CN1179401A - Method for producing crystalline form nm-class calcium carbonate - Google Patents
Method for producing crystalline form nm-class calcium carbonate Download PDFInfo
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- CN1179401A CN1179401A CN 96122558 CN96122558A CN1179401A CN 1179401 A CN1179401 A CN 1179401A CN 96122558 CN96122558 CN 96122558 CN 96122558 A CN96122558 A CN 96122558A CN 1179401 A CN1179401 A CN 1179401A
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- calcium carbonate
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- calcium oxide
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Abstract
A process for preparing nm-class calcium carbonate crystal features use of chelating agent as crystal shape controller to control the appearance of crystal, and also use of water-soluble salt as crystal shape controller to control the growing of crystal, so it can effectively control the size of crystal. Its advantages are simple technology, low cost and industrial production. Obtained nm-class calcium carbonate crystal features small size, high specific surface area, high surficial acitivity and better strengthening power when it is mixed with plastics or rubber.
Description
The present invention relates to the production method of lime carbonate.
At present, the strengthening agent that adds in rubber, the plastics is still based on carbon black and white carbon black, but along with the anxiety and the constantly crisis of global energy shortage, particularly oil, causes the carbon black price increase, and therefore, people are seeking new supporting material always.Lime carbonate is because its energy consumption is little, cost is low, raw material sources are wide, is the perfect additive of rubber, plastics, also becomes the optimal selection of new strengthening agent always, and Japan utilizes stearic acid, silane coupling agent to handle light calcium carbonate the earliest, obtains the lime carbonate of miniaturization.Miniaturization lime carbonate has reinforcing property, but because coupling agent price height, and so production cost is higher, and the miniaturization lime carbonate reinforcing effect of producing with aforesaid method is undesirable, so is difficult to apply.
The object of the present invention is to provide the production method of the nanometer grade calcium carbonate that a kind of cost is low, reinforcing effect is good.
The objective of the invention is to be achieved through the following technical solutions: proportioning according to dosage, in water, add calcium oxide (CaO), be made into lime milk solution, in lime milk solution, add sequestrant EDTA (ethylenediamine tetraacetic acid (EDTA)) earlier, or EDTA disodium (disodium ethylene diamine tetraacetate), or EDTA four sodium (tetrasodium ethylenediamine tetraacetate) (Tianjin, the said products place of production) are as crystal control agent, its add-on is 0.1～3% of a calcium oxide weight, in solution, feed carbon dioxide again and carry out carburizing reagent, temperature of reaction is controlled at 2～28 ℃, continue to add the colourless salt zinc sulfate (ZnSO soluble in water of crystal control agent again after 0.5～2 hour
4) or Tai-Ace S 150 (Al
2(SO
4)
3) or zinc chloride (ZnCl
2) or aluminum chloride (AlCl
3), add-on is 0.1～5% of a calcium oxide weight, continue to feed carbon dioxide, when pH value be neutrality, stopped reaction will the solution filtration, obtain nanometer grade calcium carbonate after the drying.The first step of the present invention adds the sequestrant purpose and is to control the pattern that calcium carbonate crystal forms, calcium ion effect in sequestrant and the emulsion, can reduce the concentration of calcium ion, the speed of response of control calcium ion and carbonic acid gas, thereby control the crystalline pattern effectively, and depending on the space structure of ethylenediamine tetraacetic acid (EDTA) class sequestrant, control crystalline oriented growth makes it develop to the big direction of specific surface area; After the crystalline pattern is determined, crystal is in metastable state, second step added colourless salt soluble in water as crystal control agent, purpose is to control the crystalline extent of growth, the positively charged ion of salt and the complexing of EDTA are better than the complexing of calcium ion and EDTA, can replace the complexing position of calcium ion, further grow up thereby hinder the metastable state crystalline, to temperature controlling, controlled the crystalline size effectively in addition.
Technology of the present invention is compared with the method that stearic acid, silane coupling agent are produced fine calcium carbonate, has the advantage that technology is simple, cost is low, is easy to suitability for industrialized production.The fine calcium carbonate particle that utilizes the present invention to produce is little, belongs to nano level, and specific surface area is big, and the surfactivity height easily mixes with rubber, plastics etc., has good reinforcing property, can be used for rubber, plastics, increases the intensity of goods, improves wear resistance, reduces cost; Can also be used for coating, paint, papermaking and other fine chemistry industry industry as adding material.
Describe content of the present invention in detail below in conjunction with embodiment.
Embodiment one,
1500 milliliters of the lime milk solutions that first preparation concentration is 10 gram calcium oxide/100 ml waters, when treating that solution temperature is reduced to 15 ℃, add EDTA 2 grams, solution is stirred and feed carbonic acid gas, speed is 0.5 liter/minute, react and add 3 gram zinc chloride after 1.5 hours, continuing to feed carbonic acid gas is 7 until the ph value, and the omnidistance reaction times is 4 hours, and product is filtered, at 120 ℃ of temperature dryings, obtain 268 gram lime carbonate.Use the sem observation crystalline form, mean diameter is 32nm, and fineness ratio is 1: 10～15.
