CN103213992B - Method for preparing nano white carbon black by taking wollastonite as raw material - Google Patents
Method for preparing nano white carbon black by taking wollastonite as raw material Download PDFInfo
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- CN103213992B CN103213992B CN201310128878.9A CN201310128878A CN103213992B CN 103213992 B CN103213992 B CN 103213992B CN 201310128878 A CN201310128878 A CN 201310128878A CN 103213992 B CN103213992 B CN 103213992B
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Abstract
The invention discloses a method for preparing nano white carbon black by taking wollastonite as a raw material. The method is characterized by comprising the following steps: preparing wollastonite powder, preparing silica sol by taking the wollastonite powder as a raw material, wherein the calcium ion is removed as much as possible in the process, and obtaining the silica sol which has high purity and controllable activity; and preparing the nano white carbon black through a precipitation reaction method by taking the high-purity silica sol as the raw material. The obtained nano white carbon black has an approximately spherical shape, has the particle size of 100nm or below and can serve as high polymers and rubber for enhancing the wear resistance and the like.
Description
Technical field
This invention belongs to inorganic non-metallic technical field of powdered material preparation, is specially a kind of method of preparing Nano carbon white taking wollastonite as raw material.
Background technology
Nano silicon is the ultra tiny novel material of a kind of important inorganic non-metallic, its particle diameter is all below 100nm, specific surface area is large, surface adsorption power is strong, chemical purity is high, dispersing property is good, the aspects such as its thermal resistance, resistance have special performance, be widely used in the various fields of high-grade daily-use makeup, medicine, environmental protection, fodder industry, fertilizer industry, chemical industry, microelectronics industry, aerospace industry, national defense industry, large-scale integrated circuit, optical fiber cable etc., therefore receive very large concern at home and abroad.
Conventional Nano carbon white preparation method has three kinds.The first is the vapor phase process taking silicon tetrachloride as raw material.Silicon tetrachloride gas is hydrolyzed in hydrogen, Oxygen Flow under hot conditions to the silicon-dioxide that makes smoke-like, make again it condense into cotton-shaped, then separation, depickling obtain product, product purity that vapor phase process makes is high, dispersity is high, particle is little, surface hydroxyl is few, thereby there is excellent reinforcing property, be generally used for meticulous filler.But this method is had relatively high expectations to appointed condition, cost of material is high, reaction process is long, production process energy consumption is large, and technology is relative complex also, thereby causes product price higher, has limited it and has applied widely.
The second is sol-gel processing.This method is taking metal alkoxide or inorganic salt as initial feed, utilizes the hydrolysis of metal alkoxide and inorganic salt or precipitin reaction to prepare the even colloidal sol of metal oxide or metal non-oxidized substance.And then carry out colloidal sol-gel conversion process, and be formed with organic polymer network or inorganic network, after gelation, then obtain product through ageing, dry and thermal treatment.In gel drying process, the volatilization of solvent, moisture causes material contracts, and must carry out aftertreatment and just can obtain nanoparticle, and the raw materials used chemical reagent that is mostly.
The third is reversed phase micelle microemulsion method.This method is the most novel one in liquid phase chemical preparation method, microemulsion is made up of tensio-active agent, cosurfactant, oil, water conventionally, first form emulsion, the solvent that dosage is little is wrapped in and in the solvent that dosage is large, forms microvesicle one by one, microvesicle surface is made up of tensio-active agent, and size is between 5-100nm.Reactant is metal or metal oxide mostly, and reactant reacts at low temperatures and makes alkoxide with alcohol.In the time that alkoxide enters in water core through micelle interfacial film, there is hydrolysis and generate metal oxide in alkoxide.The large multiplex chemical reagent of this method etc. is raw material, technological process more complicated.
Developed country's Nano carbon white is used widely abroad, and production technology, range of product and the quality of Cabot Co.,Ltd of U.S. white carbon black all occupy first place in the world.The like product of China, at aspects such as industrial scale, production technology, level of automation and product grades far away from external major company, accounts for more than 80% product needed of aggregate demand from external import at present.In view of China has become tire market the biggest in the world; rapid growth to carbon black especially doughnut by high quality rubber Nano carbon white demand, taking natural mineral as raw material, the preparation method of research Nano carbon white; reduce product cost, protection of the environment has important practical significance.
