CN113769478B - Calcium-magnesium mineralized filter material and preparation method thereof - Google Patents
Calcium-magnesium mineralized filter material and preparation method thereof Download PDFInfo
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- CN113769478B CN113769478B CN202111161222.8A CN202111161222A CN113769478B CN 113769478 B CN113769478 B CN 113769478B CN 202111161222 A CN202111161222 A CN 202111161222A CN 113769478 B CN113769478 B CN 113769478B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application discloses calcium magnesium mineralized filter material and preparation method thereof, calcium magnesium mineralized filter material includes the base member and coats in the coating of base member surface, and wherein, the base member is modified limestone, and the coating includes recrystallization calcite and recrystallization dolomite, 10g calcium magnesium mineralized filter material soaks the concentration ratio between calcium and magnesium in the soak solution that 12h obtained after in 50 mL's deionized water is calcium: magnesium is (1-3): 1, the concentration of calcium in the soak solution is 65-90 mg/L, and the concentration of magnesium in the soak solution is 20-35 mg/L, the calcium-magnesium mineralized filter material can be used for carrying out stable remineralization treatment on the drinking water with lower calcium and magnesium content, so that the concentration ratio of calcium to magnesium in the drinking water is controlled to be in accordance with the recommended value of healthy drinking water while the contents of calcium and magnesium in the drinking water are improved, and the quality of the drinking water is improved.
Description
Technical Field
The application relates to the technical field of mineralized filter materials, in particular to a calcium-magnesium mineralized filter material and a preparation method thereof
Background
Drinking water is a necessity for human life, and the quality of drinking water is closely related to human health and has a long influence on human survival and development, so that the quality of drinking water is one of the people concerned and one of the research hotspots. Inorganic components in drinking water play an important role in maintaining human health, but no matter whether the elements are macroelements or microelements, the increase or decrease of the elements exceeds a certain range, the elements can cause adverse effects on human health, and physiological or pathological changes are caused.
Calcium and magnesium are essential elements for life, are involved in various physiological activities of human bodies and are closely related to the occurrence and prevention of many common diseases and frequently encountered diseases, and drinking water is an important channel for supplementing calcium and magnesium for human beings. The world health organization issued a comprehensive survey in 2009 on the public health significance of calcium and magnesium in drinking water, and studies showed that as the calcium and magnesium content in drinking water increased, the risk of death of various diseases such as cardiovascular diseases decreased. Research shows that the contents of calcium and magnesium in drinking water are greatly related to regional diseases, such as: the high concentration ratio of calcium to magnesium in drinking water (the concentration ratio of calcium to magnesium is higher than 5.
Generally speaking, the calcium and magnesium obtained by Chinese people from drinking water are low, and the main reasons are as follows: on the first hand, in China, natural water with low calcium and magnesium contents is widely distributed; secondly, the popularity of the water purifiers is increasing day by day, and most of the water purifiers remove mineral elements such as calcium, magnesium and the like in the drinking water by using a reverse osmosis or nanofiltration technology; in a third aspect, the drinking water is usually boiled before drinking, and after boiling, part of calcium and magnesium in the drinking water can be separated out in a precipitate form and can not enter the human body, so that only part of the calcium and magnesium dissolved in the water can be absorbed by the human body. The researchers have proposed that the drinking water with low content of calcium and magnesium should be remineralized to improve the content of calcium and magnesium in the drinking water, and researches have found that the drinking water with low content of calcium and magnesium can be improved by remineralizing limestone, but the content of magnesium in the drinking water cannot be improved, and the problem that the concentration ratio of calcium to magnesium in the drinking water is unbalanced is easily caused. In addition, the application of limestone to a home-use water purifier has a limitation in that stable mineralization cannot be achieved because dissolution speed of limestone cannot be controlled. Therefore, how to stably remineralize drinking water with low calcium and magnesium contents to simultaneously improve the calcium and magnesium contents in the drinking water and control the concentration ratio of calcium to magnesium within a reasonable range has become a technical problem to be solved urgently in the water purification industry.
