CN107673384B - Method for preparing metastable vaterite calcium carbonate based on calcium glycerol method - Google Patents
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Abstract
The invention provides a method for preparing metastable vaterite calcium carbonate based on a glycerol calcium method, which comprises the following steps: step (1) preparing CCalcium triol solution (with the concentration of 0.01-1.0 mol/L) and sodium carbonate aqueous solution (with the concentration of 0.025-2.5 mol/L); mixing and stirring the calcium glycerol solution and the sodium carbonate aqueous solution in the step (1) at 0-100 ℃, fully reacting, standing and aging for 0-42 h to obtain a suspension; and (3) centrifuging the suspension obtained in the step (2), washing with absolute ethyl alcohol and deionized water, and finally centrifuging, filtering and drying the precipitate. The invention adopts a simpler double decomposition reaction system, the whole preparation method has simple process conditions, low requirements on equipment and green and environment-friendly preparation process; the vaterite CaCO can be varied by adjusting the experimental parameters (reactant concentration, mixing reaction temperature and standing aging time)3Weight ratio in the product, vaterite CaCO in calcium carbonate product3Up to 96.7% by weight.
Description
Technical Field
The invention relates to a preparation method of vaterite calcium carbonate, in particular to a method for preparing metastable vaterite calcium carbonate based on a glycerol calcium method, and belongs to the field of preparation of inorganic non-metallic powder materials.
Background
Calcium carbonate (CaCO) as an inorganic chemical product3) Is widely applied to different fields of rubber, paint, plastics, paper making, printing ink, daily chemicals, medicines and the like. At normal temperature and pressure, six kinds of CaCO with the same components and completely different structures exist in nature3Minerals, respectively amorphous CaCO3、CaCO3·H2O、CaCO3·6H2O, vaterite, aragonite, calcite, whose thermodynamic stability increases in order. Removing deviceAmorphous CaCO3In addition, other structures are crystalline; CaCO3·H2O and CaCO3·6H2O is a crystal containing crystal water; three kinds of CaCO of vaterite, aragonite and calcite3The crystals are free of water of crystallization. In the presence of CaCO3Of these three crystal structures, calcite is the most thermodynamically stable crystalline phase, usually occurring in nature in the form of limestone or marble; vaterite is the most thermodynamically unstable crystalline phase, which is artificially synthesized CaCO3The product is spherical under normal conditions, has extremely unstable performance and is easy to be converted into calcite; aragonite has a stability intermediate between that of vaterite and calcite and is characterized by a needle-like appearance.
CaCO3The preparation method of (1) comprises a physical method and a chemical method. The physical method is a preparation method of crushing raw materials into nano particles by adopting a mechanical mode, namely CaCO in the nature3Mechanically pulverizing natural limestone or marble with high content, coarse crushing, fine crushing, and grading to obtain CaCO3And (5) producing the product. In general, physically prepared CaCO3Higher density, so called heavy CaCO3. By chemical means CaCO formation by decomposition or ionic reaction3Precipitate [ Sha F, Zhu N, Bai Y, et al. controllable Synthesis of fluids CaCO3Morphologies Based on a CCUS Idea,ACS Sustainable Chemistry&Engineering,2016,4(6):3032-3044；Yang L,Chu D,Sun H,et al.Room temperature synthesis of flower-like CaCO 3 architectures,New Journal of Chemistry,2016,40(1):571-577]CaCO obtained3Known as precipitated CaCO3Or light CaCO3。
At present, a plurality of methods for preparing calcium carbonate are available, which are mainly embodied in the traditional methods such as a carbonization method, a double decomposition method, a microemulsion method, a solvothermal method and the like, and novel methods such as a self-assembly monomolecular film method, a bionic synthesis method, a thermal decomposition method and the like. The carbonization method is to produce nano CaCO3The most important industrial method belongs to Ca2+-H2O-CO2Systematic, carbonization process affecting light CaCO3Morphology and crystal form [ seeYanxin, new technology for continuous bubbling carbonization of superfine calcium carbonate, Chinese powder technology, 2003,9(2):29-31]According to the production process and CO2Gas and Ca (OH)2The contact mode of the suspension is different, and the carbonization method can be further divided into seven methods of a continuous spray carbonization method, a jacketed reaction kettle method, a batch carbonization method, a non-freezing method, a super-gravity carbonization method, an ultrasonic cavitation method and a jet absorption method [ see 'nano calcium carbonate key technology', Yanxin, Wangbeiang, Shuyue, Beijing: chemical industry publishers, 2007; the