CN1657571A - Preparation method of microspherical silica used as alkene polymerization catalyst carrier - Google Patents
Preparation method of microspherical silica used as alkene polymerization catalyst carrier Download PDFInfo
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- CN1657571A CN1657571A CN2004100394921A CN200410039492A CN1657571A CN 1657571 A CN1657571 A CN 1657571A CN 2004100394921 A CN2004100394921 A CN 2004100394921A CN 200410039492 A CN200410039492 A CN 200410039492A CN 1657571 A CN1657571 A CN 1657571A
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- Prior art keywords
- silicon
- dioxide
- gel
- acid
- microspheroidal
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 17
- 150000001336 alkenes Chemical class 0.000 title description 9
- 239000002685 polymerization catalyst Substances 0.000 title description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 229960001866 silicon dioxide Drugs 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 238000005507 spraying Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- -1 methane amide Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000007863 gel particle Substances 0.000 claims description 2
- 239000000693 micelle Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001694 spray drying Methods 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000004711 α-olefin Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000011806 microball Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 52
- 229910002027 silica gel Inorganic materials 0.000 description 30
- 239000000741 silica gel Substances 0.000 description 30
- 229910004298 SiO 2 Inorganic materials 0.000 description 29
- 239000011148 porous material Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000000017 hydrogel Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 229910002028 silica xerogel Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000000352 supercritical drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IWTBVKIGCDZRPL-LURJTMIESA-N 3-Methylbutanol Natural products CC[C@H](C)CCO IWTBVKIGCDZRPL-LURJTMIESA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100494265 Caenorhabditis elegans best-15 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241001125929 Trisopterus luscus Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000006234 n-butoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- FIABMSNMLZUWQH-UHFFFAOYSA-N propyl 2-methoxyacetate Chemical compound CCCOC(=O)COC FIABMSNMLZUWQH-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- VVDQEULQOPQUKG-UHFFFAOYSA-M sodium benzenesulfonate dodecylbenzene Chemical class [Na+].[O-]S(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCCC1=CC=CC=C1 VVDQEULQOPQUKG-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Silicon Compounds (AREA)
Abstract
A SiO2 microball as the carrier of catalyst for polymerizing ethylene or alpha-olefin is prepared through preparing silicon gel, adding modifiers A, B and C, mechanical homogenizing and fining to become sol, spray drying to become dried microspherical SiO2 gel, and calcining. It has high specific surface area and porosity.
Description
Technical field
The present invention relates to a kind of be applicable to vinyl polymerization or with the preparation method and the application of the support of the catalyst microspheroidal silicon-dioxide of alpha-olefin copolymer.
Background technology
Microspheroidal SiO
2(10～70 μ m) has been widely used in the olefin polymerization catalysis as support of the catalyst, and be more general in the particularly gas-phase fluidized-bed olefin polymerization catalysis.(US.4303566 US.4303771) discloses microspheroidal SiO to existing many patents for US.4293673, US.4303565
2As carrier, be used for fluidized-bed ethene polymerization process catalyzer.
In order to be adapted to the requirement of gas-phase fluidized-bed Fluidization Engineering, microspheroidal SiO
2Must have suitable tap density, median size and size distribution, good flowability and physical strength etc.Simultaneously, as carrier for olefin polymerization catalyst SiO
2, also to satisfy the requirement of polymerization reaction engineering, also must have bigger specific surface area and big pore volume, suitable mean pore size and pore size distribution.
At present, be widely used in the polyolefin catalyst carrier microspheroidal SiO of fluidized-bed process
2, be mainly derived from the sylopol.RTM.948 of U.S. Grace company, 2104,2210, these microspheroidals of SD490 SiO of Xp0240 and Crosfield company
2Specific surface area generally at 300m
2About/g, that have even lower.The SiO that industrial use is more
2Carrier is the microspheroidal SiO of the sylopol.RTM.955 trade mark
2, its specific surface area is 250～320m
2/ g, pore volume are 1.2～1.5cc/g, and mean pore size is about 6nm.Has above-mentioned SiO
2Physical index has satisfied the requirement of carrier for olefin polymerization catalyst preferably.
Polyolefin catalyst carrier SiO
2Physical index, directly influence polyreaction performance and following process.The patent that has (CN1339509A) has disclosed the increase of silica gel specific surface area, and olefin polymerizating activity improves, but because SiO
2The increase of specific surface area, its aperture must reduce, and directly influences the polymeric performance, and as performance of hydrogen response, ethene and α～olefin-copolymerization etc., the patent of the U.S. (US.3225023) discloses polyolefin catalyst carrier SiO
2The aperture and the relation of polymer performance.Therefore, the employed SiO of present industrial gas-phase polyethylene
2Carrier generally is controlled at 300m with specific surface area
2About/g and bigger mean pore size be advisable.
Traditional method prepares SiO
2Specific surface area bigger, the aperture is less, on the contrary the aperture is big, specific surface area has diminished again, both are conflicting.Adopt conventional preparation SiO
2Way be insoluble.Attempt to obtain simultaneously bigger specific surface area and aperture, must invent new special way, preparation polyolefin catalyst carrier SiO
2, satisfy the requirement of olefinic polyreaction.
In view of the foregoing, relevant in the world each major company researches and develops new manufacturing SiO from different angles and field
2Technology.As W.R.Grace and Co.-conn.; The Phillips oil company; Davison chemical company; E.I.du pout deNemurs and Company; SCM. chemical company etc.
