CN102275966B - Preparation method of calcium carbonate particulates - Google Patents
Preparation method of calcium carbonate particulates Download PDFInfo
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- CN102275966B CN102275966B CN 201110208798 CN201110208798A CN102275966B CN 102275966 B CN102275966 B CN 102275966B CN 201110208798 CN201110208798 CN 201110208798 CN 201110208798 A CN201110208798 A CN 201110208798A CN 102275966 B CN102275966 B CN 102275966B
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Abstract
The invention belongs to the technical field of inorganic salt materials, and specially relates to a preparation method of calcium carbonate particulates. The method comprises the following steps of adding 0.001 to 2 mol/L of a calcium salt into an 0.0005 to 1 g/L of additive solution to obtain a mixed solution, standing, adjusting a pH value of the mixed solution to a pH value of 5 to 12, through adopting different carbonate sources and corresponding different concentrations, carrying out a reaction at a temperature of 10 to 60 DEG C in an inclosed system for 10 minutes to 30 days, separating a product obtained by the previous step, and drying to obtain a desired product. Calcium carbonate particulates prepared by the method have different sizes which are in a range of 0.1 to 50 micrometers, different shapes such as a hexagonal petal shape and a globular shape, and high thermal stability. The method has the advantages of wide raw material source, low price, simple process, good operability, low pollution of adopted solvents, no toxic effect, good conformity with green chemistry requirements, and great potential for large-scale production.
Description
Technical field
The invention belongs to inorganic salt material technology field, be specifically related to a kind of preparation method of calcium carbonate microparticle.
Background technology
Calcium carbonate is one of inorganic mineral of the most extensively existing of nature.Characteristics such as on the one hand,, as important inorganic chemical industry material, calcium carbonate is wide with its raw material, nontoxicity, loading level is large, reinforcing property is good and be widely used in the industries such as building materials, rubber, plastics, coating, papermaking, daily-use chemical industry.On the other hand; as one of the main inorganic composition of biomineral (as the shell of invertebrates); calcium carbonate plays function (S. Mann, the G. A. Ozin such as the support structure that exists in organism, protection in vivo with the structure of its high-sequential and good mechanical property
nature 1996,
382, 313).Calcium carbonate has three kinds of crystal formations at occurring in nature: calcite (the most stable), aragonite, vaterite (least stable).In industrial application, the calcium carbonate of three kinds of crystal formations has purposes separately, and calcium carbonate granule also can be applied to respectively different industries due to the difference on its size, pattern.
Prepare at present calcium carbonate granule and can be divided into two classes according to the difference in carbonic acid source: carbon dioxide is as the carbonic acid source, and soluble carbonate salt is as the carbonic acid source.The many calcium carbonate preparation methods of industrial utilization belong to the former, but large-scale industrial process often exists the unmanageable problem of pattern.In recent years, utilize external bionical way, by the organic regulation and control to crystallisation process prepare different crystal forms with Bu Tong in order the calcium carbonate material of packed structures be subject to researchist's extensive concern.The organic additive adopted is varied, has small molecules to also have the macromole of molecular weight hundreds of thousands of; There is natural polymer that synthetic polymer is also arranged; Have the additive of solubility also have insoluble self-assembled monolayer etc. (F. C. Meldrum, H. Colfen,
chem. Rev. 2008,
108, 4332)
.these additives are considered to regulate the microenvironment of calcium carbonate growth, thereby obtain the different calcium carbonate microparticle of structure different performance.Wherein the additive of carboxyl, hydroxyl is a class additive that is studied many, also is proved to be calcium carbonate crystal (M. Donnet, A. Aimable that this class additive relatively is conducive to obtain having ordered structure really
et. al.J. Phys. Chem. B,
2010,
114, 12058; H. Endo, D. Schwahn, H. Colfen,
j. Chem. Phys, 2004,
120, 9410).GO is a kind of novel Two-dimensional Carbon nanostructure, has on the GO lamella than more rich hydroxyl, carboxyl etc. and contains oxygen group, may have to the crystalline growth process of calcium carbonate crystal regulating and controlling effect, but up to the present, also there is no relevant report.
