CN108840360B - Production method of low-alkalinity nano calcium carbonate - Google Patents
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- C01F11/00—Compounds of calcium, strontium, or barium
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- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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Abstract
The invention discloses a production method of low-alkalinity nano calcium carbonate, which comprises the following steps: carbonizing the calcium hydroxide suspension, and adding a crystal form regulator to obtain nano calcium carbonate slurry; standing the prepared nano calcium carbonate slurry; carbonizing the standing nano calcium carbonate slurry for the second time, and adding an auxiliary additive; carrying out surface modification on the nano calcium carbonate slurry subjected to secondary carbonization; and (5) post-treatment. The low-alkalinity nano calcium carbonate prepared by the method has stable low alkalinity, good diameter uniformity, small length-diameter ratio span and high crystal form purity, has excellent reinforcing performance as a filling agent, and can improve the tensile strength and tensile elongation of a product and reduce the tensile deformation rate.
Description
Technical Field
The invention relates to the technical field of calcium carbonate preparation, in particular to a production method of low-alkalinity nano calcium carbonate.
Background
Calcium carbonate is an inorganic salt industrial product with wide application, can be used as a filling and modifying material, is commonly used in the industries of plastics, rubber, paint, adhesives, paper making, food processing, pharmacy and the like in industry, and has close relation with the daily life of people.
The production method of calcium carbonate which is commonly used in industry at present is to introduce carbon dioxide into calcium hydroxide suspension for carbonization, then to dehydrate, dry, depolymerize and screen to obtain the finished product of calcium carbonate, if the carbonization is controlled under a certain temperature condition in the carbonization process of calcium hydroxide, and a certain crystal form regulator is added, the particle size of calcium carbonate particles can be within 100 nanometers, which is called as nano calcium carbonate, and the nano calcium carbonate has larger specific surface area, high surface activity and strong surface binding energy. The high-quality nano calcium carbonate is applied to high molecular materials, not only plays a role in increasing and filling, but also can endow some polymer composite materials with better processing performance, improve the mechanical property of the composite materials, beautify the appearance of products and play a role in functional modification.
In the process of carbonizing calcium carbonate, the temperature control in the production process, the dosage, the type and the like of the added crystal form regulator are directly related to the crystal form of the nano calcium carbonate, and the crystal form of the nano calcium carbonate prepared by the crystal form regulator for producing the nano calcium carbonate at present has low purity, poor particle size uniformity and large length-diameter ratio span; the adsorption force between particles is equivalent to the self gravity due to small size, and the surface of the untreated nano calcium carbonate is hydrophilic and oleophobic and has poor compatibility with polymers, so that the untreated nano calcium carbonate is difficult to disperse in the composite material. The poorly dispersed nano calcium carbonate not only seriously affects the appearance of the product, but also easily forms internal defects of the material due to the large-size aggregate, and cannot achieve ideal reinforcing effect on polymer materials; in addition, because calcium carbonate is a strong base and a weak acid salt, magnesium ions existing in the form of magnesium carbonate are always contained in the calcium carbonate product to a greater or lesser extent, and the magnesium carbonate has higher solubility in water than the calcium carbonate, the alkalinity obtained by hydrolysis is stronger, and the alkalinity of the prepared nano calcium carbonate is higher, so that the applicability of the nano calcium carbonate is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a production method of low-alkalinity nano calcium carbonate, which has the following specific technical scheme:
a production method of low-alkalinity nano calcium carbonate comprises the following steps:
(1) carbonizing: introducing carbon dioxide into the calcium hydroxide suspension to control the temperature for carbonization, and simultaneously adding a crystal form regulator until the pH of the slurry is less than 7.0 to obtain nano calcium carbonate slurry;
(2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry, adding an auxiliary additive into the nano calcium carbonate slurry, and stirring;
(4) surface treatment: adding a surface coating agent into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: and carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment to obtain the finished product of the low-alkalinity nano calcium carbonate.
As a further improvement of the invention, the crystal form regulator in the step (1) is a mixture of potassium bisulfate, disodium hydrogen phosphate and sodium citrate.
