CN113104877A - Preparation method and application of superfine dolomite - Google Patents
Preparation method and application of superfine dolomite Download PDFInfo
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- CN113104877A CN113104877A CN202110435993.5A CN202110435993A CN113104877A CN 113104877 A CN113104877 A CN 113104877A CN 202110435993 A CN202110435993 A CN 202110435993A CN 113104877 A CN113104877 A CN 113104877A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention discloses a preparation method of superfine dolomite and application of the superfine dolomite, relating to the technical field of dolomite processing, wherein dolomite is crushed and screened to obtain dolomite coarse powder, the dolomite coarse powder and a grinding aid are added into water and stirred uniformly to obtain dolomite slurry, the dolomite slurry is added into a stripping machine for superfine stripping to obtain superfine slurry, the superfine slurry is dehydrated, dried and crushed to obtain dolomite fine powder, the dolomite fine powder and a calcium hydroxide solution are added into a four-neck flask provided with a stirrer, then the four-neck flask is placed in a constant temperature water bath, a crystal form control agent is added while stirring, then mixed gas of air and carbon dioxide is introduced into the three-neck flask for continuous stirring reaction, the reaction liquid is spray-dried to form powder, the superfine dolomite is obtained, and the problem that the particle size of the existing dolomite powder is large is solved, the application range is small, and the superfine powder is easy to agglomerate and is difficult to uniformly disperse.
Description
Technical Field
The invention relates to the technical field of dolomite processing, in particular to a preparation method of superfine dolomite and application of the superfine dolomite.
Background
Dolomite is a common white non-metallic mineral and belongs to CaCO3And MgCO3The composite carbonate mineral is rich in Chinese reserves, and is an important calcium and magnesium resource. Dolomite as a filler has been widely used in the industries of paper making, coating, plastics, rubber, adhesives and the like.
At present, the superfine dolomite is not applied, the existing dolomite is generally dozens to hundreds of meshes, and the finest does not exceed 1000 meshes, so the application of the dolomite is also limited.
At present, the physical pulverization method is the most extensive method for producing ultrafine powder materials by virtue of the advantages of low cost, simple production process and high yield. The superfine grinding equipment mainly comprises an airflow grinder, a mechanical impact grinder, a ball mill, a vibration mill, a stirring mill, a colloid mill and the like. The crushed product has the advantages of fine particle size, narrow distribution and uniform quality, so the crushed product has the advantages of large specific surface area, high surface activity, high chemical reaction speed, high dissolution speed, high sintered body strength, unique electrical property, magnetism, optical property and the like, and is widely applied to many technical fields. However, the ultrafine powder has small size effect, interface and surface effect, and macroscopic quantum tunneling effect, so that the ultrafine powder is easy to agglomerate, is not easy to disperse in an organic medium, has poor compatibility with a matrix, and directly influences the actual efficacy of the ultrafine powder.
Therefore, how to reduce the particle size of the dolomite powder so as to improve the application range of the dolomite powder and solve the problem that the ultrafine powder is easy to agglomerate and not easy to uniformly disperse.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a preparation method of superfine dolomite and application of the superfine dolomite: the dolomite grinding aid is prepared by crushing dolomite, screening to obtain dolomite coarse powder, adding the dolomite coarse powder and the grinding aid into water, stirring well to obtain dolomite slurry, adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry, dehydrating, drying and crushing the superfine slurry to obtain dolomite fine powder, adding the dolomite fine powder and calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding the crystal form control agent while stirring, introducing mixed gas of air and carbon dioxide into the three-neck flask, continuously stirring for reaction, when the pH value is equal to 7, the reaction is stopped, and the reaction solution is spray-dried to form powder, so that the superfine dolomite is obtained, and the problems that the existing dolomite powder is large in particle size, small in application range and easy to agglomerate and disperse uniformly are solved.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of superfine dolomite comprises the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 300-350 meshes;
step two: adding the dolomite coarse powder and the grinding aid into water, and stirring for 30-50min under the condition that the stirring speed is 300-;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder;
step five: adding the dolomite fine powder and the calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding the crystal form control agent while stirring under the conditions that the temperature is 30-40 ℃ and the stirring speed is 100-500 r/min, then introducing mixed gas of air and carbon dioxide into the three-neck flask, and continuing stirring and reacting when the stirring speed is increased to 400-500 r/min;
step six: and (3) monitoring on line in real time by a conductivity meter and a pH meter in the reaction process, stopping the reaction when the pH is equal to 7, and carrying out spray drying on the reaction liquid to form powder to obtain the superfine dolomite.
