CN116969490A - 414 type basic magnesium carbonate and preparation method thereof - Google Patents

414 type basic magnesium carbonate and preparation method thereof Download PDF

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Publication number
CN116969490A
CN116969490A CN202310989862.0A CN202310989862A CN116969490A CN 116969490 A CN116969490 A CN 116969490A CN 202310989862 A CN202310989862 A CN 202310989862A CN 116969490 A CN116969490 A CN 116969490A
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magnesium carbonate
basic magnesium
sulfate solution
suspension
magnesium sulfate
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孙红娟
储凌燕
彭同江
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2004/60—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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The application provides 414 basic magnesium carbonate and a preparation method thereof, wherein the preparation method comprises the following steps: adding ammonia water into the magnesium sulfate solution, adjusting the pH value to remove impurities, filtering the suspension after the impurities are removed, and diluting or concentrating to obtain a refined magnesium sulfate solution; ammonia water and CO are injected into the refined magnesium sulfate solution 2 Stirring and heating to obtain suspension I; cooling and aging the suspension I to obtain a suspension II; filtering the suspension II to obtain filtrate and filter residue, and drying and dispersing the filter residue to obtain 414-type basic magnesium carbonate. The 414-type basic magnesium carbonate is prepared by the preparation method of the 414-type basic magnesium carbonate, and the 414-type basic magnesium carbonate has spherical and/or corolla-shaped crystal morphology. The preparation method provided by the application has the advantages of simple process, controllable product morphology and high product purity. The 414 basic magnesium carbonate provided by the application has complete appearance and uniform size.

Description

414 type basic magnesium carbonate and preparation method thereof
Technical Field
The application relates to the technical field of inorganic material preparation, in particular to 414-type basic magnesium carbonate and a preparation method thereof.
Background
Basic magnesium carbonate is an important inorganic mineral material, can exist stably under natural environment conditions, and can be used as an excellent reinforcing agent and a filling agent of high molecular polymers such as rubber, plastic and the like and used as an automobile air bag gas generating agent. In addition, the basic magnesium carbonate has the characteristics of high temperature resistance, no combustion, light texture and looseness, so that the basic magnesium carbonate is not only an environment-friendly flame retardant, but also an important intermediate raw material for preparing other fine magnesium salts. In the existing treatment method for preparing basic magnesium carbonate, the defects of complex flow, difficult shape control and the like often exist. Therefore, in order to solve the above-mentioned defects and technical problems existing in the prior art in the method for preparing basic magnesium carbonate, the application provides a preparation method for preparing 414-type basic magnesium carbonate by a one-step method of magnesium sulfate solution and 414-type basic magnesium carbonate.
Chinese patent application No. CN202110704657.6, hydrotalcite material with petal-shaped macroporous structure, its preparation method and application, mixed metal oxide and its preparation method, discloses a preparation method of hydrotalcite material with petal-shaped macroporous structure, which comprises the steps of: mixing a magnesium-containing dispersion liquid, a carbonate/bicarbonate solution and a template agent, and performing a first hydrothermal synthesis reaction on the obtained mixed liquid to obtain petal-shaped basic magnesium carbonate; the carbonate/bicarbonate solution is a carbonate solution or a bicarbonate solution; and mixing petal-shaped basic magnesium carbonate, water and sodium metaaluminate to perform a second hydrothermal synthesis reaction, so as to obtain the hydrotalcite material with the petal-shaped macroporous structure. The prepared hydrotalcite material can be used for preparing mixed metal oxide for FCC flue gas desulfurization through subsequent high-temperature roasting, and has a good desulfurization effect in FCC flue gas desulfurization. However, the preparation method is different from the preparation method, and the energy consumption required by the hydrothermal reaction in the process is higher.