Disclosure of Invention
In view of this, the embodiment of the present application provides a calcium-magnesium mineralized filter material, a preparation method thereof, and a water purification apparatus, so as to perform stable remineralization treatment on drinking water with low calcium and magnesium content, increase the calcium and magnesium content in the drinking water, and control the concentration ratio of calcium to magnesium in (1-3): 1, in the above range.
The technical scheme of the application is as follows:
in a first aspect, the present application provides a calcium-magnesium mineralized filter material, which includes a substrate and a coating layer coated on the outer surface of the substrate, wherein the substrate is modified limestone, the coating layer includes recrystallized calcite and recrystallized dolomite, and the modified limestone, the recrystallized calcite and the recrystallized dolomite have a mass ratio of the modified limestone to the recrystallized dolomite that is: the recrystallized calcite: the recrystallized dolomite is (3-10): 1: (2-3); the particle size of the modified limestone is 60 meshes-80 meshes, and the total pore volume is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 A specific surface area of 4.2 m/g 2 /g～6.7m 2 /g。
Further, the thickness of the coating layer is 40-100 μm.
In a second aspect, the present application provides a method for preparing a calcium-magnesium mineralized filter material, comprising the following steps:
(1) Providing calcite dissolving liquid, dolomite dissolving liquid and modified limestone;
(2) Atomizing the calcite dissolving solution and the dolomite dissolving solution in the atmosphere of carbon dioxide gas, introducing the modified limestone, and stirring for reaction to obtain the calcium-magnesium mineralized filter material;
in the calcium-magnesium mineralized filter material, the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite is as follows: the recrystallized calcite: the recrystallized dolomite is (3-10): 1: (2-3); the particle size of the modified limestone is 60-80 meshes, and the total pore volume is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 A specific surface area of 4.2m 2 /g～6.7m 2 /g。
Further, the total dissolved solids of the calcite dissolving solution are more than 450mg/L, and the total dissolved solids of the dolomite dissolving solution are more than 600mg/L.
Further, in the (1), the calcite dissolution solution and the dolomite dissolution solution are prepared by the following methods:
(1 a, respectively crushing a natural calcite raw material and a natural dolomite raw material, and then respectively soaking the crushed natural calcite raw material and the crushed natural dolomite raw material in deionized water;
(1b) Respectively stirring and dissolving the natural calcite raw material and the natural dolomite raw material in the atmosphere of carbon dioxide gas, wherein the partial pressure of carbon dioxide is more than 0.1 bar, and the environmental temperature is 5-10 ℃.
Further, in the (1), the modified limestone is prepared by a method comprising:
placing natural limestone raw materials with the grain size of 60 meshes to 80 meshes in a solution containing a modifier, then soaking at the temperature of 80 ℃ to 90 ℃ for 6 hours to 12 hours, filtering and drying to obtain modified limestone;
wherein the modifier is sodium citrate, malic acid, acetic acid or acetate.
Further, the volume ratio between the natural limestone raw material and the modifying agent is that the natural limestone raw material: the modifier is (3-5): 1.
further, the modifier is sodium citrate.
Further, the (2) includes the steps of:
(2a) Placing the modified limestone in a closed container, heating the closed container to 200-450 ℃, and introducing carbon dioxide gas into the closed container;
(2b) Mixing the calcite dissolving solution and the dolomite dissolving solution according to a preset proportion to obtain a reaction solution, atomizing the reaction solution in the atmosphere of carbon dioxide gas, introducing the atomized reaction solution into the closed container, and stirring for reaction to obtain the calcium-magnesium mineralized filter material.
Further, in the step (2 b), the molar ratio of the carbon dioxide gas to the calcium ions in the reaction solution to the magnesium ions in the reaction solution is the ratio of the carbon dioxide gas: calcium ion in the reaction solution: the magnesium ions in the reaction liquid are (3-6): 1: (2-5).