As a further scheme of the invention: in the second step, the weight ratio of the dolomite coarse powder to the grinding aid to the water is 50-75: 0.25-1.5: 25-50.
As a further scheme of the invention: in the fifth step, the dosage ratio of the dolomite fine powder, the calcium hydroxide solution and the crystal form control agent is 1 g: 10mL of: 0.01-0.02g, the mass concentration of the calcium hydroxide solution is 0.25-0.35mol/L, the crystal form control agent is zinc sulfate, and the flow rate of the carbon dioxide is 0.4-0.6m3/h。
As a further scheme of the invention: the preparation process of the grinding aid comprises the following steps:
s1: adding phenol into a three-neck flask provided with a condenser and a stirrer, then adding caprylic acid and triethanolamine, placing the three-neck flask into a constant temperature oil bath, and stirring and reacting for 7-9h under the conditions that the temperature is 130-;
s2: dissolving the intermediate 1 crude product in isooctane to obtain an intermediate 1 crude product solution, washing the intermediate 1 crude product solution respectively with sodium hydroxide aqueous solution and distilled water for 3-5 times to remove unreacted octanoic acid, triethanolamine and phenol, and then carrying out rotary evaporation on the intermediate 1 crude product solution to constant weight to obtain an intermediate 1;
the reaction principle is as follows:
s3: adding maleic anhydride into a four-neck flask provided with a thermometer, a stirrer and a condenser, then adding the intermediate 1, stirring at the temperature of 20-30 ℃ and the stirring speed of 100-200r/min until the reaction liquid is clear, then heating to 50-60 ℃ and continuing stirring for 30-50min until a light yellow clear solution is formed, thus obtaining an intermediate 2;
the reaction principle is as follows:
s4: adding allyl polyoxyethylene ether, the intermediate 2 and deionized water into a four-neck flask provided with a thermometer, a stirrer and a condenser, carrying out stirring reaction at a stirring speed of 100-200r/min, heating, controlling the heating rate to be 5 ℃/min, adding an initiator when the temperature is raised to 60-85 ℃, carrying out heat preservation and stirring reaction for 3-4h, cooling the reaction product to 40 ℃ after polymerization is finished, and adding a sodium hydroxide aqueous solution to adjust the pH to be 6.5-7.5 to obtain the grinding aid.
The reaction principle is as follows:
as a further scheme of the invention: in the step S1, the molar ratio of the octanoic acid to the triethanolamine is 1.6:1.0, and the dosage ratio of the octanoic acid to the phenol is 1 g: 5-10 mL.
As a further scheme of the invention: the mass fraction of the sodium hydroxide aqueous solution in step S2 was 30%.
As a further scheme of the invention: the molar ratio of the maleic anhydride to the intermediate 1 in the step S3 is 1.5-2.0: 1.0.
As a further scheme of the invention: in the step S4, the molar ratio of allyl polyoxyethylene ether to intermediate 2 is 1.0: 0.8, wherein the dosage ratio of the allyl polyoxyethylene ether to the deionized water is 1 g: 5-10mL, wherein the initiator is ammonium persulfate, and the mass fraction of the sodium hydroxide aqueous solution is 30%.
As a further scheme of the invention: the superfine dolomite prepared by the method can be applied to papermaking, coatings, plastics, rubber and adhesives.
