Glycerin-stabilized amorphous calcium carbonate as well as preparation method and application thereof

Abstract

The invention provides glycerol-stabilized amorphous calcium carbonate as well as a preparation method and application thereof. The preparation method of the glycerin-stabilized amorphous calcium carbonate comprises the following steps: dissolving a carbon source in a first solvent to obtain a first solution; dissolving a calcium source and a magnesium source in a second solvent to obtain a second solution; adding the second solution into the first solution to obtain a mixed solution, heating the mixed solution, and reacting to obtain a colloidal mixture; washing the colloidal mixture with absolute ethyl alcohol, and drying to obtain glycerol-stabilized amorphous calcium carbonate; wherein the first solvent is glycerol, and the second solvent is absolute ethyl alcohol. The preparation method disclosed by the invention is simple, does not need additional additives, and is low in raw material variety and raw material dosage, low in cost and low in production cost; the prepared calcium carbonate cluster can stably exist in a glycerol and / or absolute ethyl alcohol solution, and no agglomeration phenomenon occurs; the prepared glycerol-stabilized amorphous calcium carbonate can be used in the fields of drying, dehumidification, air water collection and the like.

Description

Technical Field

[0001] The invention relates to the technical field of amorphous calcium carbonate preparation, and in particular to glycerol-stabilized amorphous calcium carbonate and a preparation method and application thereof. Background Art

[0002] Calcium carbonate is one of the most widely distributed minerals in nature. It consists of anhydrous crystalline phases of aragonite, calcite and vaterite, hydrated crystalline phases of hemihydrate calcium carbonate, monohydrate calcium carbonate and hexahydrate calcium carbonate, and amorphous amorphous calcium carbonate. Among them, amorphous calcium carbonate is widely present in the mineralization process of organisms (such as the shells of molluscs, corals, etc.) and in synthetic mineralization systems. Amorphous calcium carbonate in organisms is very stable and can remain stable even if it is extracted from the body. This is due to the regulatory effects of inorganic ions (magnesium ions, phosphate ions, silicate ions, etc.) and acidic organic macromolecules (proteins rich in polyaspartic acid or aspartic acid, etc.) in organisms, so organisms can accurately regulate the crystallization process of amorphous calcium carbonate. Compared with the stable amorphous calcium carbonate in organisms, amorphous calcium carbonate in synthetic systems is very unstable and is easily transformed into a crystalline phase when exposed to water or heated. Therefore, how to use efficient, safe and non-toxic stabilizers to stabilize amorphous calcium carbonate has attracted much attention.

[0003] Common desiccants on the market include calcium chloride, color-changing silica gel, calcium oxide and activated carbon. When they absorb water in the air, they have the disadvantages of melting after absorbing water, low water absorption efficiency and poor water absorption effect. When placed at room temperature of 25°C and relative air humidity of 50% to 60% for 24 hours, the water absorption rate of calcium chloride dihydrate is about 75% (120% for 96 hours), the water absorption rate of magnesium chloride hexahydrate is about 50% (70% for 96 hours), the water absorption rate of calcium oxide is about 35%, the water absorption rate of glycerol is about 38%, the water absorption rate of sodium polyacrylate is about 61%, and the water absorption rate of color-changing silica gel is about 30%. Therefore, the research and development of a new generation of safe, non-toxic, efficient and environmentally friendly desiccant products is an important research topic.

[0004] Amorphous calcium carbonate does not have water-absorbing groups or ions, but when amorphous calcium carbonate particles contain a large amount of calcium ions that fail to form coordination with carbonate ions (calcium ions have strong hydrophilicity), amorphous calcium carbonate will show excellent water absorption. However, artificially synthesized amorphous calcium carbonate is prone to crystallization when it comes into contact with water, so how to prepare amorphous calcium carbonate materials with high water absorption and good cyclic stability is an urgent problem to be solved in this field. Summary of the invention

[0005] In view of this, the present invention aims at the deficiencies of the prior art and proposes a glycerol-stabilized amorphous calcium carbonate and a preparation method and application thereof, so as to solve or at least partially solve the defects of the prior art.