W.R.Grace.Co-conn company is polyolefin catalyst carrier SiO produced in USA
2One of major vendor, disclose two kinds and made SiO
2Effective ways, and be used for the catalyzer of olefinic polymerization.The US.3959174 patent has disclosed the SiO that produces than bigger serface and pore volume
2Method.At SiO
2In the preparation, mainly be to have taked minimizing SiO
2The auxiliary agent of solubleness or solvation makes SiO
2In the water-sol system of preparation, reduce SiO
2Solubleness and separate out into hydrogel, make finished product SiO through aging, washing, drying and roasting then
2Said auxiliary agent is ammonia, monohydroxy-alcohol, dibasic alcohol, ketone and salt.They can reduce the specific inductivity in the water-sol system, thereby make SiO
2Separate out into gel.In these auxiliary agent homodisperse gels, occupy certain space, washing or dry, roasting and removing.The SiO that produces
2The product physical index is: specific surface area 300m
2/ g～450m
2/ g, pore volume are 1.2ml/g～2.8ml/g.
The US.5372983 patent disclosure polyolefin catalyst carrier SiO
2Another kind of method-the azeotropic distn of preparation.At first the reaction of silicate and dilute sulphuric acid makes hydrogel, removes impurity through washing, adds C then
5～C
6Alcohol, as amylalcohol, hexanol or their mixture,, remove the moisture content in the hydrogel hole by component distillation, obtain xerogel.450 ℃～700 ℃ roastings make product SiO
2Its physical index: pore volume is 2.2ml/g～2.5ml/g, specific surface area 420m
2/ g～550m
2/ g, bulk density are 0.18～2.5g/ml.
US.5599762,5576262 patents have been improved the method for its component distillation.Mainly be the organic compound of having found that some are suitable, as the compound of alcohol ether, pure ether-ether and so on, comprising: oxyethyl group vinyl acetic monomer, tert.-butoxy propyl alcohol, Methoxy acetic acid propyl ester, n-butoxy propyl alcohol and ethoxyl ethyl propionate etc.Use these organic compound to carry out component distillation, economical and effective not only, and improved the performance of polyethylene catalysts.Improve azeotropic distillation technology, the carrier S iO that makes
2With catalyst performance be: SiO
2Specific surface area from 520m
2/ g to 530m
2/ g, pore volume are 2.4ml/g～2.6ml/g, and catalyst activity is 7000～8000Peg/gcat.h, and the product melting index is 6.5～6.8.
The US.6313061 patent has been mentioned the still unexposed so far sylopol.RTM.948 of Grace company, 955 trade mark SiO
2Manufacture method.It is predicted this SiO
2Carrying out component distillation after may being shaped by spraying obtains.
The Phillips oil company early many patents (US.3099457,3948806,4081407 are disclosed, 4152503,4436883,4246139) azeotropic distillation technology has been discussed, attempt to solve when from hydrogel, removing moisture content, avoid the contraction in hole and the problem of subsiding.Also attempted the method that the organic solvent displacement dewaters in addition.
The US.4436883 patent is selected suitable component distillation organic solvent, simultaneously, can also satisfy industrial requirement.Require this organic solvent and water section to dissolve each other or do not dissolve each other, and the boiling point organic solvent higher than water is advisable.Under agitation component distillation makes water and organic solvent eliminate with the form distillation of minimum azeotrope, and organic solvent can recycle.Consider from the economy and the validity of producing, think C
5～C
6Alcohol be advisable.As 3-methyl butanol, Pentyl alcohol, ethanol or their mixture.
The US.3948806 patent disclosure reactant aqueous solution of organosilicon and aqua ammonia or sodium hydroxide, make hydrogel, through aging, the washing removal of impurity, use oxygen containing water-soluble organic compounds, as vinyl acetic monomer, carry out the moisture content that component distillation removes in the gel and form xerogel, make the polyolefin catalyst carrier SiO of macropore at last
2
The US.4246139 patent has disclosed a kind of method of organic solvent replacing water.Sodium silicate solution and sulphuric acid soln reaction obtain hydrogel, eliminate impurity through aging washing, then with the moisture content in the organic solvent displacement gel.At first use the methyl alcohol treatment gel, wash repeatedly 2～3 times, remove partly water, and then with Ethanol Treatment washing 2～3 times, remove most water, obtain organogel, handle with ether, under critical temperature, ethanol evaporation makes xerogel.The method of this water-miscible organic solvent replacing water is though can make SiO than bigger serface and pore volume
2Product still, needs repeatedly the organic solvent displacement, repeatedly washing, and the divisible moisture content of, the organic solvent consumption is big, reclaims shortcomings such as organic solvent energy consumption and running cost height.
Davison Chemical Ltd. (JP) company has proposed two kinds of methods of making silica gel.A kind of method is a spray-drying process, and another kind is a cold method.And can control the rerum natura of silica gel.
The US.5589150 patent disclosure preparation polyolefin catalyst carrier microspheroidal SiO
2Spray-drying process.Mainly be moisture content and SiO in the control slurries
2Ratio, generally be controlled in 0.2～1.5 (weight ratio) scope, and do not use organic substance.Can regulate the physical index of silica gel,, and suitable intensity be arranged as specific surface area, pore volume, pore size distribution.Concrete experimental result is: water and SiO in the slurries
2Weight ratio is 0.35～1.33, and specific surface area is 300m
2/ g～600m
2/ g, physical strength is 1.36～2.92.