The invention has the beneficial effects that:
the invention relates to a preparation method of superfine dolomite and application of the superfine dolomite, crushing the dolomite, obtaining coarse dolomite powder through screening, adding the coarse dolomite powder and a grinding aid into water, stirring uniformly to obtain dolomite slurry, adding the dolomite slurry into a stripping machine to carry out superfine stripping to obtain superfine slurry, dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder, adding the fine dolomite powder and a calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding a crystal form control agent while stirring, then introducing mixed gas of air and carbon dioxide into the three-neck flask to continue stirring and reacting, stopping the reaction when the pH value is equal to 7, and carrying out spray drying on reaction liquid to form powder to obtain the superfine dolomite; according to the preparation method, a grinding aid is added into coarse dolomite powder, superfine slurry obtained after stripping is dried to form fine dolomite powder, the fine dolomite powder is added into a calcium hydroxide solution, then carbon dioxide is introduced in the solution under a stirring state, so that the carbon dioxide reacts with the calcium hydroxide solution to generate nano calcium carbonate, and the nano calcium carbonate is coated on the surface of the fine dolomite powder, so that the surface of the dolomite has good surface appearance, is easy to disperse into other substances, and avoids aggregation among the superfine dolomite powder;
a grinding aid is prepared simultaneously in the process of preparing superfine dolomite, an intermediate 1 is generated through the esterification reaction of caprylic acid and triethanolamine, an intermediate 2 is generated through the reaction of the intermediate 1 and maleic anhydride, the intermediate 2 reacts with allyl polyoxyethylene ether and is polymerized to generate a final product, namely the grinding aid, the allyl polyoxyethylene ether is a nonionic surfactant and has active groups, and double bonds in the nonionic surfactant can be subjected to direct polymerization.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this example is a grinding aid, the preparation process of which comprises the following steps:
s1: adding phenol into a three-neck flask provided with a condenser and a stirrer, then adding caprylic acid and triethanolamine, placing the three-neck flask into a constant-temperature oil bath, and stirring and reacting for 7 hours at the temperature of 130 ℃ and the stirring speed of 100r/min until water is completely discharged to obtain a crude product of the intermediate 1; the molar ratio of the octanoic acid to the triethanolamine is 1.6:1.0, and the dosage ratio of the octanoic acid to the phenol is 1 g: 5 mL;
s2: dissolving the intermediate 1 crude product in isooctane to obtain an intermediate 1 crude product solution, washing the intermediate 1 crude product solution respectively with a sodium hydroxide aqueous solution and distilled water for 3 times to remove unreacted octanoic acid, triethanolamine and phenol, and then carrying out rotary evaporation on the intermediate 1 crude product solution to constant weight to obtain an intermediate 1; the mass fraction of the sodium hydroxide aqueous solution is 30 percent;
s3: adding maleic anhydride into a four-neck flask provided with a thermometer, a stirrer and a condenser, then adding the intermediate 1, stirring at the temperature of 20 ℃ and the stirring speed of 100r/min until the reaction solution is clear, then heating to 50 ℃ and continuing stirring for 30min until a light yellow clear solution is formed, thus obtaining an intermediate 2; the molar ratio of the maleic anhydride to the intermediate 1 is 1.5: 1.0;
s4: adding allyl polyoxyethylene ether, an intermediate 2 and deionized water into a four-neck flask provided with a thermometer, a stirrer and a condenser, carrying out stirring reaction at a stirring speed of 100r/min, heating up, controlling the heating rate to be 5 ℃/min, adding an initiator when the temperature is raised to 60 ℃, keeping the temperature, carrying out stirring reaction for 3 hours, cooling the reaction product to 40 ℃ after polymerization is finished, adding a sodium hydroxide aqueous solution, and adjusting the pH value to be 6.5 to obtain the grinding aid; the mol ratio of the allyl polyoxyethylene ether to the intermediate 2 is 1.0: 0.8, wherein the dosage ratio of the allyl polyoxyethylene ether to the deionized water is 1 g: 5mL, wherein the initiator is ammonium persulfate, and the mass fraction of the sodium hydroxide aqueous solution is 30%.