The present invention has proved that GO is conducive to obtain the shape and appearance of calcium carbonate of ordered structure really, and the calcium carbonate granule obtained under the GO regulation and control is than the calcium carbonate granule do not obtained under any additive to have better thermal stability.In addition, the invention provides a kind of method of external mineralising, by regulating the parameters such as carbonic acid Source Type, carbonic acid source concentration, temperature, pH value of solution, calcium ion concn, organic concentration, reaction times, can obtain a series of calcium carbonate microparticles with unique morphology structure and distribution of sizes.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with high thermal stability energy calcium carbonate microparticle.
The preparation method of the calcium carbonate microparticle that the present invention proposes, concrete steps are as follows:
1, the pre-treatment of glassware: in order to obtain the uniform calcium carbonate microparticle of the unique particle diameter of structure, glassware used must carry out certain pre-treatment.At first glassware is processed 5 minutes-2 hours in organic solvent for ultrasonic, soaked 2 hours-7 days in the mixing liquid then be mixed with in proportion at acid/superoxide/water, take out, adopt organic solvent, water to clean, drying, stand-by;
2, the preparation of solution: additive is mixed with to the solution that concentration is the 0.0005-1 grams per liter, adds the calcium salt that concentration is the 0.001-2 mol/L, be mixed with the mixing solutions of calcium salt/polymkeric substance, static, the pH value of regulator solution is 5-12, takes out 10
1～10
3milliliter is loaded in beaker or flask, standby;
3, select different carbonic acid source to prepare calcium carbonate microparticle:
I) carbon dioxide of selecting carbonate slowly to decompose to obtain is as the carbonic acid source: at 10-60 ℃ of temperature, the beaker that carbonate through grinding is housed is positioned in enclosed system, the quality of carbonate is the 1-300 gram, the fineness of carbonate is the 4-400 order, covers thin film on beaker and decomposes to control it speed that produces carbonic acid gas; The rim of a cup that the mixing solutions beaker is housed in step (2) is covered with to thin film, on film, thorn has several holes, and beaker is put into to enclosed system simultaneously; React 10 minutes-30 days; Beaker is taken out, in order to products therefrom is separated;
Ii) select carbonate as direct carbonic acid source: at 10-60 ℃ of temperature, by being equipped with in step (2) in the flask of mixing solutions, to put a magnetic stir bar (length 0.2-10 centimetre), stirring velocity 1000-20000 revolution per second is set.The mixing solutions obtained in step (2) stirred after 1-30 minute, and the carbonate solution that is the 0.001-2 mol/L by freshly prepared concentration, take out 10
1～10
3milliliter joins in the mixing solutions obtained in step (2).By the flask sealing, keep temperature 10-60 ℃, react 2 minutes-2 days; Stop stirring, in order to products therefrom is separated;
4, the separation of composite particles: step (3) gained particulate is separated, and after separating, water cleans several times (being generally 3-6 time) repeatedly, and drying, obtain final calcium carbonate composite fine particle.
In the present invention, the organic solvent adopted in step (1) be in methyl alcohol, ethanol, ether, acetone, toluene or hexanaphthene etc. any, but do not get rid of the solvent of other one or more solubilized waxs and grease.
In the present invention, the acid adopted in step (1) be in hydrochloric acid, sulfuric acid, nitric acid or acetic acid etc. any, the superoxide adopted be in peracetic acid, dicumyl peroxide or hydrogen peroxide etc. any.
That in step (2), additive adopts is the GO with Two-dimensional Carbon nanostructure, containing oxygen, integrates the substitution value of group as 2-50%.Preferably the scope of substitution value is 20%-50%.
In the present invention, calcium salt described in step (2) adopts in lime acetate, calcium chloride or calcium lactate etc. any, but does not also get rid of the soluble calcium salt that other solubleness are more than or equal to 2g/100g water.
In the present invention, step (3)-i) carbonate described in be in volatile salt or bicarbonate of ammonia any, can not decompose but do not get rid of other carbonate that produces carbonic acid gas yet.The quality of placing carbonate is the 1-300 gram, and the preferred mass scope is the 5-100 gram.Step (3)-ii) carbonate described in be in sodium carbonate, salt of wormwood, volatile salt, sodium bicarbonate, saleratus or bicarbonate of ammonia any, but do not get rid of the soluble carbonate salt salt that other solubleness are more than or equal to 2g/100g water yet.
In the present invention, separation method described in step (4) adopts in suction method, decantation, dialysis method or centrifugal separation etc. any.
