CN105417565A - Cubic CaCO3 and SiO2 composite particles and preparing method thereof - Google Patents
Cubic CaCO3 and SiO2 composite particles and preparing method thereof Download PDFInfo
- Publication number
- CN105417565A CN105417565A CN201510781047.0A CN201510781047A CN105417565A CN 105417565 A CN105417565 A CN 105417565A CN 201510781047 A CN201510781047 A CN 201510781047A CN 105417565 A CN105417565 A CN 105417565A
- Authority
- CN
- China
- Prior art keywords
- composite particles
- sio
- caco
- cube
- calcium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a preparing method for cubic CaCO3 and SiO2 composite particles. The preparing method includes the steps that nano calcium carbonate prepared through a carbonization method is used as a raw material, while calcium hydroxide is carbonized into calcium carbonate, surface modification is carried out by using sulfuric acid as a crystal form control agent, polyethylene glycol as a dispersing agent and silica sol as a surface modifier, the surface of calcium carbonate is coated with nano silica sol, and the cubic CaCO3 and SiO2 composite particles are prepared through one step. Compared with a traditional method, the preparing method adopts the one-step method and has the advantages of being short in time, high in efficiency, easy to operate, low in cost and the like. The obtained cubic CaCO3 and SiO2 composite particle product is uniform in size and crystal form, pure and free of impurities and is coated completely.
Description
Technical field
The invention belongs to silica modified nano calcium carbonate technical field, particularly relate to a kind of cube CaCO
3siO
2composite particles and preparation method thereof.
Background technology
Calcium carbonate is a kind of important inorganic materials, along with the development of nanotechnology, emerging nano-calcium carbonate, as the mineral filler that a kind of character is more excellent, is widely used in the fields such as rubber, plastics, papermaking, senior ink, coating, medicine, food, makeup.Calcium carbonate brightening, reinforcement, replacement reduce to compare in polymkeric substance total cost has obvious advantage with other fillers, calcium carbonate raw material sources are wide simultaneously, and preparation process is easy to control, and cost is low.Have data to show, current calcium carbonate as the usage quantity of polymer packing up to 80%.Industrial, often for preparing the main production process of nano-calcium carbonate, and wherein there is carbonic acid gas and disperse the shortcoming that inequality, utilization ratio are not high in the solution in carborization, and obtained calcium carbonate size is uneven, crystal formation is different.
Nano-calcium carbonate obtains Nano-meter CaCO3 after coated with silica
3siO
2composite particles, considerably increases its application in industries such as rubber, plastics, papermaking, coating and polymers.Through the nano calcium carbonate composite material of coated with silica, the characteristic of calcium carbonate and silicon-dioxide can be embodied simultaneously.Can be used in some field substituting white carbon black costly, increase economic efficiency.Prepare Nano-meter CaCO3 at present
3siO
2composite particles mainly carries out surface modification by silicon dioxide granule or water glass to the calcium carbonate prepared, and its technique is roughly divided into following three kinds:
One, Fang Jingnan etc.
[1]with Yang Jinxin etc.
[2]1 μm of calcium carbonate and 30-40nm silicon dioxide granule are stirred for some time with 1000rpm, obtains composite particles presoma, then add hmds (HMDS), in 140 DEG C of reaction 5h, obtain the CaCO of finishing
3/ SiO
2composite particles, CaCO
3particle and Nano-meter SiO_2
2particle.But this method operating process is divided into two steps, more complicated, finished product and containing CaCO in addition
3particle and Nano-meter SiO_2
2the non-targeted products such as particle.
Two, Liu Run waits quietly
[3], Jiang Xiaoyi etc.
[4]with Liu Guojun etc.
[5]respectively to make calcium carbonate and 40-60nm finished product calcium carbonate by oneself for raw material, add water glass, under 80-85 DEG C of condition, use H
2sO
4regulate pH=5-9, ageing 2-4h, after filtration, washing, dry CaCO
3/ SiO
2composite particles, but the standby composite particles of this legal system is mainly with spherical or other irregularly shaped existence, and size of particles is uneven, also introduces SO in operating process
4 2-impurity.
Three, Ma Cuicui etc.
[6], Hua Yimiao etc.
[7]with Shi Qi etc.
[8]respectively to make 50-70nm calcium carbonate and 70nm finished product calcium carbonate by oneself for raw material, under 80-90 DEG C of condition, drip water glass, pass into CO simultaneously
2to keep the pH=8-9 of system, last ageing 2-4h, through washing, filter, dry 60-80nmCaCO
3/ SiO
2composite particles, but this method is divided into two steps, complicated operation, and obtained composite particles size is uneven, and crystal formation is different, and introduces more Na in modifying process
+.
