CN109574057B - Preparation method of calcium carbonate - Google Patents
Preparation method of calcium carbonate Download PDFInfo
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- C01F11/00—Compounds of calcium, strontium, or barium
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Abstract
The invention discloses a preparation method of calcium carbonate, which comprises the following steps: calcining limestone at high temperature, adding the calcined product into a mixed solution of acetone and water, and adding the mixed solution into a supercritical device for soaking to obtain lime milk; introducing lime kiln smoke containing carbon dioxide into the lime milk for carbonization to obtain coarse calcium carbonate slurry; adding the crude calcium carbonate slurry into a supercritical reaction device, adding a crystal form control agent and ethanol, sealing the device, introducing carbon dioxide for reaction, releasing pressure, cooling to room temperature, introducing into a vertical filter press for pressurization and filtration, drying the filtered calcium carbonate, and crushing to obtain the calcium carbonate. The calcium carbonate prepared by the method has high purity and high dispersibility.
Description
Technical Field
The invention relates to a preparation method of an inorganic raw material, in particular to a preparation method of calcium carbonate.
Background
Calcium carbonate is an important functional inorganic filler, has the advantages of low price, abundant reserves, stable performance, easy processing, no toxicity and the like, can obviously improve the processing performance and physical performance of materials, reduce the production cost and the like, is widely applied to the fields of plastics, rubber, coatings, papermaking and the like, and currently, the domestic current industrial preparation method of calcium carbonate is as follows:
ca (OH) at a certain concentration and a certain temperature2Introducing the washed lime kiln flue gas containing carbon dioxide into the suspension for carbonization to ensure that Ca (OH)2And (3) continuously reducing the pH value of the suspension, carbonizing to reach the end point after the pH value reaches 7.0 to prepare calcium carbonate slurry, dehydrating and drying the prepared calcium carbonate slurry, depolymerizing the dried calcium carbonate aggregate, and sieving to remove coarse particles to obtain the finished product calcium carbonate powder. Or adding saponified fatty acid into the prepared calcium carbonate slurry to coat the liquid phase surface of calcium carbonate particles, then dehydrating and drying the calcium carbonate slurry, and adding the process to prepare the calcium carbonate product with hydrophobic and oleophilic properties, namely the calcium carbonate. If on Ca (OH)2The carbonization process comprises the steps of controlling the carbonization to be carried out under a certain temperature condition, adding a certain crystal form regulator to ensure that the particle size of calcium carbonate particles is within 100 nanometers and is called as nano calcium carbonate, then aging the prepared nano calcium carbonate slurry, adding saponified fatty acid into the aged nano calcium carbonate slurry to carry out liquid phase surface coating on evenly dispersed cubic nano calcium carbonate particles, then dehydrating and drying the nano calcium carbonate slurry, depolymerizing and sieving nano calcium carbonate aggregates obtained after drying to obtain the nano active calcium carbonate. The calcium carbonate obtained by the method generally has the defects of insufficient powder fineness, poor dispersibility and products in the application processPoor self-degradation performance and the like.
In addition, because calcium carbonate is a hydrophilic compound, the defects of insufficient compatibility with organic polymers, poor dispersibility and the like exist in practical application, and a satisfactory filling reinforcing effect cannot be achieved, so that the calcium carbonate needs to be modified to improve the dispersibility and compatibility in various materials so as to achieve the effect of improving the product performance.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing calcium carbonate, comprising the steps of:
calcining limestone at 1000-1280 ℃, adding 50-80 parts of calcined product into 200-300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 30-90 min in a supercritical acetone-water system at 360-400 ℃ and 15-25 MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow rate of 0.5-1.5 m3The washed lime kiln smoke containing 30-50% of carbon dioxide is carbonized for 6-12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 70-80 ℃ is introduced into the lime milk at a speed of 200-300 mL/min;
adding 50-100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, adding 3-10 parts by weight of a crystal form control agent and 5-8 parts by weight of ethanol, introducing carbon dioxide to react for 5-8 hours under the conditions of 12-25 MPa and 60-80 ℃ after the device is sealed, then releasing the pressure, cooling to room temperature, introducing the mixture into a vertical filter press for pressurization and filtration, drying the filtered calcium carbonate, and crushing the calcium carbonate to obtain the calcium carbonate.
Preferably, the crystal form control agent comprises the following raw materials in parts by weight: 3-5 parts of polyacrylic acid, 1.5-2.5 parts of triethanolamine, 0.1-0.2 part of potassium hydrogen phthalate, 0.3-0.5 part of glycolic acid, 0.1-0.3 part of 1-ethyl-3-methylimidazolium lactic acid, 0.3-0.5 part of sodium salicylate and 0.1-0.2 part of poly dimethyl diallyl ammonium chloride.
