CN114735740A - Calcium carbonate preparation method based on ultrasonic pipeline type reactor - Google Patents

Calcium carbonate preparation method based on ultrasonic pipeline type reactor Download PDF

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CN114735740A
CN114735740A CN202210385159.4A CN202210385159A CN114735740A CN 114735740 A CN114735740 A CN 114735740A CN 202210385159 A CN202210385159 A CN 202210385159A CN 114735740 A CN114735740 A CN 114735740A
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calcium
ultrasonic
carbonate
solution
calcium carbonate
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董正亚
张�杰
朱晓晶
李志鹏
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Guangdong Laboratory Of Chemistry And Fine Chemicals
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract

The invention discloses a preparation method of calcium carbonate based on an ultrasonic pipeline type reactor, which comprises the following three steps: (1) preparing a reaction solution; (2) carrying out ultrasonic reaction; (3) and (5) performing subsequent treatment. The method utilizes the high heat and mass transfer speed, the controllable multiphase circulation and the ultrasonic cavitation effect of the ultrasonic pipeline type reactor, and realizes the controllable synthesis of the spherical calcium carbonate with good dispersibility and the grain diameter of 500nm-5 mu m by regulating and controlling the parameters of the salt solution concentration, the power of the ultrasonic pipeline type reactor, the reaction residence time, the types and the proportion of the active agents and the like.

Description

Calcium carbonate preparation method based on ultrasonic pipeline type reactor
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of calcium carbonate based on an ultrasonic pipeline type reactor.
Background
Calcium carbonate is one of the most abundant inorganic minerals in nature, is also an important inorganic chemical material, and is widely applied to industries and fields of papermaking, rubber, chemical building materials, coatings, printing ink, daily chemical industry, medicines, foods and the like due to the advantages of stable chemical property, no toxicity, no harm, good filling expansion performance, easy modification, low price, wide sources and the like. Currently, calcium carbonate is available in various forms such as needle, spindle, cube, sphere, amorphous form, etc. Among them, spherical calcium carbonate is widely used in many industries and fields such as paint, ink and plastic master batch because of its special properties such as large surface area, good dispersibility, good solubility, good smoothness and fluidity.
Nowadays, there are two main methods for producing spherical calcium carbonate: carbonization and double decomposition. The carbonization method is a mainstream process for preparing calcium carbonate in actual industrial production, and the carbonization method takes lime milk (calcium hydroxide) and carbon dioxide gas as raw materials to carry out mixing reaction to obtain the calcium carbonate, and mainly comprises the following steps according to different carbonization modes: the method comprises the following steps of (1) an intermittent bubbling carbonization method, a continuous spraying carbonization method and a supergravity method, wherein the intermittent bubbling carbonization method has low production efficiency, the regulation and control of calcium carbonate crystals are difficult to realize, and the produced calcium carbonate has coarse and uneven particle size; the continuous spray carbonization method and the hypergravity method involve large equipment investment and high production cost. The double decomposition method is a method for preparing calcium carbonate by using a soluble calcium salt and a solution containing carbonic acid salt as initial raw materials, and the method can realize the precise regulation and control of the morphology and the particle size of the prepared calcium carbonate by regulating the parameters such as the concentration of the reaction salt solution, the reaction time and the like under certain process conditions, thereby producing the calcium carbonate with high purity, uniform particle size and good dispersibility. However, the double decomposition method is widely used in experiments to study the crystallization and morphology change process of calcium carbonate, and there are few industrial production lines for producing calcium carbonate by the double decomposition method in actual industrial production, so that the preparation of a large amount of spherical calcium carbonate with high purity, uniform particle size and good dispersibility by the double decomposition method has great development value.
CN 107986313B discloses a preparation method of spherical calcium carbonate, which comprises the steps of preparing PVP-sodium stearate composite solution with a certain concentration, adding one part of PVP-sodium stearate solution into calcium chloride solution to form solution A, placing the solution on a constant speed stirrer after ultrasonic treatment to continuously stir for 1 hour, adding the other part of PVP-sodium stearate solution into sodium carbonate solution to form solution B, performing low-frequency ultrasonic treatment, placing the solution on the constant speed stirrer to continuously stir for half an hour, quickly pouring the solution A into the solution B, performing suction filtration on slurry, and washing to obtain spherical calcium carbonate particles. Although the method prepares the spherical calcium carbonate particles, the particle size is about micron level, and the preparation process is long-time consuming and complex.
