(h.m) 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
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 given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, and that the particular amounts of materials, reaction times and temperatures, process parameters, etc. shown are but one example of a suitable range, and that some insubstantial modifications and adaptations of the invention to those skilled in the art are within the scope of the invention.
All reagents used were commercial reagents unless otherwise indicated and were not further purified prior to use.
Example 1:
the preparation method of the chromium-based catalyst for the gas-phase polyethylene induced condensation process comprises the following steps:
(1) Adding 2.0g of carbon microspheres (average particle size 70-90 μm) into 80ml of hydrochloric acid solution with molar concentration of 1mol/L, and stirring uniformly to obtain hydrochloric acid solution containing carbon microspheres; slowly adding 0.5g of tetraethoxysilane into a hydrochloric acid solution containing carbon microspheres under vigorous stirring, continuously stirring, and then adding 10g of a sodium silicate aqueous solution with the mass concentration of 40% to prepare a silicon source solution; adding 2g of polyvinylpyrrolidone into the obtained silicon source solution and uniformly stirring to prepare silica gel sol; transferring the obtained silica gel sol into a microwave reaction tank for thermal aging, and carrying out microwave reaction for 1.5 hours under the conditions that the microwave power is 300W and the temperature is 80 ℃ to obtain the silica gel; washing the gel with ethanol and deionized water in turn until the gel is neutral (the gel is inspected to be free of chloride ions by using a silver nitrate solution), drying the gel, preparing the dried gel into powder, placing the powder into a muffle furnace, roasting at 800 ℃ for 7 hours, and naturally cooling the powder to room temperature to obtain 8.3g of silica gel carrier;
(2) Adding the silica gel carrier prepared in the step (1) into a mixed salt solution consisting of 20g of sodium chloride, 5g of ammonium carbonate, 5g of potassium chloride and 70g of deionized water, performing hydrothermal reaction on the obtained mixture at 120 ℃ for 4 hours after sealing, cooling to room temperature after the reaction is finished, washing the obtained solid with deionized water for 3 times (50 ml each time) after filtering, and drying to obtain 7.4g of modified silica gel carrier;
(3) Adding the modified silica gel carrier prepared in the step (2) into 50ml aqua regia to impregnate and remove sodium, sampling the sodium ion content in the silica gel carrier every 2 hours until the sodium ion content is lower than 100ppm, wherein the step is to be noted that a glass container cannot be used and a polytetrafluoroethylene container is needed to be used for impregnation; filtering after soaking and collecting the obtained solid; the obtained solid was washed with deionized water to neutrality (checked with silver nitrate solution until no chloride ion was present), and then dried to obtain a sodium-removed modified silica gel carrier of 6.1g total
(4) Drying 5.5g of the sodium-removed modified silica gel carrier prepared in the step (3) in an oven at 110 ℃ for 4 hours, adding the dried modified silica gel carrier into a drying reaction flask, injecting a mixed solution consisting of 0.173g of chromium acetate, 0.426g of basic aluminum acetate (stabilized by 1% boric acid) and 15ml of methanol into the flask under the protection of nitrogen, reacting the obtained mixture for 0.5 hours at the condition that the ultrasonic oscillation power is 120w at room temperature, filtering, and drying the obtained solid in a vacuum drying oven at 110 ℃ for 12 hours to obtain 5.2g of the chromium catalyst for the gas-phase polyethylene induced condensation state process, wherein the obtained catalyst is named as Cr/Al-B/SG-1. The catalyst prepared was characterized and the results were as follows: the specific surface area of the catalyst is 493m 2 Per gram, pore volume is 2.6ml/g; catalytic reactionThe detection results of the active metal components loaded on the agent are as follows: the loading of Cr was 1.05%, and the loading of metallic Al was 2.46%.
