CN101434393B - Method for preparing nano-scale amorphous silica from attapulgite clay - Google Patents
Method for preparing nano-scale amorphous silica from attapulgite clay Download PDFInfo
- Publication number
- CN101434393B CN101434393B CN 200710158350 CN200710158350A CN101434393B CN 101434393 B CN101434393 B CN 101434393B CN 200710158350 CN200710158350 CN 200710158350 CN 200710158350 A CN200710158350 A CN 200710158350A CN 101434393 B CN101434393 B CN 101434393B
- Authority
- CN
- China
- Prior art keywords
- attapulgite clay
- acid
- amorphous silica
- ammonium
- preparing nano
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing nanometer amorphous silica by attapulgite clay, which can reduce raw material consumption and improve product quality. The invention is characterized by comprising the following steps of roughing and crushing the raw material; ultrasonic agitation, preparing a suspending liquid, classifying purifying, and drying and crushing; mixing with a decomposer and calcining the mixture; adding an acid for reaction; filter pressing and separating the reacting substances and then washing by deionized water; and drying and crushing for obtaining active silica. The method effectively uses natural resources, and has low production cost, simple process flow and easy large-scale production. The product of silica has the purity of more than 90 percent, the grain diameter of 80 to 200nm, and better physicochemical properties.
Description
Technical field
The present invention relates to nonmetal mineral resource deep processing and inorganic chemical industry technology.A kind of method with preparing nano-scale amorphous silica from attapulgite clay of more specifically saying so.
Background technology
Silicon-dioxide is a kind of white amorphous fine powder, light weight, and its relative density is 2.319～2.653, and 1750 ℃ of fusing points have good chemical stability, and high insulativity is water insoluble and sour, is dissolved in highly basic and hydrofluoric acid.It is widely used in as chemical industry, light industries such as rubber, plastics, papermaking, coating, makeup, printing ink, toothpaste and agricultural chemicals, and its maximum purposes is the reinforced filling of rubber, and consumption accounts for more than 75% of ultimate production.
The conventional method for preparing silicon-dioxide need consume a large amount of soda ash and acid, and complex manufacturing, and production cost is higher; And utilize nonmetalliferous ore to produce silicon-dioxide is a feasible technically and also extraordinary route of economic benefit.At present existing many investigators wait with serpentine, kaolinite, sepiolite, attapulgite, wollastonite, coal gangue, wilkinite, flyash, opoka and prepare silicon-dioxide, but as a whole, the key problem in technology that utilizes nonmetalliferous ore to produce silicon-dioxide is exactly production technique how to simplify silicon-dioxide, cut down the consumption of energy and cost, enhance product performance, and makes its easy scale operation.
It is the method for raw material production nano bar-shape active silica with the attapulgite clay that Chinese patent application publication number CN1506305A discloses a kind of.This method is at first carried out ore dressing to Attapulgite, dries pulverizing then, and then adopts the molten method of acid to obtain bar-shaped silicon-dioxide.Though this method is compared with ordinary method, save the high temperature alkali fuse process, reduced production cost, because it adopts acid-soluble one-step, be difficult to removal of impurities after acid is molten, thereby the silicon-dioxide purity that makes is not high relatively; In addition, the sour molten process in this method is difficult to destroy the club shaped structure of attapulgite clay, thus make bar-shaped silicon-dioxide active relatively low.
It is the method for feedstock production white carbon black with attapulgite clay that Chinese patent application publication number CN1994880A discloses a kind of.This method is at first carried out ore dressing and pulverizing to Attapulgite, is mixed with suspension liquid then, adds concentrated acid dissolving and takes off assortedly, and then the molten water glass that makes of alkali behind the filtration washing makes the white carbon black powder thereby add the acid neutralization at last.Though this method can obtain the high relatively silicon-dioxide of purity, complex treatment process, and also it is assorted to need secondary to take off, and consume a large amount of bronsted lowry acids and bases bronsted lowries, and energy consumption and production cost are higher.
Summary of the invention
The purpose of this invention is to provide a kind of method, cut down the consumption of raw materials, improve the quality of products with preparing nano-scale amorphous silica from attapulgite clay.