[0006] The present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0008] dissolving a carbon source in a first solvent to obtain a first solution;

[0009] dissolving a calcium source and a magnesium source in a second solvent to obtain a second solution;

[0010] adding the second solution to the first solution to obtain a mixed solution, heating the mixed solution to react and obtain a colloidal mixture;

[0011] The colloidal mixture is washed with anhydrous ethanol and then dried to obtain glycerol-stabilized amorphous calcium carbonate;

[0012] Wherein, the first solvent is glycerol, and the second solvent is anhydrous ethanol.

[0013] Preferably, the carbon source includes at least one of ammonium bicarbonate, ammonium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate;

[0014] And / or, the calcium source includes at least one of calcium chloride dihydrate, calcium chloride hexahydrate, anhydrous calcium chloride, calcium bicarbonate, calcium nitrate, calcium bisulfite, calcium hypochlorite, calcium iodide, calcium permanganate, calcium perchlorate, calcium bisulfate, and calcium bromide;

[0015] And / or, the magnesium source includes at least one of magnesium chloride hexahydrate, anhydrous magnesium chloride, magnesium oxide, magnesium nitrate, magnesium sulfate, and magnesium hydroxide.

[0016] Preferably, the concentration of carbon ions in the mixed solution is less than or equal to 10 mol / L;

[0017] The concentration of calcium ions in the mixed solution is less than or equal to 10 mol / L,

[0018] The molar ratio of calcium ions to carbon ions is (0.1-10):1;

[0019] The molar ratio of calcium ions to magnesium ions is (0.1-10):1.

[0020] Preferably, the volume ratio of glycerol to anhydrous ethanol in the mixed solution is (0.01-1):(0.01-1).

[0021] Preferably, the second solution is added to the first solution to obtain a mixed solution, and the mixed solution is heated, wherein the heating temperature is less than or equal to 100°C.

[0022] Preferably, the second solution is added to the first solution and mixed to obtain a mixed solution;

[0023] Wherein, the mixing method includes at least one of stirring, ultrasound, and vortex oscillation;

[0024] The stirring rate is 100 to 10000 r / min;

[0025] The second solution is added to the first solution at a dropping speed of 0.1 to 10000 mL / min.

[0026] Preferably, after obtaining the colloidal mixture, the colloidal mixture is further subjected to impurity removal, and the impurity removal method comprises at least one of centrifugation, chromatography and dialysis.

[0027] In a second aspect, the present invention also provides a glycerol-stabilized amorphous calcium carbonate, which is prepared by the preparation method.

[0028] Preferably, the glycerol-stabilized amorphous calcium carbonate comprises amorphous calcium carbonate and glycerol, and the glycerol is located inside and / or on the outer surface of the amorphous calcium carbonate nanoparticles;

[0029] The average particle size of the glycerol-stabilized amorphous calcium carbonate is less than or equal to 50 nm.

[0030] In a third aspect, the present invention also provides an application of the glycerol-stabilized amorphous calcium carbonate in drying, dehumidification, and air water collection.

[0031] The preparation method of glycerol-stabilized amorphous calcium carbonate of the present invention has the following advantages over the prior art:

[0032] Beneficial effects:

[0033] 1. The preparation method of glycerol-stabilized amorphous calcium carbonate of the present invention comprises the following steps: adding a second solution to a first solution to obtain a mixed solution, heating the mixed solution, and reacting to obtain a colloidal mixture; washing the colloidal mixture with anhydrous ethanol, and drying the mixture in an oven at a temperature greater than or equal to 50° C. to obtain glycerol-stabilized amorphous calcium carbonate; wherein the colloidal mixture contains an amorphous calcium carbonate material, and the amorphous calcium carbonate material is stable in a mixed solution of glycerol and anhydrous ethanol; the implementation principle of the present invention is as follows: in a mixed solution of glycerol and anhydrous ethanol, carbonate ions and calcium ions form a large number of calcium carbonate clusters, and the calcium carbonate clusters contain uncoordinated calcium ions and / or carbonate ions, which can form a colloidal mixture with hydroxyl groups in glycerol molecules through electrostatic interaction; due to the stabilizing effect of glycerol molecules, the generated calcium carbonate clusters cannot further aggregate and crystallize to form crystalline phase calcium carbonate; on the other hand, the addition of magnesium ions further stabilizes the calcium carbonate clusters. In addition, magnesium ions have strong hydration ability and can hydrate amorphous calcium carbonate; by further using anhydrous ethanol to remove excess glycerol, and drying the anhydrous ethanol, a glycerol-stabilized amorphous calcium carbonate material is obtained; the preparation method of the present invention is simple, does not require additional additives, has a small number of raw material types and raw material amounts, is cheap, and has low production costs; the prepared calcium carbonate clusters can exist stably in glycerol and / or anhydrous ethanol solutions without agglomeration; the raw materials used are carbonates, calcium salts, magnesium salts and glycerol solutions, without the involvement of other toxic substances, and the preparation process and preparation results are non-toxic.

[0034] 2. The glycerol-stabilized amorphous calcium carbonate prepared by the present invention can be used in the fields of drying, dehumidification, air water collection, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the prior art descriptions. Obviously, the drawings described below are only some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0036] Figure 1 is a scanning electron microscope image of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0037] Figure 2 is a transmission electron microscopy image of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0038] Figure 3 is the electron diffraction pattern of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0039] Figure 4is the X-ray diffraction spectrum of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0040] Figure 5 is an infrared spectrum of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0041] Figure 6 This is an energy spectrum analysis diagram of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0042] Figure 7 This is a thermogravimetric curve of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1;

[0043] Figure 8 This is the water absorption curve of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1. DETAILED DESCRIPTION

[0044] To make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them.

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present invention may be in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the numbered ranges, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated in this article, it is meant to include any quoted numbers (fractions or integers) within the indicated range.

[0047] The present application embodiment provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0048] S1, dissolving a carbon source in a first solvent to obtain a first solution;

[0049] S2, dissolving the calcium source and the magnesium source in a second solvent to obtain a second solution;

[0050] S3, adding the second solution to the first solution to obtain a mixed solution, heating the mixed solution to react to obtain a colloidal mixture;

[0051] S4, washing the colloidal mixture with anhydrous ethanol and drying it to obtain glycerol-stabilized amorphous calcium carbonate;

[0052] Wherein, the first solvent is glycerol, and the second solvent is anhydrous ethanol.

[0053] The preparation method of glycerol-stabilized amorphous calcium carbonate of the present application comprises the following steps: adding a second solution to a first solution to obtain a mixed solution, heating the mixed solution, and reacting to obtain a colloidal mixture; washing the colloidal mixture with anhydrous ethanol, and drying the mixture in an oven at a temperature greater than or equal to 50° C. to obtain glycerol-stabilized amorphous calcium carbonate; wherein the colloidal mixture contains an amorphous calcium carbonate material, and the amorphous calcium carbonate material is stable in a mixed solution of glycerol and anhydrous ethanol; the implementation principle of the present invention is as follows: in a mixed solution of glycerol and anhydrous ethanol, carbonate ions and calcium ions form a large number of calcium carbonate clusters, and the calcium carbonate clusters contain uncoordinated calcium ions and / or carbonate ions, which can form a colloidal mixture with hydroxyl groups in glycerol molecules through electrostatic interaction; due to the stabilizing effect of glycerol molecules, the generated calcium carbonate clusters cannot further aggregate and crystallize to form crystalline phase calcium carbonate; on the other hand, the addition of magnesium ions further stabilizes the calcium carbonate clusters. In addition, magnesium ions have strong hydration ability and can hydrate amorphous calcium carbonate; by further using anhydrous ethanol to remove excess glycerol and drying the anhydrous ethanol, a glycerol-stabilized amorphous calcium carbonate material is obtained.