This invention adopt wollastonite be raw material, this be because wollastonite be a kind of reserves than more rich mineral, its main component is Calucium Silicate powder (CaSiO
3), adopt reasonable process to prepare Nano carbon white.Through repetition test, finally invent the white carbon black preparation method that technique is simple, cost is low, particle diameter is nanometer,, good dispersity high by the product purity a process for preparing and granularity≤100 nanometer.
Summary of the invention
This invention, taking wollastonite as raw material, taking sulphuric acid soln as solvent, is prepared Nano carbon white novel material through the wet-chemical precipitator method under normal pressure.In product preparation process, mainly comprise that raw material prepares, wollastonite fragmentation, the master operation such as speed of reaction of removing calcium ion and controlling reaction system is prepared Nano carbon white.
The technical scheme adopting:
1. wollastonite crushing and grinding.selecting reach>=more than 47% wollastonite of dioxide-containing silica is raw material, and utilizing crushing and grinding equipment is≤74 μ m by wollastonite raw material grinding to granularity, obtains the wollastonite powder raw material of preparing Nano carbon white;
2. the preparation of silicic acid sol.taking wollastonite powder that crushing and grinding was obtained as raw material, put into distilled water, be uniformly mixed with 500 ~ 800r/min stirring intensity through electric mixer, wollastonite powder is fully uniformly dispersed, make mass concentration and be 3.0% ~ 8.0% wollastonite suspension, wollastonite suspension is warmed up to 70 ~ 95 DEG C of temperature, and the sulphuric acid soln that is then 2.0 ~ 8.0mol/L by concentration is added drop-wise in wollastonite suspension with the speed of 6.0 ~ 15.0ml/min, sulfuric acid H
2sO
4with Calucium Silicate powder CaSiO
3mole ratio be 1 ~ 2.5:1, add Sodium dodecylbenzene sulfonate simultaneously, the add-on of Sodium dodecylbenzene sulfonate is 0.5 ~ 4.0% of wollastonite quality mark, treat that after sulphuric acid soln adds, continuing reaction 20 ~ 60min stops stirring, static ageing 20 ~ 60min in air, filtration, distilled water wash, obtain calcium sulfate byproduct and silicic acid sol.
prepare Nano carbon white.the silicic acid sol obtaining taking former process is as raw material, packed into new vessel in heating to 70 ~ 95 DEG C, adding concentration is 5.0 ~ 10.0 mol/L sodium hydroxide NaOH aqueous solution, fully be uniformly mixed with 200 ~ 300r/min speed with agitator, with the potential of hydrogen of this regulator solution, make pH value reach 8.0 ~ 10.5, and then control mixing speed is 500 ~ 800r/min, through 20 ~ 60min reaction times, white carbon black stops after fully precipitating stirring, reaction product is filtered, is dried, obtain Nano carbon white powder.
Utilize laser particle analyzer test product granularity, its size distribution is within the scope of 50 ~ 100nm.
Prepare in Nano carbon white process in enforcement this invention, inventor is through experiment repeatedly, think that the underlying condition that affects product white carbon black quality comprises the factors such as initial reaction concentration, stirring intensity, temperature of reaction, reaction times, auxiliary agent kind and the consumption of wollastonite suspension, to this, researchist has carried out conscientiously repeatedly groping, obtain following Changing Pattern, wherein:
(1) suspension concentration.if the initial reaction concentration of wollastonite suspension is on the low side can affect productive rate, too highly will affect particle size were.For sulphuric acid soln is mixed with wollastonite suspension, its sufficient reacting is carried out, the initial mass concentration range of the wollastonite suspension that the present invention adopts is 3.0 ~ 8.0%, when wherein mass concentration is defined as 4.0%, can obtain comparatively desirable effect.
(2) stirring intensity.for white carbon black precipitin reaction can be carried out uniformly, will be all the time in reaction process stir for packing silicic acid sol in container and the mixing solutions of the sodium hydroxide NaOH aqueous solution into, stirring intensity is 500～800r/min.When wherein stirring intensity is 600r/min, can prepare the white carbon black product of nanometer particle size.
Under different stirring intensities, the product of synthesized is analyzed through x-ray diffractometer phase structure, and its result shows, stirring intensity is little on the chemical composition impact of synthetic product, illustrates that precipitin reaction is carried out more complete.