Preferably, the crystal form control agent comprises the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of poly dimethyl diallyl ammonium chloride.
Preferably, in the third step, the obtained calcium carbonate is subjected to the following treatment processes: placing calcium carbonate in a low-temperature plasma treatment instrument for treatment for 10-15 min, then adding the calcium carbonate into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin bis (isooctyl) dimercaptoacetate into the stirrer, uniformly stirring, and then placing the mixture in a low-temperature plasma treatment instrument60And (4) carrying out radiation in a Co gamma radiation field, wherein the placing position is 130-150 Gy-1The absorption dose rate is 100-200 kGy.
Preferably, the atmosphere of the low-temperature plasma processor is argon or nitrogen; the frequency of the low-temperature plasma processor is 40-70 KHz, the power is 35-80W, and the pressure is 30-80 Pa.
Preferably, the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 1-3: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 0.5-1.5: 100.
Preferably, the method further comprises the following modification process of the calcium carbonate after the irradiation treatment: adding 15-30 parts by weight of irradiated calcium carbonate, 20-25 parts by weight of butyl acrylate, 3-5 parts by weight of allylthiourea, 5-10 parts by weight of diallyldimethylammonium chloride, 0.03-0.12 part by weight of ammonium percarbonate and 150-200 parts by weight of water into a supercritical reaction device, uniformly stirring, sealing the system, introducing carbon dioxide to react for 1-3 hours at the temperature of 60-75 ℃ under the pressure of 25-35 MPa, releasing pressure, precipitating with ethanol, drying, and eluting with butanone to remove homopolymers generated by the reaction, thereby obtaining the modified calcium carbonate.
Preferably, in the first step, the temperature rising process adopted by the calcination is as follows: heating to 600-800 ℃ at the speed of 5-10 ℃/min, preserving heat for 30min, continuously heating to 800-1000 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, then heating to 1100-1280 ℃ at the speed of 1-2 ℃/min, and preserving heat for 1-3 h.
The invention at least comprises the following beneficial effects:
(1) according to the invention, the calcined product is treated in supercritical water, so that the product purity of the generated lime milk with uniform dispersion is improved, and the prepared calcium carbonate has high purity and high dispersibility by means of carbonization in a supercritical reaction device.
(2) The calcium carbonate is subjected to low-temperature plasma treatment and further modified, so that the obtained modified calcium carbonate has high compatibility and dispersibility with organic polymers, and the performance of the organic polymers is improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1100 ℃, adding 80 parts of calcined product into 300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 60min in a supercritical acetone-water system at 380 ℃ and 22MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step twoThe flow rate of the lime milk is 1m3The lime kiln smoke containing 40 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 300 mL/min;
and step three, adding 100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 10 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 25MPa after the device is sealed, reacting for 8 hours at the temperature of 80 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying the calcium carbonate obtained after filtration, and crushing to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 30min, heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 2h, heating to 1100 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of poly dimethyl diallyl ammonium chloride.
The purity of the calcium carbonate obtained in the embodiment is 99.94%, the whiteness is 96%, and the particle size distribution is 0.5-5 um.
Example 2:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1200 ℃, adding 60 parts of calcined product into 250 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 90min in a supercritical acetone-water system at 380 ℃ and 25MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow rate of 1.2m3The lime kiln smoke containing 35 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; during the carbonization process, simultaneouslyIntroducing 80 ℃ nitrogen into the lime milk at the speed of 250 mL/min;
adding 80 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 8 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 20MPa after the device is sealed, reacting for 8 hours at the temperature of 70 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying and crushing the calcium carbonate obtained after filtration to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 30min, continuing heating to 1000 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 2h, heating to 1200 deg.C at a speed of 1 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 5 parts of polyacrylic acid, 2.5 parts of triethanolamine, 0.1 part of potassium hydrogen phthalate, 0.5 part of glycolic acid, 0.3 part of 1-ethyl-3-methylimidazolium lactic acid, 0.5 part of sodium salicylate and 0.1 part of polydimethyldiallyl ammonium chloride.
The purity of the calcium carbonate obtained in the embodiment is 99.95%, the whiteness is 97%, and the particle size distribution is 0.5-5.5 um.
