CN102002120A - Method for preparing special silica gel carrier with large pore volume and large specific surface area - Google Patents
Method for preparing special silica gel carrier with large pore volume and large specific surface area Download PDFInfo
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- CN102002120A CN102002120A CN 201010287087 CN201010287087A CN102002120A CN 102002120 A CN102002120 A CN 102002120A CN 201010287087 CN201010287087 CN 201010287087 CN 201010287087 A CN201010287087 A CN 201010287087A CN 102002120 A CN102002120 A CN 102002120A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000741 silica gel Substances 0.000 title claims abstract description 29
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 29
- 239000011148 porous material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 37
- 238000002360 preparation method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 abstract description 2
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing a special silica gel carrier with a large pore volume and a large specific surface area. The method is characterized by comprising the following process steps of: diluting industrial sodium silicate; adding inorganic acid solution dropwise at the initial temperature of between 20 and 40 DEG C, adjusting the pH value of a system to be 2 to 4, heating to the final temperature of between 80 and 100 DEG C and adding a specific surface control agent which may be one or more of glycol, ethyl acetate, glycerol, acetone and trichloroethane; preserving the heat for 2 to 4 hours and performing a hydro-thermal reaction; ageing for 1 to 2 hours; washing; drying; and performing particle size classification to obtain the final product.
Description
Technical field
The present invention relates to a kind of preparation method of silica gel, more particularly, relate to the preparation method who is suitable as high reactivity gas phase ethene polymerization catalyst special silica-gel carrier.
Background technology
In gas phase polymerization polyethylene catalysts preparation process, silica gel is used widely as a kind of carrier at present.The catalyzer that utilizes this carrier to make is mainly used in the production of LLDPE.The present silica-gel carrier that uses, its pore property is: pore volume 1.6ml/g, specific surface area, 300-350m2/g, mean particle size: 40-50 micron.Utilize the catalyst activity of this preparing carriers can only reach 3000-4000gPE/gcat, make poly production cost high like this, external current research shows, utilize large pore volume, bigger serface special silica-gel carrier, the catalyst activity of preparation can reach 6000-7000gPE/gcat, can make like this under the constant situation of production equipment production efficiency is increased substantially, production cost is further reduced.The pore property of this carrier is: pore volume: 2.4-2.8ml/g, specific surface area: 500-600m
2/ g, mean particle size: 50-150 micron.The method of U5625023 patent disclosure is that potassium or sodium silicate and mineral acid mix the formation hydrogel by a special nozzle, and washing, drying obtain specific surface 10-1000m then
2/ g, pore volume: 0.5-2.5ml/g, aperture
Silica-gel carrier.A kind of preparation method of silica-gel carrier is disclosed in patent CN1403486, when the preparation hydrogel, employing is a mother liquor with part dilute silicate solution, dilute silicate solution and mineral acid add in the reactor that mother liquor is housed simultaneously, treat to regulate when partial gel occurs the mother liquor PH5-8.5 water-sol and be converted into hydrogel fully, through the silica-gel carrier that aging, washing, drying obtain, specific surface area: 200-400m
2/ g, pore volume: 1.0-2.0ml/.
Introduced a kind of preparation method of macroporous particle silica gel in CN02127599.8, described method is because pore volume has only 0.8-1.1ml/g to be not suitable for doing the use of ethylene rolymerization catalyst carrier.Because it is relatively stricter to the requirement of activity of such catalysts and granularity to produce poly production as vapor phase process, must to be a kind of polymerizing catalyst efficiently be mainly three aspects for the requirement of carrier silica gel with employed catalyzer.1, chemical purity, 2, pore property, 3, size-grade distribution.These three conditions must all will satisfy, and could use as support of the catalyst like the gas phase polymerization polyethylene.Therefore, we have invented the large pore volume that is suitable for gas phase ethene polymerization and uses, the preparation method of bigger serface special silica-gel carrier.
Summary of the invention
The objective of the invention is to adopt industrial metasilicate is raw material, a kind of large pore volume that highly active gas phase ethene polymerization uses, preparation method of bigger serface special silica-gel carrier of being fit to is provided, adopt this method, the special silica-gel carrier of producing, its granularity, overall target excellences such as aperture, pore volume and specific surface area, thereby can be as the gas phase ethene polymerization catalyst carrier.