[1] Fang Jingnan, Hong Biyuan, Tong Wei, etc. based on CaCO
3/ SiO
2super hydrophobic surface preparation [J] of composite particles. journal of Zhejiang university (Edition), 2011-3,38 (2): 189-193.
[2] Yang Jinxin, Wen Xiufang, Pi Pihui, waits .CaCO
3siO
2the surface tissue of composite particles coating and hydrophobic performance research [J] thereof. Journal of Inorganic Materials, 2009,24 (1): 91-96.
[3] Liu Runjing, Zou Haikui, Guo Fen, etc. nuclear-shell structure type Nano-meter CaCO3
3siO
2nH
2the preparation [J] of O composite particles. investigation of materials journal, 2001,15 (1): 61-64.
[4] Jiang Xiaoyi, Xie Gang, Geng Kai, etc. application CaCO
3siO
2the research [J] of nanometer composite technology modified polypropene. Heilongjiang University's natural science journal, 2010-2,27 (1): 96-125.
[5] Liu Guojun, once Chinese. Nano-meter CaCO3
3/ SiO
2the preparation [J] of nucleocapsid structure composite particles. aerospace material technique, 2003 (3): 57-61.
[6] Ma Cuicui, old snow plum. nuclear shell structured nano-CaCO
3siO
2the preparation [J] of composite particles. chemistry world, 2010, (4): 196-213.
[7] Hua Yimiao, Yuan Jun, Yue Linhai, waits .SiO
2coated CaCO
3crystallite analysis and XPS research [J]. Chinese Journal of Inorganic Chemistry, 2001-1,1:134-138.
[8] Shi Qi, Wu Sufang. precipitator method SiO
2clad nano CaCO
3performance of the adsorbent [J]. university of chemical technology's journal, 2009-2,60 (2): 507-513.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cube CaCO
3siO
2composite particles and preparation method thereof, this method has that the time is short, efficiency is high, operation is simple, low cost and other advantages, gained cube CaCO
3siO
2composite particles product size is even, crystal formation is consistent, coated complete, pure nothing is mixed.
For solving the problems of the technologies described above, the present invention by the following technical solutions: cube CaCO
3siO
2the preparation method of composite particles, the nano-calcium carbonate obtained with carborization is for raw material, while calcium hydroxide carbonization becomes calcium carbonate, utilize that sulfuric acid is chemical additives, polyoxyethylene glycol is dispersion agent, silicon sol carries out surface modification for surface-modifying agent, Nano silica sol is coated on calcium carbonate surface, realizes a step and complete obtained cube CaCO
3siO
2composite particles.
The particle diameter of nano-calcium carbonate at 20-60nm, cube CaCO
3siO
2composite particles median size is 30-80nm.
Above-mentioned cube CaCO
3siO
2the preparation method of composite particles, comprises the following steps:
Unslaked lime drops in the water of 80 DEG C by <1>, in dispersion impeller, digest 2-4h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 4-12wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000-1200rpm line cut in dispersion impeller, add sulphuric acid soln, control carbonization temperature 10-15 DEG C, pass into CO from bottom
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add polyoxyethylene glycol and silicon sol solution, final carbonization, to pH=6.5-7.0, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
The amount of the sulfuric acid added in step <2>, polyoxyethylene glycol and silicon sol is respectively 0.6-1.0wt%, 0.5-2.0wt%, 5-20wt% by the mass percent accounting for calcium carbonate theoretical yield.
Polyoxyethylene glycol is one or more in PEG-400, PEG-600, PEG-1000.
Nano silica sol median size in silicon sol solution is 5-20nm, pH=9.0-10.5.
The cube CaCO of above-mentioned preparation method's gained
3siO
2composite particles.
For current silica modified nano calcium carbonate Problems existing, we have established a kind of cube CaCO
3siO
2the preparation method of composite particles, the nano-calcium carbonate obtained with carborization is for raw material, while calcium hydroxide carbonization becomes calcium carbonate, utilize that sulfuric acid is chemical additives, polyoxyethylene glycol is dispersion agent, silicon sol carries out surface modification for surface-modifying agent, Nano silica sol is coated on calcium carbonate surface, realizes a step and complete obtained cube CaCO
3siO
2composite particles.Wherein, dispersion agent polyoxyethylene glycol mainly contains two kinds of effects: one is produce with sulfuric acid to act synergistically, and impels system to generate a large amount of nucleus at the carbonization initial stage, and stops calcium carbonate particles reunion to be grown up in carbonization process, and reaches the effect making particle thinner; Two be system when high speed line cut disperses, it promotes that mixed gas is dispersed into a large amount of tiny bubble, effectively improves utilization rate of carbon dioxide, shortens the reaction times, reaches and reduces the effect of production cost.Relative to traditional method, the present invention adopts single stage method, has that the time is short, efficiency is high, operation is simple, low cost and other advantages, gained cube CaCO
3siO
2composite particles product size is even, crystal formation is consistent, coated complete, pure nothing is mixed.