The US.5380510 patent has disclosed silicon sol by refrigerating process, reaches the method for regulating the silica gel physical index.The advantage of this invention is not need the lyophilize step, only by freezing, thaw, washing and the hot water polymeric step is poly-just passable.The SiO that cold method makes
2Product, adjustable rerum natura is: specific surface area is from 88m
2/ g to 682m
2/ g, pore volume are 0.16ml/g～1.2ml/g.
In the patent (US3526603,5229096) of SCM.Chemical Inc. company application, the method that adds properties-correcting agent in the preparation of silica gel is disclosed.Add high molecular polymer properties-correcting agent (amino acid, protein etc.) at the preparation of silica gel initial stage, the later stage is immersed low molecule (1～4 carbon) organism.Obtain the silica gel product of different rerum naturas.The novel silica gel of this invention is to form hydrogel by silicate solutions and the acidic solution hybrid reaction with high molecular polymer properties-correcting agent, removes by washing and desalts and superpolymer, just can carry out spraying drying, does not need to wear out, step such as ammonia treatment.The gel that obtains after the spraying is put into methyl alcohol and is replaced moisture content, place 12 fens kinds after, inclining liquid layer, triplicate like this, with the same manner, put into ether then, displacement methyl alcohol, triplicate, at last, 200 ℃ of following vacuum-dryings, organism is removed in roasting, obtain the silica gel product of desirable high-specific surface area and pore volume, specific surface area is up to 812m
2/ g, pore volume can reach 2.1ml/g, and mean pore size reaches 10.3nm.
The patent (US.5861134,5976478) of E.I.du pont de Nemours and Company has disclosed silica gel fused salt reaming method.Make the silica gel product of low density and big pore volume.At first with silica gel particle and B
2O
3Mix, be heated to their fusing point, make B
2O
3Be immersed in the silica gel hole, at high temperature (450 ℃) corrode the silica gel hole wall, reach the purpose of reaming.The loose density of silica gel product can reach 0.06g/ml～0.65g/ml, and pore volume is 0.96ml/g～15.77ml/g, and the aperture is 17nm～300nm, and specific surface area also can remain 204m
2/ g～374m
2/ g.
More than each major company the organic solvent substitution method is disclosed; Azeotropic distn; Cold method; Fused salt reaming method and spray-drying process respectively have its relative merits.Yet in all multi-methods, known effective means more mainly contains following two kinds at present:
First method is supercritical drying (US.3015645).This method is that the silicon gel is carried out drying under the pressure and temperature more than the stagnation point of contained liquid, can not form liquid-gas interface, reduce surface tension, can not produce capillary force and not cause drying under the situation of contraction, be unlikely the contraction that causes the silica gel aperture and subside.Also take subcritical state to carry out Drying of gels (US.5746992,5911658).
Second method is with the gel surface hydrophobization, reduce capillary force and carry out exsiccant method (US.3015645), mainly be to adopt the hydroxyl of silicoorganic compound and gel surface to react, make the silica gel surface become hydrophobic or hydrophobic by hydrophilic, reduce surface tension, can not cause the contraction in silica gel aperture.
Yet owing to be to carry out drying under condition of high voltage, therefore, there is apparatus expensive in supercritical drying, unfavorable factors such as operational difficulty.The method of gel hydrophobization, though the non-indispensability of aforesaid device, but because when hydrophobization, use chlorinated silane compound, disilazane compound etc., with the immiscible compound of water, before hydrophobization is handled, need earlier the liquid in the hole with the solvent exchange that can mix with above-claimed cpd, therefore have that operation is long, operation is cumbersome, degradation problem under the productivity.
The organic solvent substitution method exists operation steps cumbersome, and solvent-oil ratio is big, reclaims shortcomings such as difficulty.
Azeotropic distn exists distillation time that dewaters long, solvent costliness, problem such as energy consumption is big.
Cold method exists harsh operational condition and plant issue.
There are problems such as high-temperature operation and residual impurity in fused salt reaming method.
In view of there being the problems referred to above in the prior art, the purpose of this invention is to provide a kind of supercritical drying that neither uses, also need not hydrophobization and handle, more do not want organic solvent displacement, component distillation, freezing and fused salt reaming method.
Summary of the invention
The present invention adopts the method for " gel-colloidal sol-gel ".Avoid the disadvantage of above-mentioned all methods, prepared the microspheroidal SiO of 5.0 μ m～70 μ m particle diameters
2Specific surface area is adjustable at 300m
2About/g; Mean pore size is 5nm～10nm; The aperture accounts for more than 10% greater than 100nm; Bimodal hollow shape sphere or class spherical SiO appear in pore size distribution
2The SiO that possesses the said structure feature
2,, demonstrate good comprehensive performances as carrier for olefin polymerization catalyst.