[0054] In some embodiments, the carbon source is carbonate ions, the calcium source is calcium ions, and the magnesium source is magnesium ions.

[0055] In some embodiments, the carbon source includes at least one of ammonium bicarbonate, ammonium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate.

[0056] In some embodiments, the calcium source includes at least one of calcium chloride dihydrate, calcium chloride hexahydrate, anhydrous calcium chloride, calcium bicarbonate, calcium nitrate, calcium bisulfite, calcium hypochlorite, calcium iodide, calcium permanganate, calcium perchlorate, calcium bisulfate, and calcium bromide.

[0057] In some embodiments, the magnesium source includes at least one of magnesium chloride hexahydrate, anhydrous magnesium chloride, magnesium oxide, magnesium nitrate, magnesium sulfate, and magnesium hydroxide.

[0058] In some embodiments, the concentration of carbon ions in the mixed solution is less than or equal to 10 mol / L, for example, the concentration of carbon ions can be 0.5-10 mol / L, specifically, the concentration of carbon ions is 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, and 10 mol / L.

[0059] In some embodiments, the concentration of calcium ions in the mixed solution is less than or equal to 10 mol / L. For example, the concentration of calcium ions may be 0.5 to 10 mol / L. Specifically, the concentration of calcium ions is 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, or 10 mol / L.

[0060] In some embodiments, the molar ratio of calcium ions to carbon ions is (0.1-10):1. Preferably, the molar ratio of calcium ions to carbon ions is greater than or equal to 1:1.

[0061] In some embodiments, the molar ratio of calcium ions to magnesium ions is (0.1-10):1. Preferably, the molar ratio of calcium ions to magnesium ions is greater than or equal to 1:1.

[0062] In some embodiments, the volume ratio of glycerol to anhydrous ethanol in the mixed solution is (0.01-1):(0.01-1), preferably, the volume ratio of glycerol to anhydrous ethanol is greater than or equal to 1:4.

[0063] In some embodiments, the second solution is added to the first solution to obtain a mixed solution, and the mixed solution is heated, wherein the heating temperature is less than or equal to 100°C, for example, the heating temperature is 20-100°C, and the specific heating temperature is 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C.

[0064] In some embodiments, the second solution is added to the first solution and mixed to obtain a mixed solution;

[0065] Wherein, the mixing method includes at least one of stirring, ultrasound, and vortex oscillation;

[0066] In some embodiments, the stirring rate is 100 to 10000 r / min;

[0067] In some embodiments, the second solution is added to the first solution at a dropping speed of 0.1 to 10000 mL / min.

[0068] In some embodiments, 0.2 mol of a carbon source is added to 40-100 mL of glycerol to obtain a first solution.

[0069] In some embodiments, 0.2 mol of a calcium source and 0.2-0.4 mol of a magnesium source are dissolved in 100-160 mL of anhydrous ethanol to obtain a second solution.

[0070] In some embodiments, after obtaining the colloidal mixture, the colloidal mixture is further subjected to impurity removal, and the impurity removal method comprises at least one of centrifugation, chromatography and dialysis.

[0071] The preparation method of glycerol-stabilized amorphous calcium carbonate of the present invention directly utilizes glycerol to synthesize glycerol-stabilized calcium carbonate clusters, further uses anhydrous ethanol to remove excess glycerol, and dries the anhydrous ethanol to obtain a transparent amorphous calcium carbonate material with good water absorption properties. The preparation method of the present invention is simple, does not require additional additives, has a small number of raw material types and raw material usage amounts, is cheap, and has low production costs. The prepared calcium carbonate clusters can exist stably in glycerol and / or anhydrous ethanol solutions without agglomeration. The raw materials used are carbonates, calcium salts, magnesium salts and glycerol solutions, and no other toxic substances are involved, so the preparation process and the preparation results are non-toxic.