Accompanying drawing explanation
Fig. 1 is one of nm level CaCO_3 SiO2 composite particles transmission electron microscope picture (scale 100nm)
Fig. 2 is nm level CaCO_3 SiO2 composite particles transmission electron microscope picture two (scale 100nm)
Fig. 3 is nm level CaCO_3 SiO2 composite particles transmission electron microscope picture three (scale 500nm)
Embodiment
Embodiment 1
8.74g unslaked lime drops in the water of 280g80 DEG C by <1>, in dispersion impeller, digest 2h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 4wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000rpm line cut in dispersion impeller, add 0.52g30% sulphuric acid soln, controlling carbonization temperature is 15 DEG C, passes into certain flow rate (60/120m from bottom
3.h
-1.m
-3suspension liquid) CO
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add PEG-600 and 15.60g20% silicon sol solution (its SiO of 1.04g30%
2median size is 5-10nm, pH is 9.0-10.5), final carbonization, to pH=7.0, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into a small amount of CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
Result: after testing, the particle diameter of the not coated nano-calcium carbonate synthesized in intermediate steps <2> at 20-50nm, Surface coating SiO obtained in final step <3>
2caCO
3siO
2composite particles size evenly (40-60nm), crystal formation consistent (overwhelming majority is cube, other shapes on a small quantity), completely coated.
Embodiment 2
13.32g unslaked lime drops in the water of 280g80 DEG C by <1>, in dispersion impeller, digest 2h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 6wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000rpm line cut in dispersion impeller, add 0.63g30% sulphuric acid soln, controlling carbonization temperature is 14 DEG C, passes into certain flow rate (60/120m from bottom
3.h
-1.m
-3suspension liquid) CO
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add PEG-1000 and 17.83g20% silicon sol solution (its SiO of 1.19g30%
2median size is 10-20nm, pH is 9.0-10.5), final carbonization, to pH=7.0, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into a small amount of CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
Result: after testing, the particle diameter of the not coated nano-calcium carbonate synthesized in intermediate steps <2> at 20-50nm, Surface coating SiO obtained in final step <3>
2caCO
3siO
2composite particles size evenly (40-70nm), crystal formation consistent (overwhelming majority is cube, other shapes on a small quantity), completely coated.
Embodiment 3
32.21g unslaked lime drops in the water of 280g80 DEG C by <1>, in dispersion impeller, digest 2h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 8wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000rpm line cut in dispersion impeller, add 0.64g30% sulphuric acid soln, controlling carbonization temperature is 11 DEG C, passes into certain flow rate (60/120m from bottom
3.h
-1.m
-3suspension liquid) CO
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add PEG-600 and 16.11g10% silicon sol solution (its SiO of 1.07g30%
2median size is 5-10nm, pH is 9.0-10.5), final carbonization, to pH=6.7, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into a small amount of CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
Result: after testing, the particle diameter of the not coated nano-calcium carbonate synthesized in intermediate steps <2> at 20-40nm, Surface coating SiO obtained in final step <3>
2caCO
3siO
2composite particles size evenly (30-60nm), crystal formation consistent (overwhelming majority is cube, other shapes on a small quantity), completely coated.
Embodiment 4
27.97g unslaked lime drops in the water of 280g80 DEG C by <1>, in dispersion impeller, digest 2h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 12wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000rpm line cut in dispersion impeller, add 1.0g30% sulphuric acid soln, controlling carbonization temperature is 10 DEG C, passes into certain flow rate (60/120m from bottom
3.h
-1.m
-3suspension liquid) CO
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add PEG-400 and 24.97g5% silicon sol solution (its SiO of 0.83g30%
2median size is 5-10nm, pH is 9.0-10.5), final carbonization, to pH=6.5, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into a small amount of CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
Result: after testing, the particle diameter of the not coated nano-calcium carbonate synthesized in intermediate steps <2> at 30-60nm, Surface coating SiO obtained in final step <3>
2caCO
3siO
2composite particles size evenly (40-80nm), crystal formation consistent (overwhelming majority is cube, other shapes on a small quantity), completely coated.