The invention patent CN201811350972.8 discloses a spherical nano calcium carbonate and a preparation method thereof, which comprises the following steps: dissolving sodium carbonate, potassium carbonate or ammonium bicarbonate in water to prepare CO3 2-Solution A with the concentration of 0.25-1 mol/L; dissolving calcium acetate monohydrate or calcium chloride monohydrate in water to form Ca2+Solution B with the concentration of 0.25-1 mol/L; respectively adding a certain amount of glycerol into different containers, and then respectively adding deionized water according to the volume ratio of 4:5-8:1 to prepare a solution C; respectively adding the solution A into the solution C, stirring for 3-5 minutes, then adding the solution B while stirring, and continuing stirring for 4-5 hours after the solution becomes turbid; the resulting white precipitate was centrifuged, washed repeatedly with deionized water, and dried in an oven at 60 ℃ under vacuum overnight. Although the spherical nano calcium carbonate is prepared by the method, the process is complex and the cost is high.
Therefore, how to prepare a large amount of spherical calcium carbonate with high purity, uniform particle size and good dispersibility by a double decomposition method is an important direction for researchers in the inorganic material industry at present.
Disclosure of Invention
In view of the defects of the existing spherical calcium carbonate production technology, the invention researches the existing spherical calcium carbonate production method, and finally obtains the calcium carbonate preparation method based on the ultrasonic pipeline type reactor by utilizing the high heat and mass transfer speed, the controllable multiphase circulation and the ultrasonic cavitation effect of the ultrasonic pipeline type reactor, and the method realizes the controllable synthesis of the spherical calcium carbonate with good dispersity and particle size within the range of 500nm-5 mu m by regulating and controlling the parameters of salt solution concentration, the power of the ultrasonic pipeline type reactor, reaction residence time, the types and the proportion of active agents and the like.
In order to realize the aim, the preparation method of the calcium carbonate based on the ultrasonic pipeline type reactor sequentially comprises the following steps:
(1) preparing a reaction solution: dissolving a soluble calcium salt in water and adding a first surfactant to obtain a calcium salt solution, while dissolving a carbonate in water and adding a second surfactant to obtain a carbonate solution;
(2) ultrasonic reaction: simultaneously conveying the calcium salt solution and the carbonate solution obtained in the step (1) into an ultrasonic pipeline type reactor for ultrasonic reaction to obtain calcium carbonate slurry, wherein the conveying amount of the calcium salt solution and the carbonate solution is 4-100mL/min, the molar ratio of calcium salt in the calcium salt solution to carbonate in the carbonate solution is 1:1 during conveying, and the retention time of the calcium salt solution and the carbonate solution conveyed into the ultrasonic pipeline type reactor is 0.5-40 s;
(3) and (3) subsequent treatment: and (3) filtering, washing, drying and crushing the calcium carbonate slurry obtained in the step (2) to obtain the spherical calcium carbonate.
A large amount of cavitation bubbles are generated in a pipeline in the ultrasonic pipeline type reactor under the ultrasonic action, the cavitation bubbles (and bubble groups) generate violent translational motion, surface oscillation, collision tearing and merging and aggregating to generate strong vortex and flow field disturbance, so that each cavitation bubble becomes a miniature stirrer, liquid mixing in the pipeline is obviously enhanced, the aggregation of calcium carbonate particles produced by a calcium salt solution and a carbonate solution is effectively inhibited, the problems that the convection mixing is weak and the calcium carbonate particles are easily blocked by solids in a tubular reactor are avoided, and the generated calcium carbonate particles are smaller and more uniform based on the violent motion and the stirring action of the cavitation bubbles.
Preferably, in the above preparation method, the calcium salt is a water-soluble calcium salt, which includes but is not limited to one of calcium chloride, calcium nitrate, and calcium acetate.
