CN112811456A - Nano calcium carbonate with high specific surface area and preparation method thereof - Google Patents
Nano calcium carbonate with high specific surface area and preparation method thereof Download PDFInfo
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention discloses a nano calcium carbonate with high specific surface area and a preparation method thereof, relating to the technical field of nano calcium carbonate, and comprising the following steps: (1) introducing calcium hydroxide slurry with the temperature of 20-25 ℃ into a carbonization reactor, continuously adding a nucleating agent, introducing high-pressure pure carbon dioxide gas, and stirring at a high speed to generate calcium carbonate crystal nuclei; (2) controlling the temperature of the carbonization reactor below 35 ℃, supplementing 10-15 ℃ calcium hydroxide slurry into the carbonization reactor, continuously adding a crystal nucleus growth control agent, introducing pure carbon dioxide gas, and stirring at a low speed to prepare the high-specific surface area nano calcium carbonate slurry. The method has the beneficial effects that the solubility of the calcium hydroxide in water is inversely proportional to the temperature, the nucleation and growth processes of the nano calcium carbonate are carried out in a carbonization reactor in a stepwise manner, and the nucleation and growth are strictly controlled to be carried out under different conditions, so that the nano calcium carbonate with high specific surface area is prepared.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate, in particular to nano calcium carbonate with high specific surface area and a preparation method thereof.
Background
The nano calcium carbonate is a novel superfine solid powder material developed in the 80 th of the 20 th century, and the particle size of the nano calcium carbonate is between 0.01 and 0.1 mu m. Because of the superfine nano calcium carbonate particles, the crystal structure and the surface electronic structure of the nano calcium carbonate particles are changed, and the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by the common calcium carbonate are generated. At present, the nano calcium carbonate is widely applied to industries such as rubber, plastics, papermaking, chemical building materials, printing ink, coating, sealant, adhesive and the like, particularly, the porous nano calcium carbonate is widely applied as an inorganic material by virtue of the advantages of large specific surface area, no toxicity, good biocompatibility and the like, but the structure, the performance and the application of the porous nano calcium carbonate are seriously influenced by the preparation method and the process thereof, the nano calcium carbonate prepared by different methods presents different structures and crystal forms, and great difficulty is increased on the aspects of precise control, energy conservation, environmental protection, raw material utilization and the like of the production process of the nano calcium carbonate.
The production process of the nano calcium carbonate mainly adopts a carbonization method, mainly comprises production methods such as an intermittent carbonization method, a continuous spray carbonization method, a supergravity carbonization method and the like, namely, kiln gas containing carbon dioxide gas is introduced into calcium hydroxide suspension, and proper crystal form control agent is added for carbonization to produce the calcium carbonate; because calcium hydroxide has a special solubility phenomenon, the higher the temperature is, the lower the solubility is, and in the carbonization process in the prior art, the nucleation and growth conditions of calcium carbonate are not strictly distinguished and controlled, so that the specific surface area of the nano calcium carbonate formed by reaction is large, the particles are non-uniform, the particle size distribution is wide, the product agglomeration is obvious, the quality of the prepared nano calcium carbonate is not high, and the subsequent application of the nano calcium carbonate is influenced.
Disclosure of Invention
The invention aims to solve at least one of the technical problems in the prior art and provides nano calcium carbonate with high specific surface area and a preparation method thereof.
The technical solution of the invention is as follows:
a preparation method of nano calcium carbonate with high specific surface area comprises the following steps:
(1) introducing calcium hydroxide slurry with the temperature of 20-25 ℃ into a carbonization reactor, continuously adding a nucleating agent, introducing high-pressure pure carbon dioxide gas, and stirring at a high speed to generate calcium carbonate crystal nuclei;
(2) controlling the temperature of the carbonization reactor below 35 ℃, supplementing 10-15 ℃ calcium hydroxide slurry into the carbonization reactor, continuously adding a crystal nucleus growth control agent, introducing pure carbon dioxide gas, and stirring at a low speed to prepare the high-specific surface area nano calcium carbonate slurry.
In a specific embodiment of the invention, in the step (1), high-pressure pure carbon dioxide gas is introduced, and the pressure in the carbonization reaction is kept at 0.45-0.55 MPa, more preferably, the pressure is kept at 0.5 MPa; the nucleation reaction time is controlled within 5 min.