Example 2:
this example is a grinding aid, the preparation process of which comprises the following steps:
s1: adding phenol into a three-neck flask provided with a condenser and a stirrer, then adding caprylic acid and triethanolamine, placing the three-neck flask into a constant-temperature oil bath, and stirring and reacting for 8 hours at the temperature of 135 ℃ and the stirring speed of 150r/min until water is completely discharged to obtain a crude product of the intermediate 1; the molar ratio of the octanoic acid to the triethanolamine is 1.6:1.0, and the dosage ratio of the octanoic acid to the phenol is 1 g: 8 mL;
s2: dissolving the intermediate 1 crude product in isooctane to obtain an intermediate 1 crude product solution, washing the intermediate 1 crude product solution with sodium hydroxide aqueous solution and distilled water respectively for 4 times to remove unreacted octanoic acid, triethanolamine and phenol, and then carrying out rotary evaporation on the intermediate 1 crude product solution to constant weight to obtain an intermediate 1; the mass fraction of the sodium hydroxide aqueous solution is 30 percent;
s3: adding maleic anhydride into a four-neck flask provided with a thermometer, a stirrer and a condenser, then adding the intermediate 1, stirring at the temperature of 25 ℃ and the stirring speed of 150r/min until the reaction solution is clear, then heating to 55 ℃, and continuing stirring for 40min until a light yellow clear solution is formed, thus obtaining an intermediate 2; the molar ratio of the maleic anhydride to the intermediate 1 is 1.75: 1.0;
s4: adding allyl polyoxyethylene ether, an intermediate 2 and deionized water into a four-neck flask provided with a thermometer, a stirrer and a condenser, carrying out stirring reaction at a stirring speed of 150r/min, heating up, controlling the heating rate to be 5 ℃/min, adding an initiator when the temperature is raised to 72 ℃, keeping the temperature, carrying out stirring reaction for 4 hours, cooling the reaction product to 40 ℃ after polymerization is finished, adding a sodium hydroxide aqueous solution, and adjusting the pH value to be 7.0 to obtain the grinding aid; the mol ratio of the allyl polyoxyethylene ether to the intermediate 2 is 1.0: 0.8, wherein the dosage ratio of the allyl polyoxyethylene ether to the deionized water is 1 g: 7mL, wherein the initiator is ammonium persulfate, and the mass fraction of the sodium hydroxide aqueous solution is 30%.
Example 3:
this example is a grinding aid, the preparation process of which comprises the following steps:
s1: adding phenol into a three-neck flask provided with a condenser and a stirrer, then adding caprylic acid and triethanolamine, placing the three-neck flask into a constant-temperature oil bath, and stirring and reacting for 9 hours at the temperature of 140 ℃ and the stirring speed of 200r/min until water is completely discharged to obtain a crude product of the intermediate 1; the molar ratio of the octanoic acid to the triethanolamine is 1.6:1.0, and the dosage ratio of the octanoic acid to the phenol is 1 g: 10 mL;
s2: dissolving the intermediate 1 crude product in isooctane to obtain an intermediate 1 crude product solution, washing the intermediate 1 crude product solution with a sodium hydroxide aqueous solution and distilled water respectively for 5 times to remove unreacted octanoic acid, triethanolamine and phenol, and then carrying out rotary evaporation on the intermediate 1 crude product solution to constant weight to obtain an intermediate 1; the mass fraction of the sodium hydroxide aqueous solution is 30 percent;
s3: adding maleic anhydride into a four-neck flask provided with a thermometer, a stirrer and a condenser, then adding the intermediate 1, stirring at the temperature of 30 ℃ and the stirring speed of 200r/min until the reaction solution is clear, then heating to 60 ℃ and continuing stirring for 50min until a light yellow clear solution is formed, thus obtaining an intermediate 2; the molar ratio of the maleic anhydride to the intermediate 1 is 2.0: 1.0;
s4: adding allyl polyoxyethylene ether, an intermediate 2 and deionized water into a four-neck flask provided with a thermometer, a stirrer and a condenser, carrying out stirring reaction at a stirring speed of 200r/min, heating up, controlling the heating rate to be 5 ℃/min, adding an initiator when the temperature is raised to 85 ℃, keeping the temperature, carrying out stirring reaction for 4 hours, cooling the reaction product to 40 ℃ after polymerization is finished, adding a sodium hydroxide aqueous solution, and adjusting the pH value to be 7.5 to obtain the grinding aid; the mol ratio of the allyl polyoxyethylene ether to the intermediate 2 is 1.0: 0.8, wherein the dosage ratio of the allyl polyoxyethylene ether to the deionized water is 1 g: 10mL, wherein the initiator is ammonium persulfate, and the mass fraction of the sodium hydroxide aqueous solution is 30%.
Example 4:
the embodiment is a preparation method of superfine dolomite, which comprises the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 300 meshes;
step two: adding dolomite coarse powder and the grinding aid from example 1 into water, and stirring for 30min at the stirring speed of 300r/min to obtain dolomite slurry; the weight ratio of the dolomite coarse powder to the grinding aid to the water is 50: 0.25: 25;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder;
step five: adding the dolomite fine powder and a calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding a crystal form control agent while stirring under the conditions that the temperature is 30 ℃ and the stirring speed is 100r/min, then introducing mixed gas of air and carbon dioxide into a three-neck flask, and continuing stirring and reacting when the stirring speed is increased to 400 r/min; the dosage ratio of the dolomite fine powder, the calcium hydroxide solution and the crystal form control agent is 1 g: 10mL of: 0.01g, the mass concentration of the calcium hydroxide solution is 0.25mol/L, the crystal form control agent is zinc sulfate, and the flow rate of the carbon dioxide is 0.4m3/h；
Step six: and (3) monitoring on line in real time by a conductivity meter and a pH meter in the reaction process, stopping the reaction when the pH is equal to 7, and carrying out spray drying on the reaction liquid to form powder to obtain the superfine dolomite.