Particularly preferably, in the above production method, the calcium salt is calcium chloride.
Preferably, in the above preparation method, the concentration of the calcium salt is 0.1 to 3 mol/L.
Preferably, in the above preparation method, the first surfactant is ethanol, polyvinylpyrrolidone, sodium lauryl sulfate or sodium lauryl sulfate, and polyvinylpyrrolidone is particularly preferred.
Preferably, in the above preparation method, the concentration of the first surfactant is 2 to 20 mg/mL.
Preferably, in the above preparation method, the second surfactant is two or more of ethanol, polyvinylpyrrolidone, sodium lauryl sulfate, or sodium lauryl sulfate, and polyvinylpyrrolidone and sodium lauryl sulfate are particularly preferable.
Further preferably, in the above preparation method, the concentration of sodium dodecyl sulfate in the second surfactant is 2.5 to 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 2 to 20 mg/mL.
Preferably, in the above production method, the carbonate is a water-soluble carbonate, and sodium carbonate and/or potassium carbonate is particularly preferable.
Preferably, in the above preparation method, the concentration of the carbonate is 0.1 to 3 mol/L.
Preferably, in the above preparation method, the ultrasonic power is 50-800W and the ultrasonic frequency is 18-500kHz, preferably 18-60kHz, during the ultrasonic reaction in the step (2).
Preferably, in the above preparation method, the hydraulic diameter of the pipe of the ultrasonic pipe reactor in which the ultrasonic reaction is performed in the step (2) is 0.1 to 50 mm.
Under the action of ultrasonic wave, a large amount of cavitation bubbles are generated in the pipeline, and the cavitation bubbles (and bubble groups) have violent translational motion, surface oscillation, collision tearing and combination agglomeration. These cavitation phenomena produce strong turbulence and flow field disturbances, making each cavitation bubble a micro-stirrer, significantly enhancing fluid mixing in the channel. According to the difference of the bubble radius and the ultrasonic power, each bubble (bubble group) generates different cavitation modes, such as volume oscillation, shape oscillation, transient cavitation and the like. The bubble cavitation behavior near the resonance size is most intense, and transient cavitation occurs; the farther the bubble radius is from the resonance size, the weaker its cavitation behavior, gradually changing from shape mode to volume mode and oscillation. With the increase of ultrasonic power, the bubbles are converted into regular surface wave oscillation from volume oscillation and finally become chaotic wave oscillation. There is a clear confinement effect of these oscillatory behaviors: the smaller the size of the pipeline is, the tighter the gas-liquid interface bound by the wall surface of the pipeline is, the harder the surface wave oscillation is to excite, the smaller the oscillation amplitude is under the same ultrasonic power condition, the violent acoustic current also appears near the oscillation bubble, and the violent acoustic current is mutually coupled and superposed with the internal circulation in the liquid bomb, so that the convective mixing in the liquid is obviously enhanced. Therefore, the selection of a pipeline ultrasonic pipeline reactor with appropriate power, frequency and hydraulic diameter, combined with the fluid properties of the calcium salt solution and the carbonate solution, is needed to help obtain calcium carbonate particles with uniform and controllable particle size.
Preferably, in the above preparation method, the ultrasonic pipe-type reactor used in the step (2) comprises
An ultrasonic transducer for generating ultrasonic waves;
one end of the amplitude transformer is connected with the ultrasonic transducer;
the tool head is of a columnar structure along the length direction, and one end of the tool head is connected with the other end of the amplitude transformer;
the fluid pipeline is arranged on one side, far away from the side connected with the amplitude transformer, in the tool head, or the fluid pipeline is connected with the outer side face of one side, far away from the amplitude transformer, of the tool head; the horn is configured to transmit ultrasonic waves generated by the ultrasonic transducer to the tool head, and the tool head is configured to focus ultrasonic energy within the tool head into a fluid conduit. This arrangement may enhance mixing of the fluid within the fluid conduit.