The Chinese patent application No. CN202110381838.X, named "a method for producing magnesium ammonium sulfate and basic magnesium carbonate based on boron mud", discloses a method for producing basic magnesium carbonate based on boron mud, which takes waste residue-boron mud after borax production as raw material, adds ammonium bisulfate, heats to 20-100 ℃, stirs for 10-60 min, carries out solid-liquid separation on the obtained suspension to obtain magnesium ammonium sulfate solution; and then adding ammonium carbonate into the ammonium magnesium sulfate solution serving as a raw material, stirring and reacting for 20-80 min at 20-60 ℃ to prepare basic magnesium carbonate, wherein the adopted ammonium bisulfate and ammonium carbonate raw materials have low requirements on equipment, the problems of corrosion and impurity removal of strong acid on the equipment are solved, the adopted raw materials are non-dangerous, the production cost is reduced, and the safety is improved. However, the preparation method is different from the preparation method, and the process cannot control the morphology of the product.
Disclosure of Invention
The present application aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the purposes of the application is to provide a preparation method of 414 basic magnesium carbonate with simple process, controllable product morphology and high product purity. As another example, another object of the present application is to provide a type 414 basic magnesium carbonate that is complete in morphology and uniform in size.
In order to achieve the above object, according to an aspect of the present application, there is provided a preparation method of type 414 basic magnesium carbonate, which may include: adding ammonia water into the magnesium sulfate solution, adjusting the pH value to remove impurities, filtering the suspension after the impurities are removed, and diluting or concentrating to obtain a refined magnesium sulfate solution; ammonia water and CO are injected into the refined magnesium sulfate solution 2 Stirring and heating to obtain suspension I; cooling and aging the suspension I to obtain a suspension II; filtering the suspension II to obtain filtrate and filter residue, and drying and dispersing the filter residue to obtain 414-type basic magnesium carbonate.
According to one or more exemplary embodiments of an aspect of the present application, the concentration of the aqueous ammonia added to the magnesium sulfate solution may be 3mol/L to 5mol/L, and the concentration of the aqueous ammonia injected to the refined magnesium sulfate solution may be 1mol/L to 3mol/L.
According to one or more exemplary embodiments of an aspect of the present application, the ammonia water and the CO are injected into the refined magnesium sulfate solution in terms of a molar ratio 2 The ratio of the inlet rate of (2) can be 1-4: 1.
according to one or more exemplary embodiments of an aspect of the present application, the suspension I may include basic magnesium carbonate type 414 and basic magnesium carbonate type 415 therein, and the pH of the suspension I may be 9.2 to 9.6; the suspension II may include 414 basic magnesium carbonate.
According to one or more exemplary embodiments of an aspect of the present application, the aqueous ammonia and the CO 2 Can be uniformly injected at the same timeRefining the magnesium sulfate solution; the stirring and heating may be performed under airtight conditions.
According to one or more exemplary embodiments of an aspect of the present application, the heating temperature may be 85 ℃ to 95 ℃; the stirring speed can be 0 r/min-60 r/min, and when the stirring speed is 0 r/min-10 r/min, the crystal morphology of the 414-type basic magnesium carbonate can be spherical; when the stirring speed is 10 r/min-60 r/min, the crystal morphology of the 414-type basic magnesium carbonate can be corolla-shaped.
According to one or more exemplary embodiments of an aspect of the present application, the temperature of the cooling aging may be 25 to 55 ℃ for 4 to 12 hours.
According to one or more exemplary embodiments of an aspect of the present application, the pH of the impurity removal may be 7 to 8.
According to one or more exemplary embodiments of an aspect of the present application, mg in the refined magnesium sulfate solution 2+ The concentration of the metal impurity ions may be 4.8g/L to 12g/L, and the concentration of the other metal impurity ions may be 0.01g/L to 0.5g/L.
In another aspect of the present application, there is provided a type 414 basic magnesium carbonate, wherein the type 414 basic magnesium carbonate is prepared by the above-mentioned preparation method of the type 414 basic magnesium carbonate, the crystal morphology of the type 414 basic magnesium carbonate may be spherical and/or corolla-shaped, and the particle size of the type 414 basic magnesium carbonate is equal to the particle size of ammonia water and CO injected into the refined magnesium sulfate solution 2 The molar ratio of the feed rates of (c) may be inversely proportional.
