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CN103011226A - Method for preparing nano calcium carbonate through nucleation and growth step by step - Google Patents

Method for preparing nano calcium carbonate through nucleation and growth step by step Download PDF

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Publication number
CN103011226A
CN103011226A CN2012105246174A CN201210524617A CN103011226A CN 103011226 A CN103011226 A CN 103011226A CN 2012105246174 A CN2012105246174 A CN 2012105246174A CN 201210524617 A CN201210524617 A CN 201210524617A CN 103011226 A CN103011226 A CN 103011226A
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calcium carbonate
kiln gas
nucleation
nano
growth
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CN103011226B (en
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顾庆雷
徐宇坤
顾菲菲
孟钧林
顾宗军
倪伯祥
高健健
曹继勇
张小桐
陶沈杰
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CHIZHOU KAIERTE NANO TECHNOLOGY Co Ltd
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CHIZHOU KAIERTE NANO TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for preparing nano calcium carbonate through nucleation and growth step by step, to mainly solve the problems that in the production process of the nano calcium carbonate at present, nucleation and growth of particles are carried out in one same system, so that the synthesized nano calcium carbonate is wide in particle diameter distribution, serious in agglomeration of grains and poor in dispersity. According to the method, liquid is ejected out from a nozzle of an ejector in a high speed when refined calcium hydroxide size is under the high rotation speed of pump impellers, vacuum is formed in a gas mixing chamber, a great deal of kiln gas is sucked through a gas guide tube; the kiln gas is severely mixed with the calcium hydroxide size at a throat tube, then a great deal of calcium carbonate crystal nucleus is formed instantaneously; and subsequently mixture liquid of crystal form control agent cane sugar and cane sugar is added into the calcium hydroxide size which is formed into crystal nucleus in a carburization reaction kettle, and the kiln gas is introduced to continuously react under stirring, then nano calcium carbonate with uniform synthesis particle size is grown on the calcium carbonate crystal nucleus.

Description

The preparation method of the nano-calcium carbonate of a kind of nucleation and growth proceed step by step
Technical field
The present invention relates to a kind of preparation method of nano-calcium carbonate, the preparation method of the nano-calcium carbonate of especially a kind of nucleation and growth proceed step by step.
Background technology
Existing intermittently bubbling stirring-type carborization synthesis of nano calcium carbonate is that refining calcium hydroxide slurry is housed in the carbonization still, and kiln gas enters from carbonization still bottom, makes gas-liquid mixed generate nano-calcium carbonate under mechanical stirring.To be the calcium carbonate nucleation carry out with being grown in the same system method of this synthesis of nano calcium carbonate continuously.Because the formation of nuclear does not have strict the differentiation with growth, has caused successively nucleation process.The calcium carbonate of the calcium carbonate long then nucleation in vegetative period of elder generation's nucleation is short vegetative period, because the length in vegetative period of calcium carbonate experience is different, causes granular size different.Different size particles because the surface energy difference is large between particle, cause agglomeration easily in same system.
Summary of the invention
The object of the invention is to overcome prior art in synthesis of nano calcium carbonate process, can not strictly distinguish the nucleation and growth of Nano particles of calcium carbonate, thereby cause the nano-calcium carbonate size distribution wide, the serious weakness of agglomeration between particle provides a kind of nucleation and the preparation method of the nano-calcium carbonate of the proceed step by step of growing.