Method with preparing nano-scale amorphous silica from attapulgite clay provided by the invention may further comprise the steps:
A. be raw material with the attapulgite clay of exploiting out, this attapulgite clay is roughly selected and is crushed to below 200 orders;
B. the attapulgite clay powder after pulverizing is passed through ultrasonic agitation, be mixed with suspension with deionized water, the weight percent concentration of suspension is 1～10%, by centrifugal settling it is carried out classification and purifies, and the attapulgite clay that obtains purifying is pulverized in oven dry;
C. with the attapulgite clay and the decomposition agent thorough mixing of above-mentioned purification, decomposition agent comprises ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, ammonium metaphosphate, ammonium nitrate, volatile salt, bicarbonate of ammonia, ammonium formiate, ammonium acetate, ammonium oxalate or mixed-ammonium salt, the attapulgite clay and the decomposition agent blended mass ratio of purifying are 1: 0.1～10, hybrid mode is dry method or wet method, mixture is calcined in retort furnace, calcining temperature is 350～800 ℃, and calcination time is 1～5 hour;
D. the mixture after will calcining adds acid-respons, reacts used acid and comprises sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, formic acid, acetic acid, carbonic acid, oxalic acid or mixing acid, and the concentration of acid solution is 5～50%, and temperature of reaction is 60～100 ℃;
E. reactant carry out press filtration separate, separate the solid that obtains with deionized water wash to pH=7;
F. the solids oven dry that separation is obtained, the bake out temperature of solids is 60～120 ℃, pulverizes then and promptly obtains active silica.
In the attapulgite clay as raw material of the present invention, attapulgite content is not less than 50%.
Suspension weight percent concentration with the deionized water preparation of the present invention is 1～5%.
Content quartzy in the classification Concavo-convex stick after purifying stone clay of the present invention, the feldspar mineral is not higher than 2%.
Attapulgite clay blended decomposition agent with purification of the present invention is ammonium sulfate or ammonium chloride.
The attapulgite clay of purification of the present invention and decomposition agent blended mass ratio are 1: 0.5～5.
The attapulgite clay of purification of the present invention and the hybrid mode of decomposition agent are wet-mixed.
The attapulgite clay of purification of the present invention and decomposition agent blended mixture calcining temperature in retort furnace are 400～600 ℃, and calcination time is 1～3 hour.
It is sulfuric acid or hydrochloric acid that mixture after the calcining of the present invention adds the used acid of acid-respons.
Mixture after the calcining of the present invention adds acid-respons, and temperature of reaction is 80～100 ℃.
The solids oven dry that separation is obtained of the present invention, bake out temperature is 80～100 ℃.
Method with preparing nano-scale amorphous silica from attapulgite clay provided by the invention is compared with traditional preparation process silicon-dioxide method, its substantive distinguishing features and beneficial effect are: effectively utilized natural resource, production cost is low, and technical process is simple, easily scale operation.The purity of product silicon-dioxide is more than 90%, and particle diameter has better physical and chemical performance at 80～200nm.
Description of drawings
Fig. 1 is that the method with preparing nano-scale amorphous silica from attapulgite clay obtains process flow diagram.
Fig. 2 is with the XRD figure of the prepared SiO 2 powder of the method for preparing nano-scale amorphous silica from attapulgite clay, has shown its composition and crystalline form.
Embodiment
Embodiment 1
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 500 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 the gram purification attapulgite clay and 3 the gram ammonium sulfate by the dry method thorough mixing even, then 560 ℃ the calcining 1 hour; Grind after taking out, cooling off, then handled 6 hours at 90 ℃ with 200 milliliter of 5% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 100 ℃ of oven dry, pulverize grinding and can obtaining particle diameter is that 150nm, purity are 92% white SiO 2 powder.The XRD figure of this sample is seen accompanying drawing 2.
Embodiment 2
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 500 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 the gram purification attapulgite clay and 5 the gram ammonium sulfate by the dry method thorough mixing even, then 560 ℃ the calcining 2 hours; Grind after taking out, cooling off, then handled 6 hours at 100 ℃ with 200 milliliter of 20% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 80 ℃ of oven dry, pulverize grinding and can obtaining particle diameter is that 85nm, purity are 98% white SiO 2 powder.
Embodiment 3
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 200 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 the gram purification attapulgite clay and 2 the gram ammonium sulfate by the dry method thorough mixing even, then 540 ℃ the calcining 1 hour; Grind after taking out, cooling off, then handled 12 hours at 100 ℃ with 200 milliliter of 30% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 120 ℃ of oven dry, pulverize grinding and can obtaining particle diameter is that 195nm, purity are 91% white SiO 2 powder.
Embodiment 4
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 500 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 the gram purification attapulgite clay and 3 the gram ammonium sulfate by the wet method thorough mixing even, then 560 ℃ the calcining 1 hour; Grind after taking out, cooling off, then handled 6 hours at 90 ℃ with 200 milliliter of 10% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 80 ℃ of oven dry, pulverize grinding and can obtaining particle diameter is that 105nm, purity are 94% white SiO 2 powder.