Example 3:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1100 ℃, adding 80 parts of calcined product into 300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 60min in a supercritical acetone-water system at 380 ℃ and 22MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow of 1m3The lime kiln smoke containing 40 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 300 mL/min;
and step three, adding 100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 10 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 25MPa after the device is sealed, reacting for 8 hours at the temperature of 80 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying the calcium carbonate obtained after filtration, and crushing to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 30min, heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 2h, heating to 1100 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of polydimethyldiallyl ammonium chloride;
in the third step, the obtained calcium carbonate is subjected to the following treatment processes: treating calcium carbonate in a low-temperature plasma treatment instrument for 15min, adding into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin isooctyl dimercaptoacetate into the stirrer, stirring uniformly, and placing into a container60The radiation is carried out in a Co gamma radiation field, and the placing position is selected to be 150Gy.min-1The absorbed dose rate of (1) is 200 kGy; the atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 60KHz, the power is 40W, and the pressure is 60 Pa; the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 2: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 1.5:100, the calcium carbonate is treated by low-temperature plasma, the reaction activity of the calcium carbonate is improved, and the reaction combination of the calcium carbonate, the octaaminophenyl cage-like silsesquioxane and the isooctyl dimercaptoacetate di-n-octyl tin is enhanced.
Example 4:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1200 ℃, adding 60 parts of calcined product into 250 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 90min in a supercritical acetone-water system at 380 ℃ and 25MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow rate of 1.2m3The lime kiln smoke containing 35 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 250 mL/min;
adding 80 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 8 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 20MPa after the device is sealed, reacting for 8 hours at the temperature of 70 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying and crushing the calcium carbonate obtained after filtration to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 30min, continuing heating to 1000 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 2h, heating to 1200 deg.C at a speed of 1 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 5 parts of polyacrylic acid, 2.5 parts of triethanolamine, 0.1 part of potassium hydrogen phthalate, 0.5 part of glycolic acid, 0.3 part of 1-ethyl-3-methylimidazolium lactic acid, 0.5 part of sodium salicylate and 0.1 part of polydimethyldiallyl ammonium chloride;
in the third step, the obtained calcium carbonate is subjected to the following treatment processes: treating calcium carbonate in a low-temperature plasma treatment instrument for 10min, adding into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin isooctyl dimercaptoacetate into the stirrer, stirring uniformly, and placing into a container60The radiation is carried out in a Co gamma radiation field, and the placing position is selected to be 130Gy.min-1The absorbed dose rate is 150 kGy; the atmosphere of the low-temperature plasma treatment instrument is argon; the low-temperature plasma processor has the frequency of 50KHz, the power of 50W and the pressure of 50 Pa; the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 1: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 1: 100.
Example 5:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1100 ℃, adding 80 parts of calcined product into 300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 60min in a supercritical acetone-water system at 380 ℃ and 22MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow of 1m3The lime kiln smoke containing 40 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 300 mL/min;
and step three, adding 100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 10 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 25MPa after the device is sealed, reacting for 8 hours at the temperature of 80 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying the calcium carbonate obtained after filtration, and crushing to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 30min, heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 2h, heating to 1100 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of polydimethyldiallyl ammonium chloride;
in the third step, the obtained calcium carbonate is subjected to the following treatment processes: the calcium carbonate is subjected to low-temperature plasma treatmentTreating for 15min, adding into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin isooctyl dimercaptoacetate into the stirrer, stirring, and placing in a container60The radiation is carried out in a Co gamma radiation field, and the placing position is selected to be 150Gy.min-1The absorbed dose rate of (1) is 200 kGy; adding 30 parts of irradiated calcium carbonate, 25 parts of butyl acrylate, 5 parts of allylthiourea, 10 parts of diallyl dimethyl ammonium chloride, 0.1 part of ammonium percarbonate and 200 parts of water into a supercritical reaction device according to parts by weight, uniformly stirring, sealing the system, introducing carbon dioxide to 35MPa, reacting for 3 hours at the temperature of 75 ℃, relieving pressure, precipitating with ethanol, drying, and eluting with butanone to remove homopolymers generated by the reaction, thereby obtaining modified calcium carbonate; the calcium carbonate is modified in a supercritical reaction device, so that the reaction activity of the calcium carbonate and an organic compound is improved, and the performance of the obtained calcium carbonate is more excellent.
The atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 60KHz, the power is 40W, and the pressure is 60 Pa; the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 2: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 1.5: 100;
example 6:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1200 ℃, adding 60 parts of calcined product into 250 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 90min in a supercritical acetone-water system at 380 ℃ and 25MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow rate of 1.2m3The lime kiln smoke containing 35 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 250 mL/min;
adding 80 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 8 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 20MPa after the device is sealed, reacting for 8 hours at the temperature of 70 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying and crushing the calcium carbonate obtained after filtration to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 30min, continuing heating to 1000 deg.C at a speed of 5 deg.C/min, maintaining the temperature for 2h, heating to 1200 deg.C at a speed of 1 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 5 parts of polyacrylic acid, 2.5 parts of triethanolamine, 0.1 part of potassium hydrogen phthalate, 0.5 part of glycolic acid, 0.3 part of 1-ethyl-3-methylimidazolium lactic acid, 0.5 part of sodium salicylate and 0.1 part of polydimethyldiallyl ammonium chloride;
in the third step, the obtained calcium carbonate is subjected to the following treatment processes: treating calcium carbonate in a low-temperature plasma treatment instrument for 10min, adding into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin isooctyl dimercaptoacetate into the stirrer, stirring uniformly, and placing into a container60The radiation is carried out in a Co gamma radiation field, and the placing position is selected to be 130Gy.min-1The absorbed dose rate is 150 kGy; adding 20 parts of irradiated calcium carbonate, 20 parts of butyl acrylate, 5 parts of allylthiourea, 8 parts of diallyldimethylammonium chloride, 0.08 part of ammonium persalt and 200 parts of water into a supercritical reaction device, uniformly stirring, sealing the system, introducing carbon dioxide to 30MPa, reacting for 2 hours at the temperature of 75 ℃, relieving pressure, precipitating with ethanol, drying, and eluting with butanone to remove homopolymers generated by the reaction to obtain modified calcium carbonate;
the atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 50KHz, the power is 50W, and the pressure is 50 Pa; the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 1: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 1: 100.
Comparative example 1:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1100 ℃, adding 80 parts of calcined product into 300 parts of mixed solution of acetone and water by weight, and soaking for 60min to obtain lime milk
Step two, introducing the lime milk with the flow of 1m3The lime kiln smoke containing 40 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 300 mL/min;
and step three, adding 100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 10 parts by weight of crystal form control agent and 8 parts by weight of ethanol, introducing carbon dioxide to 25MPa after the device is sealed, reacting for 8 hours at the temperature of 80 ℃, then relieving the pressure, cooling to room temperature, entering a vertical filter press for pressure filtration, drying the calcium carbonate obtained after filtration, and crushing to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 30min, heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 2h, heating to 1100 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of poly dimethyl diallyl ammonium chloride.
Comparative example 2:
a preparation method of calcium carbonate comprises the following steps:
step one, calcining limestone at 1100 ℃, adding 80 parts of calcined product into 300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 60min in a supercritical acetone-water system at 380 ℃ and 22MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow of 1m3The lime kiln smoke containing 40 percent of carbon dioxide is washed and carbonized for 12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 80 ℃ is introduced into the lime milk at the speed of 300 mL/min;
and step three, adding 10 parts of crystal form control agent and 8 parts of ethanol into 100 parts of crude calcium carbonate slurry according to parts by weight, stirring for 8 hours, then releasing pressure, cooling to room temperature, entering a vertical filter press for pressurizing and filtering, drying the filtered calcium carbonate, and then crushing to obtain the calcium carbonate.
In the first step, the temperature rise process adopted by calcination is as follows: heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 30min, heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 2h, heating to 1100 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 2 h;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of poly dimethyl diallyl ammonium chloride.
400g of each calcium carbonate is prepared according to the preparation methods of examples 1 to 6 and comparative examples 1 to 2, the calcium carbonates prepared in examples 1 to 5 and comparative examples 1 to 2 are respectively added into 600g of nitrile rubber, rubber products are obtained by using the same process, and performance tests are performed on the rubber products of each group, and the test results are shown in Table 1.