Has the beneficial effects that:
the application provides a calcium magnesium mineralized filter material and preparation method and purifier thereof, the calcium magnesium mineralized filter material includes the base member and wraps the coating in the base member surface, wherein, the base member is modified limestone, and the coating includes recrystallization calcite and recrystallization dolomite, 10g the concentration ratio between calcium and magnesium in the soak solution that obtains after calcium magnesium mineralized filter material soaks 12h in 50 mL's deionized water is calcium: magnesium is (1-3): 1, the concentration of calcium in the soak solution is 65-90 mg/L, and the concentration of magnesium in the soak solution is 20-35 mg/L, the calcium-magnesium mineralized filter material can be used for carrying out stable remineralization treatment on the drinking water with lower calcium and magnesium content, so that the concentration ratio of calcium to magnesium in the drinking water is controlled to be in accordance with the recommended value of healthy drinking water while the contents of calcium and magnesium in the drinking water are improved, and the quality of the drinking water is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a scanning electron microscope photograph of particulate modified limestone and calcium magnesium mineralized filter material according to example 1 of the present application.
FIG. 2 is an X-ray diffraction pattern of the granular modified limestone and calcium-magnesium mineralized filter material in example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application. Furthermore, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the present application, are given by way of illustration and explanation only, and are not intended to limit the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred embodiments and materials described herein are exemplary only, and are not intended to limit the scope of the present application.
It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present application may exist in a range of forms; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, for example, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
Unless otherwise indicated, reagents used in the following examples are all commercially available or may be prepared by methods known in the art. The natural limestone, dolomite and calcite, referred to in the following examples, originate from guangxi Bama, from Anshan Liaoning, and from Hebei Shijiazhuang.
The embodiment of the application provides a calcium-magnesium mineralized filter material, which comprises a substrate and a coating layer coated on the outer surface of the substrate, wherein the substrate is modified limestone, the particle size of the modified limestone is 60-80 meshes, and the total pore volume of the modified limestone is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 (ii)/g, and the specific surface area of the modified limestone is 4.2m 2 /g～6.7m 2 (ii)/g; the coating layer comprises recrystallized calcite and recrystallized dolomite, and the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite is that the modified limestone: recrystallizing calcite: the recrystallized dolomite is (3-10): 1: (2-3) soaking 10g of the calcium-magnesium mineralized filter material in 50mL of deionized water for 12 hours to obtain a soaking solution, wherein the concentration ratio of calcium to magnesium in the soaking solution is calcium: magnesium is (1-3): 1, the concentration of calcium is 65-90 mg/L and the concentration of magnesium is 20-35 mg/L in the soak solution.
In the calcium-magnesium mineralized filter material, the modified limestone is adopted as a matrix, and the reason that natural limestone is not adopted as the matrix is as follows: compared with modified limestone, the surface of the natural limestone is smoother, and the problem of 'powder falling' can occur when the outer surface of the natural limestone is coated with recrystallized calcite and recrystallized dolomite, so that the turbidity and the pH value in the soaking solution of the calcium-magnesium mineralized filter material are increased; the micro-morphology of the surface of the modified limestone is uneven, so that the adhesive force between the coating layer and the matrix is improved, and the problem of powder falling is effectively solved.
In some embodiments of the present application, the coating layer has a thickness of 40 μm to 100 μm.
The embodiment of the application also provides a preparation method of the calcium-magnesium mineralized filter material, which comprises the following steps:
s1, providing calcite solution, dolomite solution and modified limestone, wherein the particle size of the modified limestone is 60-80 meshes, and the total pore volume of the modified limestone is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 (ii)/g, and the specific surface area of the modified limestone is 4.2m 2 /g～6.7m 2 /g；
S2, atomizing the calcite dissolving solution and the dolomite dissolving solution in the atmosphere of carbon dioxide, introducing the modified limestone, and stirring for reaction to obtain the calcium-magnesium mineralized filter material, wherein the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite is as follows: recrystallizing calcite: the recrystallized dolomite is (3-10): 1: (2-3).