Embodiment 5
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 500 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 gram purification attapulgite clay and 1 gram ammonium sulfate is even with the wet method thorough mixing, then 560 ℃ of calcinings 1 hour; Grind after taking out, cooling off, then handled 24 hours at 80 ℃ with 200 milliliter of 30% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 100 ℃ of oven dry, pulverize grinding and can obtaining particle diameter is that 80nm, purity are 92% white SiO 2 powder.
Embodiment 6
The laboratory lab scale is got 10 grams and is crushed to the following attapulgite clay powder of 200 orders, adds 200 ml deionized water, and ultrasonic agitation obtains attapulgite clay suspension; This suspension centrifugal classification is purified, obtain the attapulgite clay of purifying; Get 1 gram purification attapulgite clay and 0.5 gram ammonium sulfate is even with the wet method thorough mixing, then 560 ℃ of calcinings 1 hour; Grind after taking out, cooling off, then handled 12 hours at 100 ℃ with 200 milliliter of 30% sulphuric acid soln; Carry out suction filtration after acid treatment finishes, and with deionized water wash to pH=7, at last 120 ℃ of oven dry, it is that 180nm, purity are 90% white SiO 2 powder that grinding can obtain particle diameter.
Claims (11)
1. method with preparing nano-scale amorphous silica from attapulgite clay is characterized in that this method may further comprise the steps:
A. be raw material with the attapulgite clay of exploiting out, this attapulgite clay is roughly selected and is crushed to below 200 orders;
B. the attapulgite clay powder after pulverizing is passed through ultrasonic agitation, be mixed with suspension with deionized water, the weight percent concentration of suspension is 1～10%, by centrifugal settling it is carried out classification and purifies, and the attapulgite clay that obtains purifying is pulverized in oven dry;
C. with the attapulgite clay and the decomposition agent thorough mixing of above-mentioned purification, decomposition agent comprises ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, ammonium metaphosphate, ammonium nitrate, volatile salt, bicarbonate of ammonia, ammonium formiate, ammonium acetate, ammonium oxalate or mixed-ammonium salt, the attapulgite clay and the decomposition agent blended mass ratio of purifying are 1: 0.1～10, hybrid mode is dry method or wet method, mixture is calcined in retort furnace, calcining temperature is 350～800 ℃, and calcination time is 1～5 hour;
D. the mixture after will calcining adds acid-respons, reacts used acid and comprises sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, formic acid, acetic acid, carbonic acid, oxalic acid or mixing acid, and the concentration of acid solution is 5～50%, and temperature of reaction is 60～100 ℃;
E. reactant carry out press filtration separate, separate the solid that obtains with deionized water wash to pH=7;
F. the solids oven dry that separation is obtained, the bake out temperature of solids is 60～120 ℃, pulverizes then and promptly obtains active silica.
2. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that attapulgite content is not less than 50% in the said attapulgite clay as raw material.
3. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that said suspension weight percent concentration with the deionized water preparation is 1～5%.
4. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that content quartzy in the said classification Concavo-convex stick after purifying stone clay, the feldspar mineral is not higher than 2%.
5. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that said attapulgite clay blended decomposition agent with purification is ammonium sulfate or ammonium chloride.
6. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 5 is characterized in that the attapulgite clay of said purification and decomposition agent blended mass ratio are 1: 0.5～5.
7. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 6 is characterized in that the attapulgite clay of said purification and the hybrid mode of decomposition agent are wet-mixed.
8. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 7 is characterized in that said wet-mixed mixture calcining temperature in retort furnace is 400～600 ℃, and calcination time is 1～3 hour.
9. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that it is sulfuric acid or hydrochloric acid that mixture after the said calcining adds the used acid of acid-respons.
10. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 9 is characterized in that the mixture after the said calcining adds acid-respons, and temperature of reaction is 80～100 ℃.