In the present invention, described in step (4), drying conditions is: vacuum tightness is 1-10
5pascal, temperature is 10-120 ℃, preferred range 20-100 ℃; Be 1 hour-3 days time of drying, and preferably be 2 hours to 2 days time of drying.
The present invention preferably condition is as follows:
The supersound process time described in step (1) is 10-40 minute.
Soak time described in step (1) is 4 hours-4 days.
Described in step (2), the polymer concentration scope is the 0.0025-0.5 grams per liter.
Described in step (2), the concentration of calcium salt is the 0.001-0.25 mol/L.
Regulating the pH value described in step (2) is 6-11.
Step (3)-i) described in, temperature of reaction is 15-50 ℃.
Step (3)-i) described in, the fineness of carbonate is the 50-200 order.
Step (3)-i) reaction times described in is 1 hour to 7 days.
Step (3)-ii) described in, temperature of reaction is 20-50 ℃.
Step (3)-ii) described in, magnetic stir bar length is 1-5 centimetre.
Step (3)-ii) described in, stirring velocity is the 2000-10000 order.
Step (3)-ii) described in, the mixing solutions churning time is 2-10 minute.
Step (3)-ii) described in, carbonate concentration is the 0.001-0.25 mol/L.
Step (3)-ii) reaction times described in is 5 minutes-1 day.
The present invention adopts the regulation and control of GO as the calcium carbonate crystal process, utilize oxy radical abundant on the GO lamella and the electrostatic interaction between calcium ion as some point of application, when carbonic acid source (carbon dioxide or carbonate) while with certain speed, concentration, entering into the mixing solutions of GO and calcium salt, make calcium ion and carbanion under the guiding of GO lamella, with given pace nucleation, crystallization, formation structure uniqueness, the calcium carbonate microparticle of size uniform.The calcium carbonate microparticle that utilizes the inventive method to prepare gained has different size (50 microns of 0.1-) and different-shape (six side's petal-shaped, spherical).The result of X ray polycrystalline diffraction, infrared spectra and Raman spectrum shows that the gained crystal formation is more single, and the overwhelming majority is vaterite (> 90%).The thermogravimetric analysis result shows that the content of GO in the calcium carbonate microspheres obtained is 0.01-10%, and the thermostability of the calcium carbonate microparticle obtained will be got well than the calcium carbonate microparticle obtained without any additive, and (decomposition starting temperature has improved 20-50
oc).
Prepared by the present invention has this inorganic materials of high thermal stability energy calcium carbonate microparticle, and its raw material sources are extensive, simple and easy to get, cheap, and the preparation method is simple to operation, possess the potentiality of scale operation.The solvent contamination adopted in experiment is little, the toxicological harmless effect, and it is convenient to reclaim, can be recycled, be a kind of eco-friendly green method.What is more important, by controlling simply reaction conditions (parameters such as carbonic acid Source Type, carbonic acid source concentration, temperature, pH value of solution, calcium ion concn, organic concentration, reaction times), can obtain a series of calcium carbonate microparticles with unique morphology structure (six side's petal-shaped, spherical) and distribution of sizes (50 microns of 0.1-).The calcium carbonate microparticle of these different microstructures (comprises papermaking, printing ink, coating, rubber etc.) and has broad application prospects in different industries.
The accompanying drawing explanation
Fig. 1 is the thermogravimetric curve (c) that in the scanning electron microscope diagram (a, b) of the calcium carbonate microparticle that obtains in embodiment 1 and this embodiment 1, the calcium carbonate microparticle obtained and the calcium carbonate microparticle obtained without any additive contrast.
Fig. 2 is the scanning electron microscope diagram of the calcium carbonate microparticle that obtains in embodiment 2.
Fig. 3 is the scanning electron microscope diagram of the calcium carbonate microparticle that obtains in embodiment 3.Wherein a is magnification ratio photo hour, b, the enlarged view that c is certain single microballoon different directions.
Fig. 4 is the scanning electron microscope diagram of the calcium carbonate microparticle that obtains in embodiment 4.Wherein a is magnification ratio photo hour, and b is the photo of magnification ratio when larger.