(3) temperature of reaction.preparing in Nano carbon white process, its temperature of reaction is larger for product particle size influences, and when wherein temperature range is controlled at 75～95 DEG C, the change of size of product is little; The purity of synthetic product changes little with the rising of temperature of reaction.The white carbon black particle diameter ratio wherein obtaining 78 DEG C time is more satisfactory, and median size is 70nm, and size distribution is narrower.On 78 DEG C of bases, improve 10 DEG C, under same reaction time conditions, the particle diameter of synthesizing white carbon black increases to some extent again, and median size reaches 90nm, and causes the waste of the energy.
(4) reaction times.silicic acid sol is that particle diameter and the phase structure of the reaction times of raw material while preparing Nano carbon white to synthetic product white carbon black all has a direct impact.Within the reaction times of 20～60min, along with the reaction times extends, the particle diameter of synthetic Nano carbon white product diminishes gradually, reaches after minimum value, further extends the reaction times, and the particle diameter of synthetic product increases on the contrary gradually; The phase structure of synthetic product is almost identical.At 78 DEG C, in the time that the reaction times reaches 30min, Nano carbon white particle diameter is more satisfactory, and median size is 70nm.Utilize x-ray diffractometer to carry out phase structure analysis to synthetic product, result shows, the X-ray diffraction peak value of its synthetic product is whole corresponding with Nano carbon white, is amorphous peak shape, inclusion-free peak exists, and illustrates that precipitin reaction product is all unbodied white carbon black product.
Adopt SSX-550 sem observation precipitin reaction product pattern and particle diameter, pattern is almost spherical, and particle diameter is in 100nm.
Compared with the technological method of preparing white carbon black in the past, this invention tool has the following advantages:
(1) raw material sources are extensive.China is one of more country of high-quality wollastonite reserve.Taking it as raw material, can obviously reduce the production cost of Nano carbon white.
(2) technique is simple.Whole technological process is divided into 3 large operations, and the correlation parameter that each operation need to be controlled is fewer, easily operation.
(3) production unit is more single.Water bath with thermostatic control, reaction vessel and drying plant are the large main equipments of three in whole preparation technology, all the other are large-scale hopper, mixing and the whipping device etc. of acid and alkali-resistance, and whole preparation process is all carried out under normal pressure, therefore reduced investment, industrialization instant effect, and main equipment is easily realized automatically and being controlled.
(4) Nano carbon white that utilizes present method to produce is filled up domestic production blank, dose in the high molecular polymer such as rubber, plastics a consumption that can reduce rubber, plastics, reduce costs, two can significantly improve the mechanical property of material, increase wear resisting property, replace imported Nano carbon white, obtains good economic and social benefit.
embodiment 1
The wollastonite being produced taking somewhere, Liaoning, as raw material, is prepared Nano carbon white.
Wollastonite Chemical Composition is as shown in the table.
Wollastonite Chemical Composition table
| Component | SiO 2 | CaO | Fe 2O 3 | Al 2O 3 | Loss on ignition | Whiteness | Granularity μ m |
| Massfraction % | ≥47.00 | ≥46.00 | ≤0.30 | ≤0.25 | ≤3.0 | ≥90 | ≤74 |
Utilizing jaw crusher, double roll crusher and roller milling machine etc., is≤74 μ m by wollastonite crushing and grinding to granularity.
Taking wollastonite powder that crushing and grinding was obtained as raw material, being mixed with concentration with distilled water is 6.0% wollastonite suspension, reaction vessel is inserted in water bath with thermostatic control, after stirring fully disperses its suspension, in the time that temperature of reaction system reaches 85 DEG C, 8.0mol/L sulphuric acid soln is joined in wollastonite suspension by the add-on of sulfuric acid/wollastonite powder (mol ratio) 2:1, adding speed is 7.0ml/min, add the Sodium dodecylbenzene sulfonate of wollastonite quality 1% simultaneously, fully stir and form homogeneous reaction system, after sulfuric acid adds, continue stirring reaction 30min, static ageing 40min, filtration obtains silicic acid sol.
Taking silicic acid sol as raw material, taking sodium hydroxide as adjusting agent, prepare Nano carbon white.The silicic acid sol making is proceeded in reaction vessel, insert in water bath with thermostatic control, be fully uniformly mixed with 300r/min speed with agitator, in the time that temperature of reaction system reaches 78 DEG C, add 6.0 mol/L sodium hydroxide NaOH aqueous solution, control mixing speed is 500r/min, and regulating pH value is 8.0.Fully after reaction 30min, stop, filtering, be dried, obtain Nano carbon white powder.
Utilizing the median size of laser particle analyzer test product is 70nm.