The invention provides a kind of method for preparing microspheroidal silicon-dioxide, comprise the steps:
1) providing the content of silicon-dioxide is the initial silicon gel of 20-50% (weight);
2) the described initial silicon gel of refinement makes it become the average micelle of silicon-dioxide and directly is the silicon dioxide gel of 10-100nm; Wherein, in described homogeneous micronization process, add modifier A, properties-correcting agent B and properties-correcting agent C successively, wherein,
Described modifier A is organic acid or mineral acid, and its add-on is to make that the pH of described colloidal sol is 0.5-4, is preferably 1～2;
Described properties-correcting agent B is for comprising the surfactant composition of a kind of cationic, anionic or nonionic surface active agent at least, and its usage quantity is every mole of silicon-dioxide 3.42 * 10
-5-3.42 * 10
-4Mole is preferably 6.84 * 10
-5-1.026 * 10
-4Mole;
Described properties-correcting agent C is selected from urea, methane amide or oxalic acid, or its combination, and its usage quantity is every mole of silicon-dioxide 0.085-0.85 mole, is preferably the 0.255-0.340 mole;
3) resulting silicon dioxide gel is carried out spraying drying, wherein, described spraying drying is to be that 300-370 ℃, temperature out 100-200 ℃, spraying disc rotating speed are to carry out in the atomizer of 8000-30000rpm in temperature in, preferably, described temperature in is that 320-330 ℃, temperature out 150-170 ℃, spraying disc rotating speed are 12000-20000rpm, obtains the microspheroidal silica dioxide gel of silica dioxide gel particle diameter at 10-70 μ m;
4) resulting microspheroidal silica dioxide gel is carried out roasting according to 100-200 ℃ of maintenance 1-2 hour, 200-400 ℃ maintenance 0.5-1.5 hour and 550-750 ℃ of program that kept 3-5 hour, obtain microspheroidal silicon-dioxide.
In described method, described modifier A is selected from formic acid, acetate, propionic acid, vinylformic acid, oxalic acid, group or its combination that nitric acid, hydrochloric acid and sulfuric acid are formed; And,
In described method, described properties-correcting agent B is the combination of nonionogenic tenside and cats product or nonionogenic tenside and anion surfactant, wherein, the weight ratio of nonionogenic tenside and cats product or nonionogenic tenside and anion surfactant is 0.1-2: 1, be preferably 0.5-1: 1, and described properties-correcting agent B is selected from a kind of in the group of being made up of following surfactant composition:
The surfactant composition of forming by 1 weight part fatty alcohol-polyoxyethylene ether and 2 weight part Sodium dodecylbenzene sulfonatees;
The surfactant composition of forming by 1 weight part tween and 1.5 weight part Sodium dodecylbenzene sulfonatees;
The surfactant composition of forming by this Pan of 1 weight part and 0.5 weight part Sodium dodecylbenzene sulfonate;
The surfactant composition of forming by 1 weight part tween and 1 weight part Sodium dodecylbenzene sulfonate; And
The surfactant composition of forming by 0.5 weight part aliphatic acid polyethenoxy ether and 1 weight part Sodium dodecylbenzene sulfonate.
In described method, described refinement is the refinement of carrying out in colloidal mill earlier 0.5-1 hour, handles 15-45 minute in the high-speed shearing machine of 3000-10000rpm then.
According to the present invention, described initial silicon gel is to be one of silicon gel of feedstock production with organoalkoxysilane, liquid silicon-dioxide and water glass, or its arbitrary combination, or can use the silicon gel of different sources with the described initial silicon gel of its raw material combination.
Described is that the initial silicon gel of feedstock production for example prepares in the following manner with organoalkoxysilane, liquid silicon-dioxide and water glass:
With the organoalkoxysilane is raw material, and as being raw material with the tetraethoxysilane, the second alcohol and water is a solvent, and hydrochloric acid or ammoniacal liquor are catalyzer, mix by certain molar ratio, fully stir down, it is mixed, 65 ℃ keep certain hour down, generate gel, at room temperature preserve stand-by.
With liquid silicon-dioxide is raw material, and liquid silicon-dioxide is heated to 60 ℃, constantly stirs down, slowly adds ionogen or acidic substance and regulates pH value, constantly stirs down, and the reaction certain hour generates gel, preserves stand-by under the room temperature.
Perhaps, be raw material with water glass, in reactor, add earlier 12～16% water glass, be warming up to 50～60 ℃, under constantly stirring, add mineral acid, the control pH value is between 2～6.The reaction certain hour generates gel, and through aging, washing is preserved stand-by under the room temperature.
Further, described initial silicon gel also will be through aging, washing, and at room temperature preserve stand-by.Generally speaking, prepared initial silicon gel is through more than 10 hours, and is preferably aging at the normal temperature more than 24 hours.
The present invention further provides microspheroidal silicon-dioxide by method for preparing.
The present invention also provides the support of the catalyst that contains above-mentioned microspheroidal silicon-dioxide, and with described microspheroidal silicon-dioxide be carrier vinyl polymerization or catalyst for copolymerization.
Particularly, in the present invention's " gel-colloidal sol-gel " method, the colloidal sol that relates to, mean that organoalkoxysilane, liquid silicon-dioxide and water glass are the silicon gel that raw material is made, at least a above-mentioned gel or their mixture, through mechanical homogeneous and refinement, make gel become colloidal sol, mechanical means is colloidal mill, high-speed shearing machine etc.
In the inventive method, described colloidal sol in preparation process, also need add at least a modifier A, properties-correcting agent B and properties-correcting agent C.
Above-mentioned said tin of modifier A is mineral acid or organic acid, preferably organic acid.Mineral acid is nitric acid, hydrochloric acid and sulfuric acid.Organic acid is formic acid, acetate, propionic acid, vinylformic acid, oxalic acid etc.These acid all can react with the surface hydroxyl in the silica gel, avoid silica gel particle to grow up.Modifier A can make the regulation and control of silica gel particle size on a certain size level.