Example 5:
the embodiment is a preparation method of superfine dolomite, which comprises the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 325 meshes;
step two: adding dolomite coarse powder and the grinding aid from example 2 into water, and stirring for 40min under the condition that the stirring speed is 400r/min to obtain dolomite slurry; the weight ratio of the dolomite coarse powder to the grinding aid to the water is 62: 0.85: 37;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder;
step five: adding the fine powder of dolomite and calcium hydroxide solution into the solutionPutting the four-neck flask into a constant-temperature water bath, adding a crystal form control agent under stirring at the temperature of 35 ℃ and the stirring speed of 150r/min, introducing a mixed gas of air and carbon dioxide into the three-neck flask, and continuously stirring and reacting when the stirring speed is increased to 450 r/min; the dosage ratio of the dolomite fine powder, the calcium hydroxide solution and the crystal form control agent is 1 g: 10mL of: 0.015g, the substance concentration of the calcium hydroxide solution is 0.30mol/L, the crystal form control agent is zinc sulfate, and the flow rate of the carbon dioxide is 0.5m3/h；
Step six: and (3) monitoring on line in real time by a conductivity meter and a pH meter in the reaction process, stopping the reaction when the pH is equal to 7, and carrying out spray drying on the reaction liquid to form powder to obtain the superfine dolomite.
Example 6:
the embodiment is a preparation method of superfine dolomite, which comprises the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 350 meshes;
step two: adding dolomite coarse powder and the grinding aid from example 3 into water, and stirring for 50min at the stirring speed of 500r/min to obtain dolomite slurry; the weight ratio of the dolomite coarse powder to the grinding aid to the water is 75: 1.5: 50;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder;
step five: adding the dolomite fine powder and a calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding a crystal form control agent while stirring under the conditions that the temperature is 40 ℃ and the stirring speed is 200r/min, then introducing mixed gas of air and carbon dioxide into a three-neck flask, and continuing stirring and reacting when the stirring speed is increased to 500 r/min; the dosage ratio of the dolomite fine powder, the calcium hydroxide solution and the crystal form control agent is 1 g: 10mL of: 0.02g of the substance of the calcium hydroxide solutionThe quantity concentration is 0.35mol/L, the crystal form control agent is zinc sulfate, and the flow rate of the carbon dioxide is 0.6m3/h；
Step six: and (3) monitoring on line in real time by a conductivity meter and a pH meter in the reaction process, stopping the reaction when the pH is equal to 7, and carrying out spray drying on the reaction liquid to form powder to obtain the superfine dolomite.
Comparative example 1:
comparative example 1 is a method for preparing ultrafine dolomite, comprising the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 300-350 meshes;
step two: adding the dolomite coarse powder and a grinding aid into water, and uniformly stirring to obtain dolomite slurry;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain the superfine dolomite.
The difference from examples 4 to 6 is that the reaction was carried out without adding to the calcium hydroxide solution.
Comparative example 2:
comparative example 2 is a method for preparing ultrafine dolomite, and differs from examples 4 to 6 in that a grinding aid is replaced with a grinding medium, specifically, a zirconia grinding medium.
Comparative example 3:
comparative example 3 is a preparation method of ultrafine dolomite, and is different from examples 4 to 6 in that the grinding aid is replaced by a common grinding aid in the market, and specifically sodium hexametaphosphate.
Comparative example 4:
comparative example 4 is a method for preparing ultrafine dolomite, and is different from comparative example 1 in that a grinding aid, sodium hexametaphosphate.