Compared with the prior art, the application has the beneficial effects that at least one of the following contents is included:
(1) The preparation method of 414 basic magnesium carbonate solves the problems of complex process, difficult shape control, low product purity and the like in the prior preparation technology of basic magnesium carbonate;
(2) In the preparation method of 414 basic magnesium carbonate provided by the application, ammonia water and CO are simultaneously introduced 2 The basic magnesium carbonate is prepared by a one-step method without pyrolysis, the process flow is simple and convenient, and the operation controllability is strong;
(3) The 414 basic magnesium carbonate provided by the applicationThe 414 basic magnesium carbonate prepared by the one-step method of the magnesium sulfate solution and the preparation method thereof can realize CO 2 The basic magnesium carbonate is also an important chemical raw material.
Drawings
The foregoing and other objects and features of the application will become more apparent from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows an SEM image of a corolla-shaped basic magnesium carbonate according to example 1 of the present application;
FIG. 2 shows an SEM image of spherical basic magnesium carbonate of example 2 of the present application;
figure 3 shows the XRD pattern of basic magnesium carbonate of example 1 of the present application.
Detailed Description
Hereinafter, a type 414 basic magnesium carbonate and a method of preparing the same according to the present application will be described in detail with reference to the accompanying drawings and exemplary embodiments.
Example embodiment 1
The present exemplary embodiment provides a method for preparing type 414 basic magnesium carbonate.
The principle is as follows: adding ammonia water into the magnesium sulfate solution to adjust the pH value to remove Al 3+ 、Cr 3+ 、Ni 2+ And (5) plasma impurity ions. Ammonia water and carbon dioxide are introduced into the refined magnesium sulfate solution to generate basic magnesium carbonate, and the reaction formula is as follows:
the preparation method of 414 basic magnesium carbonate mainly comprises the following steps:
s1, adding ammonia water into the magnesium sulfate solution, adjusting the pH value of the solution to remove impurities and precipitate, filtering the suspension after removing the impurities, and diluting or concentrating to obtain a refined magnesium sulfate solution.
S2, injecting ammonia water and CO into the refined magnesium sulfate solution 2 Stirring and heating, and after injection, obtaining suspension I containing 414 type basic magnesium carbonate and 415 type basic magnesium carbonate.
S3, cooling and aging the suspension I to obtain suspension II containing 414-type basic magnesium carbonate.
And S4, filtering the suspension II to obtain filtrate and filter residues, recycling the filtrate, and drying and dispersing the filter residues to obtain 414-type basic magnesium carbonate.
In the present exemplary embodiment, in step S1, the concentration of ammonia added to the magnesium sulfate solution may be 3mol/L to 5mol/L, for example, 3mol/L, 4mol/L, or 5mol/L. The pH of the impurity-removed precipitate may be 7 to 8, for example 7, 7.5 or 8. Here, an impurity removal pH of less than 7 results in low impurity ion removal rate, and an impurity removal pH of greater than 8 results in increased loss rate of magnesium ions in the solution.
In the present exemplary embodiment, in step S1, mg in the magnesium sulfate solution is refined 2+ The concentration of (C) may be 4.8g/L to 12g/L, for example 5g/L, 7g/L or 11g/L. Too high or too low a concentration of magnesium ions affects the rate of formation of basic magnesium carbonate. The concentration of other metal impurity ions may be 0.01g/L to 0.5g/L, for example 0.02g/L, 0.35g/L or 0.5g/L. Too high a concentration of impurity ions can affect the purity of the final product. Here, the other metal impurity ions may include Al 3+ 、Cr 3+ 、Ni 2+ 、Mn 2+ 、Fe 3+ And Ca 2+ Etc.
