CN108083314B - Preparation method of rice-shaped light calcium carbonate - Google Patents
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Abstract
The invention discloses a preparation method of rice-shaped light calcium carbonate, which comprises the steps of calcining limestone by natural gas, adding digestive water to complete a digestion reaction, screening, removing impurities, aging, adding a crystal form control agent, introducing lime kiln gas to carbonize, pumping into a homogenizing tank to age again, introducing purified, cooled and compressed lime kiln gas to perform a secondary carbonization reaction, and preparing calcium carbonate slurry; adding a modifier into the calcium carbonate slurry, stirring, performing filter pressing dehydration, drying, crushing and grading to obtain rice-grain-shaped light calcium carbonate; the light calcium carbonate prepared by the method is rice-grain-shaped, the long diameter is 150-200 nm, the short diameter is 30-50 nm, and the BET specific surface area is 20-22 m2The composite material has the advantages of low length-diameter ratio, high specific surface area, good dispersibility, simple and feasible process, low cost, low price and good economic benefit, and can be used for manufacturing foods, cosmetics and the like.
Description
Technical Field
The invention relates to the technical field of light calcium carbonate preparation, in particular to a preparation method of rice-shaped light calcium carbonate.
Background
Calcium carbonate is a novel inorganic filler with the largest dosage and the widest application, and is widely used as a filler and an additive in the industries of rubber, plastics, papermaking, sealing adhesives, coatings, electric wires, cables, printing ink, welding electrodes, organic synthesis, metallurgy, glass, asbestos industry, medicine, food, daily chemicals, feed and the like due to wide raw materials, low price and high whiteness, so that the calcium carbonate is a white powder material.
Calcium carbonate is classified into two main categories according to different production methods: the product prepared by taking calcite, marble, chalk, shells, limestone and the like as raw materials through mechanical crushing, superfine grinding and the like is heavy calcium carbonate expressed by GCC; the product prepared by calcining, digesting, carbonizing and post-treating limestone which is used as a raw material is called light calcium carbonate and is expressed by PCC; according to whether the surface of the calcium carbonate is modified or not, the calcium carbonate is classified into inactive calcium carbonate and active calcium carbonate, and light calcium carbonate (PCC) and heavy calcium carbonate (GCC) are both active and inactive. The active calcium is divided into dry-method activity and wet-method activity according to different modification modes, wherein the wet-method activity refers to a product subjected to activation treatment in a solution, and the dry-method activity refers to a product subjected to surface activation treatment by adopting a physical method; it can be classified into rubber PCC, plastic PCC, paper PCC, toothpaste PCC, medicinal PCC, and the like according to its use.
In recent years, with the domestic micronization and the improvement of surface treatment technology, the PCC product is developed towards specialization, refinement and functionalization, the application field is further expanded, and the PCC dosage is increased. There are many crystal shapes of PCC, such as cubic, spindle, spherical, chain, amorphous, etc., and different crystal forms have different uses, and hereinafter, detailed analysis is made for calcium carbonate of various crystal shapes, respectively.
Mono-cubic calcium carbonate
Two methods for preparing the cubic ultrafine calcium carbonate at home and abroad are a spray carbonization method for continuously feeding the calcium hydroxide suspension, and an intermittent carbonization method for the calcium hydroxide suspension. In the process of preparing nano calcium carbonate by a carbonization method, a certain amount of additive is added in the growth stage of particles, different reaction conditions are controlled, and cubic nanoparticles (with the particle size of 10-100 nm) with excellent performance can be obtained, wherein the cubic nanoparticles are spindle-shaped when the particle size is larger than 100 nm.
II, spindle-shaped calcium carbonate
The method comprises the steps of carrying out wet grinding and activating treatment on a calcium hydroxide suspension before carbonization, and then carrying out carbonization reaction to obtain a product with the particle size of 0.1-1.0 micron. And no secondary aggregation is generated in the drying process, and the dispersibility is very good.
Three, spherical superfine calcium carbonate
It is usually prepared by reacting calcium salt with carbonate in concentrated alkaline solution at low temperature. Because the product is unstable, some requirements are strictly controlled during the preparation process.
Four, chain-lock calcium carbonate
The chain-like calcium carbonate is formed by combining several to dozens of particles according to a certain direction. The product can avoid agglutination, has good dispersibility, and can be added into matrix to form three-dimensional structure to greatly improve reinforcing effect. The average particle size is generally 0.01 to 0.1 μm, and the aspect ratio is 5 to 50.