As a further improvement of the invention, in the step (1), the crystal form regulator is potassium bisulfate, disodium hydrogen phosphate and sodium citrate with the mass ratio of (1-4): (2-4): (4-8).
As a further improvement of the invention, the addition amount of the crystal form regulator in the step (1) is 0.1-1.5% of the mass of the nano calcium carbonate slurry.
As a further improvement of the invention, the carbonization temperature in the step (1) is 45-65 ℃.
As a further improvement of the invention, the auxiliary additive in the step (3) is a long-chain alkyl ammonium salt.
As a further improvement of the invention, the long-chain alkylammonium salt is at least one of dodecyldimethylbenzyl ammonium chloride, dioctadecyldimethyl ammonium bromide and octadecyl dimethyl hydroxyethyl ammonium nitrate.
As a further improvement of the invention, the surface coating agent is at least one of octadecadienoic acid, eicosatetraenoic acid and 2-propenyl acrylic acid.
The invention has the beneficial effects that: the low-alkalinity nano calcium carbonate prepared by the method has stable low alkalinity, enlarges the application range of the nano calcium carbonate and improves the acid resistance of the nano calcium carbonate; the low-alkalinity nano calcium carbonate prepared by the method has good particle size uniformity, small length-diameter ratio span and high crystal form purity, and is more beneficial to the industrial application of the nano calcium carbonate; the low-alkalinity nano calcium carbonate prepared by the method has excellent reinforcing performance as a filling agent, and can improve the tensile strength and tensile elongation of a product and reduce the tensile deformation rate.
Drawings
FIG. 1 is a graph showing particle size, aspect ratio and basicity for various examples of the present invention;
FIG. 2 is a table of performance measurements for various embodiments of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A production method of low-alkalinity nano calcium carbonate comprises the following steps:
(1) carbonizing: introducing 2.5m3/min carbon dioxide into 500kg of calcium hydroxide suspension, controlling the temperature at 45 ℃ for carbonization, and simultaneously adding 0.5kg of mixed crystal form regulator of potassium bisulfate, disodium hydrogen phosphate and sodium citrate in a mass ratio of 1:2:4 until the pH of the slurry is less than 7.0 to obtain nano calcium carbonate slurry;
(2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: 1m of calcium carbonate is pumped into the aged nano calcium carbonate slurry3Min carbon dioxide, and simultaneously adding 3kg dodecyl dimethyl benzyl ammonium chloride into the nano calcium carbonate slurry, and stirring;
(4) surface treatment: adding 5kg of octadecadienoic acid and 2-propenyl acrylic acid in the mass ratio of 1:2 into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: and carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment to obtain the finished product of the low-alkalinity nano calcium carbonate.
Example 2
A production method of low-alkalinity nano calcium carbonate comprises the following steps:
(1) carbonizing: introducing 2.5m3/min carbon dioxide into 500kg of calcium hydroxide suspension, controlling the temperature to be 55 ℃ for carbonization, and simultaneously adding 5kg of mixed crystal form regulator of potassium bisulfate, disodium hydrogen phosphate and sodium citrate in a mass ratio of 3:2:6 until the pH value of the slurry is less than 7.0 to obtain nano calcium carbonate slurry;
(2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: 1m of calcium carbonate is pumped into the aged nano calcium carbonate slurry3Min carbon dioxide, and simultaneously adding 3kg dioctadecyl dimethyl ammonium bromide into the nano calcium carbonate slurry, and stirring;
(4) surface treatment: adding 5kg of eicosatetraenoic acid and 2-propenyl acrylic acid in a mass ratio of 1:2 into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: and carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment to obtain the finished product of the low-alkalinity nano calcium carbonate.