In a specific embodiment of the invention, in the steps (1) and (2), the mass percentage concentration of the calcium hydroxide slurry is 8-10%.
In a specific embodiment of the invention, in the step (1), the introduction amount of the calcium hydroxide slurry is 45-55% of the volume of the carbonization reactor; in the step (2), the supplement amount of the calcium hydroxide slurry is 25-35% of the volume of the carbonization reactor.
In one embodiment of the invention, in the step (1), the stirring speed is 920-1000 r/min, more preferably 960 r/min; in the step (2), the stirring speed is 60-100 r/min, and more preferably 80 r/min.
In a specific embodiment of the invention, in the step (1), the nucleating agent is ammonium carbonate, and the addition amount of the nucleating agent is 0.45-0.55% of the mass of the generated dry-based nano calcium carbonate, and more preferably 0.5%.
In a specific embodiment of the invention, in the step (2), the crystal nucleus growth control agent is oleic acid, and the addition amount of the crystal nucleus growth control agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate.
In one embodiment of the present invention, the method further comprises the step (3): and adding a composite surface treatment agent into the prepared high-specific-surface-area nano calcium carbonate slurry for surface treatment, wherein the composite surface treatment agent comprises stearic acid, cocoa butter and caustic soda, and the mass ratio of the stearic acid to the cocoa butter to the caustic soda is 4.5-5.5: 0.5-1.5, and is more preferably 5:5: 1.
In a specific embodiment of the present invention, the step (3) specifically includes: and introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 75-85 ℃, adding a composite surface treatment agent into the activation reaction kettle, wherein the addition amount of the composite surface treatment agent is 5-8% of the mass of the dry-based nano calcium carbonate, and stirring at the speed of 600-700 r/min for 1.5-2.5%.
The nano calcium carbonate with high specific surface area is obtained by adopting the preparation method.
The invention has at least one of the following beneficial effects:
1. according to the method, the nucleation and growth processes of the nano calcium carbonate are carried out step by step in the carbonization reactor, and as the solubility of the calcium hydroxide in water is inversely proportional to the temperature, during the nucleation process, the calcium hydroxide slurry with the concentration of 8-10% and the temperature of 20-25 ℃ is added to 45-55% of the volume of the carbonization reactor, high-pressure pure carbon dioxide gas is introduced, and the high-speed stirring is carried out, so that the calcium hydroxide slurry and the carbon dioxide gas are fully contacted, and a large number of calcium carbonate crystal nuclei are generated; during the growth process, calcium hydroxide slurry with lower temperature is supplemented, the temperature of the carbonization reactor is controlled to be below 35 ℃ so as to improve the solubility of calcium hydroxide in water, normal-pressure pure carbon dioxide gas is introduced, the reaction is stirred at low speed under normal pressure, and the calcium hydroxide slurry and the carbon dioxide gas grow on calcium carbonate crystal nuclei by controlling the reaction rate, so that the nano calcium carbonate with high specific surface area is prepared.
2. The invention also adopts the composite surface treating agent to modify the surface of the nano calcium carbonate, and the composite surface treating agent formed by stearic acid, cocoa butter and caustic soda is subjected to saponification reaction with the surface of the nano calcium carbonate, so that the prepared nano calcium carbonate has good dispersibility and is not easy to agglomerate.
Detailed Description
A preparation method of nano calcium carbonate with high specific surface area comprises the following steps:
(1) calcining limestone to generate calcium oxide, and adding the calcium oxide into the limestone to digest the limestone to generate calcium hydroxide slurry; introducing calcium hydroxide slurry with the mass percentage concentration of 8-10% and the temperature of 20-25 ℃ into a carbonization reactor, wherein the introduction amount of the calcium hydroxide slurry is 45-55% of the volume of the carbonization reactor, continuously adding ammonium carbonate, the addition amount of the ammonium carbonate is 0.45-0.55% of the mass of the generated dry-based nano calcium carbonate, then introducing high-pressure pure carbon dioxide gas, keeping the pressure in the carbonization reaction at 0.45-0.55 MPa, stirring at a high speed of 920-1000 r/min, and generating calcium carbonate crystal nuclei within 5min generally;
(2) controlling the temperature of a carbonization reactor to be below 35 ℃, supplementing 10-15 ℃ calcium hydroxide slurry into the carbonization reactor, wherein the supplement amount of the calcium oxide slurry is 25-35% of the volume of the carbonization reactor, continuously adding oleic acid, the addition amount of the oleic acid is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate, introducing normal-pressure pure carbon dioxide gas, stirring at a low speed of 60-100 r/min, and reacting at normal pressure to prepare the high-specific surface area nano calcium carbonate slurry;
(3) introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 75-85 ℃, adding a composite surface treatment agent into the activation reaction kettle, wherein the adding amount of the composite surface treatment agent is 5-8% of the mass of the dry-based nano calcium carbonate, and stirring at the speed of 600-700 r/min for 1.5-2.5 h; the mass ratio of stearic acid, cocoa butter and caustic soda is 4.5:4.5: 0.5.