11. the method with preparing nano-scale amorphous silica from attapulgite clay according to claim 1 is characterized in that the said solids oven dry that separation is obtained, bake out temperature is 80～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710158350 CN101434393B (en) | 2007-11-16 | 2007-11-16 | Method for preparing nano-scale amorphous silica from attapulgite clay |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710158350 CN101434393B (en) | 2007-11-16 | 2007-11-16 | Method for preparing nano-scale amorphous silica from attapulgite clay |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101434393A CN101434393A (en) | 2009-05-20 |
| CN101434393B true CN101434393B (en) | 2010-11-10 |
Family
ID=40709053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710158350 Expired - Fee Related CN101434393B (en) | 2007-11-16 | 2007-11-16 | Method for preparing nano-scale amorphous silica from attapulgite clay |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101434393B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179357A (en) * | 2011-02-28 | 2011-09-14 | 盱眙博图凹土高新技术开发有限公司 | Method for preparing water-based attapulgite conductive coating |
| CN106976995A (en) * | 2017-06-05 | 2017-07-25 | 合肥永泰新型建材有限公司 | A kind of river sewage inorganic agent and preparation method |
| CN108867170B (en) * | 2018-06-14 | 2020-11-24 | 安徽紫江复合材料科技有限公司 | High-ink-absorptivity coated paper for high-speed printing machine and preparation method thereof |
| CN109205633B (en) * | 2018-08-31 | 2023-09-22 | 林焕 | Novel nanoclay preparation system |
| CN109574024B (en) * | 2019-01-14 | 2022-03-25 | 中国科学院兰州化学物理研究所 | Method for preparing silicon dioxide nano material by using natural one-dimensional nano clay mineral |
| CN110252248B (en) * | 2019-07-09 | 2020-04-14 | 山东百普瑞世环境科技有限公司 | Composite silicon dioxide antibacterial adsorption material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6036765A (en) * | 1998-04-01 | 2000-03-14 | Southern Clay Products | Organoclay compositions and method of preparation |
| CN1506305A (en) * | 2002-12-10 | 2004-06-23 | 合肥工业大学 | Production process of nano rod-like active silica with attapulgite and clay |
| CN1994880A (en) * | 2006-12-26 | 2007-07-11 | 中国科学院南京土壤研究所 | Process for preparing white carbon black using attapulgite clay |
-
2007
- 2007-11-16 CN CN 200710158350 patent/CN101434393B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6036765A (en) * | 1998-04-01 | 2000-03-14 | Southern Clay Products | Organoclay compositions and method of preparation |
| CN1506305A (en) * | 2002-12-10 | 2004-06-23 | 合肥工业大学 | Production process of nano rod-like active silica with attapulgite and clay |
| CN1994880A (en) * | 2006-12-26 | 2007-07-11 | 中国科学院南京土壤研究所 | Process for preparing white carbon black using attapulgite clay |
Non-Patent Citations (2)
| Title |
|---|
| 许红忠 等.由凹凸棒粘土研制活性二氧化硅.建材地质.1994,(2(总第72期）),48-50. |
| 许红忠等.由凹凸棒粘土研制活性二氧化硅.建材地质.1994,(2(总第72期)),48-50. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101434393A (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101434393B (en) | Method for preparing nano-scale amorphous silica from attapulgite clay | |
| CN101596490B (en) | Dry and wet method integration mineral processing technology for diatomite ore | |
| CN101318684A (en) | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation | |
| CN101691275B (en) | Method for preparing nano mineral fiber | |
| CN103288091A (en) | Method for preparing white carbon black by utilizing water glass with low modulus through carbonizing method of precipitation | |
| CN103435046A (en) | Preparation technology of high-dispersity white carbon black for snow tire | |
| CN101318685A (en) | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone activation of activation tank | |
| CN1994880B (en) | Process for preparing white carbon black using attapulgite clay | |
| CN107934986A (en) | Biomass ash resource utilization method | |
| CN1956923A (en) | Process for production of precipitated silica from olivine | |
| CN101306819B (en) | Process for abstracting white carbon black from fly ash or slag | |
| CN105439156A (en) | Method for preparing rubber and plastics filler by use of microsilica and carbide slag | |
| CN104313695A (en) | Mullite nano-whisker prepared by using pyrite tailing as raw material and preparation method of mullite nano-whisker | |
| CN107500325A (en) | A kind of gangue produces nano alumina powder jointed method | |
| CN102452656A (en) | Method for purifying low-grade bentonite | |
| CN103435051A (en) | Production technology of high-dispersity white carbon black for green tire | |
| CN102303912A (en) | Post-treatment and purification process of iron oxide red for high-property soft magnetic ferrite | |
| CN103435050A (en) | Method for preparing white carbon black from monocrystalline silicon environment-friendly waste mortar | |
| CN110272051A (en) | The method for preparing white oxide silicon nano material using oil shale semi-coke | |
| RU2394764C1 (en) | Method of producing silicon dioxide | |
| CN108394903A (en) | A kind of preparation method of nanometer silicon carbide micro mist | |
| CN105149084A (en) | Dry-wet-method mineral separation method used for African sandy diatomite ore | |
| CN1219698C (en) | Production process of nano rod-like active silica with attapulgite and clay | |
| CN1315723C (en) | Method for preparing high-purity ultrnfine silicone powder and aluminium sulphate using kadin as raw material | |
| CN102633267A (en) | Preparation method of nano SiO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20111116 |