top end of the window body; decryption of the production and application technology of nano calcium carbonate, editions by showpin, Beijing: chemical industry Press, 2009]. The double decomposition method comprises adding water-soluble calcium salt (such as CaCl)2Etc.) and water-soluble carbonate under appropriate conditions to prepare CaCO3The method of (Tangxiuhua, preparation and application of nano calcium carbonate, Sichuan chemical industry, 2006,9(4): 20-23)]Is of Ca2+-H2O-CO3 2-System, CaCO produced3The crystal form and morphology are mainly influenced by temperature, pH, solvent system, additives and other factors (such as stirring, ultrasonic waves) and the like. However, the cations generated by the conventional double decomposition reaction are difficult to clean, a large amount of water is required, the production cost is higher, and the obtained CaCO3The crystal form of (a) is difficult to control. The microemulsion method is used for preparing nano CaCO3Of Ca2+-R-CO3 2-System, CaCO produced by the method3The particle size is small and the purity is high, but the reaction conditions are severe. The solvothermal method is a method of slowly producing a product by dissolving one or more precursors in a non-aqueous solvent under liquid phase or supercritical conditions, which allows the reaction to be carried out at lower temperatures, but with lower yields. The self-assembly monomolecular film method mainly utilizes a highly ordered monomolecular film as a matrix, effectively controls the particle size distribution, the geometric structure and the stability of nano particles nucleated and grown on the monomolecular film, and has higher requirements on reaction equipment and reaction conditions. The bionic synthesis method is a novel preparation technology for synthesizing by simulating the reaction in the organism and the structure of natural substances, has wide development prospect, but the reaction time is generally longerLong, the selectivity to the template is also relatively high. The thermal decomposition of calcium bicarbonate is also a method for preparing CaCO3The novel process [ patent application No.: 201210161303.2]Can prepare CaCO with different shapes and structures3。
The preparation of vaterite CaCO by a double decomposition method has been disclosed3A number of patents including: a method for preparing vaterite calcium carbonate with a micron spindle filamentous structure (publication number: CN105399128A), a method and a device for preparing the vaterite by using a magnetic field (publication number: CN106495196A), vaterite calcium carbonate microspheres and a preparation method thereof (publication number: CN104692439A), a method for preparing micron needle-like vaterite calcium carbonate (publication number: CN105883877A), spherical calcium carbonate particles and a preparation method thereof (publication number: CN105329929A), a method for preparing single-crystal-form vaterite type nano calcium carbonate by using a microemulsion system (publication number: CN103570052B), a method for preparing calcite phase and/or vaterite phase calcium carbonate (publication number: CN102557099B), but for the vaterite CaCO 102557099B3The preparation method based on the calcium glycerol method is not reported in relevant documents.
In view of the above, the present invention provides a method for preparing metastable vaterite calcium carbonate based on a calcium glycerol method, so as to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the existing products and provides a method for preparing metastable vaterite calcium carbonate based on a calcium glycerol method, which adopts a simpler double decomposition reaction system to prepare vaterite CaCO by the calcium glycerol method3And calcite CaCO3。
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing metastable vaterite calcium carbonate based on a calcium glycerol method comprises the following steps:
fully dissolving calcium chloride powder in glycerol to obtain glycerol calcium solutions with different concentrations, wherein the step is very important; fully dissolving sodium carbonate powder in deionized water to obtain sodium carbonate aqueous solutions with different concentrations;
step (2) mixing and stirring the calcium glycerol solution and the sodium carbonate aqueous solution in the step (1) at a certain temperature, fully reacting, standing and aging for a certain time to obtain a suspension;
and (3) centrifuging the suspension obtained in the step (2), washing the obtained white powder with absolute ethyl alcohol and deionized water in sequence to remove calcium chloride, sodium chloride and sodium carbonate, centrifuging and filtering the precipitate, and drying at the temperature of 80-120 ℃ for 5-12 hours.
Further, in the step (1), the calcium chloride is anhydrous calcium chloride, the sodium carbonate is anhydrous sodium carbonate or hydrated sodium carbonate, the molar ratio of the calcium chloride to the sodium carbonate is 1:1, and the volume ratio of the glycerol to the water is 2.5: 1.