In some embodiments of the present application, the TDS of the calcite dissolution is greater than 450mg/L and the TDS of the dolomite dissolution is greater than 600mg/L.
In some embodiments of the present application, the calcite dissolving solution and the dolomite dissolving solution in step S1 are prepared by the following method:
s1.1, respectively crushing a natural calcite raw material and a natural dolomite raw material, and then respectively soaking the crushed natural calcite raw material and the crushed natural dolomite raw material in deionized water;
s1.2, respectively stirring and dissolving a natural calcite raw material and a natural dolomite raw material in the atmosphere of carbon dioxide gas, wherein the partial pressure of carbon dioxide is more than 0.1 bar, and the environmental temperature is 5-10 ℃.
In some embodiments of the present application, for step S1.1, the crushed natural calcite and dolomite raw materials are each in particulate form, for example, having a particle size of 0.1cm to 0.5cm, to facilitate dissolution.
In other embodiments of the present application, for step S1.1, the crushed natural calcite and dolomite raw materials are each in a powdered form, e.g., 60 mesh to 300 mesh in size, to facilitate dissolution.
It can be understood that the shapes and sizes of the crushed natural calcite raw material and the crushed natural dolomite raw material are not particularly limited, and only the condition that the materials are easily stirred and dissolved in deionized water in the atmosphere of carbon dioxide gas is met.
By way of example, a calcite dissolution solution is prepared by: weighing natural calcite according to the weight, and crushing the natural calcite into a particle structure with the particle size of 0.1-0.5 cm to obtain a granular natural calcite raw material; adding deionized water into the natural calcite raw material to fully soak the natural calcite raw material in the deionized water; and finally, stirring and dissolving the natural calcite raw material in the atmosphere of carbon dioxide gas to dissolve the natural calcite raw material into deionized water to obtain a calcite dissolving solution. The main mineral component of the natural calcite is calcium carbonate (CaCO) 3 ) Under the action of carbon dioxide and water, calcium carbonate can generate calcium bicarbonate (Ca (HCO) dissolved in water 3 ) 2 )。
By way of example, the preparation method of the dolomite dissolving solution comprises the following steps: weighing natural dolomite according to the amount, and then crushing the natural dolomite into a particle structure with the particle size of 0.1-0.5 cm to obtain a granular natural dolomite raw material; then, adding deionized water into the natural dolomite raw material to fully soak the natural dolomite raw material in the deionized water; and finally, stirring and dissolving the natural dolomite raw material in the atmosphere of carbon dioxide gas to dissolve the natural dolomite raw material in the deionized water to obtain the dolomite dissolving solution. The main mineral component of natural dolomite is calcium carbonate (CaCO) 3 ) And magnesium carbonate (MgCO) 3 ) Under the action of carbon dioxide and water, calcium carbonate can generate calcium bicarbonate (Ca (HCO) dissolved in water 3 ) 2 ) Magnesium carbonate produces water-soluble magnesium bicarbonate (Mg (HCO) 3 ) 2 )。
In some embodiments of the present application, the modified limestone in step S1 is prepared by the following method:
the natural limestone raw material with the grain size of 60 meshes to 80 meshes is placed in a solution containing a modifier, then is soaked for 6 hours to 12 hours at the temperature of 80 ℃ to 90 ℃, and is filtered and dried to obtain the modified limestone, wherein the modifier is sodium citrate, malic acid, acetic acid or acetate.