The preparation process is carried out by utilizing the self-developed ultrasonic pipeline type reactor, the ultrasonic pipeline type reactor is provided with the columnar tool head structure, and the fluid pipeline is arranged at one side, far away from the side connected with the amplitude transformer, in the tool head or is connected with the outer side surface of the tool head, far away from the side of the amplitude transformer, so that the processing cost of the fluid pipeline is low, the connection of the fluid pipeline and the tool head is easier, and meanwhile, the dispersed ultrasonic energy can be ensured to be gathered in the fluid pipeline when the length and the volume of the fluid pipeline are large. The specific structure of the self-developed ultrasonic pipeline reactor adopted by the invention is detailed in Chinese patent application CN 202110953049.9.
Preferably, in the above preparation method, the calcium carbonate slurry obtained in step (2) is filtered in step (3), then washed with deionized water 2-5 times to remove impurities, and then dried at a temperature of 60-120 ℃ for 1-20h and pulverized to obtain spherical calcium carbonate.
In summary, compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the self-developed ultrasonic pipeline type reactor with high heat and mass transfer speed, controllable multiphase prevalence and ultrasonic cavitation effect to finally obtain the calcium carbonate preparation method based on the ultrasonic pipeline type reactor, and the method realizes the controllable synthesis of the spherical calcium carbonate with good dispersity and with the grain diameter within the range of 500nm-5 mu m by regulating and controlling the parameters of calcium salt and carbonate solution concentration, the type and the amount of a first surfactant in the calcium salt solution, the type and the amount of a second surfactant in the calcium salt solution, the structure, the power and the frequency of the ultrasonic pipeline type reactor, the residence time of reaction liquid and the like, has simple preparation method process, can realize continuous preparation, can completely realize mechanical operation, and further can prepare the spherical calcium carbonate on a large scale, and further provides a cheap calcium carbonate powder material with stable performance for related industries.
Drawings
FIG. 1 is a scanning electron micrograph of calcium carbonate particles prepared in preparation example 1;
FIG. 2 is a scanning electron micrograph of calcium carbonate particles prepared in preparation example 3;
FIG. 3 is a scanning electron micrograph of calcium carbonate particles prepared in preparation example 4;
fig. 4 is a scanning electron micrograph of calcium carbonate particles prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to specific embodiments and the accompanying drawings, but the scope of the present invention is not limited to the embodiments.
The starting materials used in the following examples are all commercially available unless otherwise specified.
The ultrasonic pipeline type reactor is self-developed, and the specific structure thereof is detailed in Chinese patent application CN202110953049.9, which comprises
An ultrasonic transducer for generating ultrasonic waves;
one end of the amplitude transformer is connected with the ultrasonic transducer;
the tool head is of a columnar structure along the length direction, and one end of the tool head is connected with the other end of the amplitude transformer;
the fluid pipeline is arranged on one side, far away from the side connected with the amplitude transformer, in the tool head, or the fluid pipeline is connected with the outer side face of one side, far away from the amplitude transformer, of the tool head; the horn is used for transmitting the ultrasonic wave generated by the ultrasonic transducer to the tool head, and the tool head is used for converging the ultrasonic wave energy in the tool head into a fluid pipeline. The hydraulic diameter of the pipe is 25mm, so that the mixing of the fluid in the fluid pipe can be enhanced.
Preparation of example 1
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding polyvinylpyrrolidone serving as a first surfactant, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of calcium chloride in the calcium chloride solution is 0.5mol/L, and the concentration of polyvinylpyrrolidone serving as the first surfactant is 5 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant, namely sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.5mol/L, the concentration of sodium dodecyl sulfate is 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 5 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 19ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the retention time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 30s, the ultrasonic power is 500W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, the obtained scanning electron microscope image is shown in fig. 1, and the calcium carbonate particles prepared by analysis have a uniform spherical structure, the average particle size of the calcium carbonate particles is 562nm, and the morphology is uniform.
Preparation of example 2
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding polyvinylpyrrolidone serving as a first surfactant, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of calcium chloride in the calcium chloride solution is 0.5mol/L, and the concentration of polyvinylpyrrolidone serving as the first surfactant is 5 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant of sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.5mol/L, the concentration of sodium dodecyl sulfate is 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 5 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 19ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the retention time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 30s, the ultrasonic power is 150W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared by the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, and after analysis, the prepared calcium carbonate particles have a uniform spherical structure, the average particle size of the particles is 0.9 μm, and the morphology is uniform.