Embodiment two,
Zinc chloride among the embodiment one is replaced with aluminum chloride, and other conditions are all identical in embodiment one, obtain lime carbonate 270 grams, and the crystal mean diameter is 28nm, and fineness ratio is 1: 9～17.
Embodiment three,
Be mixed with 11 tons of lime milk solutions with 1 ton of calcium oxide and 10 tons of water, when treating that solution temperature is reduced to 15 ℃, add 20 kilograms of EDTA disodiums, solution is stirred and feed carbonic acid gas, gaseous tension is 1.2 normal atmosphere, react and add 40 kilograms of zinc chloride after 1.5 hours, continuing to feed carbonic acid gas is 7 until the ph value, and the omnidistance reaction times is 4 hours, and product is filtered, at 120 ℃ of temperature dryings, obtain 1.7 tons of lime carbonate.
Claims (1)
1. the production method of a crystalline form nm-class calcium carbonate, it is characterized in that in the lime milk solution of calcium oxide and water, adding earlier sequestrant ethylenediamine tetraacetic acid (EDTA) or disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate as crystal control agent, its add-on is 0.1～3% of a calcium oxide weight, in solution, feed carbon dioxide again and carry out carburizing reagent, temperature of reaction is controlled at 2～28 ℃, continue to add the colourless salt zinc sulfate (ZnSO soluble in water of crystal control agent again after 0.5～2 hour
4) or Tai-Ace S 150 (Al
2(SO
4)
3) or zinc chloride (ZnCl
2) or aluminum chloride (AlCl
3), add-on is 0.1～5% of a calcium oxide weight, continue to feed carbon dioxide, when pH value be neutrality, stopped reaction will the solution filtration, obtain nanometer grade calcium carbonate after the drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122558 CN1179401A (en) | 1996-10-16 | 1996-10-16 | Method for producing crystalline form nm-class calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122558 CN1179401A (en) | 1996-10-16 | 1996-10-16 | Method for producing crystalline form nm-class calcium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1179401A true CN1179401A (en) | 1998-04-22 |
Family
ID=5127351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96122558 Pending CN1179401A (en) | 1996-10-16 | 1996-10-16 | Method for producing crystalline form nm-class calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1179401A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372300A (en) * | 2010-08-10 | 2012-03-14 | 上海华明高技术（集团）有限公司 | Preparation method of needle-like nano calcium carbonate |
| CN102701255A (en) * | 2012-06-21 | 2012-10-03 | 石家庄市红日钙业有限公司 | Method for high-concentration carbonization production of spherical nano calcium carbonate |
| CN104512921A (en) * | 2013-12-06 | 2015-04-15 | 江南大学 | Method for preparing nanometer calcium carbonate by using long chain tertiary amine |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN105883880A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of sheet superfine calcium carbonate for paper coating |
| CN107021515A (en) * | 2017-04-25 | 2017-08-08 | 井陉县天顺钙业有限公司 | Control precipitated calcium carbonate length of particle than method |
| CN107601540A (en) * | 2016-07-11 | 2018-01-19 | 中国石油天然气股份有限公司 | The method that single controlling agent prepares different-shape calcium carbonate |
| CN108586969A (en) * | 2017-12-26 | 2018-09-28 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin |
| 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 |
| CN115353138A (en) * | 2022-08-10 | 2022-11-18 | 中南大学 | Preparation method of food-grade light calcium carbonate |
-
1996
- 1996-10-16 CN CN 96122558 patent/CN1179401A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372300A (en) * | 2010-08-10 | 2012-03-14 | 上海华明高技术（集团）有限公司 | Preparation method of needle-like nano calcium carbonate |
| CN102701255A (en) * | 2012-06-21 | 2012-10-03 | 石家庄市红日钙业有限公司 | Method for high-concentration carbonization production of spherical nano calcium carbonate |
| CN104512921A (en) * | 2013-12-06 | 2015-04-15 | 江南大学 | Method for preparing nanometer calcium carbonate by using long chain tertiary amine |
| CN104512921B (en) * | 2013-12-06 | 2017-01-25 | 江南大学 | Method for preparing nanometer calcium carbonate by using long chain tertiary amine |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN105883880A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of sheet superfine calcium carbonate for paper coating |
| CN107601540B (en) * | 2016-07-11 | 2019-12-10 | 中国石油天然气股份有限公司 | Method for preparing calcium carbonate with different morphologies by using single control agent |
| CN107601540A (en) * | 2016-07-11 | 2018-01-19 | 中国石油天然气股份有限公司 | The method that single controlling agent prepares different-shape calcium carbonate |
| CN107021515A (en) * | 2017-04-25 | 2017-08-08 | 井陉县天顺钙业有限公司 | Control precipitated calcium carbonate length of particle than method |
| CN107021515B (en) * | 2017-04-25 | 2019-02-26 | 井陉县天顺钙业有限公司 | The method for controlling precipitated calcium carbonate length of particle ratio |
| CN108586969A (en) * | 2017-12-26 | 2018-09-28 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin |
| 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 |
| CN115353138A (en) * | 2022-08-10 | 2022-11-18 | 中南大学 | Preparation method of food-grade light calcium carbonate |
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