A kind of preparation method of large pore volume bigger serface special silica-gel carrier is characterized in that:
Processing step comprises:
1, be the industrial metasilicate of 3.1-3.4 with modulus, the mass content that is diluted to concentration and is silicon-dioxide is a 10-20% industrial metasilicate solution; Down dripping mass content at initial temperature 20-40 ℃ is the inorganic acid solution of 15-25%, and mineral acid is selected from one or more of sulfuric acid, nitric acid, phosphoric acid; Regulation system PH to 2-4, keeping the final pH value of regulating is 3-4;
2, be warming up to outlet temperature 80-100 ℃, add the specific surface control agent; The specific surface control agent is selected from ethylene glycol, ethyl acetate, glycerol, and acetone, one or more of trichloroethane, the add-on of specific surface control agent is the 1-5% of water glass mass content;
3, with outlet temperature insulation 2-4 hour, carry out hydro-thermal reaction; At room temperature ageing 1-2 hour then; Wash, mode of washing is selected from washing, one or more that alcohol is washed, and being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Carry out size classification then, obtain the finished product.
The pore property that obtains the finished product is:
Silicon-dioxide: greater than 99.7%; Pore volume: 2.5-2.8ml/g; Specific surface area: 500-600m2/g; Mean particle size 50-150 micron.
Foregoing invention is by kind of regulating initial temperature, outlet temperature and specific surface control agent and the purpose that content reaches the adjustment hole characteristic.The pore property of different types of specific surface control product is different.
The preferred technical solution of the present invention: it is characterized in that:
Processing step comprises:
1, be the industrial metasilicate of 3.2-3.3 with modulus, the mass content that is diluted to concentration and is silicon-dioxide is a 15-20% industrial metasilicate solution; Down dripping mass content at initial temperature 30-40 ℃ is the inorganic acid solution of 15-25%, and mineral acid is selected from one or more of sulfuric acid, nitric acid, phosphoric acid; Regulation system PH to 3-4, keeping the final pH value of regulating is 3.5-4;
2, be warming up to outlet temperature 90-100 ℃, add the specific surface control agent; The specific surface control agent is selected from ethylene glycol, ethyl acetate, glycerol, and acetone, one or more of trichloroethane, the add-on of specific surface control agent is the 1-4% of water glass mass content;
3, with outlet temperature insulation 3-4 hour, carry out hydro-thermal reaction; At room temperature ageing 1-1.5 hour then, washing, drying is carried out size classification then, obtains the finished product.
The invention has the advantages that: adopt technology of the present invention, make the physical and chemical performance of this silica-gel carrier reach, dioxide-containing silica (butt) is greater than 99.7%, and the BET specific surface area is 450-600m
2/ g, volume of voids are 2.0-2.7, and mean particle size is the index request of 75-150 μ m.Whole technological process need not to use the strict process raw material, and the reaction times of the present invention is 2-5 hour.Hydro-thermal reaction adds the specific surface control agent simultaneously, and in reaction process, the primary particle of hydrogel is grown up gradually and rearranged.Organic solvent molecule and silica gel surface hydroxyl carry out graft reaction and through spraying drying rapid drying, have prevented the contraction in aperture, thereby silica gel structure is fixed up at last.The present invention adopts the prepared special silica-gel carrier dioxide-containing silica of common raw material greater than 99.7%.
Embodiment
Embodiment one,
1, with modulus be 3.1 industrial metasilicate, the mass content that is diluted to concentration and is silicon-dioxide is 10% industrial metasilicate solution; Dripping mass content down 20 ℃ of initial temperatures is 25% sulphuric acid soln, regulation system PH to 2-4, and keeping the final pH value of regulating is 3.5-4;
2, be warming up to outlet temperature 95-100 ℃, add specific surface control agent glycerol, the add-on of specific surface control agent is 1% of a water glass mass content;
3, with outlet temperature insulation 2 hours, carry out hydro-thermal reaction; Ageing at room temperature is 2 hours then; Wash, being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 400 ℃; Carry out size classification then, mean particle size 75-150 micron obtains moisture less than 10% macroporous microsphere silica gel the finished product.
Its experimental data such as table one.
Table one: the physical and chemical performance table of special silica-gel carrier embodiment
Embodiment two,
1, with modulus be 3.2 industrial metasilicate, the mass content that is diluted to concentration and is silicon-dioxide is 15% industrial metasilicate solution; Dripping mass content down 30 ℃ of initial temperatures is 20% sulphuric acid soln, regulation system PH to 2-4, and keeping the final pH value of regulating is 3.5-4;
2, be warming up to outlet temperature 80-85 ℃, add specific surface control agent ethyl acetate, the add-on of specific surface control agent respectively is 3% of a water glass mass content;
3, with outlet temperature insulation 3 hours, carry out hydro-thermal reaction; Ageing at room temperature is 1 hour then; Wash, being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 500 ℃; Carry out size classification then, mean particle size 75-150 micron obtains moisture less than 10% macroporous microsphere silica gel the finished product.