Embodiment
Following examples are that the present invention is further elaborated, for the technician to association area and industry, show use known for inventor preferred forms of the present invention, but do not limit content of the present invention and scope.Can modify and not exceed scope of the present invention following embodiment, for the technician of this area and relevant industries, be apparent by following examples for implementing the inventive method.Therefore, in the scope of claims and equivalent thereof, can by from the following specifically describes different modes and implement the present invention.
embodiment 1:
All glassware of using in experiment are carried out to pre-treatment, and method is as follows: first in ethanol ultrasonic 30 minutes, take out and use deionized water rinsing afterwards.The mixed solvent that the ratio that to put into concentrated nitric acid/hydrogen peroxide/water be 1:1:1 according to volume ratio mixes soaks 2 days, takes out, and cleans Air drying with acetone.Prepare 100 milliliters of the GO aqueous solution of 0.0025 grams per liter, then add a certain amount of calcium chloride to be mixed with the calcium chloride solution of 0.01 mol/L, the pH to 7.5 of regulator solution.To fill polyethylene film on the beaker cover of solution, prick 12 pin holes on film.Get 20 gram volatile salts, being ground to fineness is 100 purpose powder, is placed in 50 ml beakers, and polyethylene film on the beaker lid, with 25 holes of pinprick.Then put into together with the above-mentioned beaker that fills solution the moisture eliminator that volume is about 10 liters, airtight, start reaction at the temperature of 25 ± 1 ℃.React after 24 hours, by the suspension liquid centrifugation of gained, water cleans and centrifugal alternately each three times.The powder obtained is at 40 ℃, and vacuum tightness is about 10
5the condition of Pa is dried in lower 12 hours.Obtain desired product.As can be seen from Figure 1, the calcium carbonate microparticle obtained in this embodiment has the micro-sphere structure of nucleocapsid pattern, and size is between the 10-15 micron.Than the calcium carbonate microparticle without any obtaining under additive (Fig. 1 (c) b), (Fig. 1 (c) heat decomposition temperature a) will exceed approximately 20 to the calcium carbonate microparticle obtained in this embodiment
oc.
embodiment 2:
The glassware treatment process is in the same manner as in Example 1.Prepare 100 milliliters of the GO aqueous solution of 0.025 grams per liter, then add a certain amount of calcium chloride to be mixed with the calcium chloride solution of 0.01 mol/L, the pH to 7.5 of regulator solution.Other subsequent operationss, all with embodiment 1, just will extend to 4 days the reaction times.The calcium carbonate microparticle obtained is shown in Fig. 2, is also the microballoon with nucleocapsid structure, and size is between the 15-20 micron.The microballoon just obtained with respect to embodiment 1, surface is looser, coarse, can obviously see the sheet of composition and the space between sheet.
embodiment 3:
The glassware treatment process is in the same manner as in Example 1.Prepare 100 milliliters of the GO aqueous solution of 0.0025 grams per liter, add a certain amount of calcium chloride to be mixed with the calcium chloride solution of 0.001 mol/L, the pH of regulator solution is 8, by filling polyethylene film on the beaker cover of solution, pricks 8 pin holes on film.Get 20 gram volatile salts, being ground to fineness is 100 purpose powder, is placed in 50 ml beakers, and polyethylene film on the beaker lid, with 20 holes of pinprick.Then put into together with the above-mentioned beaker that fills solution the moisture eliminator that volume is about 10 liters, airtight, start reaction at the temperature of 30 ± 1 ℃.React after 5 hours, by the suspension liquid centrifugation of gained, water cleans and centrifugal alternately each three times.The powder obtained is at 40 ℃, and vacuum tightness is about the condition oven dry in lower 12 hours of 10Pa.Obtain desired product.As can be seen from Figure 3, the calcium carbonate microparticle obtained in this embodiment has six side's petal-shaped structures, is to be piled up and form along certain direction by the lamella of 10 microns of diameters, also has the nucleocapsid pattern, and size is between the 25-30 micron.
embodiment 4:
The glassware treatment process is in the same manner as in Example 1.Prepare 60 milliliters of the GO aqueous solution of 0.2 grams per liter, add a certain amount of calcium chloride to be mixed with the calcium chloride solution of 0.0417 mol/L, the pH of regulator solution is 9, above-mentioned solution is transferred in 250 milliliters of round-bottomed flasks, fixing whole flask, put into the magnetic stir bar that length is 5 centimetres, it is 10000 revolution per seconds that stirring velocity is set.It is 40 ± 1 ℃ that temperature of reaction is set, and in above-mentioned solution stirring after 5 minutes, adds fast 20 milliliters of the sodium carbonate solutions of freshly prepared 0.125 mol/L, and reaction starts.React after 1 hour, by the suspension liquid centrifugation of gained, water cleans and centrifugal alternately each three times.The powder obtained is at 25 ℃, and vacuum tightness is about the condition oven dry in lower 24 hours of 100Pa.Obtain desired product.As can be seen from Figure 4, the calcium carbonate microparticle obtained in this embodiment is the microballoon of diameter between the 3-4 micron, and surface is comparatively loose.