In the present exemplary embodiment, in step S2, the refined magnesium sulfate solution obtained in step S1 may be placed in a closed reaction vessel with stirring and heating means, and the refined magnesium sulfate solution in the reaction vessel may be simultaneously and uniformly injected with ammonia water and technical grade CO at a concentration 2 。
Further, in step S2, to ensure ammonia and CO 2 Evenly introduced into the reaction kettle, the feeding mode of ammonia water can be spraying, CO 2 Can be uniformly introduced into the reaction kettle through an aeration pipe.
In the present exemplary embodiment, in step S2, the concentration of the aqueous ammonia injected into the purified magnesium sulfate solution may be 1mol/L to 3mol/L, for example, 1mol/L, 1.7mol/L, or 2.81mol/L. Here, too low a concentration of ammonia may result in too great a decrease in concentration of the magnesium sulfate solution.
In the present exemplary embodiment of the present application,in step S2, ammonia and CO 2 The pH of the suspension in the reaction vessel may be brought to a value of 9.2 to 9.6, for example 9.2, 9.4 or 9.6 after the injection. Here, too low a pH value may result in a low magnesium precipitation rate.
In the present exemplary embodiment, in step S2, ammonia water and CO are injected into the refined magnesium sulfate solution in terms of molar ratio 2 The ratio of the inlet rate of (2) can be 1-4: 1, for example 1: 1. 2: 1. 3:1 or 4:1. here, ammonia and CO 2 Too large a ratio of the rate of passage results in a final product other than basic magnesium carbonate, and too small a ratio of the rate of passage results in incomplete shape of basic magnesium carbonate.
In the present exemplary embodiment, in step S2, the heated reaction temperature may be 85 to 95 ℃, for example 86 ℃,90 ℃, or 94 ℃. Here, the precipitated product is magnesium carbonate trihydrate instead of basic magnesium carbonate at low reaction temperatures, and too high a reaction temperature increases the process energy consumption. The stirring speed may be 0r/min to 60r/min, for example 0r/min, 20r/min or 40r/min. Here, too high stirring speed may cause the basic magnesium carbonate to be destroyed.
Further, when the stirring speed is 0 r/min-10 r/min, the crystal morphology of the obtained 414-type basic magnesium carbonate can be spherical. When the stirring speed is 10 r/min-60 r/min, the crystal morphology of the obtained 414-type basic magnesium carbonate can be corolla-shaped.
In the present exemplary embodiment, in step S2, the ideal chemical formula of the type 414 basic magnesium carbonate may be 4MgCO 3 ·Mg(OH) 2 ·4H 2 The ideal chemical formula of the O, 415-type basic magnesium carbonate can be 4MgCO 3 ·Mg(OH) 2 ·5H 2 O。
In the present exemplary embodiment, in step S3, the temperature of the cool-down aging may be 25 ℃ to 55 ℃, for example, 25 ℃, 35 ℃, or 48 ℃. Here, too low an aging temperature may cause a slow crystallization rate of the product, and too high an aging temperature may increase energy consumption. The aging time may be from 4 hours to 12 hours, for example 5 hours, 8 hours or 11 hours. Here, if the aging time is too short, the basic magnesium carbonate is poorly crystallized, and if the crystallization time is too long, the overall process time is lengthened.
In the present exemplary embodiment, in step S4, the obtained type 414 basic magnesium carbonate may meet the standards of the first-grade or superior product in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Example embodiment 2
The present exemplary embodiment provides a type 414 basic magnesium carbonate.
Form 414 basic magnesium carbonate may be prepared by the preparation method of form 414 basic magnesium carbonate described in the above first exemplary embodiment.
In the present exemplary embodiment, the crystal morphology of the type 414 basic magnesium carbonate may be spherical and/or corolla-like. When it is spherical, the diameter of the spherical particles may be 5 μm to 14 μm, the individual crystals constituting the spherical particles may be plate-like, and the plate diameter may be 14nm to 20nm. When it is in the form of a corolla, the diameter of the corolla particles may be 5 μm to 30. Mu.m, the individual crystals constituting the corolla may be in the form of a sheet, and the sheet diameter may be 10nm to 16nm.