Fifthly, amorphous calcium carbonate
Amorphous calcium carbonate, i.e. non-crystalline calcium carbonate, is a new product. Compared with the prior crystal product, the specific surface area of the crystal product is as high as 600m2(ii)/g, about 20 times of the conventional product; the specific gravity of the powder is 1.6-2.5 g/m3Is slightly lighter than common products, has excellent water solubility which is 30 times of that of the common products, and breaks through the concept that calcium carbonate is difficult to dissolve in water.
Sixthly, rice grain-shaped calcium carbonate
Rice-shaped calcium carbonate is an emerging product studied in recent years and is named because its appearance is similar to that of rice. Compared with common spindle calcium carbonate, the rice-shaped calcium carbonate has smaller length-diameter ratio, higher specific surface area and better dispersibility, and has huge application potential in food and cosmetics. However, in the currently disclosed preparation technology, the obtained rice-shaped calcium carbonate has a large particle size and a small specific surface, and is actually only an upgraded substitute of spindle calcium carbonate, and the application effect of the spindle calcium carbonate cannot be exerted.
In summary, in the currently published light calcium carbonate preparation process technology, no report is available about the preparation of ultrafine rice-shaped calcium carbonate, especially the rice-shaped calcium carbonate which can meet the absorption requirements in the food and cosmetic industries.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of rice-shaped light calcium carbonate which can be applied to food and cosmetics.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for preparing rice-shaped light calcium carbonate comprises the following steps,
step one, limestone is taken and calcined by natural gas to prepare calcium oxide;
step two, mixing calcium oxide and digestive water according to the mass ratio of 1: 3-1: 6, placing the mixture into a digestion kettle for digestion reaction after mixing, screening the mixture by a vibrating screen with 300-400 meshes after the digestion reaction is finished, removing impurities to obtain calcium hydroxide refined pulp, and aging the calcium hydroxide refined pulp in an aging tank for more than 40 hours;
step three, adjusting the concentration of the aged calcium hydroxide fine slurry to 1-1.5 mol/L, adding a crystal form control agent accounting for 0.1-0.5% of the dry basis weight of limestone, and adjusting the temperature to 30-40 ℃;
step four, conveying the calcium hydroxide fine slurry prepared in the step three to a carbonization kettle for carbonization, leading the filling coefficient of the carbonization kettle to be 0.80-0.85, introducing purified, cooled and compressed lime kiln gas for carbonization reaction, wherein the kiln gas flow is 60-70 m3Min, wherein the volume content of carbon dioxide is 30-35%, and carbonization is stopped when the pH of a reaction system is 6.5-7.5;
pumping the carbonized calcium hydroxide fine slurry into a homogenizing tank for aging for 6-12 hours, introducing purified, cooled and compressed lime kiln gas for secondary carbonization reaction, wherein the kiln gas flow is 10-20 m3The reaction system is characterized by comprising the following steps of (1)/min, wherein the volume content of carbon dioxide is 30-35%, and when the pH value of the reaction system is 6.5-7.5, the carbonization is stopped to prepare calcium carbonate slurry;
adding a modifier accounting for 3-4% of the dry weight of limestone into the calcium carbonate slurry, stirring and heating to 80-90 ℃, and stirring for 30-60 minutes;
and seventhly, sequentially carrying out filter pressing dehydration, drying, crushing and grading on the slurry obtained in the sixth step to obtain the rice-grain-shaped light calcium carbonate, wherein the long diameter of the rice-grain-shaped light calcium carbonate is 150-200 nm, the short diameter of the rice-grain-shaped light calcium carbonate is 30-50 nm, and the BET specific surface area of the rice-grain-shaped light calcium carbonate is 20-22 m2/g。
As a preferable technical scheme, the limestone has the external dimension of 10-18 cm, the purity is more than or equal to 99.0 percent in percentage of CaCO3, and the whiteness is more than or equal to 95.0.
According to the preferable technical scheme, the pH value range of the digestion water is 6.0-8.0, and the use temperature of the digestion water is 50-60 ℃.
As a preferable technical scheme, the crystal form control agent comprises ethylenediamine, diethylenetriamine and triethylene tetramine.