[0072] Based on the same inventive concept, the present invention also provides a glycerol-stabilized amorphous calcium carbonate, which is prepared by the above-mentioned preparation method.

[0073] In some embodiments, the glycerol-stabilized amorphous calcium carbonate comprises amorphous calcium carbonate and glycerol, magnesium ions are present in the amorphous calcium carbonate, the glycerol is located inside and / or on the outer surface of the amorphous calcium carbonate nanoparticles, and the glycerol is tightly combined with the amorphous calcium carbonate nanoparticles.

[0074] In some embodiments, the mass ratio of amorphous calcium carbonate to glycerol in the glycerol-stabilized amorphous calcium carbonate is 1:1.

[0075] In some embodiments, the average particle size of the glycerol-stabilized amorphous calcium carbonate is less than or equal to 50 nm.

[0076] Based on the same inventive concept, the present invention also provides an application of glycerol-stabilized amorphous calcium carbonate in the fields of drying, dehumidification, air water collection, etc.

[0077] The following further describes the glycerol-stabilized amorphous calcium carbonate of the present application and its preparation method and application with specific examples. This section further describes the content of the present invention in conjunction with specific examples, but should not be construed as limiting the present invention. If not specifically stated, the technical means adopted in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0078] Example 1

[0079] The present application embodiment provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0080] S1. Dissolve 0.2 mol of ammonium bicarbonate powder in 100 mL of glycerol at 60° C. until the solution becomes clear, to obtain a first solution;

[0081] S2, dissolving 0.2 mol of calcium chloride dihydrate and 0.4 mol of magnesium chloride hexahydrate in 100 mL of anhydrous ethanol to obtain a second solution;

[0082] S3, adding the second solution to the first solution, stirring at 500 r / min to obtain a mixed solution, heating the mixed solution to 60° C., reacting for 1 min to obtain a colloidal mixture;

[0083] S4, ultrasonically dispersing the colloidal mixture into anhydrous ethanol, then centrifuging at a speed of 8000 r / min, and collecting the white colloidal precipitate after centrifugation; further dispersing the white colloidal precipitate with anhydrous ethanol, and centrifuging and washing twice;

[0084] Finally, the washed white colloidal precipitate was placed in an oven at 60° C. to dry, and finally a glycerol-stabilized amorphous calcium carbonate material was obtained.

[0085] Example 2

[0086] The present application embodiment provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0087] S1. Under the condition of 60° C., 0.2 mol of sodium carbonate powder was dissolved in 100 mL of glycerol until the solution became clear, thereby obtaining a first solution;

[0088] S2, dissolving 0.2 mol of calcium chloride dihydrate and 0.4 mol of magnesium chloride hexahydrate in 100 mL of anhydrous ethanol to obtain a second solution;

[0089] S3, adding the second solution to the first solution, stirring at 500 r / min to obtain a mixed solution, heating the mixed solution to 60° C., reacting for 1 min to obtain a colloidal mixture;

[0090] S4, ultrasonically dispersing the colloidal mixture into anhydrous ethanol, then centrifuging at a speed of 8000 r / min, and collecting the white colloidal precipitate after centrifugation; further dispersing the white colloidal precipitate with anhydrous ethanol, and centrifuging and washing twice;

[0091] Finally, the washed white colloidal precipitate was placed in an oven at 60° C. to dry, and finally a glycerol-stabilized amorphous calcium carbonate material was obtained.

