CN101139734A - Method for preparing calcium carbonate crystal whisker - Google Patents
Method for preparing calcium carbonate crystal whisker Download PDFInfo
- Publication number
- CN101139734A CN101139734A CNA2007101295240A CN200710129524A CN101139734A CN 101139734 A CN101139734 A CN 101139734A CN A2007101295240 A CNA2007101295240 A CN A2007101295240A CN 200710129524 A CN200710129524 A CN 200710129524A CN 101139734 A CN101139734 A CN 101139734A
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- CN
- China
- Prior art keywords
- calcium carbonate
- crystal whisker
- carbonate crystal
- polyvinyl alcohol
- calcium chloride
- 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.)
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Abstract
The invention relates to a preparation method for special shape of carbonate crystal, in particular to a preparation method for calcium carbonate whisker with higher slenderness ratio. The method is an improvement for prior preparation process of soluble Ca2+ and CO32-, and adds polyvinyl alcohol water solution with mass ratio of polyvinyl alcohol: calcium chloride being 1:12 to 1:8 and concentrate being 2g multiplied by L-1 in 100mL calcium chloride water solution with concentrate being 0.001 to 0.05mol multiplied by L-1; and then, slowly add soluble carbonate water solution in same volume and identical concentrate with that of the calcium chloride water solution in heated and mixed conditions, so that white sediment can be created in the water system; and finally calcium carbonate whisker can be received through solid-liquid separation for water scrubbing sediment and drying process.
Description
Technical field
The present invention relates to a kind of preparation method of carbonate crystal of specific form, is that a kind of preparation has the method than the calcium carbonate crystal whisker of high length-diameter ratio exactly.
Background technology
Whisker is as a kind of monocrystal material, and structure near-complete, its intensity and modulus are near theoretical value, and simultaneously, it has higher length-to-diameter ratio, and similar staple fibre is that a kind of good reinforcing and toughening is material modified.In numerous crystal whisker materials, calcium carbonate crystal whisker has abundant raw material, cost performance height, widely used characteristics, has had widely in industries such as building materials, rubber, plastics, papermaking, coating, printing ink, daily use chemicals, feed, food, medicine and has used.We can say that calcium carbonate crystal whisker is an another new packing material after nano-calcium carbonate, with respect to industrialized developing and all comparatively sophisticated fine particle calcium carbonate of market development, coarse whiting and nano-calcium carbonate, calcium carbonate crystal whisker still is not tame virgin land, and boundless development and application prospect is arranged.
The calcium carbonate crystal whisker that studies show that according to present stage has the scope of following main application:
1. calcium carbonate crystal whisker is in the application of reinforced plastics aspect of performance.Fiber reinforcement and filling capacity are arranged; Good smooth surface performance; Processibility is good; Reinforced composite materials reprocessing cycle, use properties are good; Cheap, so aspect engineering plastics, have vast market prospect.
2. the application in friction materials.Calcium carbonate crystal whisker is the best materials that replacement has the asbestos of environmental pollution, has development prospect.
3. calcium carbonate crystal whisker replaces particle lime carbonate to make papermaking filler.Because calcium carbonate crystal whisker has special column directivity, can be parallel when making papermaking filler and be closely aligned with the body paper surface, and also its whiteness and fillibility are all very high, compare with the paper of filling with granular calcium carbonate, demonstrate superior printing adaptability.Especially in the paper of some particular requirements, more show its bigger application prospect.
4. be applied to coatings industry.Calcium carbonate crystal whisker adds in the coating, not only can significantly improve the viscosity of compound system, and can improve splitting resistance, sticking power, intensity etc.
The preparation method of calcium carbonate crystal whisker has following several at present:
1. Soluble Ca
2+And CO
3 2-Preparation method, these class methods are with certain density Soluble Ca
2+Salt and solubility CO
3 2-Salt mixes, and control certain reaction temperature, the concentration of solution, reaction times, stirring intensity react the generation calcium carbonate crystal whisker.General Ca commonly used
2+Salt is Ca (NO
3)
2, CaCl
2Deng, CO commonly used
3 2-Salt has Na
2CO
3, K
2CO
3Deng.Little with phosphoric acid and the resulting whisker length-to-diameter ratio of phosphoric acid salt crystal formation control agent in the prior art, condition is wayward; And when selecting polyoxyethylene glycol as the crystal formation control agent for use, its production cost is higher.
2.Ca (HCO
3)
2Preparation method, for example Chinese invention patent application 03134287.6 and Chinese invention patent 200410022834.9 disclosed methods.This method is that limestone powder is scattered in the water, feeds CO
2Gas is made Ca (HCO earlier
3)
2The aqueous solution is then by control Ca (HCO
3)
2Solution, heat-up rate, stirring velocity etc., make calcium carbonate crystal whisker, its Heating temperature is generally about 75 ℃ in process of production.This method is to temperature controlling, heat-up rate, the having relatively high expectations of processing condition such as stirring intensity, and preparation technology is comparatively complicated.
