CN101234776A - Process for preparing nano calcium carbonate - Google Patents
Process for preparing nano calcium carbonate Download PDFInfo
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- CN101234776A CN101234776A CNA200710036012XA CN200710036012A CN101234776A CN 101234776 A CN101234776 A CN 101234776A CN A200710036012X A CNA200710036012X A CN A200710036012XA CN 200710036012 A CN200710036012 A CN 200710036012A CN 101234776 A CN101234776 A CN 101234776A
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Abstract
The invention relates to a method for preparing high-purity and high-whiteness spherical nanometer calcium carbonate; by using electroslag stone as starting material, after impurity is removed by simple pretreatment process, by adding crystal control agent and polymer surfactant, the high-purity and high-whiteness spherical nanometer calcium carbonate is prepared by a chemical reaction method. Firstly, the electroslag stone is physically and chemically treated; calcium chloride solution is obtained after the impurity is removed,; temperature of carbonization reaction is controlled at 6-18 DEG C; the nanometer calcium carbonate with a grain diameter of 50nm can be prepared by adding the crystal control agent and polymer surfactant of 0.5-5.0 percent; the nanometer calcium carbonate can be applied to fields such as rubber, plastic, papermaking, paint, ink, medicine and daily chemical industry, etc. The method for preparing the high-purity and high-whiteness spherical nanometer calcium carbonate has low cost, high economic efficiency and simple process which can realize industrialization continuous production.
Description
Technical field
The present invention relates to a kind ofly, belong to inorganic salts nano material manufacture method in the chemical field by the electroslag novel method that is equipped with nano-calcium carbonate made of stones.Can eliminate of the pollution of electroslag stone on the one hand by this method to environment; Can turn waste into wealth on the other hand, realize the resource circulation utilization, obtain huge economic benefit.
Technical background
Utilize preparation of ethyne by carbide, can produce a large amount of by products when preparing polyvinyl chloride by vapor phase process---electroslag stone.All there is about 3 * 10 every year in China according to statistics
8Ton electroslag stone, the processing for electroslag stone does not at present also have good method, mainly uses it for and produces interior wall coating, cement, processing waste water, sweetening agent or light calcium carbonate etc., utilizes the added value of product of these method preparations not high, low in economic efficiency.Simultaneously when utilizing that electroslag is made of stones to be equipped with light calcium carbonate, owing to contain other impurity such as a large amount of carbon powders and iron in the electroslag stone, cause indexs such as the whiteness of calcium carbonate product and purity not reach requirement.Nano-calcium carbonate can be used for aspects such as rubber, plastics, papermaking, coating, printing ink, medicine and daily-use chemical industry.Patent CN1058005A has described a kind of electroslag method that is equipped with technical calcium carbonate made of stones, and this method need be with high-temperature roasting removal of impurities again after the oven dry of electroslag stone, complex process, and energy consumption is big, and economic benefit is low.Patent CN200510020830.1, CN200410093237.5 etc. have described a kind of electroslag method that is equipped with calcium carbonate superfine powder made of stones, and this method adopts conventional Bubbling method at intermittence to carry out carbonization, and carbonization time is long, the utilization ratio of carbonic acid gas is low, and aforesaid method can not make nano level lime carbonate.Patents such as CN02114174.6, CN 02109349.0 have been described the method for preparing nano-calcium carbonate, yet these methods need be starting raw material with lime carbonate or calcium hydroxide, are not suitable for handling electroslag stone.In order to overcome the deficiency of prior art, the present invention has carried out a large amount of tests to the electroslag nano-calcium carbonate that is equipped with made of stones, study at aspects such as the control of the removal of impurities of electroslag stone, leaching, nano-calcium carbonate crystal formation and carbonization processs, the present invention arises at the historic moment in this case.
Summary of the invention
The objective of the invention is to utilize cheap electroslag stone for basic raw material prepares the spherical nanometer calcium carbonate of high purity, high whiteness, can be used for aspects such as rubber, plastics, papermaking, coating, printing ink, medicine and daily-use chemical industry.
Solution of the present invention is: a kind of by the electroslag method that is equipped with nano-calcium carbonate made of stones, it is characterized in that carrying out according to the following steps:
(1) electroslag stone slurry pre-treatment.
A. electroslag stone slurry is pumped into rotor-vibrating screen, this rotor-vibrating screen is furnished with three layers of screen cloth, and the upper strata is 10 purpose coarse nets, and the middle level is 50 purpose screen clothes, and lower floor is 150 purpose fine-structure meshes, removes the impurity of particle diameter greater than 0.1mm through pre-treatment.