[0092] Example 3

[0093] The present application embodiment provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0094] S1. Dissolve 0.2 mol of ammonium carbonate powder in 100 mL of glycerol at 60° C. until the solution becomes clear to obtain a first solution;

[0095] S2, dissolving 0.2 mol of calcium chloride dihydrate and 0.2 mol of magnesium chloride hexahydrate in 100 mL of anhydrous ethanol to obtain a second solution;

[0096] S3, adding the second solution to the first solution, stirring at 500 r / min to obtain a mixed solution, heating the mixed solution to 60° C., reacting for 1 min to obtain a colloidal mixture;

[0097] S4, ultrasonically dispersing the colloidal mixture into anhydrous ethanol, then centrifuging at a speed of 12000 r / min, and collecting the white colloidal precipitate after centrifugation; further dispersing the white colloidal precipitate with anhydrous ethanol, and centrifuging and washing twice;

[0098] Finally, the washed white colloidal precipitate was placed in an oven at 60° C. to dry, and finally a glycerol-stabilized amorphous calcium carbonate material was obtained.

[0099] Example 4

[0100] The present application embodiment provides a method for preparing glycerol-stabilized amorphous calcium carbonate, comprising the following steps:

[0101] S1. Dissolve 0.2 mol of ammonium bicarbonate powder in 40 mL of glycerol at 60° C. until the solution becomes clear, to obtain a first solution;

[0102] S2, dissolving 0.2 mol of calcium chloride dihydrate and 0.4 mol of magnesium chloride hexahydrate in 160 mL of anhydrous ethanol to obtain a second solution;

[0103] S3, adding the second solution to the first solution, stirring at 500 r / min to obtain a mixed solution, heating the mixed solution to 60° C., reacting for 1 min to obtain a colloidal mixture;

[0104] S4, ultrasonically dispersing the colloidal mixture into anhydrous ethanol, then centrifuging at a speed of 8000 r / min, and collecting the white colloidal precipitate after centrifugation; further dispersing the white colloidal precipitate with anhydrous ethanol, and centrifuging and washing twice;

[0105] Finally, the washed white colloidal precipitate was placed in an oven at 60° C. to dry, and finally a glycerol-stabilized amorphous calcium carbonate material was obtained.

[0106] Performance Testing

[0107] Figure 1 This is a scanning electron microscope image of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0108] from Figure 1 It can be seen that the particle size of amorphous calcium carbonate is less than 50nm.

[0109] Figure 2 is a transmission electron micrograph of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1, Figure 3 This is the electron diffraction pattern of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0110] from Figures 2-3 It can be seen that amorphous calcium carbonate is prepared.

[0111] Figure 4 This is the X-ray diffraction spectrum of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0112] from Figure 4 It can be seen that there is no obvious diffraction peak, proving that amorphous calcium carbonate is prepared.

[0113] Figure 5 This is the infrared spectrum of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0114] from Figure 5 As can be seen, there is no 713cm in the picture -1 The infrared peak of , proves that what is prepared is amorphous calcium carbonate.

[0115] Figure 6 This is an energy spectrum analysis diagram of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1. It can be seen from the figure that the magnesium-calcium ratio in the amorphous calcium carbonate is about 1:5, most of the magnesium ions are washed away by anhydrous ethanol, and the magnesium ions cannot completely enter the amorphous calcium carbonate, but only a small amount enters to stabilize the amorphous calcium carbonate.

[0116] Figure 7 This is a thermogravimetric curve of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0117] from Figure 7 It can be seen that the glycerol content of the amorphous calcium carbonate prepared in Example 1 is about 47%.

[0118] Figure 8This is the water absorption curve of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1.

[0119] Specifically, the water absorption test method of the glycerol-stabilized amorphous calcium carbonate prepared in Example 1 is as follows: the glycerol-stabilized amorphous calcium carbonate sample prepared in Example 1 is exposed to an environment with different relative humidity, and the water absorption of the sample in the air is obtained by weighing the change in the sample mass at different times. Specifically, the water absorption calculation formula is: (mass of the sample after water absorption in the air - mass of the initial sample) / mass of the initial sample = water absorption; the relative humidity in the environment in this solution is 40%-50%, 50%-60%, 60%-70%, 70%-80%, 80%-90%, 90%-100%, respectively, and the relative humidity can be measured using a hygrometer or a constant temperature and humidity chamber.