As an improvement to the technical scheme, the modifier is a mixture of food-grade monoglyceride and diglyceride, and the mixing ratio of the monoglyceride to the diglyceride is 1: 3-1: 5.
due to the adoption of the technical scheme, the invention has the beneficial effects that: the light calcium carbonate prepared by the method is rice-grain-shaped, the long diameter is 150-200 nm, the short diameter is 30-50 nm, and the BET specific surface area is 20-22 m2The composite material has the advantages of low length-diameter ratio, high specific surface area, good dispersibility, simple and feasible process, low cost, low price and good economic benefit, and can be used for manufacturing foods, cosmetics and the like.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:
FIG. 1 is an electron micrograph of rice-grain-shaped precipitated calcium carbonate produced in accordance with an example of the present invention.
Detailed Description
The invention is further illustrated below with reference to the figures and examples. In the following detailed description, certain exemplary embodiments of the present invention are described by way of illustration only. Needless to say, a person skilled in the art realizes that the described embodiments can be modified in various different ways without departing from the spirit and scope of the present invention. Accordingly, the drawings and description are illustrative in nature and not intended to limit the scope of the claims.
The first embodiment is as follows:
a method for preparing rice-shaped light calcium carbonate comprises the following steps,
step one, limestone is taken and calcined by natural gas to prepare calcium oxide;
step two, mixing calcium oxide and digestive water according to the mass ratio of 1:5, placing the mixture into a digestion kettle for digestion reaction after mixing, screening the mixture by a vibrating screen with 320 meshes after the digestion reaction is finished, removing impurities to obtain calcium hydroxide refined slurry, and aging the calcium hydroxide refined slurry in an aging tank for 50 hours;
step three, adjusting the concentration of the aged calcium hydroxide seminal plasma to 1.2mol/L, adding a crystal form control agent accounting for 0.4 percent of the dry basis weight of limestone, and adjusting the temperature to 30 ℃; the crystal form control agent comprises a mixture of ethylenediamine, diethylenetriamine and triethylene tetramine, wherein the weight ratio of ethylenediamine, diethylenetriamine and triethylene tetramine is 2: 2: 1, and mixing.
Step four, conveying the calcium hydroxide fine pulp prepared in the step three to 50m3The stainless steel stirring carbonization kettle is carbonized to ensure that the filling coefficient of the carbonization kettle is 0.80, purified, cooled and compressed lime kiln gas is introduced for carbonization reaction, and the kiln gas flow is 60m3Min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7;
pumping the carbonized calcium hydroxide fine slurry into a homogenizing tank for aging for 6 hours, and introducing purified, cooled and compressed lime kiln gas for secondary carbonization reaction, wherein the kiln gas flow is 10m3The reaction system is characterized by comprising the following steps of (1)/min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7 to prepare calcium carbonate slurry;
step six, adding a modifier which accounts for 3.5 percent of the dry basis weight of the limestone into the calcium carbonate slurry, stirring and heating to 80 ℃, and stirring for 45 minutes; the modifier is a mixture of food-grade monoglyceride and diglyceride, and the mixing ratio of the monoglyceride to the diglyceride is 1: 4.
and seventhly, sequentially carrying out filter pressing dehydration, drying, crushing and grading on the slurry obtained in the sixth step to obtain the rice-grain-shaped light calcium carbonate, wherein the long diameter of the rice-grain-shaped light calcium carbonate is 150-200 nm, the short diameter of the rice-grain-shaped light calcium carbonate is 30-50 nm, and the BET specific surface area of the rice-grain-shaped light calcium carbonate is 20.15m2/g。
Specific indexes of limestone selected in this example are shown in table 1:
TABLE 1
FIG. 1 shows an electron micrograph of the rice-grain-shaped precipitated calcium carbonate produced in this example.
Specific indexes of the selected digested water in this example are shown in table 2:
TABLE 2
Example two:
a method for preparing rice-shaped light calcium carbonate comprises the following steps,
step one, limestone is taken and calcined by natural gas to prepare calcium oxide;
step two, mixing calcium oxide and digestive water according to the mass ratio of 1:5, placing the mixture into a digestion kettle for digestion reaction after mixing, screening the mixture by a vibrating screen with 320 meshes after the digestion reaction is finished, removing impurities to obtain calcium hydroxide refined slurry, and aging the calcium hydroxide refined slurry in an aging tank for 45 hours;
step three, adjusting the concentration of the aged calcium hydroxide seminal plasma to 1.5mol/L, adding a crystal form control agent accounting for 0.5 percent of the dry basis weight of limestone, and adjusting the temperature to 33 ℃; the crystal form control agent comprises a mixture of ethylenediamine, diethylenetriamine and triethylene tetramine, wherein the weight ratio of ethylenediamine, diethylenetriamine and triethylene tetramine is 1: 1: 1, and mixing.