(4) And (3) carrying out filter pressing dehydration, drying, crushing and grading on the nano calcium carbonate slurry subjected to surface treatment to obtain a finished product.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A preparation method of nano calcium carbonate with high specific surface area comprises the following steps:
(1) calcining limestone to generate calcium oxide, and adding the calcium oxide into the limestone to digest the limestone to generate calcium hydroxide slurry; introducing calcium hydroxide slurry with the mass percentage concentration of 8% and the temperature of 20 ℃ into a carbonization reactor, wherein the introduction amount of the calcium hydroxide slurry is 45% of the volume of the carbonization reactor, continuously adding ammonium carbonate, the addition amount of the ammonium carbonate is 0.45% of the mass of the generated dry-based nano calcium carbonate, introducing high-pressure pure carbon dioxide gas, keeping the pressure in the carbonization reaction at 0.45MPa, stirring at a high speed of 920r/min, and controlling the reaction time within 5min to generate calcium carbonate crystal nuclei;
(2) controlling the temperature of a carbonization reactor at 20 ℃, supplementing calcium hydroxide slurry with the temperature of 10 ℃ into the carbonization reactor, wherein the supplement amount of the calcium oxide slurry is 25 percent of the volume of the carbonization reactor, continuously adding oleic acid, the addition amount of the oleic acid is 0.2 percent of the mass of the generated dry-based nano calcium carbonate, introducing normal-pressure pure carbon dioxide gas, stirring at a low speed of 60r/min, and reacting at normal pressure to prepare the high-specific surface area nano calcium carbonate slurry;
(3) introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 75 ℃, adding the composite surface treating agent in an amount of 5% of the mass of the dry-based nano calcium carbonate, adding the composite surface treating agent into the activation reaction kettle, and stirring at a speed of 600r/min for 2.5 hours; the mass ratio of stearic acid, cocoa butter and caustic soda is 4.5:4.5: 0.5.
(4) And (3) carrying out filter pressing dehydration, drying, crushing and grading on the nano calcium carbonate slurry subjected to surface treatment to obtain a finished product.
Example 2
A preparation method of nano calcium carbonate with high specific surface area comprises the following steps:
(1) calcining limestone to generate calcium oxide, and adding the calcium oxide into the limestone to digest the limestone to generate calcium hydroxide slurry; introducing 9 mass percent of calcium hydroxide slurry with the temperature of 22 ℃ into a carbonization reactor, wherein the introduction amount of the calcium hydroxide slurry is 50 percent of the volume of the carbonization reactor, continuously adding ammonium carbonate, the addition amount of the ammonium carbonate is 0.5 percent of the mass of the generated dry-based nano calcium carbonate, introducing high-pressure pure carbon dioxide gas, keeping the pressure in the carbonization reaction at 5MPa, stirring at a high speed of 960r/min, and controlling the reaction time within 5min to generate calcium carbonate crystal nuclei;
(2) controlling the temperature of a carbonization reactor at 25 ℃, supplementing calcium hydroxide slurry with the temperature of 12 ℃ into the carbonization reactor, wherein the supplement amount of the calcium oxide slurry is 30 percent of the volume of the carbonization reactor, continuously adding oleic acid, the addition amount of the oleic acid is 0.3 percent of the mass of the generated dry-based nano calcium carbonate, introducing normal-pressure pure carbon dioxide gas, stirring at a low speed of 80r/min, and reacting at normal pressure to prepare the high-specific surface area nano calcium carbonate slurry;
(3) introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 80 ℃, adding a composite surface treatment agent into the activation reaction kettle, wherein the addition amount of the composite surface treatment agent is 6% of the mass of the dry-based nano calcium carbonate, and stirring at the speed of 650r/min for 2 hours; the mass ratio of the stearic acid to the cocoa butter to the caustic soda is 5:5: 1.