Claims (7)
1. a cube CaCO
3siO
2the preparation method of composite particles, it is characterized in that: the nano-calcium carbonate obtained with carborization is for raw material, while calcium hydroxide carbonization becomes calcium carbonate, utilize that sulfuric acid is chemical additives, polyoxyethylene glycol is dispersion agent, silicon sol carries out surface modification for surface-modifying agent, Nano silica sol is coated on calcium carbonate surface, realizes a step and complete obtained cube CaCO
3siO
2composite particles.
2. cube CaCO according to claim 1
3siO
2the preparation method of composite particles, is characterized in that: the particle diameter of described nano-calcium carbonate at 20-60nm, described cube CaCO
3siO
2composite particles median size is 30-80nm.
3. cube CaCO according to claim 1
3siO
2the preparation method of composite particles, is characterized in that comprising the following steps:
Unslaked lime drops in the water of 80 DEG C by <1>, in dispersion impeller, digest 2-4h with rotating speed 1000rpm; Gained calcium hydroxide suspension liquid is crossed 200 mesh standard sieves, then adds the suspension liquid that water is made into massfraction 4-12wt%, ageing 24h, stand-by;
<2> is by calcium hydroxide suspension liquid in step <1>, disperse with rotating speed 1000-1200rpm line cut in dispersion impeller, add sulphuric acid soln, control carbonization temperature 10-15 DEG C, pass into CO from bottom
2and N
2mixed gas carry out carbonization; After starting carburizing reagent 5min, add polyoxyethylene glycol and silicon sol solution, final carbonization, to pH=6.5-7.0, obtains nano-complex particle slurries;
Slurries water-bath in step <2> is heated to 80 DEG C by <3>, passes into CO in this process
2and N
2mixed gas keep pH=6.5-7.0, the calcium hydroxide carbonization that is wrapped by is complete, and be incubated ageing 1h, finally by filtration, washing, dry, to obtain final product.
4. cube CaCO according to claim 3
3siO
2the preparation method of composite particles, is characterized in that the amount of sulfuric acid, polyoxyethylene glycol and the silicon sol added in step <2> is respectively 0.6-1.0wt%, 0.5-2.0wt%, 5-20wt% by the mass percent accounting for calcium carbonate theoretical yield.
5. cube CaCO according to claim 3
3siO
2the preparation method of composite particles, is characterized in that: described polyoxyethylene glycol is one or more in PEG-400, PEG-600, PEG-1000.
6. cube CaCO according to claim 3
3siO
2the preparation method of composite particles, is characterized in that: the Nano silica sol median size in described silicon sol solution is 5-20nm, pH=9.0-10.5.
7. the cube CaCO of arbitrary preparation method's gained described in claim 1 to 6
3siO
2composite particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510781047.0A CN105417565A (en) | 2015-11-13 | 2015-11-13 | Cubic CaCO3 and SiO2 composite particles and preparing method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510781047.0A CN105417565A (en) | 2015-11-13 | 2015-11-13 | Cubic CaCO3 and SiO2 composite particles and preparing method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105417565A true CN105417565A (en) | 2016-03-23 |
Family
ID=55496187
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510781047.0A Pending CN105417565A (en) | 2015-11-13 | 2015-11-13 | Cubic CaCO3 and SiO2 composite particles and preparing method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105417565A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105819484A (en) * | 2016-03-11 | 2016-08-03 | 广西大学 | Preparation method and dispersing method of nano CaCO3/SiO2 composite particle |
CN105883882A (en) * | 2016-04-19 | 2016-08-24 | 广西大学 | Aqueous slurry of nano calcium carbonate as well as preparation method and application thereof |
CN105907206A (en) * | 2016-06-14 | 2016-08-31 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of high-hardness abrasion-resistant water-borne wood paint |
CN106398448A (en) * | 2016-06-14 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for environment-friendly waterborne paint |
CN109422287A (en) * | 2017-08-23 | 2019-03-05 | 范佳晨 | A kind of preparation method of calcium carbonate-silica composite powder |
CN109796035A (en) * | 2019-03-01 | 2019-05-24 | 燕卓君 | A kind of preparation method of calcium carbonate superfine powder |
CN111606345A (en) * | 2020-05-28 | 2020-09-01 | 金三江(肇庆)硅材料股份有限公司 | Preparation method of light calcium carbonate and silicon dioxide composite material |
CN113861939A (en) * | 2021-10-19 | 2021-12-31 | 兰州交通大学 | Micro-nano calcium carbonate @ silicon dioxide composite material with super-hydrophobic property and preparation method and application thereof |
