CN112876878A - Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof - Google Patents
Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-high whiteness pigment-grade core-shell structure type nano calcium carbonate and a preparation method thereof, relating to the technical field of nano calcium carbonate, and comprising the following steps: (1) adding one or more of ammonium chloride, ammonium bromide and ammonium iodide into the calcium hydroxide slurry, and filtering to obtain a fine filtrate; (2) adding a crystal nucleating agent and a crystal control agent into the fine filtrate, and introducing pure carbon dioxide gas for carbonization reaction to obtain nano calcium carbonate slurry; (3) heating water, adding a surfactant into the water, and continuously adding mutton fat to form uniform emulsion; then adding titanium dioxide into the emulsion, and stirring to form a surface coating agent; (4) and adding the surface coating agent into the nano calcium carbonate slurry for dispersion. The invention has the beneficial effects that the titanium dioxide is coated on the surface of the nano calcium carbonate, so that the dispersibility of the nano calcium carbonate is improved, and the nano calcium carbonate has the advantages of high refractive index, high whiteness value and the like of the titanium dioxide, and can replace the application of the titanium dioxide in the field of pigments.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate, in particular to ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate 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, carbon dioxide gas is introduced into a calcium hydroxide suspension, and a proper crystal form control agent is added for carbonization to produce the calcium carbonate; however, the solubility of calcium hydroxide in water is low, so that calcium ions and carbon dioxide can not react sufficiently, the reaction speed is slow, nano calcium carbonate particles formed by the reaction are not uniform, the particle size is difficult to control, the particle size distribution is wide, and the product agglomeration is obvious. In addition, calcium hydroxide has a special solubility phenomenon, and the higher the temperature is, the lower the solubility is, so that the traditional process needs to react with carbon dioxide at a low temperature, resulting in severe reaction conditions.
Titanium dioxide (TiO)2) Is a white inorganic pigment which exists in nature in three crystal forms of an anatase structure, a rutile structure and a brookite structure. Has non-toxicity, optimal opacity, whiteness and brightness, stable physical and chemical properties and is the best white pigment at present. The method is widely applied to industries such as coating, plastics, papermaking, printing ink, chemical fiber, rubber and the like. Because of the large market demand, high price and the growing shortage of high-quality titanium sources, the production of titanium dioxide substitutes is the first solution to the problem.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a pigment-grade core-shell structure type nano calcium carbonate with ultrahigh whiteness and a preparation method thereof.
The technical solution of the invention is as follows:
a preparation method of ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate comprises the following steps:
(1) adding one or more of ammonium chloride, ammonium bromide and ammonium iodide into the calcium hydroxide slurry for reaction, and filtering the mixed solution after the reaction to obtain a fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal control agent into the fine filtrate, and introducing pure carbon dioxide gas for carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water, adding a surfactant into the water, and continuously adding mutton fat to form uniform emulsion; then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent;
(4) and (3) adding the surface coating agent obtained in the step (3) into the nano calcium carbonate slurry obtained in the step (2), and dispersing to obtain the ultrahigh-whiteness pigment core-shell structure type nano calcium carbonate.
In one embodiment of the invention, in the step (1), ammonium bromide is separately added into the calcium hydroxide slurry for reaction, and the mass ratio of the calcium hydroxide slurry to the ammonium bromide is 70-78: 192-200, and more preferably 74: 196.
In one embodiment of the invention, in the step (1), ammonium iodide is added into the calcium hydroxide slurry separately for reaction, and the mass ratio of the calcium hydroxide slurry to the ammonium iodide is 70-78: 280-300, and more preferably 74: 290.
In a specific embodiment of the invention, in the step (1), the mixed solution after the reaction is filtered, the filtrate is taken, and the filtrate is subjected to sand filtration and activated carbon filtration to obtain the fine filtrate containing calcium ions.
In a specific embodiment of the invention, in the step (2), the crystal nucleating agent is ammonium carbonate, and the addition amount of the crystal nucleating agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate.
In a specific embodiment of the invention, the crystal form control agent is honey, and the addition amount of the crystal form control agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate.
In a specific embodiment of the present invention, the step (3) specifically includes: heating water to 75-85 ℃, adding a surfactant into the water, and continuously adding mutton fat to form uniform emulsion; then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent;
in a specific embodiment of the invention, the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 9-11: 1:1:1, and more preferably 10:1:1: 1.