Example 2
The steps for catalyzing the ethylene polymerization reaction are as follows:
5g of the catalyst Cr/Al-B/SG-1 were placed in a quartz tube, heated to 650℃under oxygen for 12 hours and cooled to room temperature. Then, in a gas-phase fluidized bed with a seed bed, nitrogen with the temperature of 80 ℃ is used for blowing the seed bed, moisture and oxygen in the seed bed are removed, and after the polymerization conditions are reached, raw material gas consisting of ethylene, butylene and hydrogen is introduced, the content of each component is adjusted, and a polymerization reaction test is carried out: the total pressure of the reactor is 2MPa, the ethylene partial pressure is 1.2MPa, and the temperature of the reactor is kept at 100 ℃; the induced condensing agent is isopentane, the content of isopentane is more than or equal to 99.0 wt%, and the balance is other alkane. The polymerization results were: the activity of the catalyst Cr/Al-B/SG-1 is 6.68kg PE/gcat; the melting point Tm of the obtained polyethylene product is 120.9 ℃; the space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method is 125 kg/(h.m) 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
Example 3:
preparation procedure of chromium-based catalyst for polyethylene-induced condensing process by gas phase method referring to example 1, the difference is that ethyl orthosilicate in step (1) is changed to isopropyl orthosilicate, and the amount of isopropyl orthosilicate is 0.4g: the resulting catalyst was designated Cr/Al-B/SG-2. The catalyst prepared was characterized and the results were as follows: the specific surface area of the catalyst is 481m 2 /g, pore volume is 2.3ml/g; the active metal component loaded on the catalyst has the following detection result: the loading of Cr was 0.99%, and the loading of metallic Al was 2.27%.
The procedure for catalyzing the polymerization of ethylene was as described in reference to example 2, except that the catalyst Cr/Al-B/SG-1 was changed to Cr/Al-B/SG-2; the catalytic result is: the activity of the catalyst Cr/Al-B/SG-2 is 6.23kg PE/gcat; the melting point Tm of the resulting polyethylene product was 118.7 ℃. The space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method is 116kg/(h·m 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
Example 4
The procedure for the preparation of chromium-based catalysts for the gas-phase polyethylene-induced condensing process is described with reference to example 1, with the difference that step (2) is omitted; the rest of the procedure was the same as in example 1, and the catalyst obtained was designated Cr/Al-B/SG-3. The catalyst prepared was characterized and the results were as follows: the specific surface area of the catalyst was 403m 2 Per gram, pore volume is 1.8ml/g; the active metal component loaded on the catalyst has the following detection result: the loading of Cr was 0.86%, and the loading of metallic Al was 1.63%.
The procedure for catalyzing the polymerization of ethylene was as described in reference to example 2, except that the catalyst Cr/Al-B/SG-1 was changed to Cr/Al-B/SG-3; the catalytic result is: the activity of the catalyst Cr/Al-B/SG-3 is 5.40kg PE/gcat; the melting point Tm of the resulting polyethylene product was 116.7 ℃. The space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method was 101 kg/(h.m) 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
Example 5:
preparation procedure of chromium-based catalyst for vapor-phase polyethylene-induced condensing process referring to example 1, the difference is that the reaction condition "reaction at room temperature under ultrasonic vibration power of 120w for 0.5h" of step (4) is changed to "stirring reaction at room temperature for 6h": the resulting catalyst was designated Cr/Al-B/SG-4. The catalyst prepared was characterized and the results were as follows: the specific surface area of the catalyst was 490m 2 Per gram, pore volume is 2.6ml/g; the detection results of the active metal components supported on the catalyst are as follows: the loading of Cr was 1.01%, and the loading of metallic Al was 2.38%.
The procedure for catalyzing the polymerization of ethylene was as described in reference to example 2, except that the catalyst Cr/Al-B/SG-1 was changed to Cr/Al-B/SG-2; the catalytic result is: the activity of the catalyst Cr/Al-B/SG-2 is 6.59kg PE/gcat; the melting point Tm of the resulting polyethylene product was 119.4 ℃. The space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method is 123 kg/(h.m) 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
Example 6:
the procedure for ethylene polymerization was as described in reference to example 2, except that the induced condensing agent in the condenser was mixed pentane, with the following specific composition: the mass fraction of n-pentane is 58%, the mass fraction of isopentane is 41%, and the balance is impurities such as water vapor and other alkanes. The method comprises the steps of carrying out a first treatment on the surface of the The catalytic result is: the activity of the catalyst Cr/Al-B/SG-1 is 6.61kg PE/gcat; the melting point Tm of the resulting polyethylene product was 120.3 ℃. The space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method was 124 kg/(h.m) 3 ). The reactor can be operated for a long period of time, and the blocking of the catalyst caking and the distributing plate are not found in 4 days of operation.