The grain sizes of the ultrafine dolomite of examples 4 to 6 and comparative examples 1 to 4 were measured, and the results are shown in the following table:
as shown in the table above, the particle size of the superfine dolomite of examples 4-6 is mainly distributed between 1-30 μm, the particle size of comparative example 1 is mainly distributed below 10 μm, the particle size is increased after the nano calcium carbonate is coated compared with examples 4-6, the particle size of comparative example 2 is mainly distributed above 30 μm, which shows that the grinding aid of the invention has better grinding effect than grinding medium, the particle size of comparative example 3 is mainly distributed between 10-50 μm, which shows that the grinding effect of common grinding aid on the market is better than that of grinding medium, but the grinding aid of the invention is not better than that of comparative example 4, the particle size of comparative example 4 is distributed between 1-30 μm, the particle size is smaller than that of examples 4-6, and further shows that the particle size is increased after the nano calcium carbonate is coated.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. The preparation method of the superfine dolomite is characterized by comprising the following steps:
the method comprises the following steps: crushing dolomite, and screening to obtain coarse dolomite powder with the particle size of 300-350 meshes;
step two: adding the dolomite coarse powder and a grinding aid into water, and uniformly stirring to obtain dolomite slurry;
step three: adding the dolomite slurry into a stripping machine for superfine stripping to obtain superfine slurry;
step four: dehydrating, drying and crushing the superfine slurry to obtain fine dolomite powder;
step five: adding the dolomite fine powder and a calcium hydroxide solution into a four-neck flask provided with a stirrer, then placing the four-neck flask into a constant-temperature water bath, adding a crystal form control agent while stirring, and then introducing a mixed gas of air and carbon dioxide into the three-neck flask to continue stirring and reacting;
step six: stopping the reaction when the pH value is equal to 7, and spray-drying the reaction solution to form powder to obtain the superfine dolomite;
the preparation process of the grinding aid comprises the following steps:
s1: adding phenol into a three-neck flask provided with a condenser and a stirrer, then adding caprylic acid and triethanolamine, placing the three-neck flask into a constant temperature oil bath, and stirring and reacting for 7-9h under the conditions that the temperature is 130-;
s2: dissolving the intermediate 1 crude product in isooctane to obtain an intermediate 1 crude product solution, washing the intermediate 1 crude product solution respectively with sodium hydroxide aqueous solution and distilled water for 3-5 times to remove unreacted octanoic acid, triethanolamine and phenol, and then carrying out rotary evaporation on the intermediate 1 crude product solution to constant weight to obtain an intermediate 1;
s3: adding maleic anhydride into a four-neck flask provided with a thermometer, a stirrer and a condenser, then adding the intermediate 1, stirring at the temperature of 20-30 ℃ and the stirring speed of 100-200r/min until the reaction liquid is clear, then heating to 50-60 ℃ and continuing stirring for 30-50min until a light yellow clear solution is formed, thus obtaining an intermediate 2;
s4: adding allyl polyoxyethylene ether, the intermediate 2 and deionized water into a four-neck flask provided with a thermometer, a stirrer and a condenser, carrying out stirring reaction at a stirring speed of 100-200r/min, heating, controlling the heating rate to be 5 ℃/min, adding an initiator when the temperature is raised to 60-85 ℃, carrying out heat preservation and stirring reaction for 3-4h, cooling the reaction product to 40 ℃ after polymerization is finished, and adding a sodium hydroxide aqueous solution to adjust the pH to be 6.5-7.5 to obtain the grinding aid.
2. The method for preparing ultrafine dolomite according to claim 1, wherein the weight ratio of the dolomite coarse powder, the grinding aid and the water in the second step is 50-75: 0.25-1.5: 25-50.
3. The method for preparing ultrafine dolomite according to claim 1, wherein the dosage ratio of the fine dolomite powder, the calcium hydroxide solution and the crystal form control agent in step five is 1 g: 10mL of: 0.01-0.02g, the mass concentration of the calcium hydroxide solution is 0.25-0.35mol/L, the crystal form control agent is zinc sulfate, and the flow rate of the carbon dioxide is 0.4-0.6m3/h。
4. Use of the ultrafine dolomite produced according to the process of claim 1 in paper manufacture, paints, plastics, rubbers, adhesives.
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| CN113956681A (en) * | 2021-11-15 | 2022-01-21 | 亚士创能科技(上海)股份有限公司 | Tourmaline coated with calcium carbonate and preparation method and application thereof |
| CN114807510A (en) * | 2022-05-09 | 2022-07-29 | 首钢水城钢铁（集团）有限责任公司 | Method for controlling rephosphorization in tapping process of high-titanium molten iron smelted by converter |
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