Ben Xiang institute obtains XRD spectra, SEM and the laser particle analyzer test of precipitin reaction product and shows: synthetic product is unbodied silicon-dioxide, and peak shape is corresponding one by one with white carbon black, and inclusion-free peak exists; Pattern almost spherical; Granularity is nano level, and median size is 70nm.
Claims (4)
1. prepare a method for Nano carbon white taking wollastonite as raw material, the raw material that the method is used comprises wollastonite, sulfuric acid and sodium hydroxide, it is characterized in that concrete grammar is as follows:
(1) selecting reach >=more than 47% wollastonite of dioxide-containing silica is raw material, and grinding to granularity is the wollastonite powder raw material of < 74 μ m;
(2) wollastonite powder raw material is put into distilled water, be uniformly mixed with 500 ~ 800r/min stirring intensity through electric mixer, be prepared into the wollastonite suspension of certain mass concentration, be warming up to 70 ~ 95 DEG C, then the sulphuric acid soln that is 2.0 ~ 8.0mol/L by concentration is added drop-wise in wollastonite suspension with the speed of 6.0 ~ 15.0ml/min, sulfuric acid H
2sO
4with Calucium Silicate powder CaSiO
3mole ratio be 1 ~ 2.5:1, add Sodium dodecylbenzene sulfonate simultaneously, the add-on of Sodium dodecylbenzene sulfonate is 0.5 ~ 4% of wollastonite quality mark, treat that after sulphuric acid soln adds, continuing reaction 20 ~ 60min stops stirring, static ageing 20 ~ 60min in air, filtration, distilled water wash, obtain calcium sulfate byproduct and silicic acid sol;
(3) taking the silicic acid sol that obtains as raw material, packed into new vessel in heating to certain temperature, adding concentration is 5 ~ 10 mol/L sodium hydroxide NaOH aqueous solution, fully be uniformly mixed with 200 ~ 300r/min speed, make the pH value of solution reach 8.0 ~ 10.5, then controlling mixing speed is 500 ~ 800r/min, after fully precipitating, 20 ~ 60min white carbon black stops, to reaction product filter, the dry Nano carbon white powder that obtains, the size distribution of the Nano carbon white powder wherein, obtaining is within the scope of 50-100nm.
2. a kind of method of preparing Nano carbon white taking wollastonite as raw material according to claim 1, is characterized in that the finite concentration that the water described in method is mixed with certain density wollastonite suspension is 3.0～8.0%.
3. a kind of method of preparing Nano carbon white taking wollastonite as raw material according to claim 1, it is characterized in that described in method taking the silicic acid sol that obtains as raw material, packed into new vessel in heating to 70～95 DEG C temperature range.
4. a kind of method of preparing Nano carbon white taking wollastonite as raw material according to claim 1, it is characterized in that adding sulphuric acid soln to add Sodium dodecylbenzene sulfonate described in method, the add-on of Sodium dodecylbenzene sulfonate is 0.5 ~ 4% of wollastonite quality mark simultaneously.
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| CN106564924B (en) * | 2016-09-27 | 2018-08-03 | 内蒙古工业大学 | The method for preparing white carbon black co-product calcium chloride using calcium silicates one-step method |
| CN106629744A (en) * | 2016-12-14 | 2017-05-10 | 东海县羽泉硅微粉有限公司 | Preparation method of nano silicon dioxide |
| CN114538997B (en) * | 2022-02-25 | 2023-03-14 | 大连环球矿产股份有限公司 | Preparation method of composite silicate nitrogen fertilizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048370A (en) * | 1989-06-29 | 1991-01-09 | 济南槐荫化工总厂 | Process for production of silicasol |
| CN1482061A (en) * | 2002-09-10 | 2004-03-17 | 新余钢铁有限责任公司 | Method for producing nanometer silicon dioxide using datolite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048370A (en) * | 1989-06-29 | 1991-01-09 | 济南槐荫化工总厂 | Process for production of silicasol |
| CN1482061A (en) * | 2002-09-10 | 2004-03-17 | 新余钢铁有限责任公司 | Method for producing nanometer silicon dioxide using datolite |
Non-Patent Citations (2)
| Title |
|---|
| 硅灰石酸溶法制取白炭黑工艺研究;陈天虎;《非金属矿》;19951231(第3期);45-46、59 * |
| 陈天虎.硅灰石酸溶法制取白炭黑工艺研究.《非金属矿》.1995,(第3期),45-46、59. * |
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