B. the above-mentioned pretreated electroslag stone slurry of learning from else's experience adds an amount of water and ammonium chloride stirring and dissolving, obtains a suspension, and control pH value of solution value 〉=7 make Mg
2+, Fe
3+Respectively with Mg (OH)
2And Fe (OH)
3Sedimentary form is removed, and obtains the calcium chloride clear liquid through clarification or after filtering.
D. above-mentioned calcium chloride clear liquid is filtered through millipore filtration, remove the micro-insolubles in the calcium chloride solution, the millipore filtration aperture is the 1.0-50.0 micron, obtains the calcium chloride solution of purifying.
(2) to add crystal formation control agent and macromolecular compound in the calcium chloride solution behind above-mentioned purifying be tensio-active agent and feed carbon dioxide and carry out carburizing reagent.
A. with oxalic acid, metal ion chelation agent (as EDTA etc.), phosphoric acid salt (as dicalcium phosphate etc.), chlorate (as zinc chloride, magnesium chlorides etc.) wherein a kind of, two or more composition is the crystal formation control agent, preferably two or more composition; Crystal formation control agent add-on is 0.05%～10%, more preferably 0.1%～5.0%.
B. be tensio-active agent with a kind of macromolecular compound, it is characterized in that a kind of macromolecular compound of block type, be made up of two or more polymer segment of different nature, an end has lipophilicity, another terminal possess hydrophilic property; Concrete example such as polystyrene-b-acrylic copolymer, polystyrene-b-polystyrene/copolymer-maleic anhydride etc.; Block type polymer tensio-active agent add-on is 0.05%～10%, more preferably 0.1%～5.0%.
C. crystal formation control agent, polymeric surface active agent are added in the calcium chloride solution behind the above-mentioned purifying, feed carbon dioxide after fully dissolving stirs, up to pH=7.5～8 is reaction end, control reaction temperature is at 6 ℃～18 ℃ in the carbonization process, filtration obtains nano-calcium carbonate, and ammonium chloride filtrate is reused.
(3) drying.Above-mentioned nano-calcium carbonate is cleaned the chlorion after drying, obtain the spheric nano-calcium carbonate, particle diameter is about 50nm.
To remove out impurity technology simple and convenient for electroslag stone slurry among the present invention, can realize industrialized continuous production, do not need complicated procedures of forming such as high-temperature roasting, and energy consumption is low; Adopt crystal formation control agent and block type polymer tensio-active agent to prepare nano-calcium carbonate and have that particle diameter is little, advantage such as be difficult for reuniting, specific surface area is big; With electroslag stone is basic raw material, and cost is low, economic benefit is high; Problem such as three wastes processing realizes the resource circulation utilization in the time of can solving vapor phase process and prepare polyvinyl chloride.
Specific embodiments
Get a certain amount of electroslag stone slurry, add an amount of water and ammonium chloride stirring and dissolving, control pH value of solution value 〉=7, and control [Ca through vibration screening
2+]＜3.5mol/L adds Fe
2+1.5 Liang superoxol doubly, stirring reaction 0.5 hour obtains the calcium chloride clear liquid after the filtration; Is that 20 microns millipore filtration filters with above-mentioned calcium chloride clear liquid through the aperture, removes the micro-insolubles in the calcium chloride solution, obtains the calcium chloride solution of purifying.The oxalic acid, the dicalcium phosphate mixing solutions that add 1.0% (in CaO) are the crystal formation control agent, the polystyrene of 1.5% (in CaO)-b-polystyrene/copolymer-maleic anhydride is a dispersion agent, fully feeding carbon dioxide after the stirring and dissolving is reaction end up to pH=7.5～8, control reaction temperature is at 6 ℃～18 ℃ in the carbonization process, filtration obtains nano-calcium carbonate, clean the chlorion after drying, obtain spherical nanometer calcium carbonate, particle diameter is about 50nm.
Claims (8)
1. one kind by the electroslag method that is equipped with nano-calcium carbonate made of stones, after it is characterized in that electroslag stone slurry carried out the pre-treatment removal of impurities, adds an amount of water and ammonium chloride stirring and dissolving, controls the pH value of solution value, obtains the calcium chloride clear liquid after the filtration.With above-mentioned calcium chloride clear liquid via hole diameter is that 5～20 microns millipore filtration filters, adding 0.1～3.0% oxalic acid, dicalcium phosphate mixing solutions in filtrate is the crystal formation control agent, 0.1～3.5% polystyrene-b-polystyrene/copolymer-maleic anhydride is a dispersion agent, fully feeding carbon dioxide after the stirring and dissolving is reaction end up to pH=7.5～8, obtains nano-calcium carbonate after filtering, washing.