Its experimental data such as table two.
Table two: the physical and chemical performance table of special silica-gel carrier embodiment
Embodiment three:
1, with modulus be 3.3 industrial metasilicate, the mass content that is diluted to concentration and is silicon-dioxide is 20% industrial metasilicate solution; Dripping mass content down 40 ℃ of initial temperatures is 18% sulphuric acid soln, regulation system PH to 2-4, and keeping the final pH value of regulating is 3.5-4;
2, be warming up to outlet temperature 90-95 ℃, add specific surface control agent ethylene glycol, the add-on of specific surface control agent is 3% of a water glass mass content;
3, with outlet temperature insulation 2 hours, carry out hydro-thermal reaction; Ageing at room temperature is 2 hours then; Wash, being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 600 ℃; Carry out size classification then, mean particle size 75-150 micron obtains moisture less than 10% macroporous microsphere silica gel the finished product.
Its experimental data such as table three.
Table three: the physical and chemical performance table of special silica-gel carrier embodiment
Embodiment four:
1, with modulus be 3.4 industrial metasilicate, the mass content that is diluted to concentration and is silicon-dioxide is 20% industrial metasilicate solution; Dripping mass content down 20 ℃ of initial temperatures is 15% sulphuric acid soln, regulation system PH to 2-4, and keeping the final pH value of regulating is 3.5-4;
2, be warming up to outlet temperature 95-100 ℃, add specific surface control agent glycerol and acetone mixed solution, glycerol and acetone mass content respectively account for 50%, and the add-on of specific surface control agent is 4% of a water glass mass content;
3, with outlet temperature insulation 2 hours, carry out hydro-thermal reaction; Ageing at room temperature is 2 hours then; Wash, being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 400 ℃; Carry out size classification then, mean particle size 75-150 micron obtains moisture less than 10% macroporous microsphere silica gel the finished product.
Its experimental data such as table four.
Table four: the physical and chemical performance table of special silica-gel carrier embodiment
Claims (2)
1. the preparation method of a large pore volume bigger serface special silica-gel carrier is characterized in that:
Processing step comprises:
1) be the industrial metasilicate of 3.1-3.4 with modulus, the mass content that is diluted to concentration and is silicon-dioxide is the industrial metasilicate solution of 10-20%; Down dripping mass content at initial temperature 20-40 ℃ is the inorganic acid solution of 15-25%, and mineral acid is selected from one or more of sulfuric acid, nitric acid, phosphoric acid; Regulation system PH to 2-4, keeping the final pH value of regulating is 3-4;
2) be warming up to outlet temperature 80-100 ℃, add the specific surface control agent; The specific surface control agent is selected from ethylene glycol, ethyl acetate, glycerol, and acetone, one or more of trichloroethane, the add-on of specific surface control agent is the 20-30% of water glass mass content;
3) with outlet temperature insulation 2-4 hour, carry out hydro-thermal reaction; At room temperature ageing 1-2 hour then; Wash, mode of washing is selected from washing, one or more that alcohol is washed, and being washed to the sodium ion mass content is below 0.05%; Drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Carry out size classification then, obtain the finished product.
The pore property that obtains the finished product is:
Silicon-dioxide: greater than 99.7%; Pore volume: 2.5-2.8ml/g; Specific surface area: 500-600m2/g; Mean particle size 50-150 micron.