Comparative example 1
The preparation step of the chromium-based catalyst for the vapor phase polyethylene induced condensing process is referred to step (4) in example 1, except that the sodium-removed modified silica gel carrier in step (4) is changed to a general commercially available 955 silica gel powder; the resulting catalyst was designated Cr/Al-B/SG-4. The catalyst prepared was characterized and the results were as follows: the specific surface area of the catalyst is 288m 2 Per gram, pore volume is 1.5ml/g; the active metal component loaded on the catalyst has the following detection result: the loading of Cr was 0.71%, and the loading of metallic Al was 1.39%.
The procedure of ethylene polymerization was as described in reference to example 2, except that the catalyst Cr/Al-B/SG-1 was changed to Cr/Al-B/SG-4; the catalytic result is: the activity of the catalyst Cr/Al-B/SG-6 is 4.17kg PE/gcat; the melting point Tm of the resulting polyethylene product was 115.8 ℃. The space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method is 110 kg/(h.m) 3 ). The reactor was run for 4 hours and severe caking of the fluidized bed reactor was observed, blocking the distribution plate and the reaction was not continued.
Comparative example 2
Procedure for ethylene polymerization referring to example 2, except that no induced condensing agent was used in the gas phase fluidized bed, in the dry state. The catalytic result is: the activity of the catalyst Cr/Al-B/SG-1 is 8.86kg PE/gcat; the polyethylene product obtainedMelting point Tm is 116.2 ℃; the space-time yield STY after 1 hour of operation of the fluidized bed reactor by the gas phase method is 85 kg/(h.m) 3 )。
Claims (10)
1. The preparation method of the chromium-based catalyst for the vapor-phase polyethylene induced condensation process is characterized by comprising the following steps of:
(1) Slowly adding organic silicate into the acid solution containing the carbon microspheres, continuously stirring, and then adding sodium silicate aqueous solution to prepare silicon source solution; adding a template agent into the obtained silicon source solution and uniformly stirring to obtain silica gel sol; aging the obtained silica gel sol to obtain silica gel; drying the obtained silica gel and preparing into powder; roasting the obtained powder to obtain a silica gel carrier;
(2) Adding the silica gel carrier prepared in the step (1) into a mixed salt solution composed of sodium chloride, ammonium carbonate and potassium chloride to react to prepare a modified silica gel carrier;
(3) Adding the modified silica gel carrier prepared in the step (2) into aqua regia, and soaking to reduce the content of sodium ions contained in the aqueous solution to prepare a sodium-removed modified silica gel carrier;
(4) Adding the sodium-removed modified silica gel carrier prepared in the step (3), chromium salt and a cocatalyst into an organic solvent, soaking for a period of time, filtering, and drying the obtained solid to obtain the chromium catalyst for the gas-phase polyethylene induced condensation state process.
2. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, wherein said organosilicate in step (1) is one of ethyl orthosilicate or isopropyl orthosilicate.
3. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, wherein said calcination conditions in step (1) are: the roasting temperature is 650-800 ℃; the roasting time is 7-10h.
4. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, wherein said carbon microspheres in step (1) have an average particle size of 70-90 μm.
5. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, characterized by said reducing sodium ion content in step (3) to less than 100ppm.
6. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, wherein said organic solvent in step (4) is one of methanol, ethanol or isopropanol.
7. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, characterized by: the chromium salt in the step (4) is selected from one of chromium acetate, chromium trichloride hexahydrate or chromium sulfate.
8. The method for preparing a chromium-based catalyst for a vapor phase polyethylene induced condensing process according to claim 1, characterized by: the cocatalyst in the step (4) consists of aluminum acetate and boric acid.
9. The catalyst prepared by the preparation method of the chromium-based catalyst for the vapor-phase polyethylene induced condensing process of claim 1, which is characterized in that the catalyst takes sodium-removed modified silica gel as a carrier, chromium salt as active metal and aluminum acetate and boric acid as cocatalysts; wherein the specific surface area of the catalyst is 450-520m 2 Per gram, the pore volume is 2.1-2.6 ml/g; the content of metal aluminum in the catalyst is 1.0-4.0%, the content of metal chromium is 0.8-1.1%, and the molar ratio of metal aluminum to metal chromium is 2:1-4:1.
10. The chromium-based catalyst prepared by the preparation method according to claim 1 or the chromium-based catalyst according to claim 9 is applicable to long-period operation of gas-phase fluidized-bed ethylene polymerization in a condensed state.
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