The technical solution used in the present invention is as follows:
The preparation method of the nano-calcium carbonate of a kind of nucleation and growth proceed step by step comprises two processes of calcium carbonate nucleation and growth, and it is independently to carry out in the system at two, and detailed process is as follows:
(1) unslaked lime is digested with hot water, impurity removal and purification, and be cooled to below 25 ℃, be mixed with the calcium hydroxide slurry that concentration expressed in percentage by weight is 4.0-8.0%, stand-by;
(2) kiln gas is after spraying and dedusting, foam dust-removing, and adopting pressure is the roots blower of 75-80Kpa, is cooled to below 30 ℃ with the kiln gas compression and through tubular cooler, and is stand-by;
(3) calcium hydroxide slurry is under the pump impeller high speed rotating, liquid forms vacuum with the nozzle ejection of high speed from ejector at mixing chamber, sucks a large amount of kiln gas by airway, acutely mix with calcium hydroxide slurry at the trunnion place, moment forms a large amount of calcium carbonate nucleus;
The slurry that (4) will form the calcium carbonate nucleus is sent in the gap bubbling stirring-type carbonization still, the mixed solution that adds chemical additives sucrose and lactose, under agitation pass into kiln gas and continue carburizing reagent, when the pH of reaction solution value less than 7, be the carbonization terminal point, at the synthetic uniform nano-calcium carbonate of size of calcium carbonate nucleus growth.
The throughput ratio of described calcium hydroxide slurry and kiln gas is controlled by variable valve, and wherein the amount of kiln gas is the 0.5-3.0% of calcium hydroxide slurry carbonization aequum.
The volumetric concentration of carbon dioxide is 25.0-35.0% in the described kiln gas.
The add-on of described chemical additives sucrose and lactose is for generating the 0.3-1.5% of calcium carbonate quantity.
The invention has the advantages that:
The nucleus of calcium carbonate is to adopt ejector to carry out continuously under stable state, so nucleus is uniform and stable; The growth of calcium carbonate is to carry out in gap bubbling stirring-type carbonization still.The nucleation of calcium carbonate is strictly distinguished with growth and is carried out under different conditions, has avoided the nucleating growth phase length of the existing gap bubbling stirring nano-calcium carbonate that carborization synthesized experience different, causes size distribution wide, bad dispersibility, the serious weakness of reuniting.
Description of drawings
Fig. 1 is ejector, wherein, and (1) nozzle, (2) mixing section, (3) negative pressure chamber, (4) slurry inlet pipe, (5) kiln gas ingress pipe, (6) slurry outlet pipe.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should be appreciated that these embodiment do not limit the scope of the invention, in the situation of spirit and scope of the invention, those skilled in the art can make changes and improvements in order to implement to the present invention under different conditions.
Embodiment 1
When actual production, the useful volume of gap bubbling stirring-type carbonization still is 10 cubic metres, the starting temperature of calcium hydroxide slurry is 25 ℃, concentration expressed in percentage by weight is 5.0%, the temperature of kiln gas is 28 ℃ after pressure is 78Kpa roots blower compression cooling, and the concentration expressed in percentage by volume of carbon dioxide is 30% in the kiln gas.
4 groups of the ZSL-1-40 type injector of calcium hydroxide slurry by the Zaoqiang County jetting stream vacuum instrument factory production of effluent north are squeezed into the carbonization still, and the total flux of control calcium hydroxide slurry is 0.4 cubic metre of per minute, the total flux of kiln gas is 1.2 cubic metres of per minutes.In 25 minutes, 10 cubic metres of slurries are squeezed into the carbonization still.
Then in the carbonization still, add 3.0 kilograms of chemical additives sucrose and 3.0 kilograms of mixed solutions that are made into of lactose, adopt bubbling to stir carborization, the flow of control kiln gas is 5 cubic metres of per minutes, carbonization after 1 hour 50 minutes the pH value reduce to and be the carbonization terminal point below 7.0.
The slurry of getting after the carbonization records calcium carbonate particle diameter 50-60nm in the TEM Electronic Speculum, and size distribution is even, good dispersity, and without agglomeration.
Embodiment 2
Adopt the similar method of embodiment 1, the concentration expressed in percentage by weight of calcium hydroxide slurry is 6.5%, and control calcium hydroxide slurry total flux be 0.3 cubic metre of per minute, the total flux of kiln gas is 1.2 cubic metres of per minutes, other conditions are constant, in 33 minutes 10 cubic metres of slurries squeezed into the carbonization still.