TABLE 1
| Fracture ofElongation/percent | Tensile strength/MPa | hardness/A | |
| Example 1 | 425 | 4.5 | 75.8 |
| Example 2 | 426 | 4.6 | 76.1 |
| Example 3 | 465 | 5.4 | 83.2 |
| Example 4 | 467 | 5.5 | 83.4 |
| Example 5 | 476 | 5.8 | 86.5 |
| Example 6 | 477 | 5.9 | 86.7 |
| Comparative example 1 | 354 | 3.2 | 63.2 |
| Comparative example 2 | 336 | 2.8 | 50.5 |
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (7)
1. The preparation method of calcium carbonate is characterized by comprising the following steps:
calcining limestone at 1000-1280 ℃, adding 50-80 parts of calcined product into 200-300 parts of mixed solution of acetone and water according to parts by weight, adding into a supercritical device, and soaking for 30-90 min in a supercritical acetone-water system at 360-400 ℃ and 15-25 MPa to obtain lime milk; the volume ratio of acetone to water in the supercritical acetone-water system is 3: 1;
step two, introducing the lime milk with the flow rate of 0.5-1.5 m3The washed lime kiln smoke containing 30-50% of carbon dioxide is carbonized for 6-12 hours to obtain crude calcium carbonate slurry; in the carbonization process, nitrogen gas at 70-80 ℃ is introduced into the lime milk at a speed of 200-300 mL/min;
adding 50-100 parts by weight of crude calcium carbonate slurry into a supercritical reaction device, then adding 3-10 parts by weight of a crystal form control agent and 5-8 parts by weight of ethanol, introducing carbon dioxide to react for 5-8 hours under the conditions of 12-25 MPa and 60-80 ℃ after the device is sealed, then releasing the pressure, cooling to room temperature, entering a vertical filter press for pressurization and filtration, drying and crushing calcium carbonate obtained after filtration to obtain calcium carbonate;
the crystal form control agent is formed by mixing the following raw materials in parts by weight: 3-5 parts of polyacrylic acid, 1.5-2.5 parts of triethanolamine, 0.1-0.2 part of potassium hydrogen phthalate, 0.3-0.5 part of glycolic acid, 0.1-0.3 part of 1-ethyl-3-methylimidazolium lactic acid, 0.3-0.5 part of sodium salicylate and 0.1-0.2 part of poly dimethyl diallyl ammonium chloride.
2. The preparation method of calcium carbonate according to claim 1, wherein the crystal form control agent is prepared by mixing the following raw materials in parts by weight: 4 parts of polyacrylic acid, 2 parts of triethanolamine, 0.2 part of potassium hydrogen phthalate, 0.4 part of glycolic acid, 0.2 part of 1-ethyl-3-methylimidazolium lactic acid, 0.4 part of sodium salicylate and 0.2 part of poly dimethyl diallyl ammonium chloride.
3. The process for the preparation of calcium carbonate according to claim 1, wherein in step three, the calcium carbonate obtained is subjected to the following treatment: placing calcium carbonate in a low-temperature plasma treatment instrument for treatment for 10-15 min, then adding the calcium carbonate into a stirrer, adding octaaminophenyl cage-like silsesquioxane and di-n-octyl tin bis (isooctyl) dimercaptoacetate into the stirrer, uniformly stirring, and then placing the mixture in a low-temperature plasma treatment instrument60And (4) carrying out radiation in a Co gamma radiation field, wherein the placing position is 130-150 Gy-1The absorption dose rate is 100-200 kGy.
4. The method for producing calcium carbonate according to claim 3, wherein the atmosphere of the low-temperature plasma processor is argon or nitrogen; the frequency of the low-temperature plasma processor is 40-70 kHz, the power is 35-80W, and the pressure is 30-80 Pa.
5. The method for preparing calcium carbonate according to claim 3, wherein the weight ratio of the octaaminophenyl cage-like silsesquioxane to the calcium carbonate is 1-3: 100; the mass ratio of the isooctyl dimercaptoacetate di-n-octyl tin to the calcium carbonate is 0.5-1.5: 100.
6. The method of preparing calcium carbonate according to claim 3, further comprising subjecting the irradiated calcium carbonate to the following modification process: adding 15-30 parts by weight of irradiated calcium carbonate, 20-25 parts by weight of butyl acrylate, 3-5 parts by weight of allylthiourea, 5-10 parts by weight of diallyldimethylammonium chloride, 0.03-0.12 part by weight of ammonium percarbonate and 150-200 parts by weight of water into a supercritical reaction device, uniformly stirring, sealing the system, introducing carbon dioxide to react for 1-3 hours at the temperature of 60-75 ℃ under the pressure of 25-35 MPa, releasing pressure, precipitating with ethanol, drying, and eluting with butanone to remove homopolymers generated by the reaction, thereby obtaining the modified calcium carbonate.
7. The method for preparing calcium carbonate according to claim 1, wherein in the first step, the calcination is carried out by using a temperature rise process comprising: heating to 600-800 ℃ at the speed of 5-10 ℃/min, preserving heat for 30min, continuously heating to 800-1000 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, then heating to 1100-1280 ℃ at the speed of 1-2 ℃/min, and preserving heat for 1-3 h.
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