In the present exemplary embodiment, the particle size of the 414-type basic magnesium carbonate and the ammonia water and CO injected into the refined magnesium sulfate solution 2 Molar ratio of the feed rate (NH) 3 ·H 2 O/CO 2 ) May be inversely proportional.
For a better understanding of the above-described exemplary embodiment 2 of the present application, it is further described below with reference to specific examples.
Example 1
FIG. 1 shows an SEM image of a corolla-shaped basic magnesium carbonate according to example 1 of the present application; figure 3 shows the XRD pattern of basic magnesium carbonate of example 1 of the present application.
Adding 3mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 7.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in table 1.
TABLE 1 main chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 7.687 0.028 0.094 0.0025 0.008 0.045 0.022
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 3mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the feed rates (in terms of molar ratio) was 1:1, the reaction is stopped when the pH value of the reaction system is 9.2 under the condition that the stirring speed is 20r/min and the temperature is 85 ℃. Aging at 25deg.C for 4 hr, filtering to obtain filtrate and residue, wherein the filtrate is basic magnesium carbonate, and the residue is 414 basic magnesium carbonate as shown in FIG. 3. As shown in fig. 1, the basic magnesium carbonate is corolla-shaped and has a complete morphology. The average particle diameter of the 414 basic magnesium carbonate was 29.5. Mu.m.
As can be seen, in the preparation method of example 1, the stirring speed was 20r/min, and the finally obtained 414-type basic magnesium carbonate was corolla-shaped.
The type 414 basic magnesium carbonate obtained in example 1 was tested and compared with a standard pair of first grade products, and the comparison is shown in Table 2. The basic magnesium carbonate meets the standard of first grade products in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Table 2 product testing
Project Test value Index (first grade)
Magnesium oxide (MgO) w/% 41.1 40.0～43.5
Calcium oxide (CaO) w/% 0.30 ≤0.70
Hydrochloric acid insoluble w/% 0.09 ≤0.15
Moisture w/% 1.8 ≤3.0
Firing decrement w/% 55 54～58
Chloride (in Cl) w/% 0.05 ≤0.10
Iron (Fe) w/% 0.008 ≤0.02
Manganese (Mn) w/% 0.001 ≤0.004
Sulfate (in SO) 4 Meter) w/% 0.10 ≤0.15
Fineness (0.15 mm) w/% 0.02 ≤0.03
Bulk Density/(g/ml) 0.15 ≤0.2
Example 2
Fig. 2 shows an SEM image of spherical basic magnesium carbonate of example 2 of the present application.
Adding 5mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 8.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 3.
TABLE 3 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 12.0 0.050 0.025 0.0025 0.010 0.030 0.028
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 1mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the feed rates (in terms of molar ratio) was 4:1, the reaction is stopped when the pH value of the reaction system is 9.6 under the condition that the stirring speed is 0r/min and the temperature is 95 ℃. Aging at 55deg.C for 4 hr, filtering the reaction product after aging to obtain filtrate and residue, wherein the filtrate can be recycled, and the residue is414 basic magnesium carbonate. As shown in fig. 2, the obtained type 414 basic magnesium carbonate is spherical and has complete morphology. The average particle diameter of basic magnesium carbonate type 414 in this example was 12.2. Mu.m.
It can be seen that the stirring speed in the preparation method of example 2 was 0r/min, and the finally obtained 414-type basic magnesium carbonate was spherical.
The 414 basic magnesium carbonate obtained in example 2 was tested and compared with a standard pair of superior products, as shown in Table 4. The basic magnesium carbonate meets the standard of superior products in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Table 4 product testing
Example 3
Adding 5mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 8.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 5.
TABLE 5 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 12.0 0.050 0.025 0.0025 0.010 0.030 0.028
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 2mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the introduction rate (in terms of mole ratio) was 3:1, the reaction is stopped when the pH value of the reaction system is 9.4 under the condition that the stirring speed is 60r/min and the temperature is 90 ℃. Aging at 30deg.C for 12 hr, filtering the reaction product to obtain filtrate and residue, wherein the filtrate is recyclable, the residue is the 414 type basic magnesium carbonate, and the obtained 414 type basic magnesium carbonate is corolla-shaped and has an average particle diameter of 18.3 μm.