Then add 4.5 kilograms of chemical additives sucrose and 7.5 kilograms of mixed solutions that are made into of lactose in the carbonization still, adopt bubbling to stir carborization, the flow of control kiln gas is 5 cubic metres of per minutes, carbonization after 2 hours 15 minutes the pH value reduce to and be the carbonization terminal point below 7.0.
The slurry of getting after the carbonization records nano-calcium carbonate particle diameter 55-65nm in the TEM Electronic Speculum, and size distribution is even, good dispersity, and without agglomeration.
Embodiment 3
Adopt the similar method of embodiment 1, the concentration expressed in percentage by weight of calcium hydroxide slurry is 8.0%, and control calcium hydroxide slurry total flux be 0.4 cubic metre of per minute, the total flux of kiln gas is 1.6 cubic metres of per minutes, other conditions are constant, in 25 minutes 10 cubic metres of slurries squeezed into the carbonization still.
Then add 7 kilograms of chemical additives sucrose and 5 kilograms of mixed solutions that are made into of lactose in the carbonization still, adopt bubbling to stir carborization, the flow of control kiln gas is 5 cubic metres of per minutes, carbonization after 2 hours 40 minutes the pH value reduce to and be the carbonization terminal point below 7.0.
The slurry of getting after the carbonization is recording particle diameter at 50-60nm in the TEM Electronic Speculum, and size distribution is even, good dispersity, and without agglomeration.
Reference examples
Adopt the similar condition of embodiment 2, the temperature of calcium hydroxide slurry is 25 ℃, and concentration expressed in percentage by weight is 7.5%, and calcium hydroxide slurry is directly squeezed in the reactor, and the temperature of kiln gas is 28 ℃, and the concentration expressed in percentage by volume of carbonic acid gas is 30% in the kiln gas.
Add 4.5 kilograms of chemical additives sucrose and 7.5 kilograms of mixed solutions that are made into of lactose in the carbonization still, adopt bubbling to stir carborization, the flow of control kiln gas is 5 cubic metres of per minutes, carbonization after 2 hours 50 minutes the pH value reduce to and be the carbonization terminal point below 7.0.
The slurry of getting after the carbonization records nano-calcium carbonate particle diameter 40-90nm in the TEM Electronic Speculum, and size distribution is wider, and the part agglomeration is arranged.
By the comparative analysis of embodiment and case of comparative examples, the nano-calcium carbonate that is synthesized by the present invention is that being grown in two different systems of calcium carbonate nucleation and calcium carbonate carried out, and size distribution is even, and good dispersity is without agglomeration.In same system, to carry out continuously and adopt the bubbling stirring-type carbonization of existing gap, the nucleation and growth of calcium carbonate, so the size distribution of synthesis of nano calcium carbonate is wide, bad dispersibility.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.

Claims (4)

1. the preparation method of the nano-calcium carbonate of a nucleation and the proceed step by step of growing is characterized in that, comprises two processes of calcium carbonate nucleation and growth, and it is independently to carry out in the system at two, and detailed process is as follows:
(1) unslaked lime is digested with hot water, impurity removal and purification, and be cooled to below 25 ℃, be mixed with the calcium hydroxide slurry that concentration expressed in percentage by weight is 4.0-8.0%, stand-by;
(2) kiln gas is after spraying and dedusting, foam dust-removing, and adopting pressure is the roots blower of 75-80Kpa, is cooled to below 30 ℃ with the kiln gas compression and through tubular cooler, and is stand-by;
(3) calcium hydroxide slurry is under the pump impeller high speed rotating, liquid forms vacuum with the nozzle ejection of high speed from ejector at mixing chamber, sucks a large amount of kiln gas by airway, acutely mix with calcium hydroxide slurry at the trunnion place, moment forms a large amount of calcium carbonate nucleus;
The slurry that (4) will form the calcium carbonate nucleus is sent in the gap bubbling stirring-type carbonization still, the mixed solution that adds chemical additives sucrose and lactose, under agitation pass into kiln gas and continue carburizing reagent, when the pH of reaction solution value less than 7, be the carbonization terminal point, at the synthetic uniform nano-calcium carbonate of size of calcium carbonate nucleus growth.