In some embodiments of the present application, the volume ratio between the natural limestone feedstock and the modifier is the natural limestone feedstock: the modifier is (3-5): 1, the modifying effect of the natural limestone is limited when the addition amount of the modifying agent is too much or too little. The preferred modifier is sodium citrate which can induce the irregular growth of aragonite and calcite crystals on the surface of the limestone, so that the micro-topography of the surface of the modified limestone is uneven to facilitate the coating of the recrystallized calcite and the recrystallized dolomite. When malic acid, acetic acid or acetate is used as a modifier, the modified limestone obtained has an irritating taste, thereby increasing the difficulty of washing work.
In some embodiments of the present application, step S2 comprises the steps of:
s2.1, placing the modified limestone in a closed container, heating the closed container to 200-450 ℃, and introducing carbon dioxide gas into the closed container;
s2.2, mixing the calcite solution and the dolomite solution according to a preset ratio to obtain a reaction solution, atomizing the reaction solution in the atmosphere of carbon dioxide gas, introducing the atomized reaction solution into the closed container, and stirring for reaction to obtain the calcium-magnesium mineralized filter material.
In some embodiments of the present application, the closed vessel in step S2.1 and step S2.2 is a tube furnace.
In some embodiments of the present application, for step S2.2, calcium ions and magnesium ions in the reaction solution react sufficiently under the atmosphere of carbon dioxide gas and water vapor to generate calcium carbonate and magnesium carbonate, so as to coat the outer surface of the modified limestone to form recrystallized calcite and recrystallized dolomite, wherein the molar ratio among the carbon dioxide gas participating in the reaction, the calcium ions in the reaction solution, and the magnesium ions in the reaction solution is carbon dioxide gas: calcium ion in the reaction solution: the magnesium ions in the reaction solution are (3-6): 1: (2-5) so that the mass ratio of the recrystallized calcite to the recrystallized dolomite in the finally obtained calcium-magnesium mineralized filter material is recrystallized calcite: recrystallized dolomite is 1: (2-3).
It should be noted that, in step S2.2, if the calcite dissolution solution and the dolomite dissolution solution are not premixed, but enter the sealed container through two channels respectively and then are mixed, the problem of non-uniform growth of recrystallized crystals may be caused, thereby adversely affecting the stability of the calcium-magnesium mineralized filter material.
The calcium-magnesium mineralized filter material provided by the embodiment of the application can be applied to a water purifying device, the type of the water purifying device is not particularly limited, for example, the calcium-magnesium mineralized filter material can be a gradually-tightening type water purifying device, a self-cleaning type water purifying device and the like, and the calcium-magnesium mineralized filter material can be selected according to actual needs.
The calcium-magnesium mineralized filter material and the preparation method thereof are described in detail below with reference to specific examples, comparative examples and experimental examples.
Example 1
The embodiment provides a calcium-magnesium mineralized filter material and a preparation method thereof, and the calcium-magnesium mineralized filter material comprises a matrix and a coating layer coated on the outer surface of the matrix, wherein the matrix is modified limestone with a particle structure, the coating layer comprises recrystallized calcite and recrystallized dolomite, and the thickness of the coating layer is 45 micrometers; the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite is as follows: recrystallizing calcite: the recrystallized dolomite is 10:1:2.