(4) And (3) carrying out filter pressing dehydration, drying, crushing and grading on the nano calcium carbonate slurry subjected to surface treatment to obtain a finished product.
Example 3
A preparation method of nano calcium carbonate with high specific surface area comprises the following steps:
(1) calcining limestone to generate calcium oxide, and adding the calcium oxide into the limestone to digest the limestone to generate calcium hydroxide slurry; introducing 10 mass percent of calcium hydroxide slurry at the temperature of 25 ℃ into a carbonization reactor, wherein the introduction amount of the calcium hydroxide slurry is 55 percent of the volume of the carbonization reactor, continuously adding ammonium carbonate, the addition amount of the ammonium carbonate is 0.55 percent of the mass of the dry-based nano calcium carbonate, introducing high-pressure pure carbon dioxide gas, keeping the pressure in the carbonization reaction at 0.55MPa, stirring at a high speed of 1000r/min, and controlling the reaction time within 5min to generate calcium carbonate crystal nuclei;
(2) controlling the temperature of a carbonization reactor at 30 ℃, supplementing calcium hydroxide slurry with the temperature of 15 ℃ into the carbonization reactor, wherein the supplement amount of the calcium oxide slurry is 35 percent of the volume of the carbonization reactor, continuously adding oleic acid, the addition amount of the oleic acid is 0.4 percent of the mass of the generated dry-based nano calcium carbonate, introducing normal-pressure pure carbon dioxide gas, stirring at a low speed of 100r/min, and stirring at normal pressure to prepare the nano calcium carbonate slurry with high specific surface area;
(3) introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 85 ℃, adding a composite surface treatment agent into the activation reaction kettle, wherein the addition amount of the composite surface treatment agent is 8% of the mass of the dry-based nano calcium carbonate, and stirring at the speed of 700r/min for 1.5 hours; the mass ratio of stearic acid, cocoa butter and caustic soda is 5.5:5.5: 1.5.
(4) And (3) carrying out filter pressing dehydration, drying, crushing and grading on the nano calcium carbonate slurry subjected to surface treatment to obtain a finished product.
Comparative example 1
Steps (1) and (2) in example 1 were modified to: calcining limestone to generate calcium oxide, and adding the calcium oxide into the limestone to digest the limestone to generate calcium hydroxide slurry; introducing calcium hydroxide slurry with the mass percentage concentration of 8% and the temperature of 20 ℃ into a carbonization reactor, wherein the introduction amount of the calcium hydroxide slurry is 70% of the volume of the carbonization reactor, continuously adding ammonium carbonate and oleic acid, the addition amount of the ammonium carbonate is 0.45% of the mass of the generated dry-based nano calcium carbonate, the addition amount of the oleic acid is 0.1% of the mass of the generated dry-based nano calcium carbonate, introducing high-pressure pure carbon dioxide gas, keeping the pressure in the carbonization reaction at 0.45MPa, and stirring at the speed of 920r/min until the carbonization end point to obtain the nano calcium carbonate slurry;
the steps (3) and (4) are the same as in example (1).
Comparative example 2
Step (3) in example 1 was removed, and the procedure was otherwise the same as in example 1.
The specific surface area, oil absorption value, dispersibility and the like of the nano calcium carbonate prepared in examples 1 to 3 and comparative examples 2 were measured, and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the specific surface area and the oil absorption value of the nano calcium carbonate prepared in examples 1 to 3 are obviously lower than those of comparative example 1 (the nucleation and the growth are carried out synchronously) and comparative example 2 (the surface treatment is not carried out), and the secondary particle size of the nano calcium carbonate prepared in examples 1 to 3 is below 280nm and is obviously lower than those of comparative example 1 and comparative example 2, so that the nano calcium carbonate with small particle size and large specific surface area can be prepared by carrying out the nucleation and the growth processes of the nano calcium carbonate in a carbonization reactor in a stepwise manner, adopting the composite surface treatment agent and modifying the surface of the nano calcium carbonate, the oil absorption value is low, and meanwhile, the nano calcium carbonate has good dispersibility and is not easy to agglomerate.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the nano calcium carbonate with high specific surface area is characterized by comprising the following steps:
(1) introducing calcium hydroxide slurry with the temperature of 20-25 ℃ into a carbonization reactor, continuously adding a nucleating agent, introducing high-pressure pure carbon dioxide gas, and stirring at a high speed to generate calcium carbonate crystal nuclei;
(2) controlling the temperature of the carbonization reactor below 35 ℃, supplementing 10-15 ℃ calcium hydroxide slurry into the carbonization reactor, continuously adding a crystal nucleus growth control agent, introducing pure carbon dioxide gas, and stirring at a low speed to prepare the high-specific surface area nano calcium carbonate slurry.