2. the preparation method of nano-calcium carbonate of a kind of nucleation according to claim 1 and growth proceed step by step, it is characterized in that, the throughput ratio of described calcium hydroxide slurry and kiln gas is controlled by variable valve, and wherein the amount of kiln gas is the 0.5-3.0% of calcium hydroxide slurry carbonization aequum.
3. the preparation method of the nano-calcium carbonate of a kind of nucleation according to claim 1 and growth proceed step by step is characterized in that the volumetric concentration of carbon dioxide is 25.0-35.0% in the described kiln gas.
4. the preparation method of the nano-calcium carbonate of a kind of nucleation according to claim 1 and growth proceed step by step is characterized in that, the add-on of described chemical additives sucrose and lactose is for generating the 0.3-1.5% of calcium carbonate quantity.
CN201210524617.4A 2012-12-07 2012-12-07 A kind of preparation method of nano-calcium carbonate of coring and increment proceed step by step Active CN103011226B (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601227A (en) * 2013-09-11 2014-02-26 宜兴天力化工纳米科技有限公司 Pre-nucleation reactor of nanometer calcium carbonate and preparation technology of the nanometer calcium carbonate
CN103738993A (en) * 2013-12-04 2014-04-23 芜湖卓越纳米新材料有限公司 Carbonation reactor of energy-efficient nano calcium carbonate and preparation method of energy-efficient nano calcium carbonate
CN104016391A (en) * 2014-04-10 2014-09-03 连州市凯恩斯纳米材料有限公司 Method for preparing nanometer calcium carbonate for organic silicone electronic sealant by adopting continuous carbonization device
CN104897437A (en) * 2015-06-01 2015-09-09 金川集团股份有限公司 Automatic sampling device and method for nelson effluent concentrate
CN105417567A (en) * 2015-11-26 2016-03-23 恩平粤怡化工有限公司 High-performance nano calcium carbonate producing method applied to silicone adhesive
CN107601541A (en) * 2017-09-30 2018-01-19 广西华洋矿源材料有限公司 A kind of production method of nano-calcium carbonate
CN107758718A (en) * 2017-11-17 2018-03-06 宁波普莱斯帝金属制品有限公司 A kind of method that calcium carbonate superfine powder nano-powder is prepared with calcite
CN108083312A (en) * 2017-12-01 2018-05-29 江西势通钙业有限公司 A kind of carbonization reactor and preparation small particle, polymolecularity, the method for low oil factor nano-calcium carbonate
CN110228986A (en) * 2018-12-13 2019-09-13 湖北工业大学 A method of promoting quick lime carbonization
CN110255596A (en) * 2019-06-19 2019-09-20 常熟美特钙业有限公司 A kind of continuous carbonation technique preparing calcium carbonate
CN110357138A (en) * 2019-07-19 2019-10-22 恩平燕怡新材料有限公司 A kind of nanometer calcium carbonate injection carbonization method and system
CN111003722A (en) * 2019-08-28 2020-04-14 安徽省宣城市华纳新材料科技有限公司 Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive
CN111874935A (en) * 2020-08-18 2020-11-03 浙江省建德市正发药业有限公司 Preparation method of large-particle calcium carbonate
CN112028101A (en) * 2020-07-20 2020-12-04 建德华明科技有限公司 Preparation method of dispersible calcium carbonate
CN112811456A (en) * 2021-01-26 2021-05-18 江西势通钙业有限公司 Nano calcium carbonate with high specific surface area and preparation method thereof
CN113562757A (en) * 2021-08-06 2021-10-29 池州市贵兴非矿新材料有限公司 Processing technology of nano calcium carbonate
CN113797874A (en) * 2021-09-23 2021-12-17 广西大学 A device for preparing precipitated calcium carbonate using supercritical carbon dioxide