The above-mentioned properties-correcting agent B that it is said is a kind of composition of tensio-active agent.At least comprise a kind of cationic, anionic and nonionic surface active agent in the composition.Combined tensio-active agent is better than single tensio-active agent effect.Properties-correcting agent B can reduce surface tension of liquid, when making the water evaporates in the silica gel hole, reduces capillary force, thereby can suppress the contraction in hole and subside.
Above-mentioned said properties-correcting agent C is the material of urea, methane amide and so on, in the preparation of silica gel process, plays the effect of similar template, makes silica gel particle form network structure at three-dimensional space, the size in control aperture.
Through the colloidal sol of above-mentioned processing and modification,, form the dried silicon gel of microspheroidal by spraying drying.After the roasting, make and be suitable for carrier for olefin polymerization catalyst.
With liquid Si O
2Be raw material, the present invention implements as follows:
A certain amount of liquid silicon-dioxide of weighing at first, wherein dioxide-containing silica is 40% (wt/wt).Be heated to 50～80 ℃, constantly stir down, slowly drip acidic substance, the concentration of acid is that 3.0～10.0% (wt/wt) adjusting pH value reaches 5～8, reacts 2～3 hours, generates gel, and it is aging to spend the night.
The silicon gel of above-mentioned preparation makes silicon sol through the mechanical means homogeneous micronization.At first, reach certain colloid size, then, handled 1～2 hour with high-speed shearing machine again, it is homogenized through milling treatment of colloid 2～4 hours.In the Gel Treatment process, slowly add modifier A, B and C in proper order.Every mole of SiO
2Using modifier A is that 20～30ml concentration is 1.46mol/L, and the pH value of regulating colloidal sol is 0.5～3, and preferably pH value is 1-2; Add properties-correcting agent B10～15ml then, be preferably 20～30ml, concentration is 3.42 * 10
-3Mol/L; Add properties-correcting agent C at last, 10～30ml, best 15～20ml, its concentration is 17mol/L.The colloidal sol for preparing is placed the ageing of spending the night.
At last, the colloidal sol that ageing is good was handled 20～30 minutes through high-speed shearing machine again, then carried out spraying drying, made the microspheroidal SiO of 10 μ m～70 μ m
2Gel.Spray-dired processing condition are: temperature in is 200 ℃～350 ℃, and temperature out is 100 ℃～200 ℃, and the solid content of slurries is 20～40% (wt/wt).The revolution of spraying disc is 8000～12000 rev/mins.
The microballoon SiO that spraying drying obtains
2,, obtain final finished through the rotary roasting furnace roasting.The program control temperature curve of experience three phases is finished roasting process.The fs temperature is controlled at 100 ℃～120 ℃, keeps 1～2 hour, removes residual moisture content; The subordinate phase temperature rises to 200 ℃～400 ℃, keeps 2 hours, removes organism or nitrate in the silica gel.Phase III is the constant temperature calcining stage, according to required SiO
2Specific surface area size is regulated maturing temperature, and general maturing temperature is controlled between 600 ℃～750 ℃, keeps 2 hours, removes the lip-deep part hydroxyl of silica gel.
Advantage of the present invention is: only by colloidal sol is added properties-correcting agent, spraying drying is shaped, and just can obtain desirable microspheroidal SiO
2Product satisfies the requirement of polyolefin catalyst carrier.The preparation method is easy, and production process is easy to control, and cost is lower, does not have the three wastes substantially.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention be not limited only to for embodiment.
Embodiment 1
With 500ml (SiO
2Content 〉=28%) tetraethoxysilane is dissolved in ethanol-aqueous solution of 200ml30% (v/v), under agitation, drip an acidic catalyst, the polycondensation that under 65 ℃, is hydrolyzed, after reaction finished, inclining supernatant liquid, reaction product was soaked 10 hours with deionized water, use washing with alcohol then, the gel that obtains, at room temperature age overnight.
Above-mentioned gel is put into colloidal mill and was carried out refinement one hour, during beginning, slowly adds rare nitric acid (1.46mol/L), and pH value is transferred to till 1～2.Add 20ml again, content is 3.42 * 10
-3The tensio-active agent of mol/L, tensio-active agent is made up of 1 part of (wt) fatty alcohol-polyoxyethylene ether and 2 parts of (wt) dodecylbenzene benzene sulfonic acid sodium salts.The urea soln that adds 50ml (17mol/L) then.Handled 30 minutes with high-speed shearing machine more at last, its revolution is controlled at 7000～10000 rev/mins.
With the above-mentioned colloidal sol that makes, under 60 ℃, carry out spraying drying.The atomizer temperature in is controlled at 320 ℃, and temperature out is 170 ℃, and the atomizing disk revolution is controlled at about 20000r.p.m (40Hz), generates microspheroidal SiO
2Xerogel, average footpath is 20 μ m.
With the microspheroidal SiO that generates
2, put into rotary roasting furnace, under 100 ℃～120 ℃, kept one hour, remove residual moisture content, afterwards, temperature is upgraded to 200～400 ℃, keeps 1 hour, removes organic constituent and nitrate radical.Be warming up to 600 ℃ at last, kept 2 hours, make microspheroidal SiO
2Product, its specific surface area are 320m
2/ g, mean pore size is 5.5nm, average footpath is 18 μ m.