2. The preparation method of nano calcium carbonate with high specific surface area according to claim 1, wherein in the step (1), high-pressure pure carbon dioxide gas is introduced, the pressure in the carbonization reaction is kept at 0.45-0.55 MPa, and the reaction time is controlled within 5 min.
3. The method for preparing nano calcium carbonate with high specific surface area according to claim 1, wherein in the steps (1) and (2), the mass percentage concentration of the calcium hydroxide slurry is 8-10%.
4. The preparation method of nano calcium carbonate with high specific surface area according to claim 1, wherein in the step (1), the introduction amount of the calcium hydroxide slurry is 45-55% of the volume of the carbonization reactor; in the step (2), the supplement amount of the calcium hydroxide slurry is 25-35% of the volume of the carbonization reactor.
5. The preparation method of nano calcium carbonate with high specific surface area according to claim 1, wherein in the step (1), the stirring speed is 920-1000 r/min; in the step (2), the stirring speed is 60-100 r/min.
6. The method for preparing nano calcium carbonate with high specific surface area according to claim 1, wherein in the step (1), the nucleating agent is ammonium carbonate, and the addition amount of the nucleating agent is 0.45-0.55% of the mass of the generated dry nano calcium carbonate.
7. The method for preparing nano calcium carbonate with high specific surface area according to claim 1, wherein in the step (2), the crystal nucleus growth control agent is oleic acid, and the addition amount of the crystal nucleus growth control agent is 0.1-0.5% of the mass of the generated dry nano calcium carbonate.
8. The method for preparing nano calcium carbonate with high specific surface area according to claim 1, characterized by further comprising the step (3): and adding a composite surface treatment agent into the prepared high-specific-surface-area nano calcium carbonate slurry for surface treatment, wherein the addition amount of the composite surface treatment agent is 5-8% of the mass of the dry-based nano calcium carbonate, and the composite surface treatment agent comprises stearic acid, cocoa butter and caustic soda.
9. The method for preparing nano calcium carbonate with high specific surface area according to claim 8, wherein the step (3) specifically comprises the following steps: introducing the prepared high-specific surface area nano calcium carbonate slurry into an activation reaction kettle, heating the high-specific surface area nano calcium carbonate slurry to 75-85 ℃, adding a composite surface treating agent into the activation reaction kettle, and stirring at the speed of 600-700 r/min for 1.5-2.5 h; the mass ratio of the stearic acid to the cocoa butter to the caustic soda is 4.5-5.5: 0.5-1.5.
10. A nano calcium carbonate with high specific surface area, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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Cited By (3)
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| CN114752322A (en) * | 2022-05-20 | 2022-07-15 | 广东高士高科实业有限公司 | Low-density high-strength flame-retardant adhesive |
| CN116769253A (en) * | 2023-08-24 | 2023-09-19 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
| CN116789157A (en) * | 2023-05-19 | 2023-09-22 | 广西华纳新材料股份有限公司 | Preparation method of nano calcium carbonate for automobile welding seam sealant |
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| CN114752322A (en) * | 2022-05-20 | 2022-07-15 | 广东高士高科实业有限公司 | Low-density high-strength flame-retardant adhesive |
| CN116789157A (en) * | 2023-05-19 | 2023-09-22 | 广西华纳新材料股份有限公司 | Preparation method of nano calcium carbonate for automobile welding seam sealant |
| CN116769253A (en) * | 2023-08-24 | 2023-09-19 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
| CN116769253B (en) * | 2023-08-24 | 2023-12-12 | 山东路德新材料股份有限公司 | Geogrid modified polypropylene engineering plastic and preparation method and application thereof |
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