As can be seen, in the preparation method of example 3, the stirring speed was 60r/min, and the finally obtained 414-type basic magnesium carbonate was corolla-shaped.
The type 414 basic magnesium carbonate obtained in example 3 was tested and compared with a standard pair of first class products, as shown in Table 6. The basic magnesium carbonate meets the standard of first grade products in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Table 6 product testing
Project Test value Index (first grade)
Magnesium oxide (MgO) w/% 42.8 40.0～43.5
Calcium oxide (CaO) w/% 0.20 ≤0.70
Hydrochloric acid insoluble w/% 0.10 ≤0.15
Moisture w/% 2.0 ≤3.0
Firing decrement w/% 56 54～58
Chloride (in Cl) w/% 0.03 ≤0.10
Iron (Fe) w/% 0.01 ≤0.02
Manganese (Mn) w/% 0.003 ≤0.004
Sulfate (in SO) 4 Meter) w/% 0.10 ≤0.15
Fineness (0.15 mm) w/% 0.02 ≤0.03
Bulk Density/(g/ml) 0.16 ≤0.2
Example 4
Adding 5mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 7.5, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 7.
TABLE 7 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 4.80 0.020 0.013 0.0012 0.010 0.015 0.020
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 3mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the introduction rate (in terms of mole ratio) was 3:1, the reaction is stopped when the pH value of the reaction system is 9.3 under the condition that the stirring speed is 60r/min and the temperature is 85 ℃. Aging at 40 ℃ for 6 hours, filtering the reaction product after aging to obtain filtrate and filter residue, wherein the filtrate can be recycled, the filter residue is the 414 basic magnesium carbonate, and the obtained 414 basic magnesium carbonate is in a corolla shape and has an average particle size of 17.5 mu m.
As can be seen, in the preparation method of example 4, the stirring speed was 60r/min, and the finally obtained 414-type basic magnesium carbonate was corolla-shaped.
The type 414 basic magnesium carbonate obtained in example 4 was tested and compared with a standard pair of first class products, as shown in Table 8. The basic magnesium carbonate meets the standard of first grade products in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Table 8 product testing
Project Test value Index (first grade)
Magnesium oxide (MgO) w/% 41.8 40.0～43.5
Calcium oxide (CaO) w/% 0.20 ≤0.70
Hydrochloric acid insoluble w/% 0.10 ≤0.15
Moisture w/% 2.0 ≤3.0
Firing decrement w/% 55 54～58
Chloride (in Cl) w/% 0.05 ≤0.10
Iron (Fe) w/% 0.01 ≤0.02
Manganese (Mn) w/% 0.002 ≤0.004
Sulfate (in SO) 4 Meter) w/% 0.08 ≤0.15
Fineness (0.15 mm) w/% 0.025 ≤0.03
Bulk Density/(g/ml) 0.15 ≤0.2
Example 5
Adding 4mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 8.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 9.
TABLE 9 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 8.82 0.005 0.030 0.0028 0.016 0.025 0.024
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 2mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the introduction rate (in terms of mole ratio) was 3:1, the reaction is stopped when the pH value of the reaction system is 9.2 under the condition that the stirring speed is 60r/min and the temperature is 95 ℃. Aging at 55deg.C for 8 hr, filtering the reaction product to obtain filtrate and residue, wherein the filtrate is recyclable, the residue is the 414 type basic magnesium carbonate, and the obtained 414 type basic magnesium carbonate has corolla shape and average particle diameter of 17.9 μm.
As can be seen, in the preparation method of example 5, the stirring speed was 60r/min, and the finally obtained 414-type basic magnesium carbonate was corolla-shaped.