2. according to right 1 described requirement, it is characterized in that impurity-removing method is that electroslag stone slurry is pumped into rotor-vibrating screen, this rotor-vibrating screen is furnished with three layers of screen cloth, the upper strata is 10～30 purpose coarse nets, the middle level is 30～100 purpose screen clothes, lower floor is 100～200 purpose fine-structure meshes, removes the impurity of particle diameter greater than 0.1mm through pre-treatment.
3. according to right 1 described requirement, the above-mentioned pretreated electroslag stone slurry that it is characterized in that learning from else's experience adds an amount of water and ammonium chloride stirring and dissolving, obtains a suspension, and control pH value of solution value 〉=7 make Mg
2+, Fe
3+Respectively with Mg (OH)
2And Fe (OH)
3Sedimentary form is removed, and obtains the calcium chloride clear liquid through clarification or after filtering.
4. according to right 1 described requirement, it is characterized in that above-mentioned calcium chloride clear liquid is carried out filtering with microporous membrane, remove the micro-insolubles in the calcium chloride solution, the millipore filtration aperture is the 1.0-50.0 micron, obtains the calcium chloride solution of purifying.
5. according to right 1 described requirement, it is characterized in that adding in the calcium chloride solution behind above-mentioned purifying crystal formation control agent and macromolecular compound and be tensio-active agent and feed carbon dioxide and carry out carbonization, make spherical nanometer calcium carbonate.
6. the method for nano-calcium carbonate preparation according to claim 4, it is characterized in that at the crystal formation control agent that the calcium chloride solution carbonization process adopts be oxalic acid, metal ion chelation agent (as EDTA etc.), phosphoric acid salt (as dicalcium phosphate etc.), wherein a kind of, two or more composition of chlorate (as zinc chloride, magnesium chloride etc.).
7. the method for nano-calcium carbonate preparation according to claim 4, it is characterized in that the macromolecular compound that adopts is a tensio-active agent in the calcium chloride solution carbonization process, it is characterized by a kind of macromolecular compound of block type, polymer segment of different nature by two or more is formed, one end has lipophilicity, another terminal possess hydrophilic property is as polystyrene-b-acrylic copolymer etc.
8. the method for nano-calcium carbonate preparation according to claim 4 is characterized in that temperature of reaction is controlled at 6 ℃～18 ℃ in carbonization process.
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| CNA200710036012XA CN101234776A (en) | 2007-10-31 | 2007-10-31 | Process for preparing nano calcium carbonate |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823748A (en) * | 2010-04-30 | 2010-09-08 | 汪晋强 | Method for preparing calcium carbonate co-produced industrial salt and Na2SiO3a.5H2O with yellow phosphorus slag |
| CN101844791A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate from yellow phosphorus furnace slag to co-produce industrial salt and silicon gel |
| CN101844790A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate from yellow phosphorus furnace slag to co-produce industrial salt and water glass |
| CN101844792A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate and co-producing sodium chloride and anhydrous partial silicon by using yellow phosphorus slag |
| CN101920981A (en) * | 2009-04-08 | 2010-12-22 | 王嘉兴 | Material recycling method for producing calcium carbonate by ammonium carbonization method |
| CN102583481A (en) * | 2012-01-18 | 2012-07-18 | 兰州交通大学 | Method for preparing spherical nanometer calcium carbonate particles of different grain diameters by reverse microemulsion method |
| CN102602973A (en) * | 2012-01-13 | 2012-07-25 | 中国中材国际工程股份有限公司 | Method for synthesizing ultrafine calcium carbonate by utilizing carbide slag |
| CN102910662A (en) * | 2012-10-25 | 2013-02-06 | 上海应用技术学院 | Preparation method of granularity-controllable CaCO3 |
| CN102910665A (en) * | 2012-11-06 | 2013-02-06 | 荣殿相 | Method for producing industrial grade calcium chloride by taking calcium carbide slurry as raw material |
| CN105417569A (en) * | 2015-12-28 | 2016-03-23 | 常熟市宏宇钙化物有限公司 | Preparation method of rodlike nano-calcium carbonate |
| CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
| CN108439447A (en) * | 2018-05-07 | 2018-08-24 | 复旦大学 | A kind of preparation method with layer structure calcium carbonate |
| CN110065960A (en) * | 2019-05-30 | 2019-07-30 | 潘海平 | A kind of preparation method of the spherical calcium carbonate powder of nanometer |
| CN111253780A (en) * | 2020-03-31 | 2020-06-09 | 江西势通钙业有限公司 | Transparent nano calcium carbonate for high-grade ink and preparation method and device thereof |
| CN112299466A (en) * | 2020-12-07 | 2021-02-02 | 江西华明纳米碳酸钙有限公司 | Preparation method of nano calcium carbonate for cement mortar |
| CN112878049A (en) * | 2021-01-21 | 2021-06-01 | 冯岩 | Towel easy to absorb water and capable of being dried quickly and preparation method thereof |
| CN113860347A (en) * | 2021-10-27 | 2021-12-31 | 广西合山市华纳新材料科技有限公司 | Preparation method of stable and controllable vegetable pepper-shaped calcium carbonate particles with ultra-large particle size |
| CN116239903A (en) * | 2023-03-06 | 2023-06-09 | 湖北工业大学 | Preparation method of carbide slag-based carbonized inorganic refrigeration coating |
-
2007
- 2007-10-31 CN CNA200710036012XA patent/CN101234776A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920981A (en) * | 2009-04-08 | 2010-12-22 | 王嘉兴 | Material recycling method for producing calcium carbonate by ammonium carbonization method |
| CN101844791A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate from yellow phosphorus furnace slag to co-produce industrial salt and silicon gel |
| CN101844790A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate from yellow phosphorus furnace slag to co-produce industrial salt and water glass |
| CN101844792A (en) * | 2010-02-11 | 2010-09-29 | 汪晋强 | Method for preparing calcium carbonate and co-producing sodium chloride and anhydrous partial silicon by using yellow phosphorus slag |
| CN101823748A (en) * | 2010-04-30 | 2010-09-08 | 汪晋强 | Method for preparing calcium carbonate co-produced industrial salt and Na2SiO3a.5H2O with yellow phosphorus slag |
| CN102602973B (en) * | 2012-01-13 | 2014-06-18 | 中国中材国际工程股份有限公司 | Method for synthesizing ultrafine calcium carbonate by utilizing carbide slag |
| CN102602973A (en) * | 2012-01-13 | 2012-07-25 | 中国中材国际工程股份有限公司 | Method for synthesizing ultrafine calcium carbonate by utilizing carbide slag |
| CN102583481A (en) * | 2012-01-18 | 2012-07-18 | 兰州交通大学 | Method for preparing spherical nanometer calcium carbonate particles of different grain diameters by reverse microemulsion method |
| CN102583481B (en) * | 2012-01-18 | 2014-04-23 | 兰州交通大学 | Method for preparing spherical nanometer calcium carbonate particles of different grain diameters by reverse microemulsion method |
| CN102910662A (en) * | 2012-10-25 | 2013-02-06 | 上海应用技术学院 | Preparation method of granularity-controllable CaCO3 |
| CN102910665A (en) * | 2012-11-06 | 2013-02-06 | 荣殿相 | Method for producing industrial grade calcium chloride by taking calcium carbide slurry as raw material |
| CN105417569A (en) * | 2015-12-28 | 2016-03-23 | 常熟市宏宇钙化物有限公司 | Preparation method of rodlike nano-calcium carbonate |
| CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
| CN108439447A (en) * | 2018-05-07 | 2018-08-24 | 复旦大学 | A kind of preparation method with layer structure calcium carbonate |
| CN110065960A (en) * | 2019-05-30 | 2019-07-30 | 潘海平 | A kind of preparation method of the spherical calcium carbonate powder of nanometer |
| CN111253780A (en) * | 2020-03-31 | 2020-06-09 | 江西势通钙业有限公司 | Transparent nano calcium carbonate for high-grade ink and preparation method and device thereof |
| CN112299466A (en) * | 2020-12-07 | 2021-02-02 | 江西华明纳米碳酸钙有限公司 | Preparation method of nano calcium carbonate for cement mortar |
| CN112878049A (en) * | 2021-01-21 | 2021-06-01 | 冯岩 | Towel easy to absorb water and capable of being dried quickly and preparation method thereof |
| CN113860347A (en) * | 2021-10-27 | 2021-12-31 | 广西合山市华纳新材料科技有限公司 | Preparation method of stable and controllable vegetable pepper-shaped calcium carbonate particles with ultra-large particle size |
| CN113860347B (en) * | 2021-10-27 | 2023-09-08 | 广西合山市华纳新材料科技有限公司 | Preparation method of super-large-particle-size stable and controllable cayenne pepper-shaped calcium carbonate particles |
| CN116239903A (en) * | 2023-03-06 | 2023-06-09 | 湖北工业大学 | Preparation method of carbide slag-based carbonized inorganic refrigeration coating |
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