In one embodiment of the present invention, the surfactant is sodium lauryl sulfate.
In one embodiment of the present invention, in the step (3), the titanium dioxide is rutile type titanium dioxide.
In a specific embodiment of the invention, in the step (4), the addition amount of the surface coating agent is 1-5% of the mass of the dry-based nano calcium carbonate slurry.
The ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate is prepared by the preparation method.
The invention has at least one of the following beneficial effects:
1. according to the invention, one or more of ammonium chloride, ammonium bromide and ammonium iodide are added into the calcium hydroxide slurry to generate calcium chloride or/and calcium bromide or/and calcium iodide and ammonia water, so that the solubility of calcium ions in water is improved, the calcium ions and carbon dioxide gas are convenient to carry out carbonization reaction, the reaction speed is high, the nucleation and growth rate of calcium carbonate crystals are convenient to control, and simultaneously, ammonium carbonate is added as a nucleating agent, and oleic acid is used as a crystal form control agent to form uniform-particle nano calcium carbonate.
2. According to the invention, the surface of the nano calcium carbonate is coated with the coating agent formed by the surfactant, the mutton fat and the titanium dioxide, so that the titanium dioxide is stably coated on the surface of the nano calcium carbonate to form a core-shell structure, the dispersibility of the nano calcium carbonate is improved, and the nano calcium carbonate expresses TiO of the coating layer to a great extent2The product has the advantages of high refractive index, high whiteness, etc. of titanium dioxide, and the price of nano calcium carbonate is lower than that of TiO2The price per se is low, so that the nano calcium carbonate prepared by the method can replace TiO2The method is applied to the fields of papermaking fillers, coatings, pigments and the like.
Detailed Description
A preparation method of ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate comprises the following steps:
(1) calcining limestone, and keeping a certain degree of raw combustion to generate calcium oxide; adding hot water into calcium oxide for digestion, and respectively sieving the digested lime milk with 80-mesh, 120-mesh, 200-mesh, 300-mesh and 400-mesh sieves to generate calcium hydroxide slurry; adding one or more of ammonium chloride, ammonium bromide and ammonium iodide into the calcium hydroxide slurry for reaction, filtering the mixed solution after the reaction to obtain a filtrate, and performing sand filtration and active carbon filtration on the filtrate to obtain a fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal form control agent into the fine filtrate, wherein the crystal nucleating agent is ammonium carbonate, the addition amount of the crystal nucleating agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate, the crystal form control agent is honey, the addition amount of the crystal form control agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate, and introducing pure carbon dioxide gas for carrying out carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water to 75-85 ℃, adding a surfactant into the water, and uniformly stirring, wherein the surfactant is preferably sodium dodecyl sulfate; continuously adding the mutton fat, stirring to form uniform emulsion, then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent; the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 9-11: 1:1: 1.
(4) Adding the surface coating agent in the step (3) into the nano calcium carbonate slurry in the step (2), wherein the adding amount of the surface coating agent is 2-4% of the mass of the dry-based nano calcium carbonate, and dispersing for 40-60 min by using a high-speed dispersion machine;
(5) and (3) carrying out filter pressing dehydration, drying, crushing and grading on the nano calcium carbonate slurry coated on the surface 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 ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate comprises the following steps:
(1) calcining limestone, and keeping a certain degree of raw combustion to generate calcium oxide; adding hot water into calcium oxide for digestion, and respectively sieving the digested lime milk with 80-mesh, 120-mesh, 200-mesh, 300-mesh and 400-mesh sieves to generate calcium hydroxide slurry; adding ammonium bromide into the calcium hydroxide slurry for reaction, wherein the mass ratio of the calcium hydroxide slurry to the ammonium bromide is 72:194, generating calcium bromide and ammonia water, filtering the mixed solution after the reaction to obtain filtrate, and performing sand filtration and active carbon filtration on the filtrate to obtain fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal form control agent into the fine filtrate, wherein the crystal nucleating agent is ammonium carbonate, the addition amount of the crystal nucleating agent is 0.1 percent of the mass of the generated dry-based nano calcium carbonate, the crystal form control agent is honey, the addition amount of the crystal form control agent is 0.1 percent of the mass of the generated dry-based nano calcium carbonate, and pure carbon dioxide gas is introduced for carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water to 75 ℃, adding a surfactant sodium dodecyl sulfate into the water, uniformly stirring, continuously adding mutton fat to form uniform emulsion, then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent; the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 9:1:1: 1.