Further, in the step (1), the concentration of the calcium glycerol solution is 0.01-1.0 mol/L, and the concentration of the sodium carbonate aqueous solution is 0.025-2.5 mol/L.
Further, the temperature of the calcium glycerol solution and the sodium carbonate aqueous solution in the step (2) is 0-100 ℃, and the two solutions are firstly kept at the same temperature for 30min before being mixed, and then are mixed at the temperature.
Further, the standing and aging time in the step (2) is 0-42 h.
Further, the anhydrous calcium chloride, anhydrous sodium carbonate, hydrated sodium carbonate and glycerol are all analytical grade with a concentration of more than 99%, and the raw material using the analytical grade is vaterite-producing CaCO3The water is deionized water.
The calcium carbonate prepared by the method for preparing the metastable vaterite calcium carbonate based on the calcium glycerol method contains a vaterite phase (main phase) and other CaCO3A crystalline phase (secondary phase), and a vaterite phase at a mass ratio of up to 96.7%.
Further, the research on CaCO by different reactant concentrations, different mixed reaction temperatures and different standing and aging times is respectively carried out3Influence of crystal form and vaterite phase content.
Further, the crystal form of calcium carbonate and the content of the vaterite phase are controlled by changing the concentrations of the reactants of the calcium glycerolate solution and the sodium carbonate aqueous solution, the mixing reaction temperature or the standing aging time.
The calcium glycerol method is to fully dissolve anhydrous calcium chloride powder in glycerol to obtain calcium glycerol solution, and mix with sodium carbonate water solution to prepare CaCO3A controllable and simple method. The method for preparing CaCO3The method comprises the following three steps:
n(CH2OH)3+CaCl2→CaCl2·n(CH2OH)3(n-4 or 6) (1)
CaCl2·n(CH2OH)3+H2O→n(CH2OH)3+H2O+Ca2++2Cl-(2)
Ca2++CO3 2-→CaCO3(3)
Reaction (1) is a process of forming a glycerin calcium complex having a coordination number of 4 or 6, and anhydrous calcium chloride is added to glycerin to spontaneously form the complex; reaction (2) is a complex decomplexation process of Ca2+Release into an aqueous solution; reaction (3) is formation of CaCO in the system3The process of (1). The essence of the calcium glycerol method is double decomposition, but the innovation point is that when the calcium glycerol complex formed before the reaction is mixed with the aqueous solution of sodium carbonate (the viscosity of glycerol is larger than that of ethylene glycol), the decomplexation process can control CaCO3A crystalline form of (a).
The invention has the beneficial effects that:
1. the calcium glycerol method adopts a simpler double decomposition reaction system, the whole preparation method has simple process conditions, low requirements on equipment, low cost of raw materials and equipment, and green and environment-friendly preparation process;
2. vaterite CaCO in calcium carbonate product3The weight ratio of the component (a) is up to 96.7 percent, and the method is a method for efficiently and rapidly preparing the metastable vaterite;
3. the method for preparing the metastable vaterite calcium carbonate based on the calcium glycerol method can prepare the vaterite CaCO by adjusting experimental parameters (reactant concentration, mixed reaction temperature and standing and aging time)3Aragonite CaCO3And calcite CaCO3And altering vaterite CaCO3Weight ratio in the product;
4. the whole experimental operation process is continuous and controllable, and the industrial production is easy to realize.
Drawings
FIG. 1 shows CaCO prepared under different standing and aging times with fixed reactant concentration and mixed reaction temperature3An XRD pattern of (a), (b), (10), (C)60 and (d)42h, wherein V and C represent vaterite and calcite, respectively);
FIG. 2 shows CaCO prepared at different mixed reaction temperatures with a fixed reactant concentration and standing aging time3An XRD pattern of (a), (b), (C), (d)100 ℃, V, A and C represent vaterite, aragonite and calcite, respectively);
FIG. 3 shows CaCO prepared at different reactant concentrations at a certain mixed reaction temperature and standing aging time3The XRD pattern of (a)0.01mol/L, 0.025mol/L, (b)0.4mol/L, 1mol/L, (c)1.0mol/L, 2.5 mol/L).
Detailed Description
For better understanding of the present invention, the contents of the present invention will be further explained below with reference to the drawings and examples, but the contents of the present invention are not limited to the following examples.