CN115557524A (en) * 2022-09-23 2023-01-03 广西华纳新材料股份有限公司 High-whiteness and high-dispersibility nano calcium carbonate and preparation method thereof

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601227A (en) * 2013-09-11 2014-02-26 宜兴天力化工纳米科技有限公司 Pre-nucleation reactor of nanometer calcium carbonate and preparation technology of the nanometer calcium carbonate
CN103738993A (en) * 2013-12-04 2014-04-23 芜湖卓越纳米新材料有限公司 Carbonation reactor of energy-efficient nano calcium carbonate and preparation method of energy-efficient nano calcium carbonate
CN103738993B (en) * 2013-12-04 2015-11-04 芜湖卓越纳米新材料有限公司 A kind of carbonization reactor of energy-saving nano-calcium carbonate and preparation method
CN104016391A (en) * 2014-04-10 2014-09-03 连州市凯恩斯纳米材料有限公司 Method for preparing nanometer calcium carbonate for organic silicone electronic sealant by adopting continuous carbonization device
CN104897437A (en) * 2015-06-01 2015-09-09 金川集团股份有限公司 Automatic sampling device and method for nelson effluent concentrate
CN105417567A (en) * 2015-11-26 2016-03-23 恩平粤怡化工有限公司 High-performance nano calcium carbonate producing method applied to silicone adhesive
CN107601541A (en) * 2017-09-30 2018-01-19 广西华洋矿源材料有限公司 A kind of production method of nano-calcium carbonate
CN107758718B (en) * 2017-11-17 2020-08-28 池州市富华粉体科技有限公司 Method for preparing superfine calcium carbonate nano powder from calcite
CN107758718A (en) * 2017-11-17 2018-03-06 宁波普莱斯帝金属制品有限公司 A kind of method that calcium carbonate superfine powder nano-powder is prepared with calcite
CN108083312A (en) * 2017-12-01 2018-05-29 江西势通钙业有限公司 A kind of carbonization reactor and preparation small particle, polymolecularity, the method for low oil factor nano-calcium carbonate
CN110228986A (en) * 2018-12-13 2019-09-13 湖北工业大学 A method of promoting quick lime carbonization
CN110255596A (en) * 2019-06-19 2019-09-20 常熟美特钙业有限公司 A kind of continuous carbonation technique preparing calcium carbonate
CN110357138A (en) * 2019-07-19 2019-10-22 恩平燕怡新材料有限公司 A kind of nanometer calcium carbonate injection carbonization method and system
CN111003722A (en) * 2019-08-28 2020-04-14 安徽省宣城市华纳新材料科技有限公司 Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive
CN112028101A (en) * 2020-07-20 2020-12-04 建德华明科技有限公司 Preparation method of dispersible calcium carbonate
CN112028101B (en) * 2020-07-20 2023-01-10 建德华明科技有限公司 Preparation method of dispersible calcium carbonate
CN111874935A (en) * 2020-08-18 2020-11-03 浙江省建德市正发药业有限公司 Preparation method of large-particle calcium carbonate
CN111874935B (en) * 2020-08-18 2023-02-28 浙江省建德市正发药业有限公司 Preparation method of large-particle calcium carbonate
CN112811456A (en) * 2021-01-26 2021-05-18 江西势通钙业有限公司 Nano calcium carbonate with high specific surface area and preparation method thereof
CN113562757A (en) * 2021-08-06 2021-10-29 池州市贵兴非矿新材料有限公司 Processing technology of nano calcium carbonate
CN113797874A (en) * 2021-09-23 2021-12-17 广西大学 A device for preparing precipitated calcium carbonate using supercritical carbon dioxide
CN113797874B (en) * 2021-09-23 2023-03-10 广西大学 A device for preparing precipitated calcium carbonate using supercritical carbon dioxide
CN115557524A (en) * 2022-09-23 2023-01-03 广西华纳新材料股份有限公司 High-whiteness and high-dispersibility nano calcium carbonate and preparation method thereof

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