the preparation method of the calcium-magnesium mineralized filter material comprises the following steps:
s10, preparing a calcite dissolving solution and a dolomite dissolving solution: weighing 10g of natural calcite and 10g of natural dolomite, crushing the natural calcite and the natural dolomite into granules (the particle size is 0.1 cm-0.5 cm), cleaning the granular natural calcite and the granular natural dolomite, and putting the granules into a closed glass vessel respectively; then, respectively adding deionized water into the glass ware filled with the granular natural calcite and the granular natural dolomite until the corresponding granular rock materials are completely submerged; finally, stirring and reacting under the atmosphere of carbon dioxide gas (the carbon dioxide partial pressure is 0.15bar, and the ambient temperature is 10 ℃) to enable granular natural calcite and granular natural dolomite to be respectively dissolved in corresponding deionized water, and obtaining a calcite dissolved solution and a dolomite dissolved solution, wherein the TDS of the calcite dissolved solution is 462mg/L, and the TDS of the dolomite dissolved solution is 680mg/L;
s20, preparing modified limestone: weighing natural limestone according to a certain amount, washing the natural limestone with deionized water, crushing the natural limestone into 70-mesh powdery limestone, and then putting the crushed powdery limestone into 50mL of 0.05mol/L sodium citrate solution to ensure that the volume ratio of the powdery limestone to the sodium citrate is the powdery limestone: the sodium citrate is 3:1, soaking at 85 ℃ for 9 hours to enable the micro-topography of the surface of limestone to be uneven, filtering and drying to obtain granular modified limestone;
s30, coating the modified limestone: placing the granular modified limestone prepared in the step S1.2 into a tubular furnace, heating the tubular furnace to 350 ℃, introducing carbon dioxide gas into the tubular furnace, mixing the calcite solution and the dolomite solution prepared in the step S1.1 according to a preset ratio to obtain a reaction solution, atomizing the reaction solution in the atmosphere of the carbon dioxide gas, and introducing the atomized reaction solution into the tubular furnace, wherein the molar ratio of the carbon dioxide gas to the calcium ions in the reaction solution to the magnesium ions in the reaction solution is carbon dioxide: calcium ion in reaction solution: the magnesium ions in the reaction solution were 5:1: and 2, stopping heating the tubular furnace every 0.5h and continuously stirring to prevent the granular modified limestone from being cemented, and continuously reacting for 4h to coat the outer surface of the granular modified limestone to form recrystallized calcite and recrystallized dolomite to obtain the calcium-magnesium mineralized filter material.
Fig. 1 shows a scanning electron microscope image of the granulated modified limestone obtained in step S20 and a scanning electron microscope image of the calcium-magnesium mineralized filter obtained in step S30, in which the surface of the granulated modified limestone without coating treatment is smooth, and the surface of the granulated modified limestone after coating treatment is distributed with recrystallized calcite and dolomite, and the surface is rough.
Fig. 2 shows an X-ray diffraction pattern of the granulated modified limestone obtained in step S20 and an X-ray diffraction pattern of the calcium-magnesium mineralized filter material obtained in step S30, in which the main mineral component of the granulated modified limestone without coating treatment is calcite, the characteristic peak of the calcite is weakened and the characteristic peak of the dolomite is strengthened after coating treatment, that is, the main mineral components of the granulated modified limestone after coating treatment are calcite and dolomite.
The total pore volume, the average pore diameter and the specific surface area of the granular modified limestone prepared in the step S20 and the calcium-magnesium mineralized filter material prepared in the step S30 are detailed in the following table 1:
TABLE 1 Total pore volume, mean pore diameter and specific surface area summary of particulate modified limestone and calcium-magnesium mineralized filter materials
As can be seen from table 1, compared with the granular modified limestone which is not coated, the total pore volume, the average pore diameter and the specific surface area of the calcium-magnesium mineralized filter material obtained by coating the granular modified limestone are significantly increased, which is beneficial to improving the dissolution rate of calcium and magnesium in the calcium-magnesium mineralized filter material.
Example 2
Compared with the calcium-magnesium mineralized filter material in embodiment 1, the calcium-magnesium mineralized filter material in this embodiment is different only in that: the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite in the calcium-magnesium mineralized filter material is that the modified limestone: recrystallizing calcite: recrystallized dolomite is 6:1:3.
compared with the preparation method of the calcium-magnesium mineralized filter material in example 1, the preparation method of the calcium-magnesium mineralized filter material in this example is different only in that: in step S30, the molar ratio of the carbon dioxide gas participating in the reaction, the calcium ions in the reaction solution, and the magnesium ions in the reaction solution is carbon dioxide gas: calcium ion in the reaction solution: the magnesium ions in the reaction solution were 4:1:3.