3. urea water solution.This method is to prepare calcium carbonate whisker with the carbonic acid gas that soluble calcium salt and hydrolysis of urea produce under High Temperature High Pressure, and this method requires high to temperature and pressure, and this technology requires relatively also higher to production unit.
4.Ca (OH)
2-CO
2The gas liquid reaction method.The crystal formation of finished product with difficulty control, often generated with granular calcium carbonate during this method was produced.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, the method for preparing the yellow soda ash whisker that technology is easy to control, this method are to existing Soluble Ca
2+And CO
3 2-A kind of improvement of preparation method.
Method of the present invention is to be 0.001～0.05molL in 100mL concentration
-1Calcium chloride water in, add polyvinyl alcohol: the mass ratio of calcium chloride is 1: 12～1: 8, and concentration is 2gL
-1Polyvinyl alcohol water solution, system is heated to 70～96 ℃, under agitation condition, slowly add the aqueous solution with the isocyatic soluble carbon hydrochlorate of calcium chloride water equal-volume, continue to stir, generate white precipitate in the system, through the solid-liquid separation water washing precipitate, carry out drying treatment again, obtain calcium carbonate crystal whisker.
The soluble carbon hydrochlorate that is added among the present invention is yellow soda ash preferably.
The concentration of the calcium chloride water that is adopted in the invention process is preferably 0.02～0.04molL
-1, the polyvinyl alcohol water solution volume ratio of adding is 1: 10, the system Heating temperature is 80～90 ℃.
Among the preparation method of the present invention, after adding polyvinyl alcohol water solution, can in system, add the crystal seed of a spot of yellow soda ash whisker, to promote crystallisation process.
Present method has following characteristics:
1. method is simple, easy handling;
2. synthetic used instrument is simple, and cost of material is cheap;
3. generated time cycle weak point is less demanding to reaction conditions;
4. product has characteristics such as slipperiness, length-to-diameter ratio is big, output is high, purity height preferably.
Description of drawings
Accompanying drawing 1 is the calcium carbonate crystal whisker stereoscan photograph of method preparation of the present invention with accompanying drawing 2.
Embodiment
The present invention is in technological test, get the calcium chloride water 100mL of different concns respectively, the polyvinyl alcohol water solution that adds different amounts more therein respectively as the crystal formation control agent, system is heated to 70～96 ℃ again, and then, continue to stir at the aqueous solution of slow adding under agitation condition with the isocyatic solubility chlorination of calcium chloride water equivalent salt.At this moment generate the throw out of white in the system gradually, behind reaction terminating, carry out solid-liquid separation, and wash throw out with water, again throw out is carried out drying treatment, promptly obtained calcium carbonate crystal whisker.
Test shows:
1, when the concentration of calcium carbonate aqueous solution greater than 0.05molL
-1The time can generate the crystal formation and the crystallization of aragonitic crystal form calcium carbonate of calcite type, and increase with the crystallization content of the crystal formation that increases calcite type of calcium carbonate aqueous solution concentration.The calcium carbonate aqueous solution concentration range is at 0.001～0.05molL
-1The time products therefrom crystal formation comparatively desirable, be the aragonitic crystal formation basically, but the concentration of calcium carbonate aqueous solution is low excessively, its production efficiency is low excessively.
2, the polyvinyl alcohol amount that adds in the reaction system, bigger to the influence of the form of product crystal formation and product, the calcite type crystallization of the polyvinyl alcohol amount hour product of adding increases, and then easily generates the reunion of whisker when the polyvinyl alcohol amount of being gone into is excessive.In the polyvinyl alcohol water solution that adds, polyvinyl alcohol: the mass ratio of calcium chloride was at 1: 12～1: 8, and concentration is 2gL
-1The time comparatively desirable.
3, the temperature of reaction system also should be considered the influence of product.When the system temperature of reaction was hanged down, the calcite type crystallization in the product increased, degradation; The quality of the high product of temperature of reaction is good, but temperature when too high energy consumption also will raise.When correlation test showed reaction, system was heated to 70～96 ℃ better.
The preferred processing parameter of the present invention is: the concentration of the calcium chloride water that system is used is 0.02～0.04molL
-1The polyvinyl alcohol that adds: the mass ratio of calcium chloride is 1: 10, and its concentration is 2gL
-1The temperature of system heating is 80～90 ℃.In addition, employed soluble carbon hydrochlorate is a yellow soda ash.Adopt its cost of carbonate lower, and aborning basically to not influence of environment.If add the crystal seed of a spot of calcium carbonate crystal whisker in reaction system, its effect will be better.