The 414 basic magnesium carbonate obtained in example 5 was tested and compared with the standard pair of superior products, as shown in table 10. The basic magnesium carbonate meets the standard of superior products in HG/T2959-2010 industrial hydrated basic magnesium carbonate.
Table 10 product testing
Comparative example 1
Adding 4mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 8.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 11.
TABLE 11 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 8.82 0.005 0.030 0.0028 0.016 0.025 0.024
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 2mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 Is introduced intoThe rate ratio (in terms of mole ratio) was 0.5:1, the reaction is stopped when the pH value of the reaction system is 9.2 under the condition that the stirring speed is 60r/min and the temperature is 95 ℃. Aging at 55 ℃ for 8 hours, filtering the reaction product after the aging is finished to obtain filtrate and filter residue, wherein the obtained filter residue is 414 basic magnesium carbonate, but has low crystal morphology integrity and poor crystallinity.
Comparative example 1 compared with example 5, the preparation method was carried out only on ammonia water and CO 2 Is different in terms of the rate ratio of the introduction. Ammonia and CO in molar ratio of comparative example 1 2 The feed rate of (2) was 0.5:1, the product obtained in comparative example 1 is 414 basic magnesium carbonate, but the crystal morphology is low in integrity and poor in crystallinity. Example 5 Ammonia Water and CO 2 The rate of passage is 3:1, example 5 gives a basic magnesium carbonate 414 which is corolla-shaped and meets the standard of superior products in HG/T2959-2010 Industrial hydrated basic magnesium carbonate. Thus, it can be seen that: ammonia and CO 2 Too small a ratio of the rate of introduction may result in incomplete morphology of the basic magnesium carbonate.
Comparative example 2
Adding 4mol/L ammonia water into the magnesium sulfate solution to adjust the pH value of the solution to 8.0, and filtering the suspension after impurity removal to obtain refined magnesium sulfate solution, wherein the ion concentration of the refined magnesium sulfate solution is shown in Table 12.
TABLE 12 principal chemical Components of refined magnesium sulfate solution
Element(s) Mg Al Ca Cr Fe Ni Mn
Concentration (g/L) 8.82 0.005 0.030 0.0028 0.016 0.025 0.024
The refined magnesium sulfate solution is placed in a closed reaction kettle with a stirring and heating device, 2mol/L ammonia water is introduced in a spraying mode, and industrial grade CO is introduced through an aeration pipe 2 Ammonia and CO 2 The ratio of the introduction rate (in terms of mole ratio) was 5:1, the reaction is stopped when the pH value of the reaction system is 9.2 under the condition that the stirring speed is 60r/min and the temperature is 95 ℃. Aging at 55 ℃ for 8 hours, filtering the reaction product after the aging is finished to obtain filtrate and filter residue, wherein the obtained filter residue is a mixture of basic magnesium carbonate and magnesium hydroxide.
Comparative example 2 compared with example 5, the preparation method was carried out only on ammonia water and CO 2 Is different in terms of the rate ratio of the introduction. Ammonia and CO in molar ratio of comparative example 2 2 The rate of passage is 5:1, the product obtained in comparative example 2 is a mixture of basic magnesium carbonate and magnesium hydroxide. Example 5 Ammonia Water and CO 2 The rate of passage is 3:1, example 5 gives a basic magnesium carbonate 414 which is corolla-shaped and meets the standard of superior products in HG/T2959-2010 Industrial hydrated basic magnesium carbonate. Thus, it can be seen that: ammonia and CO 2 Too large a ratio of the rate of passage results in a final product that is not pure basic magnesium carbonate.
In summary, the advantages of the present application include at least one of the following:
(1) The preparation method of 414 basic magnesium carbonate provided by the application has the advantages of simple process flow and controllable product morphology;
(2) The preparation method of 414 basic magnesium carbonate provided by the application uses CO 2 Preparation of basic magnesium carbonate as carbon source and CO 2 Provides a way for recycling;
(3) The preparation method of 414 basic magnesium carbonate provided by the application controls ammonia water and CO 2 The particle size of the basic magnesium carbonate can be controlled by the introducing rate;
(4) The preparation method of the 414 basic magnesium carbonate can control the morphology of the basic magnesium carbonate by controlling the stirring speed;
(5) In the preparation method of 414 basic magnesium carbonate, the magnesium ion precipitation rate is higher than 90 percent, and the loss rate of magnesium ions is low;
(6) The 414 basic magnesium carbonate provided by the application has complete appearance and uniform size.