Preparation of example 3
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding a first surfactant polyvinylpyrrolidone, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of the calcium chloride in the calcium chloride solution is 0.5mol/L, and the concentration of the first surfactant polyvinylpyrrolidone is 5 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant of sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.5mol/L, the concentration of sodium dodecyl sulfate is 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 5 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 60ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the retention time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 10s, the ultrasonic power is 500W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, the obtained scanning electron microscope image is shown in fig. 2, and the calcium carbonate particles prepared by analysis have a uniform spherical structure, the average particle size of the particles is 1.7 μm, and the morphology is uniform.
Preparation of example 4
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding polyvinylpyrrolidone serving as a first surfactant, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of calcium chloride in the calcium chloride solution is 0.1mol/L, and the concentration of polyvinylpyrrolidone serving as the first surfactant is 2 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant of sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.1mol/L, the concentration of sodium dodecyl sulfate is 2.5mmol/L, and the concentration of polyvinylpyrrolidone is 2 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 4ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the retention time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 1.5s, the ultrasonic power is 50W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, the obtained scanning electron microscope image is shown in fig. 3, and the calcium carbonate particles prepared by analysis have a uniform spherical structure, the average particle size of the calcium carbonate particles is 538nm, and the morphology is uniform.
Preparation of example 5
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding a first surfactant polyvinylpyrrolidone, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of the calcium chloride in the calcium chloride solution is 0.5mol/L, and the concentration of the first surfactant polyvinylpyrrolidone is 10 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant of sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.5mol/L, the concentration of sodium dodecyl sulfate is 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 10 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 50ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the retention time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 12s, the ultrasonic power is 50W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, and after analysis, the prepared calcium carbonate particles have a uniform spherical structure, the average particle size of the particles is 1.1 mu m, and the morphology is uniform.
Comparative examples
Comparative example 1
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding a first surfactant polyvinylpyrrolidone, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of the calcium chloride in the calcium chloride solution is 0.5mol/L, and the concentration of the first surfactant polyvinylpyrrolidone is 10 mg/mL; and simultaneously adding sodium carbonate into water, adding a second surfactant of sodium dodecyl sulfate and polyvinylpyrrolidone, and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 0.5mol/L, the concentration of sodium dodecyl sulfate is 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 10 mg/ml.
(2) Ultrasonic reaction: conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction to obtain calcium carbonate slurry, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 10ml/min, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the residence time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 0.6s, the ultrasonic power is 0, and the ultrasonic frequency is 0.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example were dispersed in ethanol and observed for morphology by a scanning electron microscope, and the obtained scanning electron microscope image is shown in fig. 4, and through analysis, the prepared calcium carbonate particles have a spherical structure, but have nonuniform morphology and nonuniform particle size, and the average particle size of the particles is 2.3 μm.
Comparative example 2
(1) Preparing a reaction solution: dissolving calcium chloride in water, adding surfactant polyvinylpyrrolidone and sodium dodecyl sulfate, and uniformly stirring to obtain a calcium chloride solution, wherein the concentration of calcium chloride in the calcium chloride solution is 1mol/L, and the concentrations of the first surfactant polyvinylpyrrolidone and the sodium dodecyl sulfate are both 10 mg/mL; simultaneously, adding sodium carbonate into water and uniformly stirring to obtain a sodium carbonate solution, wherein the concentration of sodium carbonate in the sodium carbonate solution is 1 mol/L.
(2) Ultrasonic reaction: and (2) conveying the calcium chloride solution and the sodium carbonate solution obtained in the step (1) into an ultrasonic pipeline reactor for ultrasonic reaction, wherein the flow rates of the calcium chloride solution and the sodium carbonate solution are both 19ml/min, so as to obtain calcium carbonate slurry, the molar ratio of the calcium chloride in the calcium chloride solution to the sodium carbonate in the sodium carbonate solution is 1:1 during conveying, the residence time of the calcium chloride solution and the sodium carbonate solution conveyed into the ultrasonic pipeline reactor is 30s, the ultrasonic power is 500W, and the ultrasonic frequency is 20 KHz.