(4) And (3) adding the surface coating agent obtained in the step (3) into the nano calcium carbonate slurry obtained in the step (2), wherein the adding amount of the surface coating agent is 1% of the mass of the dry-based nano calcium carbonate, and dispersing for 40min by using a high-speed dispersion machine to obtain the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate.
(5) 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 ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate comprises the following steps:
(1) calcining limestone, and keeping a certain degree of raw combustion to generate calcium oxide; adding hot water into calcium oxide for digestion, and respectively sieving the digested lime milk with 80-mesh, 120-mesh, 200-mesh, 300-mesh and 400-mesh sieves to generate calcium hydroxide slurry; adding ammonium bromide into the calcium hydroxide slurry for reaction, wherein the mass ratio of the calcium hydroxide slurry to the ammonium bromide is 74:196, generating calcium bromide and ammonia water, filtering the mixed solution after the reaction to obtain filtrate, and performing sand filtration and active carbon filtration on the filtrate to obtain fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal form control agent into the fine filtrate, wherein the crystal nucleating agent is ammonium carbonate, the addition amount of the crystal nucleating agent is 0.2 percent of the mass of the generated dry-based nano calcium carbonate, the crystal form control agent is honey, the addition amount of the crystal form control agent is 0.2 percent of the mass of the generated dry-based nano calcium carbonate, and pure carbon dioxide gas is introduced for carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water to 80 ℃, adding a surfactant sodium dodecyl sulfate into the water, uniformly stirring, continuously adding mutton fat to form uniform emulsion, then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent; the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 10:1:1: 1. .
(4) And (3) adding the surface coating agent obtained in the step (3) into the nano calcium carbonate slurry obtained in the step (2), wherein the adding amount of the surface coating agent is 2% of the mass of the dry-based nano calcium carbonate, and dispersing for 50min by using a high-speed dispersion machine to obtain the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate.
(5) 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 ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate comprises the following steps:
(1) calcining limestone, and keeping a certain degree of raw combustion to generate calcium oxide; adding hot water into calcium oxide for digestion, and respectively sieving the digested lime milk with 80-mesh, 120-mesh, 200-mesh, 300-mesh and 400-mesh sieves to generate calcium hydroxide slurry; adding ammonium iodide into the calcium hydroxide slurry for reaction, wherein the mass ratio of the calcium hydroxide slurry to the ammonium iodide is 74:290, generating calcium iodide and ammonia water, filtering the mixed solution after the reaction to obtain a filtrate, and performing sand filtration and activated carbon filtration on the filtrate to obtain a fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal form control agent into the fine filtrate, wherein the crystal nucleating agent is ammonium carbonate, the addition amount of the crystal nucleating agent is 0.3 percent of the mass of the generated dry-based nano calcium carbonate, the crystal form control agent is honey, the addition amount of the crystal form control agent is 0.3 percent of the mass of the generated dry-based nano calcium carbonate, and pure carbon dioxide gas is introduced for carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water to 85 ℃, adding a surfactant sodium dodecyl sulfate into the water, uniformly stirring, continuously adding mutton fat to form uniform emulsion, then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent; the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 11:1:1: 1. .
(4) And (3) adding the surface coating agent obtained in the step (3) into the nano calcium carbonate slurry obtained in the step (2), wherein the adding amount of the surface coating agent is 3% of the mass of the dry-based nano calcium carbonate, and dispersing for 60min by using a high-speed dispersion machine to obtain the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate.
(5) 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 4
The difference from example 1 is that: in the step (2), the addition of the crystal nucleating agent is 0.4 percent of the mass of the generated dry-based nano calcium carbonate, and the addition of the crystal control agent is 0.4 percent of the mass of the generated dry-based nano calcium carbonate; in the step (4), the addition amount of the surface coating agent is 4% of the solid content in the nano calcium carbonate slurry.
The rest is the same as example 1.
Example 5
The difference from example 1 is that: in the step (2), the addition of the crystal nucleating agent is 0.5 percent of the mass of the generated dry-based nano calcium carbonate, and the addition of the crystal control agent is 0.5 percent of the mass of the generated dry-based nano calcium carbonate; in the step (4), the addition amount of the surface coating agent is 5% of the solid content in the nano calcium carbonate slurry.