[0120] from Figure 8 It can be seen that the greater the relative humidity in the air, the more obvious the water absorption effect of the amorphous calcium carbonate of the present invention.

[0121] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing glycerol-stabilized amorphous calcium carbonate, characterized in that: The following steps are involved: dissolving a carbon source in a first solvent to obtain a first solution; dissolving a calcium source and a magnesium source in a second solvent to obtain a second solution; adding the second solution to the first solution to obtain a mixed solution, heating the mixed solution to react and obtain a colloidal mixture; The colloidal mixture is washed with anhydrous ethanol and then dried to obtain glycerol-stabilized amorphous calcium carbonate; Wherein, the first solvent is glycerol, and the second solvent is anhydrous ethanol.

2. The method for preparing amorphous calcium carbonate stabilized by glycerol as claimed in claim 1, characterized in that: The carbon source includes at least one of ammonium bicarbonate, ammonium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate; And / or, the calcium source includes at least one of calcium chloride dihydrate, calcium chloride hexahydrate, anhydrous calcium chloride, calcium bicarbonate, calcium nitrate, calcium bisulfite, calcium hypochlorite, calcium iodide, calcium permanganate, calcium perchlorate, calcium bisulfate, and calcium bromide; And / or, the magnesium source includes at least one of magnesium chloride hexahydrate, anhydrous magnesium chloride, magnesium oxide, magnesium nitrate, magnesium sulfate, and magnesium hydroxide.

3. The method for preparing amorphous calcium carbonate stabilized by glycerol as claimed in claim 1, characterized in that: The concentration of carbon ions in the mixed solution is less than or equal to 10 mol / L; The concentration of calcium ions in the mixed solution is less than or equal to 10 mol / L, The molar ratio of calcium ions to carbon ions is (0.1-10):1; The molar ratio of calcium ions to magnesium ions is (0.1-10):

1.

4. The method for preparing amorphous calcium carbonate stabilized by glycerol as claimed in claim 1, characterized in that: The volume ratio of glycerol to anhydrous ethanol in the mixed solution is (0.01-1):(0.01-1).

5. The method for preparing glycerol-stabilized amorphous calcium carbonate according to claim 1, wherein: The second solution is added to the first solution to obtain a mixed solution, and the mixed solution is heated, wherein the heating temperature is less than or equal to 100°C.

6. The method for preparing glycerol-stabilized amorphous calcium carbonate according to claim 1, wherein: adding the second solution to the first solution, mixing, and obtaining a mixed solution; Wherein, the mixing method includes at least one of stirring, ultrasound, and vortex oscillation; The stirring rate is 100 to 10000 r / min; The second solution is added to the first solution at a dropping speed of 0.1 to 10000 mL / min.

7. The method for preparing glycerol-stabilized amorphous calcium carbonate according to claim 1, wherein: After obtaining the colloidal mixture, the colloidal mixture is further subjected to impurity removal, and the impurity removal method comprises at least one of centrifugation, chromatography and dialysis.

8. A glycerol-stabilized amorphous calcium carbonate, characterized in that: The preparation method is as described in any one of claims 1 to 7.

9. The glycerol-stabilized amorphous calcium carbonate according to claim 8, wherein The glycerol-stabilized amorphous calcium carbonate comprises amorphous calcium carbonate and glycerol, and the glycerol is located inside and / or on the outer surface of amorphous calcium carbonate nanoparticles; The average particle size of the glycerol-stabilized amorphous calcium carbonate is less than or equal to 50 nm.

10. Use of the glycerol-stabilized amorphous calcium carbonate as claimed in any one of claims 8 to 9 in drying, dehumidification and air water collection.

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