The method for preparing the metastable vaterite calcium carbonate based on the calcium glycerol method specifically comprises the following steps:
fully dissolving calcium chloride powder in glycerol to obtain glycerol calcium solutions with different concentrations, wherein the step is very important; fully dissolving sodium carbonate powder in deionized water to obtain sodium carbonate aqueous solutions with different concentrations;
step (2) mixing and stirring the calcium glycerol solution and the sodium carbonate aqueous solution in the step (1) at a certain temperature, fully reacting, standing and aging for a certain time to obtain a suspension;
when different aging times are studied on CaCO3When crystal form and vaterite phase content are affected, mixing calcium glycerol solution and sodium carbonate water solution, stirring for 2min for full reaction, and aging for different timesThe aging time is 0-42 h;
when different reaction temperatures were investigated for CaCO3When the crystal form and the vaterite phase content are influenced, firstly, simultaneously placing a calcium glycerol solution and a sodium carbonate aqueous solution at a certain temperature for 30min before mixing, wherein the temperature range is 0-100 ℃, then mixing the calcium glycerol solution and the sodium carbonate aqueous solution, and simultaneously placing the mixture at the temperature for heat preservation for 60 min;
when investigating different reactant concentrations versus CaCO3When the crystal form and the content of the vaterite phase are influenced, the molar ratio of calcium chloride to sodium carbonate is kept to be 1:1, the concentration of the calcium glycerol solution is 0.01-1.0 mol/L, and the concentration of the sodium carbonate aqueous solution is 0.025-2.5 mol/L;
and (3) centrifuging the suspension obtained in the step (2), washing the obtained white powder with absolute ethyl alcohol and deionized water in sequence to remove calcium chloride, sodium chloride and sodium carbonate, centrifuging and filtering the precipitate, and drying at the temperature of 80-120 ℃ for 5-12 hours.
Wherein, the calcium chloride is anhydrous calcium chloride, the sodium carbonate is anhydrous sodium carbonate or hydrated sodium carbonate, the molar ratio of the calcium chloride to the sodium carbonate is 1:1, the volume ratio of the glycerol to the water is 2.5:1, the anhydrous calcium chloride, the anhydrous sodium carbonate, the hydrated sodium carbonate and the glycerol are all analytical grade, and the purity of the deionized water is more than 99%.
Study of different aging times on CaCO3Influence of Crystal form and vaterite phase content
Example one
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.06g of Na2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1) at room temperature (20 ℃), stirring for 2min to enable the calcium glycerol solution and the sodium carbonate aqueous solution to fully react, and not aging at room temperature (20 ℃), namely aging for 0 min;
3) centrifuging the unaged mixture suspension obtained in step 2), and then washing with anhydrous ethanol twice and deionized water twiceWashing, washing with absolute ethyl alcohol to remove calcium chloride, washing with deionized water to remove sodium carbonate and sodium chloride, centrifuging, filtering, collecting the obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 1(a), and the results revealed that CaCO was obtained3Is composed of two phases of vaterite and calcite, and the content of the obtained vaterite phase (aging time 0min) is up to 96.7 percent.
Example two
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.24g of Na2CO3·H2Completely dissolving O in 9.82mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1) at room temperature (20 ℃), stirring for 2min to fully react, and then aging for 10min at room temperature (20 ℃);
3) and (3) after the aging time is terminated, centrifuging the mixture suspension obtained in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 1(b), and the results revealed that CaCO was obtained3Is composed of two phases of vaterite and calcite, and the content of the obtained vaterite phase (aging time of 10min) is as high as 78.5 percent.
EXAMPLE III
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.06g of Na2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1) at room temperature (20 ℃), stirring for 2min to fully react, and then aging for 60min at room temperature (20 ℃);
3) and (3) after the aging time is terminated, centrifuging the mixture suspension obtained in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 1(c), and the results revealed that CaCO was obtained3Is composed of two phases of vaterite and calcite, and the content of the obtained vaterite phase (aging time 60min) is as high as 60.8 percent.
Example four
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.06g of Na2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1) at room temperature (20 ℃), stirring for 2min to fully react, and then aging for 42h at room temperature (20 ℃);
3) and (3) after the aging time is terminated, centrifuging the mixture suspension obtained in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 1(d), and the results revealed that CaCO was obtained3The vaterite content is only 4.8% due to the fact that the vaterite phase (aging time 42h) is composed of two phases of vaterite and calcite, and the content of the vaterite phase is rapidly reduced and the content of the calcite phase is rapidly increased along with the prolonging of the aging time (0 min-42 h) in the first comparative example, the second comparative example and the third comparative example, which shows that the vaterite prepared by the calcium glycerolate method is not high in stability.