Embodiment 2
With 500ml (SiO
2Content 〉=28%) tetraethoxysilane is dissolved in ethanol-aqueous solution of 250ml30% (v/v), under agitation, drip an acidic catalyst (0.5mol acid/mol tetraethoxysilane), 70 ℃ were reacted one hour down, the product that generates soaked 8 hours through deionized water, used washing with alcohol again, it is aging to spend the night under 60 ℃, makes silica dioxide gel.
With above-mentioned silica dioxide gel, put into colloidal mill, carried out thinning processing 1.5 hours.The processing initial stage slowly adds acrylic acid solution, and its concentration is 1.46mol/L, and transferring to pH value is 0.5～1.0, adds 10ml (3.42 * 10 then
-3Mol/L) surfactant composition.This surfactant composition is made up of 1 part of (wt) tween and 1.5 parts of (wt) Sodium dodecylbenzene sulfonatees.Add 30ml at last, the formamide soln of 17mol/L.After milling treatment of colloid is intact, handled 30 minutes with high-speed shearing machine, its revolution is controlled at about 10000 rev/mins again.Make silicon dioxide gel.
With above-mentioned silicon dioxide gel, keep 60 ℃ under, carry out spraying drying, the atomizer temperature in is controlled at 300 ℃, temperature out is 150 ℃, and the atomizing disk revolution is controlled at 30000r.p.m (during 40Hz) and generates the microspheroidal silica xerogel, and median size is 15 μ m.
With the microspheroidal silica xerogel that generates, put into rotary roasting furnace, kept one hour, remove moisture content at 110～120 ℃, be warming up to 300～450 ℃ then, kept 1 hour, and removed organism, last, be warming up to 620 ℃, kept 2 hours, and obtained the finished product, the specific surface area of silica gel is 310m
2/ g, mean pore size is 6.0nm, median size is 13 μ m.
Embodiment 3
With the liquid silicon-dioxide of 500ml 40% (wt/wt), constantly stir down, be heated to 60 ℃, slowly drip ammonium chloride solution.Its concentration is 10%, add the 30ml ammonium chloride solution after, keep 60 ℃, it is aging to spend the night, and generates the silicon gel.
With above-mentioned silicon gel, after deionized water soaks and washs, put into colloidal mill and carried out thinning processing one hour.After 10 minutes, begin to add dilute hydrochloric acid (2%) through milling treatment of colloid, transferring to pH value is 1～2.Add combinations-of surfactants then and claim 20ml, content is 3.42 * 10
-3Mol/L, surfactant composition is made up of the Sodium dodecylbenzene sulfonate of 1 part of (wt) Si Pan and 0.5 part (wt).The aqueous solution of urea that adds 60ml (17mol/L) at last.After thinning processing finishes, handled 20 minutes with high-speed shearing machine, its revolution is 7000 rev/mins again.Make silicon dioxide gel.
With the above-mentioned silicon dioxide gel that makes, keep 60 ℃ under, carry out spraying drying.The temperature in of atomizer is 320 ℃, and temperature out is 170 ℃, and the atomizing disk revolution is 20000r.p.m (30Hz), generates the microspheroidal silica xerogel, and median size is 13 μ m.
With above-mentioned silica xerogel, place rotary roasting furnace, under 110～120 ℃, kept one hour, remove remaining moisture content, temperature rises to 300～400 ℃ then, keeps one hour, removes organism and inorganics.Be warming up to 650 ℃ at last, kept 1.5 hours, obtain microspheroidal silicon-dioxide finished product.Its specific surface area is 290m
2/ g, mean pore size is 7.2nm.Median size is 12 μ m.
Embodiment 4
With the liquid silicon-dioxide of 500ml (40%), constantly stir down, be heated to 60 ℃, slowly drip rare nitric acid (2mol/L), transferring to pH value is 6～7.The powerful stirring after 30 minutes, the room temperature placement is spent the night aging, generates silica dioxide gel at last.
With above-mentioned gel, after deionized water immersion and washing, put into the colloidal mill thinning processing 1 hour.Handle after 10 minutes, begin to add acetic acid solution (1.46mol/L), regulating pH value is 0.5～1.5.Add surfactant composition 50ml (3.42 * 10 then
-3Mol/L), surfactant composition is made up of 1 part of (wt) tween and 1 part of (wt) Sodium dodecylbenzene sulfonate.The formamide soln that adds 100ml (17mol/L) at last finishes through the colloidal mill thinning processing, handles 30 minutes with high-speed shearing machine again, and its revolution is 8000 rev/mins, makes silicon dioxide gel.
With above-mentioned colloidal sol, adopt the similarity condition of example 3, carry out spraying drying and roasting, obtain the silicon-dioxide finished product at last.Its surface-area is 305m
2/ g, mean pore size is 6.5nm, median size is 12 μ m.
Embodiment 5
With modulus is 3.2, and concentration is 15% water glass solution 800ml, puts into reactor, be warming up to 50 ℃, constantly stir down, slowly add dilute sulphuric acid (26%), transferring to pH value is about 6, react after 30 minutes, generate hydrogel, then carried out acidification 1～2 hour, incline and acid solution, use the deionized water thorough washing, make the Na ion content be lower than 0.5%, it is aging to spend the night.