Example 3
A production method of low-alkalinity nano calcium carbonate comprises the following steps:
(1) carbonizing: introducing 2.5m3/min carbon dioxide into 500kg of calcium hydroxide suspension, controlling the temperature to be 65 ℃ for carbonization, and simultaneously adding 7.5kg of mixed crystal form regulator of potassium bisulfate, disodium hydrogen phosphate and sodium citrate in a mass ratio of 3:3:5 until the pH of the slurry is less than 7.0 to obtain nano calcium carbonate slurry;
(2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: 1m of calcium carbonate is pumped into the aged nano calcium carbonate slurry3Min carbon dioxide, and simultaneously adding 3kg of sodium octadecyl dimethyl hydroxyethyl ammonium nitrate into the nano calcium carbonate slurry, and stirring;
(4) surface treatment: adding 5kg of octadecadienoic acid, eicosatetraenoic acid and 2-propenyl acrylic acid in a mass ratio of 1:1:2 into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: and carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment to obtain the finished product of the low-alkalinity nano calcium carbonate.
Comparative example
A production method of low-alkalinity nano calcium carbonate comprises the following steps:
(1) carbonizing: introducing 2.5m3/min carbon dioxide into 500kg of calcium hydroxide suspension, controlling the temperature to be 55 ℃ for carbonization, and simultaneously adding 7.5kg of sodium sulfate as a crystal form regulator until the pH of the slurry is less than 7.0 to obtain nano calcium carbonate slurry;
(2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: 1m of calcium carbonate is pumped into the aged nano calcium carbonate slurry3Stirring with carbon dioxide/min;
(4) surface treatment: adding 5kg of 2-propenyl acrylic acid into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: and carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment to obtain the finished product of the low-alkalinity nano calcium carbonate.
Data measurement is carried out on the low-alkalinity nano calcium carbonate obtained in the examples 1 to 3 and the comparative example, and detailed data are shown in figure 1; in addition, an application detection test is carried out on the low-alkalinity nano calcium carbonate, different rubbers are prepared from the low-alkalinity nano calcium carbonate obtained in the examples 1 to 3 and the comparative examples according to the same process, and the performance detection is carried out according to national standards GB/T13477-2002 and GB/T1741-2007, which are shown in figure 2 in detail.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. The production method of the low-alkalinity nano calcium carbonate is characterized by comprising the following steps:
(1) carbonizing: introducing carbon dioxide into the calcium hydroxide suspension to control the temperature for carbonization, and simultaneously adding a crystal form regulator until the pH of the slurry is less than 7.0 to obtain nano calcium carbonate slurry; (2) aging: standing the prepared nano calcium carbonate slurry until the pH value of the nano calcium carbonate slurry is stable;
(3) secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry, adding an auxiliary additive into the nano calcium carbonate slurry, and stirring;
(4) surface treatment: adding a surface coating agent into the nano calcium carbonate slurry subjected to secondary carbonization for surface modification, and stirring;
(5) and (3) post-treatment: carrying out filter pressing, centrifugal dehydration, drying, depolymerization and sieving on the nano calcium carbonate slurry subjected to surface treatment in sequence to obtain a finished product of low-alkalinity nano calcium carbonate;
the crystal form regulator in the step (1) is a mixture of potassium bisulfate, disodium hydrogen phosphate and sodium citrate;
in the step (1), the crystal form regulator is potassium bisulfate, disodium hydrogen phosphate and sodium citrate with the mass ratio of (1-4): (2-4): (4-8);
the addition amount of the crystal form regulator in the step (1) is 0.1-1.5% of the mass of the nano calcium carbonate slurry;
the carbonization temperature in the step (1) is 45-65 ℃;
the auxiliary additive in the step (3) is long-chain alkyl ammonium salt; the long-chain alkyl ammonium salt is at least one of dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium bromide and octadecyl dimethyl hydroxyethyl ammonium nitrate;
the surface coating agent is at least one of octadecadienoic acid, eicosatetraenoic acid and 2-propenyl acrylic acid.
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Denomination of invention: A production method of low alkalinity nano calcium carbonate Effective date of registration: 20230814 Granted publication date: 20210319 Pledgee: Industrial and Commercial Bank of China Co.,Ltd. Xuancheng Xuanzhou Sub branch Pledgor: ANHUI YANGLIUQING CALCIUM INDUSTRY TECHNOLOGY CO.,LTD. Registration number: Y2023980052080 |