2. according to the described preparation method of claim 1, it is characterized in that:
Processing step comprises:
1) be the industrial metasilicate of 3.2-3.3 with modulus, the mass content that is diluted to concentration and is silicon-dioxide is the industrial metasilicate solution of 15-20%; Down dripping mass content at initial temperature 30-40 ℃ is the inorganic acid solution of 15-25%, and mineral acid is selected from one or more of sulfuric acid, nitric acid, phosphoric acid; Regulation system PH to 3-4, keeping the final pH value of regulating is 3.5-4;
2) be warming up to outlet temperature 90-100 ℃, add the specific surface control agent; The specific surface control agent is selected from ethylene glycol, ethyl acetate, glycerol, and acetone, one or more of trichloroethane, the add-on of specific surface control agent is the 20-25% of water glass mass content;
3) with outlet temperature insulation 3-4 hour, carry out hydro-thermal reaction; Ageing at room temperature then, washing, drying is carried out size classification then, obtains the finished product.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145897A (en) * | 2011-04-19 | 2011-08-10 | 冷水江三A化工有限责任公司 | Large-pore-volume silicon dioxide with nanoparticle structure and preparation method thereof |
| CN102382216A (en) * | 2011-05-26 | 2012-03-21 | 中国海洋石油总公司 | Preparation method of silica gel carrier for ethylene polymerization catalyst |
| CN102530970A (en) * | 2012-03-01 | 2012-07-04 | 冷水江三A化工有限责任公司 | Preparation method of toothpaste abrasive silicon dioxide |
| CN102960560A (en) * | 2012-11-23 | 2013-03-13 | 重庆优宝生物技术有限公司 | Composite acidifier for reducing post-weaning diarrhea rate |
| CN103464216A (en) * | 2013-09-26 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene |
| CN105813977A (en) * | 2013-12-12 | 2016-07-27 | 日产化学工业株式会社 | Silica particle, method for producing same, and silica sol |
| CN108794667A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | Silica-gel carrier and loaded catalyst and preparation method thereof |
| CN108794668A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | Silica-gel carrier and loaded catalyst and preparation method thereof |
| CN108794666A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method and polyethylene of vinyl polymerization |
| CN108794665A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method and polyethylene of vinyl polymerization |
| CN111072818A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Metallocene catalyst and preparation method thereof |
| CN111072798A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Silica gel and preparation method and application thereof |
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| CN1403486A (en) * | 2001-09-03 | 2003-03-19 | 中国石油天然气股份有限公司 | A kind of preparation method of silica gel carrier |
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| CN101624431A (en) * | 2009-08-19 | 2010-01-13 | 中国海洋石油总公司 | Method for preparing special silica-gel carrier of ethylene polymerization catalyst in a slurry process |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145897B (en) * | 2011-04-19 | 2012-10-24 | 冷水江三A化工有限责任公司 | Large-pore-volume silicon dioxide with nanoparticle structure and preparation method thereof |
| CN102145897A (en) * | 2011-04-19 | 2011-08-10 | 冷水江三A化工有限责任公司 | Large-pore-volume silicon dioxide with nanoparticle structure and preparation method thereof |
| CN102382216A (en) * | 2011-05-26 | 2012-03-21 | 中国海洋石油总公司 | Preparation method of silica gel carrier for ethylene polymerization catalyst |
| CN102382216B (en) * | 2011-05-26 | 2013-01-16 | 中国海洋石油总公司 | Preparation method of silica gel carrier for ethylene polymerization catalyst |
| CN102530970B (en) * | 2012-03-01 | 2014-02-19 | 冷水江三A化工有限责任公司 | Preparation method of toothpaste abrasive silicon dioxide |
| CN102530970A (en) * | 2012-03-01 | 2012-07-04 | 冷水江三A化工有限责任公司 | Preparation method of toothpaste abrasive silicon dioxide |
| CN102960560B (en) * | 2012-11-23 | 2014-09-10 | 重庆优宝生物技术有限公司 | Composite acidifier for reducing post-weaning diarrhea rate |
| CN102960560A (en) * | 2012-11-23 | 2013-03-13 | 重庆优宝生物技术有限公司 | Composite acidifier for reducing post-weaning diarrhea rate |
| CN103464216A (en) * | 2013-09-26 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene |
| CN105813977A (en) * | 2013-12-12 | 2016-07-27 | 日产化学工业株式会社 | Silica particle, method for producing same, and silica sol |
| CN108794667A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | Silica-gel carrier and loaded catalyst and preparation method thereof |
| CN108794668A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | Silica-gel carrier and loaded catalyst and preparation method thereof |
| CN108794666A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method and polyethylene of vinyl polymerization |
| CN108794665A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method and polyethylene of vinyl polymerization |
| CN111072818A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Metallocene catalyst and preparation method thereof |
| CN111072798A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Silica gel and preparation method and application thereof |
| CN111072818B (en) * | 2018-10-22 | 2022-10-14 | 中国石油化工股份有限公司 | Metallocene catalyst and preparation method thereof |
| CN111072798B (en) * | 2018-10-22 | 2022-10-14 | 中国石油化工股份有限公司 | Silica gel and preparation method and application thereof |
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