Study of different reaction temperatures on CaCO3Influence of Crystal form and vaterite phase content
EXAMPLE five
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.24g of Na2CO3·H2Completely dissolving O in 9.82mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) simultaneously preserving the heat of the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1 in an ice-water bath at 0 ℃ for 30min, mixing the two solutions, and continuously preserving the heat at 0 ℃ for 60 min;
3) and (3) after the reaction time is terminated, centrifuging the mixture suspension in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the resulting product, as shown in FIG. 2(a), revealed that the resulting CaCO3 consisted of vaterite and calcite phases with the vaterite phase (reaction temperature 0 ℃ C.) content as high as 91.2%.
EXAMPLE six
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.06g of Na2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) simultaneously preserving the heat of the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1 in an ice-water bath at 60 ℃ for 30min, mixing the two solutions, and continuously preserving the heat at 60 ℃ for 60 min;
3) after the reaction time is over, centrifuging the mixture suspension in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, and collecting the obtained white solidAnd drying the powder in an electric heating constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 2(c), and the results revealed that CaCO was obtained3The content of the obtained vaterite phase (with the reaction temperature of 60 ℃) is reduced to 70.9 percent, the content of newly generated aragonite is 1.3 percent, and in the third comparative example and the fifth comparative example, the content of the vaterite phase is rapidly reduced along with the increase of the reaction temperature (between 0 and 60 ℃), the content of the calcite phase is rapidly increased, and the aragonite phase appears at 60 ℃, so that the reaction temperature obviously influences the content of the vaterite phase prepared by the calcium glycerol method, and the increase of the temperature is not beneficial to the formation of metastable vaterite and is promoted to generate the aragonite.
EXAMPLE seven
1) 1.11g of CaCl2Completely dissolving in 25mL of glycerol to prepare a calcium glycerol solution with the concentration of 0.4 mol/L; 1.06g of Na2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 1 mol/L;
2) simultaneously preserving the heat of the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1 in an ice-water bath at 100 ℃ for 30min, mixing the two solutions, and continuously preserving the heat at 100 ℃ for 60 min;
3) and (3) after the reaction time is terminated, centrifuging the mixture suspension in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifugal tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 2(d), and the results revealed that CaCO was obtained3Consists of three phases of vaterite, calcite and aragonite, the content of the obtained vaterite phase (reaction temperature 100 ℃) is reduced to 32.5 percent, the content of newly generated aragonite is 32.3 percent, the content of the vaterite phase is rapidly reduced along with the increase of the reaction temperature (60-100 ℃) in the third comparative example, the fifth comparative example and the sixth comparative example, the aragonite phase appears at 60 ℃,the contents of the calcite phase and the aragonite phase rise rapidly, which indicates that the reaction temperature significantly affects the content of the vaterite phase produced by the calcium glycerol process, and the temperature rise does not favor the formation of metastable vaterite, but rather promotes the formation of aragonite.
Investigation of different reactant concentrations vs. CaCO3Influence of Crystal form and vaterite phase content
Example eight
1) Weighing CaCl according to the molar ratio of 1:12And Na2CO3Pulverizing, adding 0.028g CaCl2Completely dissolved in 25mL of glycerol to prepare a calcium glycerol solution with a concentration of 0.01mol/L, and accordingly, 0.027g of Na was weighed2CO3Completely dissolving the sodium carbonate into 10mL of deionized water to prepare a sodium carbonate solution with the concentration of 0.025 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1 at room temperature (20 ℃), stirring for 2min to enable the calcium glycerol solution and the sodium carbonate aqueous solution to fully react, and not aging, namely, the aging time is 10 min;
3) centrifuging the unaged mixture suspension in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting the obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifuge tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 3(a), and the results revealed that CaCO was obtained3The composite material consists of two phases of vaterite (main phase) and calcite (secondary phase), and the lower concentration (0.01mol/L) of the calcium glycerol solution can greatly improve the content of the vaterite phase, wherein the content of the vaterite phase is as high as 95.7 percent.