Claims (2)
1. the preparation method of a calcium carbonate microparticle is characterized in that concrete steps are as follows:
(1), the pre-treatment of glassware: at first glassware is processed 5 minutes-2 hours in organic solvent for ultrasonic, then soak 2 hours-7 days in the mixing solutions be mixed with in proportion at acid, superoxide, water, take out, adopt organic solvent, water to clean, drying, stand-by;
(2), the preparation of solution: additive is mixed with to the polymers soln that concentration is the 0.0005-1 grams per liter, adds the calcium salt that concentration is the 0.001-2 mol/L, be mixed with the mixing solutions of calcium salt, polymkeric substance, static, the pH value of regulator solution is 5-12, takes out 10
1～10
3milliliter is loaded in beaker or flask, standby;
(3), select different carbonic acid source to prepare calcium carbonate microparticle:
I) carbon dioxide of selecting carbonate slowly to decompose to obtain is as the carbonic acid source: at 10-60 ℃ of temperature, the beaker that carbonate through grinding is housed is positioned in enclosed system, the quality of carbonate is the 1-300 gram, the fineness of carbonate is the 4-400 order, covers thin film on beaker and decomposes to control it speed that produces carbonic acid gas; The rim of a cup that the mixing solutions beaker is housed in step (2) is covered with to thin film, on film, thorn has some holes, and this beaker is put into to enclosed system simultaneously; React 10 minutes-30 days;
Ii) select carbonate as direct carbonic acid source: at 10-60 ℃ of temperature, by being equipped with in step (2) in the flask of mixing solutions, to put the magnetic stir bar that a length is 0.5-5 centimetre, stirring velocity 1000-20000 revolution per second is set; The mixing solutions obtained in step (2) stirred after 1-30 minute, and the carbonate solution that is the 0.001-2 mol/L by freshly prepared concentration, take out 10
1～10
3milliliter joins in the mixing solutions obtained in step (2); By the flask sealing, keep temperature 10-60 ℃, react 2 minutes-1 day;
(4), the separation of composite particles: step (3) gained particulate is separated, and after separating, water cleans several times repeatedly, and drying, obtain final calcium carbonate microparticle;
In described step (2), additive adopts the GO with Two-dimensional Carbon nanostructure, containing oxygen, integrates the substitution value of group as 2-50%.
2. the preparation method of calcium carbonate microparticle according to claim 1, is characterized in that the calcium carbonate microparticle made has the different size of 50 microns of 0.1-, and have six side's petal-shaped, spherical different-shape; The weight percent of the content of GO in calcium carbonate microparticle is 0.01-10%.
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| CN102583234A (en) * | 2012-03-06 | 2012-07-18 | 上海理工大学 | Digital fluid particle preparation device |
| CN102874857B (en) * | 2012-09-10 | 2014-12-10 | 浙江大学 | Method for preparing sheet-shaped calcium carbonate by thermally decomposing shell through hydrothermal process |
| CN108163879A (en) * | 2018-02-24 | 2018-06-15 | 陕西学前师范学院 | A kind of preparation method of the calcium carbonate of different-shape and phase structure |
| CN109771379A (en) * | 2019-03-06 | 2019-05-21 | 常州大学 | A kind of calcium carbonate solid dispersion of curcumin and preparation method thereof |
| CN111592026B (en) * | 2020-05-11 | 2023-05-09 | 贺州学院 | Preparation method of discus-shaped micron calcium carbonate |
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| WO2007061073A1 (en) * | 2005-11-25 | 2007-05-31 | New Lime Kenkyusha Co., Inc. | Crossed-disk-, hamburger- or disk-shaped vaterite type calcium carbonate and process for producing the same |
| JP2009067605A (en) * | 2007-09-10 | 2009-04-02 | Oita Univ | Method for producing aragonite type calcium carbonate with hexagonal plate form |
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