Although a type 414 basic magnesium carbonate of the present application and a method of preparing the same have been described above by way of example embodiments, it should be apparent to those skilled in the art that various modifications and adaptations may be made to the example embodiments of the present application without departing from the spirit and scope of the application as defined in the appended claims.

Claims (10)

1. A method for preparing 414 basic magnesium carbonate, which is characterized by comprising the following steps:
adding ammonia water into the magnesium sulfate solution, adjusting the pH value to remove impurities, filtering the suspension after the impurities are removed, and diluting or concentrating to obtain a refined magnesium sulfate solution;
ammonia water and CO are injected into the refined magnesium sulfate solution 2 Stirring and heating to obtain suspension I;
cooling and aging the suspension I to obtain a suspension II;
filtering the suspension II to obtain filtrate and filter residue, and drying and dispersing the filter residue to obtain 414-type basic magnesium carbonate.
2. The method for producing basic magnesium carbonate according to claim 414, wherein the concentration of aqueous ammonia added to the magnesium sulfate solution is 3mol/L to 5mol/L, and the concentration of aqueous ammonia injected into the purified magnesium sulfate solution is 1mol/L to 3mol/L.
3. The method for producing basic magnesium carbonate according to claim 414, wherein the aqueous ammonia and the CO are injected into the purified magnesium sulfate solution in terms of molar ratio 2 The ratio of the inlet rate of (2) is 1-4: 1.
4. the preparation method of 414 basic magnesium carbonate according to claim 1, wherein the suspension I comprises 414 basic magnesium carbonate and 415 basic magnesium carbonate, and the pH value of the suspension I is 9.2-9.6; the suspension II comprises 414 basic magnesium carbonate.
5. The method for producing 414 basic magnesium carbonate according to claim 1, wherein the aqueous ammonia and the CO 2 Simultaneously and uniformly injecting the magnesium sulfate into the refined magnesium sulfate solution; the stirring and heating are performed under airtight conditions.
6. The method for preparing 414 basic magnesium carbonate according to claim 1 or 5, wherein the heating temperature is 85 ℃ to 95 ℃; the stirring speed is 0 r/min-60 r/min, and when the stirring speed is 0 r/min-10 r/min, the crystal morphology of the 414-type basic magnesium carbonate is spherical; when the stirring speed is 10 r/min-60 r/min, the crystal morphology of the 414-type basic magnesium carbonate is corolla-shaped.
7. The method for preparing 414-type basic magnesium carbonate according to claim 1, wherein the temperature of cooling and aging is 25-55 ℃ for 4-12 h.
8. The method for preparing 414 basic magnesium carbonate according to claim 1, wherein the pH of the removed impurities is 7 to 8.
9. The method for preparing 414 basic magnesium carbonate according to claim 1, wherein Mg in the refined magnesium sulfate solution 2+ The concentration of the metal impurity ions is 4.8g/L to 12g/L, and the concentration of the other metal impurity ions is 0.01g/L to 0.5g/L.
10. A basic magnesium carbonate form 414, wherein the basic magnesium carbonate form 414 is prepared by the preparation method of the basic magnesium carbonate form 414 according to any one of claims 1 to 9, the basic magnesium carbonate form 414 has spherical and/or corolla crystal morphology, and the particle size of the basic magnesium carbonate form 414 is equal to that of ammonia water and CO injected into the refined magnesium sulfate solution 2 Is inversely proportional to the molar ratio of the feed rates.
CN202310989862.0A 2023-08-07 2023-08-07 414 type basic magnesium carbonate and preparation method thereof Pending CN116969490A (en)

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