(3) And (3) filtering and drying: and (3) filtering the calcium carbonate slurry obtained in the step (2), washing the white product obtained after filtering with water for 3 times, drying in an oven at 60 ℃ for 12 hours after washing, and crushing to obtain solid calcium carbonate particles.
The calcium carbonate particles prepared in the preparation example are dispersed in ethanol, and the morphology is observed by using a scanning electron microscope, and through analysis, the prepared calcium carbonate particles have a spherical structure, but have uneven morphology and uneven particle size, and the average particle size is 559 nm.
In addition, it should be noted that the inventor of the present invention has carried out a great deal of experiments to demonstrate the present invention, and the above examples are only partially verified and do not fully cover the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and modifications and variations of the present invention are also intended to fall within the scope of the appended claims. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. A calcium carbonate preparation method based on an ultrasonic pipeline type reactor is characterized by sequentially comprising the following steps:
(1) preparing a reaction solution: dissolving a soluble calcium salt in water and adding a first surfactant to obtain a calcium salt solution, while dissolving a carbonate in water and adding a second surfactant to obtain a carbonate solution;
(2) ultrasonic reaction: simultaneously conveying the calcium salt solution and the carbonate solution obtained in the step (1) to an ultrasonic pipeline type reactor for ultrasonic reaction to obtain calcium carbonate slurry, wherein the conveying amount of the calcium salt solution and the carbonate solution is 4-100mL/min, the molar ratio of calcium salt in the calcium salt solution to carbonate in the carbonate solution is 1:1 during conveying, and the residence time of the calcium salt solution and the carbonate solution conveyed to the ultrasonic pipeline type reactor is 0.5-40 s;
(3) and (3) subsequent treatment: and (3) filtering, washing, drying and crushing the calcium carbonate slurry obtained in the step (2) to obtain the spherical calcium carbonate.
2. The method for preparing calcium carbonate according to claim 1, wherein the calcium salt is a water-soluble calcium salt, such as one of calcium chloride, calcium nitrate, and calcium acetate.
3. The process for producing calcium carbonate according to claim 1, wherein the concentration of the calcium salt is 0.1 to 3 mol/L.
4. The process for the preparation of calcium carbonate according to claim 1, wherein the first surfactant is ethanol, polyvinylpyrrolidone, sodium lauryl sulfate or sodium dodecyl sulfate, particularly preferably polyvinylpyrrolidone.
5. The method of preparing calcium carbonate according to claim 1, wherein the concentration of the first surfactant is 2 to 20 mg/mL.
6. The method for producing calcium carbonate according to claim 1, wherein the second surfactant is two or more of ethanol, polyvinylpyrrolidone, sodium lauryl sulfate, and polyvinylpyrrolidone and sodium lauryl sulfate are particularly preferable.
7. The method of producing calcium carbonate according to claim 6, wherein the second surfactant is polyvinylpyrrolidone and sodium lauryl sulfate.
8. The method for preparing calcium carbonate according to claim 7, wherein the concentration of sodium dodecyl sulfate in the second surfactant is 2.5 to 12.5mmol/L, and the concentration of polyvinylpyrrolidone is 2 to 20 mg/mL.
9. Process for the preparation of calcium carbonate according to claim 1, characterized in that the carbonate is a water-soluble carbonate, particularly preferably sodium carbonate and/or potassium carbonate.
10. The process for preparing calcium carbonate according to claim 1, wherein the ultrasonic power of the ultrasonic reaction in the step (2) is 50-800W, and the ultrasonic frequency is 18-500kHz, preferably 18-60 kHz.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN115872940A (en) * 2023-02-28 2023-03-31 山东金佑星水环境科技有限公司 Sodium dichloroisocyanurate particles and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115872940A (en) * 2023-02-28 2023-03-31 山东金佑星水环境科技有限公司 Sodium dichloroisocyanurate particles and preparation method thereof

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