example 3
Compared with the calcium-magnesium mineralized filter material in embodiment 1, the calcium-magnesium mineralized filter material in this embodiment is different only in that: the mass ratio of the modified limestone to the recrystallized calcite to the recrystallized dolomite in the calcium-magnesium mineralized filter material is that the modified limestone: recrystallizing calcite: recrystallized dolomite is 3:1:3.
compared with the preparation method of the calcium-magnesium mineralized filter material in example 1, the preparation method of the calcium-magnesium mineralized filter material in this example is different only in that: in step S30, the molar ratio of the carbon dioxide gas participating in the reaction, the calcium ions in the reaction solution, and the magnesium ions in the reaction solution is carbon dioxide gas: calcium ion in the reaction solution: the magnesium ions in the reaction solution were 6:1:5.
comparative example
Compared with the calcium-magnesium mineralized filter material in example 1, the calcium-magnesium mineralized filter material in the comparative example is only characterized in that: the matrix of the calcium-magnesium mineralized filter material is unmodified granular natural limestone, and the grain size of the matrix is the same as that of the modified limestone in the embodiment 1.
Compared with the preparation method of the calcium-magnesium mineralized filter material in the embodiment 1, the preparation method of the calcium-magnesium mineralized filter material in the comparative example is only different in that: step S20 is omitted.
Test example 1
Ten parts of natural limestone (ten parallel samples) of 10g each was collected in Guangxi Bama according to a quartering method, ten parts of modified limestone was prepared from the ten parts of natural limestone by the step S1.2 in example 1, the ten parts of modified limestone were placed in one erlenmeyer flask, 50mL of deionized water was added to each erlenmeyer flask to sufficiently soak the corresponding modified limestone, the TDS, calcium concentration and magnesium concentration of the soaking solution in each erlenmeyer flask were measured every one hour for ten times, and the mean value was taken between the parallel samples.
Ten parts of calcium-magnesium mineralized filter materials (ten parallel samples) are prepared from ten parts of modified limestone according to the preparation method of the calcium-magnesium mineralized filter materials in example 1, each part is 10g, the ten parts of calcium-magnesium mineralized filter materials are respectively placed in a conical flask, then 50mL of deionized water is respectively added into each conical flask to fully soak the corresponding calcium-magnesium mineralized filter materials, the TDS, the calcium concentration and the magnesium concentration of the soaking liquid in each conical flask are measured every other hour for ten times, the TDS average value, the calcium concentration average value and the magnesium concentration average value of the ten parallel samples are respectively taken every time, and the experimental results are detailed in the following table 2
Table 2 immersion test results of test example 1
As can be seen from table 2, the modified limestone coated with recrystallized calcite and recrystallized dolomite is able to release not only calcium ions but also magnesium ions, and the concentration ratio of calcium ions to magnesium ions in the soak is calcium ions: magnesium ions are (1-3): 1, meets the recommended ratio of healthy drinking water.
Test example 2
Ten calcium-magnesium mineralized filter materials (ten parallel samples) of example 1 and ten calcium-magnesium mineralized filter materials (ten parallel samples) of a comparative example are taken respectively, each sample is 10g, each calcium-magnesium mineralized filter material is placed in a conical flask, 50mL of deionized water is added into each conical flask to fully soak the corresponding calcium-magnesium mineralized filter material, the TDS, the turbidities and the pH of the soaking liquid in each conical flask are measured once after soaking for twelve hours and twenty-four hours, the TDS average value, the turbidity average value and the pH average value of the ten parallel samples of the calcium-magnesium mineralized filter materials of example 1 are measured each time, and the TDS average value, the turbidity average value and the pH average value of the ten parallel samples of the calcium-magnesium mineralized filter materials of the comparative example are measured, and the results are detailed in the following table 3:
table 3 immersion test results of test example 2
As can be seen from table 3, compared with modified limestone, the surface of natural limestone is relatively smooth, the problem of "dusting" can occur when the outer surface of the natural limestone is coated with recrystallized calcite and recrystallized dolomite, and the micro-morphology of the surface of the modified limestone is uneven, so that the adhesion between the coating layer and the substrate is improved, and the problem of "dusting" is effectively improved, so that the TDS, the turbidity and the pH in the soaking solution of the calcium-magnesium mineralized filter material of comparative example 1 are significantly increased compared with those in the calcium-magnesium mineralized filter material of example 1.