-
2015
- 2015-11-13 CN CN201510781047.0A patent/CN105417565A/en active Pending
Non-Patent Citations (2)
Title |
---|
郑岚等: ""立方形超细碳酸钙的制备研究"", 《无机盐工业》 * |
马翠翠等: ""核-壳结构纳米CaCO3/SiO2复合粒子"", 《化学世界》 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105819484A (en) * | 2016-03-11 | 2016-08-03 | 广西大学 | Preparation method and dispersing method of nano CaCO3/SiO2 composite particle |
CN105883882A (en) * | 2016-04-19 | 2016-08-24 | 广西大学 | Aqueous slurry of nano calcium carbonate as well as preparation method and application thereof |
CN105883882B (en) * | 2016-04-19 | 2019-02-22 | 广西大学 | Water-soluble serous and preparation method thereof, the application of a kind of nanometer grade calcium carbonate |
CN105907206A (en) * | 2016-06-14 | 2016-08-31 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of high-hardness abrasion-resistant water-borne wood paint |
CN106398448A (en) * | 2016-06-14 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for environment-friendly waterborne paint |
CN109422287A (en) * | 2017-08-23 | 2019-03-05 | 范佳晨 | A kind of preparation method of calcium carbonate-silica composite powder |
CN109796035A (en) * | 2019-03-01 | 2019-05-24 | 燕卓君 | A kind of preparation method of calcium carbonate superfine powder |
CN109796035B (en) * | 2019-03-01 | 2021-04-23 | 湖南金箭新材料科技有限公司 | Preparation method of superfine calcium carbonate |
CN111606345A (en) * | 2020-05-28 | 2020-09-01 | 金三江(肇庆)硅材料股份有限公司 | Preparation method of light calcium carbonate and silicon dioxide composite material |
CN111606345B (en) * | 2020-05-28 | 2020-12-15 | 金三江(肇庆)硅材料股份有限公司 | Preparation method of light calcium carbonate and silicon dioxide composite material |
CN113861939A (en) * | 2021-10-19 | 2021-12-31 | 兰州交通大学 | Micro-nano calcium carbonate @ silicon dioxide composite material with super-hydrophobic property and preparation method and application thereof |
CN113861939B (en) * | 2021-10-19 | 2023-09-12 | 兰州交通大学 | Micro-nano calcium carbonate@silicon dioxide composite material with super-hydrophobic property and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105417565A (en) | Cubic CaCO3 and SiO2 composite particles and preparing method thereof | |
CN101774623B (en) | Industrial preparation method of rice-shaped ultra-fine activated calcium carbonate | |
CN102924980B (en) | Surface modified titanium dioxide particles and preparation method thereof | |
CN103570027B (en) | A kind of SiO 2/ ZrO 2/ Al 2o 3the preparation method of compound nano-hollow sphere | |
CN102154720A (en) | Preparation method of cellulose fibres | |
CN102926198A (en) | Spinning sizing agent | |
CN108004611A (en) | A kind of method that cellulose fiber by solvent method spinning solution is prepared using the dry pulp dregs of rice | |
CN101798088B (en) | Method for preparing white carbon black by utilizing silicon tetrachloride | |
CN103922378B (en) | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum | |
CN111777089A (en) | Preparation method of high-purity vaterite type calcium carbonate microspheres | |
CN108807947A (en) | A kind of preparation method of lithium sulfur battery anode material | |
CN103754914A (en) | Preparation method for submicron active calcium carbonate special for PVC and with low oil absorption value | |
CN105819484B (en) | A kind of Nano-meter CaCO33/SiO2The preparation method and dispersing method of compound particle | |
EP3677548A1 (en) | Method for manufacturing ultra-porous nano-sio2 | |
CN111484024A (en) | Preparation method of silicon dioxide with low oil absorption value and high specific surface area | |
CN109485736A (en) | A method of preparing nanocrystal cellulose | |
CN112876878A (en) | Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof | |
CN109929126A (en) | A kind of preparation method of the redisperse of water after drying type Nanowire cellulose | |
CN102701282B (en) | Preparation method of CaWO4 hollow spheres | |
CN104211072A (en) | Nano silicon dioxide production process technology | |
CN105271344B (en) | A kind of preparation method of strobile pattern calcite type micron order calcium carbonate granule | |
CN111534003A (en) | Masterbatch production process for improving coloring uniformity of plastic masterbatch | |
CN111533951B (en) | Preparation method of aluminum silicate-white carbon black composite filler | |
CN102092723A (en) | Method for preparing high dispersing white carbon black with ammonia precipitation method | |
CN101844805A (en) | Method for preparing aqueous high-dispersion nano titanium dioxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160323 |
|
RJ01 | Rejection of invention patent application after publication |