With the above-mentioned silica dioxide gel that makes, put into colloidal mill, carried out thinning processing one hour.Handle after 10 minutes, beginning slowly adds formic acid (1.46mol/L) solution, and transferring to pH value is 2～3.Add 20ml surfactant composition (3.42 * 10 then
-3Mol/L).The composition of tensio-active agent is made up of 0.5 part of (wt) aliphatic acid polyethenoxy ether and 1 part of (wt) Sodium dodecylbenzene sulfonate.The aqueous solution of urea that adds 50ml (17mol/L) at last.After the colloidal mill thinning processing finishes, handled 30 minutes with high-speed shearing machine, its revolution is 3000 rev/mins, makes silicon dioxide gel again.
With above-mentioned colloidal sol, be heated to 60 ℃, carry out spraying drying.The atomizer temperature in is 350 ℃, and temperature out is 180 ℃.The atomizing disk revolution is controlled at 25000r.p.m (35Hz), generates the microspheroidal silica xerogel, and median size is 17 μ m.
With the above-mentioned silica xerogel that makes, place rotary roasting furnace, at 110～120 ℃, kept one hour, remove residual moisture content, temperature rises to 200～400 ℃ then, keeps one hour, removes organism and inorganics.Rise to 640 ℃ at last, kept 2 hours, obtain the microspheroidal silica product, its specific surface area is 280m
2/ g, mean pore size is 7.5nm, median size is 15 μ m.
Embodiment 6
The silica gel of embodiment 1～5 prepared microspheroidal silicon-dioxide and Grace company 955 trades mark as carrier, is prepared six batches of polyethylene catalysts, carry out the lab scale activity rating, examine or check its activity index.
Preparation of Catalyst:
Take by weighing 30g microspheroidal silicon-dioxide, place the roasting bottle, under the condition that constantly vacuumizes, 600 ℃ of constant temperature kept 4 hours.Naturally be cooled to room temperature, good seal is put in the moisture eliminator, preserves stand-by.
Under the protection of nitrogen hydrogen, inject 20ml toluene in reaction flask, then add 1ml (2 * 10
-3Mol/L) triethyl aluminum under 60 ℃, stirred 30 minutes, added the silica supports that 2.000g activates then, flooded 30 minutes, filtered at last, drained.
With the active ingredient mother liquor (TiCl that has prepared
3: MgCl
2: THF=1: 1.3: 120) 30ml is injected in the above-mentioned reaction flask, when silica supports becomes greyish-green by purple, under 60 ℃, stirs 2 hours, drains then.Silicon-dioxide is faint yellow mobile shape.Add AlEl this moment again
3Toluene solution 1ml handled after 30 minutes, drained, and obtained polyethylene catalysts.
Evaluating catalyst:
In 200ml glass slurry-phase reactor, carry out activity rating.At first carry out reactor baking and nitrogen replacement and handle, reach absolute anaerobic and anhydrous.Under constantly stirring, inject 100ml toluene, 2.5ml (2 * 10 in proper order
-3Mol/L) catalyzer of triethyl aluminum, 0.1g.Temperature of reaction is 60 ℃, carries out 2 hours polyreaction under the normal pressure.End with 10ml ethanol at last, filter, washing and oven dry product obtain white group spheric polyethylene product, weighing and calculated activity index.Polymerizing condition and activity index are listed in the table 1.
Table 1 200ml slurry-phase reactor vinyl polymerization evaluation result
| Embodiment number | The carrier rerum natura | Polymeric reaction condition | Catalyst activity | ||||||
| Specific surface area | Mean pore size | Median size | Catalytic amount | ???Al/Ti | Temperature of reaction | Reaction times | Active | Industrial production | |
| ?m 2/g | ?nm | ?μm | ?g | ??mol/mol | ??℃ | ??h | ??Peg/gcot | ??Peg/gcot | |
| ??1 | ?320 | ?5.5 | ?18 | ?0.087 | ????100 | ??60 | ??2 | ??25.5 | ??6100 |
| ??2 | ?310 | ?6.0 | ?13 | ?0.102 | ????100 | ??60 | ??2 | ??26.7 | ??6400 |
| ??3 | ?290 | ?7.2 | ?12 | ?0.120 | ????100 | ??60 | ??2 | ??25.8 | ??6200 |
| ??4 | ?305 | ?6.5 | ?12 | ?0.150 | ????100 | ??60 | ??2 | ??27.0 | ??6500 |
| ??5 | ?280 | ?7.5 | ?15 | ?0.098 | ????100 | ??60 | ??2 | ??27.8 | ??6700 |
| ??Grace ??955 | ?320 | ?5.9 | ?14 | ?0.101 | ????100 | ??60 | ??2 | ??25.6 | ??6100 |
Annotate: (1) is the industrial polyethylene catalysts of carrier with Grace company 955 trade mark silicon-dioxide.Lab scale evaluation activity is 25.6, and the industrial production substantial activity is 6100.With these data, calculate the industrial activity level of embodiment 1～5.
(2) industrial production activity refers to producing 100000 tons of LLDPE fluidized-bed reactor practical application evaluating datas per year, and its operational condition is pressure 2.0MPa, 80 ℃ of temperature, ethene and 1-butylene copolymerization.