Example nine
1) Weighing CaCl according to the molar ratio of 1:12And Na2CO3Powder, 2.775g CaCl2Completely dissolved in 25mL of glycerol to prepare a 1.0mol/L glycerol calcium solution, and 3.10g of Na was weighed in accordance with the amount2CO3·H2Completely dissolving O in 9.55mL of deionized water to prepare a sodium carbonate solution with the concentration of 2.5 mol/L;
2) mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step 1 at room temperature (20 ℃), stirring for 2min to enable the calcium glycerol solution and the sodium carbonate aqueous solution to fully react, and not aging, namely, the aging time is 10 min;
3) centrifuging the unaged mixture suspension in the step 2), then washing with absolute ethyl alcohol twice and washing with deionized water twice, removing calcium chloride by washing with absolute ethyl alcohol, removing sodium carbonate and sodium chloride by washing with deionized water, centrifuging, filtering, collecting the obtained white solid, drying in an electrothermal constant-temperature air-blast drying oven for 5-12h, and finally storing the white powder in a centrifuge tube for subsequent detection. XRD examination of the obtained product was carried out as shown in FIG. 3(c), and the results revealed that CaCO was obtained3Is composed of two phases, vaterite (minor phase) and calcite (major phase), the higher concentration of the calcium glycerolate solution (1.0mol/L) also increases the content of the vaterite phase, which is 87.2% higher than in comparative examples two and eight, and both the lower and higher concentrations of the calcium glycerolate solution increase the content of the vaterite phase, so that the optimum concentration of the calcium glycerolate solution is 0.01mol/L, corresponding to a concentration of 0.025mol/L in the aqueous sodium carbonate solution.
All of the features disclosed in this specification, or all of the methods of making disclosed, may be combined in any combination, except features and/or steps that are mutually exclusive. Any feature disclosed in this specification (including any accompanying claims and abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The above description is only a non-limiting embodiment of the present invention, and many embodiments can be derived, and it will be apparent to those skilled in the art that many modifications and improvements can be made without departing from the inventive concept and without making creative efforts, and these embodiments are all within the protection scope of the present invention.
Claims (5)
1. A method for preparing metastable vaterite calcium carbonate based on a calcium glycerol method is characterized by comprising the following steps:
fully dissolving calcium chloride powder in glycerol to obtain a calcium glycerol solution; fully dissolving sodium carbonate powder in deionized water to obtain a sodium carbonate aqueous solution, wherein the molar ratio of calcium chloride to sodium carbonate is 1:1, and the volume ratio of glycerol to water is 2.5: 1;
step (2) mixing and stirring the calcium glycerol solution and the sodium carbonate aqueous solution in the step (1) at 0-100 ℃, fully reacting, standing and aging to obtain a suspension;
step (3) carrying out centrifugal treatment on the suspension obtained in the step (2), washing the obtained white powder with absolute ethyl alcohol and deionized water in sequence to remove calcium chloride, sodium chloride and sodium carbonate, finally centrifuging and filtering the precipitate, and drying at the temperature of 80-120 ℃ for 5-12 hours;
the calcium chloride in the step (1) is anhydrous calcium chloride, and the sodium carbonate is anhydrous sodium carbonate or hydrated sodium carbonate;
before mixing the calcium glycerol solution and the sodium carbonate aqueous solution in the step (2), preserving heat for 30min at the same temperature, and then mixing at the temperature; and (3) standing and aging for 0-42 h in the step (2).
2. The method for preparing metastable vaterite calcium carbonate based on calcium glyceroxide process of claim 1, wherein the concentration of calcium glyceroxide solution in step (1) is 0.01mol/L and the concentration of sodium carbonate aqueous solution is 0.025 mol/L.
3. The method for preparing metastable vaterite calcium carbonate based on glycerol calcium method according to claim 1, wherein the anhydrous calcium chloride, anhydrous sodium carbonate, hydrated sodium carbonate and glycerol are all analytical grade with concentration more than 99%, and the water is deionized water.
4. The method for preparing metastable vaterite calcium carbonate based on the glycerol-calcium method according to claim 1, characterized in that the calcium carbonate prepared by the method comprises a vaterite phase and a calcite phase, and the mass ratio of the vaterite phase is up to 96.7%.
5. The method for preparing metastable vaterite calcium carbonate based on calcium glyceroxide process of claim 1, wherein the content of the vaterite phase in the calcium carbonate is controlled by changing the concentration of the reactants of calcium glyceroxide solution and aqueous solution of sodium carbonate, the mixing reaction temperature or the standing aging time.
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