Step four, conveying the calcium hydroxide fine pulp prepared in the step three to 50m3The stainless steel stirring carbonization kettle is carbonized to ensure that the filling coefficient of the carbonization kettle is 0.80, purified, cooled and compressed lime kiln gas is introduced for carbonization reaction, the kiln gas flow is 65m3Min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7;
pumping the carbonized calcium hydroxide fine slurry into a homogenizing tank for aging for 12 hours, introducing purified, cooled and compressed lime kiln gas for secondary carbonization reaction, wherein the kiln gas flow is 15m3The reaction system is characterized by comprising the following steps of (1)/min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7 to prepare calcium carbonate slurry;
adding a modifier accounting for 4 percent of the dry weight of the limestone into the calcium carbonate slurry, stirring and heating to 85 ℃, and stirring for 50 minutes; the modifier is a mixture of food-grade monoglyceride and diglyceride, and the mixing ratio of the monoglyceride to the diglyceride is 1: 3.
and seventhly, sequentially carrying out filter pressing dehydration, drying, crushing and grading on the slurry obtained in the sixth step to obtain the rice-grain-shaped light calcium carbonate, wherein the long diameter of the rice-grain-shaped light calcium carbonate is 150-200 nm, the short diameter of the rice-grain-shaped light calcium carbonate is 30-50 nm, and the BET specific surface area of the rice-grain-shaped light calcium carbonate is 20.37m2/g。
The specific indexes of limestone and the digestion water selected in the embodiment are similar to those of the first embodiment.
Example three:
a method for preparing rice-shaped light calcium carbonate comprises the following steps,
step one, limestone is taken and calcined by natural gas to prepare calcium oxide;
step two, mixing calcium oxide and digestive water according to the mass ratio of 1:5, placing the mixture into a digestion kettle for digestion reaction after mixing, screening the mixture by a vibrating screen with 320 meshes after the digestion reaction is finished, removing impurities to obtain calcium hydroxide refined slurry, and aging the calcium hydroxide refined slurry in an aging tank for 60 hours;
step three, adjusting the concentration of the aged calcium hydroxide fine slurry to 1mol/L, adding a crystal form control agent accounting for 0.3 percent of the dry basis weight of limestone, and adjusting the temperature to 32 ℃; the crystal form control agent comprises a mixture of ethylenediamine, diethylenetriamine and triethylene tetramine, wherein the weight ratio of ethylenediamine, diethylenetriamine and triethylene tetramine is 1: 3: 2, and mixing.
Step four, conveying the calcium hydroxide fine pulp prepared in the step three to 50m3The stainless steel stirring carbonization kettle is carbonized to ensure that the filling coefficient of the carbonization kettle is 0.80, purified, cooled and compressed lime kiln gas is introduced for carbonization reaction, and the kiln gas flow is 70m3Min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7;
step five, pumping the carbonized calcium hydroxide fine slurry into a homogenizing tank for aging for 8 hours, and introducing into a lime kiln after purification, cooling and compressionThe gas is subjected to secondary carbonization reaction, and the kiln gas flow is 20m3The reaction system is characterized by comprising the following steps of (1)/min, wherein the volume content of carbon dioxide is 30-32%, and the carbonization is stopped when the PH of the reaction system is 7 to prepare calcium carbonate slurry;
step six, adding a modifier accounting for 3.8 percent of the dry basis weight of the limestone into the calcium carbonate slurry, stirring and heating to 90 ℃, and stirring for 30 minutes; the modifier is a mixture of food-grade monoglyceride and diglyceride, and the mixing ratio of the monoglyceride to the diglyceride is 1: 5.