The rest is the same as example 1.
Comparative example 1
The difference from example 1 is that: the traditional carbonization process is adopted, namely, calcium hydroxide slurry is directly subjected to carbonization reaction with carbon dioxide gas.
The rest is the same as example 1.
Comparative example 2
The difference from example 1 is that: titanium dioxide is not added in the surface coating agent.
The rest is the same as example 1.
The specific surface area, oil absorption value, whiteness, refractive index and the like of the nano calcium carbonate prepared in the examples 1 to 3 and the 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, whiteness and refractive index of the nano calcium carbonate prepared in examples 1 to 5 are all significantly higher than those of comparative example 1 (carbonized by a traditional method), comparative example 2 (no titanium dioxide is added in the surface coating agent), and the oil absorption value is lower than those of comparative example 1 (carbonized by a traditional method) and comparative example 2 (no titanium dioxide is added in the surface coating agent), so that the solubility of calcium ions in water can be improved by adding one or more of ammonium chloride, ammonium bromide and ammonium iodide into the calcium hydroxide slurry, the carbonization reaction rate can be controlled, the particle size of the generated nano calcium carbonate can be conveniently controlled, and the dispersibility can be improved; the invention also enables the titanium dioxide to be stably coated on the surface of the nano calcium carbonate by coating the coating agent containing the titanium dioxide on the nano calcium carbonate, so that the prepared nano calcium carbonate has the advantages of high refractive index, high whiteness value and the like of the titanium dioxide, thereby being capable of replacing the application of the titanium dioxide in the field of pigments
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. A preparation method of ultrahigh whiteness pigment-grade core-shell structure type nano calcium carbonate is characterized by comprising the following steps:
(1) adding one or more of ammonium chloride, ammonium bromide and ammonium iodide into the calcium hydroxide slurry for reaction, and filtering the mixed solution after the reaction to obtain a fine filtrate containing calcium ions;
(2) adding a crystal nucleating agent and a crystal control agent into the fine filtrate, and introducing pure carbon dioxide gas for carbonization reaction to obtain nano calcium carbonate slurry;
(3) heating water, adding a surfactant into the water, and continuously adding mutton fat to form uniform emulsion; then adding titanium dioxide into the emulsion, and continuously stirring to form a surface coating agent;
(4) and (3) adding the surface coating agent obtained in the step (3) into the nano calcium carbonate slurry obtained in the step (2), and dispersing to obtain the ultrahigh-whiteness pigment core-shell structure type nano calcium carbonate.
2. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (1), ammonium bromide is added into calcium hydroxide slurry for reaction, and the mass ratio of the calcium hydroxide slurry to the ammonium bromide is 70-78: 192-200.
3. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (1), ammonium iodide is added into calcium hydroxide slurry for reaction, and the mass ratio of the calcium hydroxide slurry to the ammonium iodide is 70-78: 280-300.
4. The method for preparing the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (1), the mixed solution after reaction is filtered, filtrate is obtained, and the filtrate is subjected to sand filtration and activated carbon filtration to obtain fine filtrate containing calcium ions.
5. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (2), the crystal nucleating agent is ammonium carbonate, and the addition amount of the crystal nucleating agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate.
6. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (2), the crystal form control agent is honey, and the addition amount of the crystal form control agent is 0.1-0.5% of the mass of the generated dry-based nano calcium carbonate.
7. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (3), water is heated to 75-85 ℃, and the mass ratio of the water to the surfactant, the mutton fat and the titanium dioxide is 9-11: 1:1: 1.
8. The method for preparing the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (3), the surfactant is sodium dodecyl sulfate, and the titanium dioxide is rutile titanium dioxide.
9. The preparation method of the ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate according to claim 1, wherein in the step (4), the addition amount of the surface coating agent is 1-5% of the mass of the dry-based nano calcium carbonate.
10. The ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN113233490A (en) * | 2021-06-02 | 2021-08-10 | 桐乡市思远环保科技有限公司 | Method for preparing nano calcium carbonate by using natural calcium carbonate |
| CN115109437A (en) * | 2022-07-12 | 2022-09-27 | 龙佰禄丰钛业有限公司 | Preparation method of composite titanium dioxide |
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