Be not difficult to find out from table 1, the silica supports that embodiment 1～5 makes, its physical index is basic identical, and specific surface area is at 300m
2About/g, mean pore size is between 5～8nm, and median size is about 13 μ m.Rerum natura basically identical with comparative example Grace company 955 trade mark silica supports.Therefore under identical processing condition, the activity of ethylene polymerization also is close.Further prove the microspheroidal silicon-dioxide that arrives involved in the present invention, can be used as the polyethylene catalysts carrier fully, and alternative Grace company 955 silica gel.And preparing easyly, cost is low, helps producing the various trade mark LLDPE resins of high quality, low price.
Claims (17)
1. a method for preparing microspheroidal silicon-dioxide comprises the steps:
1) providing the content of silicon-dioxide is the initial silicon gel of 20-50% (weight);
2) the described initial silicon gel of refinement makes it become the average micelle of silicon-dioxide and directly is the silicon dioxide gel of 10-100nm; Wherein, in described homogeneous micronization process, add modifier A, properties-correcting agent B and properties-correcting agent C successively, wherein,
Described modifier A is organic acid or mineral acid, and its add-on is to make that the pH of described colloidal sol is 0.5-4;
Described properties-correcting agent B is for comprising the surfactant composition of a kind of cationic, anionic or nonionic surface active agent at least, and its usage quantity is every mole of silicon-dioxide 3.42 * 10
-5-3.42 * 10
-4Mole;
Described properties-correcting agent C is selected from urea, methane amide or oxalic acid, or its combination, and its usage quantity is every mole of silicon-dioxide 0.085-0.85 mole;
3) resulting silicon dioxide gel is carried out spraying drying, wherein, described spraying drying is to be that 300-370 ℃, temperature out 100-200 ℃, spraying disc rotating speed are 8000-30000rpm in temperature in, obtains the microspheroidal silica dioxide gel of silica dioxide gel particle diameter at 10-70 μ m;
4) resulting microspheroidal silica dioxide gel is carried out roasting according to 100-200 ℃ of maintenance 1-2 hour, 200-400 ℃ maintenance 0.5-1.5 hour and 550-750 ℃ of program that kept 3-5 hour, obtain microspheroidal silicon-dioxide.
2. the method for claim 1, wherein described modifier A is selected from formic acid, acetate, propionic acid, vinylformic acid, oxalic acid, group or its combination that nitric acid, hydrochloric acid and sulfuric acid are formed.
3. the method for claim 1, wherein adding of described modifier A makes that the pH value of colloidal sol is 1～2.
4. the method for claim 1, wherein, described properties-correcting agent B is the combination of nonionogenic tenside and cats product or nonionogenic tenside and anion surfactant, wherein, the weight ratio of nonionogenic tenside and cats product or nonionogenic tenside and anion surfactant is 0.1-2: 1.
5. method as claimed in claim 4, wherein, the weight ratio of described nonionogenic tenside and cats product or nonionogenic tenside and anion surfactant is 0.5-1: 1.
6. as claim 4 or 5 described methods, wherein, described properties-correcting agent B is selected from a kind of in the group of being made up of following surfactant composition:
The surfactant composition of forming by 1 weight part fatty alcohol-polyoxyethylene ether and 2 weight part Sodium dodecylbenzene sulfonatees;
The surfactant composition of forming by 1 weight part tween and 1.5 weight part Sodium dodecylbenzene sulfonatees;
The surfactant composition of forming by this Pan of 1 weight part and 0.5 weight part Sodium dodecylbenzene sulfonate;
The surfactant composition of forming by 1 weight part tween and 1 weight part Sodium dodecylbenzene sulfonate; And
The surfactant composition of forming by 0.5 weight part aliphatic acid polyethenoxy ether and 1 weight part Sodium dodecylbenzene sulfonate.
7. the consumption of the method for claim 1, wherein described properties-correcting agent B is every mole of silicon-dioxide 6.84 * 10
-5-1.026 * 10
-4Mole.
8. the consumption of the method for claim 1, wherein described properties-correcting agent C is every mole of silicon-dioxide 0.255-0.340 mole.
9. the method for claim 1, wherein described temperature in is that 320-330 ℃, temperature out 150-170 ℃, spraying disc rotating speed are 12000-20000rpm.
10. the method for claim 1, wherein described refinement is the refinement of carrying out in colloidal mill earlier 0.5-1 hour, handles 15-45 minute in the high-speed shearing machine of 3000-10000rpm then.
11. the method for claim 1, wherein described initial silicon gel is to be one of silicon gel of feedstock production with organoalkoxysilane, liquid silicon-dioxide and water glass, or its arbitrary combination, or with its raw material combination.
12. method as claimed in claim 11, wherein, described organoalkoxysilane is a tetraethoxysilane.
13. method as claimed in claim 11, wherein, described initial silicon gel is aging through the normal temperature more than 10 hours.
14. method as claimed in claim 13, wherein, described wearing out more than 24 hours.
15. microspheroidal silicon-dioxide as the described method preparation of one of claim 1-14.
16. contain the support of the catalyst of microspheroidal silicon-dioxide as claimed in claim 15.
17. with microspheroidal silicon-dioxide as claimed in claim 16 be carrier vinyl polymerization or catalyst for copolymerization.
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| CN100355654C (en) * | 2005-12-30 | 2007-12-19 | 中国科学院上海硅酸盐研究所 | Process for preparing silicon dioxide hollow ball material with hexagonal phase penetrating mesopore orbit |
| CN100369942C (en) * | 2006-01-26 | 2008-02-20 | 吉林市吉清科技开发有限公司 | Method and apparatus for preparing microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst |
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