and seventhly, sequentially carrying out filter pressing dehydration, drying, crushing and grading on the slurry obtained in the sixth step to obtain the rice-grain-shaped light calcium carbonate, wherein the long diameter of the rice-grain-shaped light calcium carbonate is 150-200 nm, the short diameter of the rice-grain-shaped light calcium carbonate is 30-50 nm, and the BET specific surface area of the rice-grain-shaped light calcium carbonate is 21.52m2/g。
The specific indexes of limestone and the digestion water selected in the embodiment are similar to those of the first embodiment. The specific technical indexes of the rice-shaped light calcium carbonate prepared by controlling the process parameters in the first, second and third examples are shown in table 3:
TABLE 3
The light calcium carbonate prepared by the method is rice-grain-shaped, the long diameter is 150-200 nm, the short diameter is 30-50 nm, and the BET specific surface area is 20-22 m2The composite material has the advantages of low length-diameter ratio, high specific surface area, good dispersibility, simple and feasible process, low cost, low price and good economic benefit, and can be used for manufacturing foods, cosmetics and the like.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. A method for preparing rice-shaped light calcium carbonate is characterized in that: comprises the following steps of (a) carrying out,
step one, limestone is taken and calcined by natural gas to prepare calcium oxide;
step two, mixing calcium oxide and digestive water according to the mass ratio of 1: 3-1: 6, placing the mixture into a digestion kettle for digestion reaction after mixing, screening the mixture by a vibrating screen with 300-400 meshes after the digestion reaction is finished, removing impurities to obtain calcium hydroxide refined pulp, and aging the calcium hydroxide refined pulp in an aging tank for more than 40 hours;
the pH value range of the digestion water is 6.0-8.0, and the use temperature of the digestion water is 50-60 ℃;
step three, adjusting the concentration of the aged calcium hydroxide fine slurry to 1-1.5 mol/L, adding a crystal form control agent accounting for 0.1-0.5% of the dry basis weight of limestone, and adjusting the temperature to 30-40 ℃;
the crystal form control agent comprises ethylenediamine, diethylenetriamine and triethylene tetramine;
step four, conveying the calcium hydroxide fine slurry prepared in the step three to a carbonization kettle for carbonization, leading the filling coefficient of the carbonization kettle to be 0.80-0.85, introducing purified, cooled and compressed lime kiln gas for carbonization reaction, wherein the kiln gas flow is 60-70 m3Min, wherein the volume content of carbon dioxide is 30-35%, and carbonization is stopped when the pH of a reaction system is 6.5-7.5;
pumping the carbonized calcium hydroxide fine slurry into a homogenizing tank for aging for 6-12 hours, introducing purified, cooled and compressed lime kiln gas for secondary carbonization reaction, wherein the kiln gas flow is 10-20 m3Min, wherein the volume content of carbon dioxide is 30-35%, and the carbonization is stopped when the pH of a reaction system is 6.5-7.5 to prepare calcium carbonate slurry;
adding a modifier accounting for 3-4% of the dry weight of limestone into the calcium carbonate slurry, stirring and heating to 80-90 ℃, and stirring for 30-60 minutes;
the modifier is a mixture of food-grade monoglyceride and diglyceride, and the mixing ratio of the monoglyceride to the diglyceride is 1: 3-1: 5;
and seventhly, sequentially carrying out filter pressing dehydration, drying, crushing and grading on the slurry obtained in the sixth step to obtain the rice-grain-shaped light calcium carbonate, wherein the long diameter of the rice-grain-shaped light calcium carbonate is 150-200 nm, the short diameter of the rice-grain-shaped light calcium carbonate is 30-50 nm, and the BET specific surface area of the rice-grain-shaped light calcium carbonate is 20-22 m2/g。
2. The process for producing rice-shaped light calcium carbonate according to claim 1, wherein: the limestone has the external dimension of 10-18 cm and the purity of CaCO3The percentage content of the white cast iron is more than or equal to 99.0 percent, and the whiteness is more than or equal to 95.0.
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| CN111559752A (en) * | 2020-05-20 | 2020-08-21 | 建德市双超钙业有限公司 | Production method of nano calcium carbonate for PE direct film blowing |
| CN111874933A (en) * | 2020-08-14 | 2020-11-03 | 王权广 | Quick preparation process of rice-grain light calcium carbonate |
| CN115571903A (en) * | 2022-09-09 | 2023-01-06 | 广东翔龙科技股份有限公司 | Preparation method of high-end calcium carbonate applied to sunscreen cream |
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| CN107792872A (en) * | 2017-10-20 | 2018-03-13 | 马鞍山博广纳米新材料有限公司 | A kind of preparation technology of spindle nano-calcium carbonate |
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| CN107792872A (en) * | 2017-10-20 | 2018-03-13 | 马鞍山博广纳米新材料有限公司 | A kind of preparation technology of spindle nano-calcium carbonate |
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| 一种高分散、高填充、无载体纳米碳酸钙母料的制备;谢文清;《广东化工》;20101231;第37卷(第12期);第45-47页 * |
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