Produce with above-mentioned optimizing technology parameters, resulting product is very desirable, long 15～60 μ m of its calcium carbonate crystal whisker, diameter 0.2～2 μ m, length-to-diameter ratio 20～30; The stereoscan photograph that its form provides referring to accompanying drawing.
Claims (4)
1. a method for preparing calcium carbonate crystal whisker is characterized in that in 100mL concentration be 0.001～0.05molL
-1Calcium chloride water in, add polyvinyl alcohol: the mass ratio of calcium chloride is 1: 12～1: 8, and concentration is 2gL
-1Polyvinyl alcohol water solution, system is heated to 70～96 ℃, under agitation condition, slowly add the aqueous solution with the isocyatic soluble carbon hydrochlorate of calcium chloride water equal-volume, continue to stir, generate white precipitate in the system, through the solid-liquid separation water washing precipitate, carry out drying treatment again, obtain calcium carbonate crystal whisker.
2. the method for preparing calcium carbonate crystal whisker according to claim 1 is characterized in that the soluble carbon hydrochlorate that is added is a yellow soda ash.
3. the method for preparing calcium carbonate crystal whisker according to claim 2 is characterized in that calcium chloride concentration is 0.02～0.04molL
-1, the polyvinyl alcohol of adding: the mass ratio of calcium chloride is 1: 10, the system Heating temperature is 80～90 ℃.
4. according to claim 1 or the 2 or 3 described methods that prepare calcium carbonate crystal whisker, after it is characterized in that adding polyvinyl alcohol water solution, in system, add the crystal seed of a spot of calcium carbonate crystal whisker again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101295240A CN101139734A (en) | 2007-06-28 | 2007-06-28 | Method for preparing calcium carbonate crystal whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101295240A CN101139734A (en) | 2007-06-28 | 2007-06-28 | Method for preparing calcium carbonate crystal whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101139734A true CN101139734A (en) | 2008-03-12 |
Family
ID=39191836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101295240A Pending CN101139734A (en) | 2007-06-28 | 2007-06-28 | Method for preparing calcium carbonate crystal whisker |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101139734A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424415A (en) * | 2011-09-14 | 2012-04-25 | 陕西科技大学 | Preparation method for needle cluster-like micrometer-scale calcium carbonate |
| CN103189315A (en) * | 2010-10-26 | 2013-07-03 | Omya发展股份公司 | Production of high purity precipitated calcium carbonate |
| CN103628124A (en) * | 2013-11-12 | 2014-03-12 | 西安交通大学 | Low-voltage direct-current electrolysis preparation method of calcium carbonate whisker |
| CN113213498A (en) * | 2021-05-21 | 2021-08-06 | 香港理工大学 | Cement-based material carbonization recycling method and calcium carbonate whisker material |
| CN114377637A (en) * | 2021-12-21 | 2022-04-22 | 莱阳市明军纺织助剂厂 | Intelligent manufacturing equipment and processing technology of environment-friendly auxiliary agent |
-
2007
- 2007-06-28 CN CNA2007101295240A patent/CN101139734A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103189315A (en) * | 2010-10-26 | 2013-07-03 | Omya发展股份公司 | Production of high purity precipitated calcium carbonate |
| US8992875B2 (en) | 2010-10-26 | 2015-03-31 | Omya International Ag | Production of high purity precipitated calcium carbonate |
| US9725330B2 (en) | 2010-10-26 | 2017-08-08 | Omya International Ag | Production of high purity precipitated calcium carbonate |
| CN102424415A (en) * | 2011-09-14 | 2012-04-25 | 陕西科技大学 | Preparation method for needle cluster-like micrometer-scale calcium carbonate |
| CN102424415B (en) * | 2011-09-14 | 2013-07-24 | 陕西科技大学 | Preparation method for needle cluster-like micrometer-scale calcium carbonate |
| CN103628124A (en) * | 2013-11-12 | 2014-03-12 | 西安交通大学 | Low-voltage direct-current electrolysis preparation method of calcium carbonate whisker |
| CN113213498A (en) * | 2021-05-21 | 2021-08-06 | 香港理工大学 | Cement-based material carbonization recycling method and calcium carbonate whisker material |
| CN113213498B (en) * | 2021-05-21 | 2024-01-23 | 香港理工大学 | Cement-based material carbonization recycling method and calcium carbonate whisker material |
| CN114377637A (en) * | 2021-12-21 | 2022-04-22 | 莱阳市明军纺织助剂厂 | Intelligent manufacturing equipment and processing technology of environment-friendly auxiliary agent |
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Open date: 20080312 |