Test example 3
Ten parts of the calcium-magnesium mineralized filter material (ten parallel samples) according to example 1, ten parts of the calcium-magnesium mineralized filter material (ten parallel samples) according to example 2, ten parts of the calcium-magnesium mineralized filter material (ten parallel samples) according to example 3 and ten parts of the calcium-magnesium mineralized filter material (ten parallel samples) according to a comparative example, each part being 10g, were respectively placed in a conical flask, 50mL of deionized water was then respectively added into each conical flask to fully soak the corresponding calcium-magnesium mineralized filter material, and after soaking for twelve hours, the calcium concentration and magnesium concentration of the soaking solution in each conical flask were measured, and the ratio of the calcium concentration to the magnesium concentration was calculated, wherein the mean values between the parallel samples were taken, and the results are detailed in table 4 below:
table 4 immersion test results of test example 3
From table 4, it can be seen that calcite is recrystallized in the coating layer of the calcium-magnesium mineralized filter material: recrystallized dolomite is 1: (2-3), the concentration ratio of calcium to magnesium in the soak solution obtained after 10g of the calcium-magnesium mineralized filter material is soaked in 50mL of deionized water for 12 hours is calcium: magnesium is (1-3): 1, according with the recommended ratio of healthy drinking water.
The calcium-magnesium mineralized filter material and the preparation method thereof provided by the embodiments of the present application are described in detail above, and the principles and embodiments of the present application are explained by applying specific examples herein, and the description of the above embodiments is only used to help understand the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (8)
1. The preparation method of the calcium-magnesium mineralized filter material is characterized by comprising the following steps:
(1) Providing calcite dissolving solution, dolomite dissolving solution and modified limestone, wherein the particle size of the modified limestone is 60-80 meshes, and the total pore volume of the modified limestone is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 (ii)/g, and the specific surface area of the modified limestone is 4.2m 2 /g～6.7m 2 /g；
(2) Placing the modified limestone in a closed container, heating the closed container to 200-450 ℃, introducing carbon dioxide gas into the closed container, mixing the calcite solution and the dolomite solution according to a preset proportion in the atmosphere of the carbon dioxide gas to obtain a reaction solution, atomizing the reaction solution, introducing the atomized reaction solution into the closed container, and stirring for reaction to obtain the calcium-magnesium mineralized filter material;
wherein, in the (1), the calcite dissolving solution and the dolomite dissolving solution are prepared by the following method:
(1a) Respectively crushing a natural calcite raw material and a natural dolomite raw material, and then respectively soaking the crushed natural calcite raw material and the crushed natural dolomite raw material in deionized water;
(1b) Respectively stirring and dissolving the natural calcite raw material and the natural dolomite raw material in the atmosphere of carbon dioxide gas, wherein the partial pressure of carbon dioxide is more than 0.1 bar, and the environmental temperature is 5-10 ℃.
2. The method according to claim 1, wherein the calcite dissolution solution has a total dissolved solids of greater than 450mg/L and the dolomite dissolution solution has a total dissolved solids of greater than 600mg/L.
3. The method according to claim 1, wherein in the step (1), the modified limestone is prepared by:
placing natural limestone raw materials with the grain size of 60 meshes to 80 meshes in a solution containing a modifier, then soaking at the temperature of 80 ℃ to 90 ℃ for 6 hours to 12 hours, filtering and drying to obtain modified limestone;
wherein the modifier is sodium citrate, malic acid, acetic acid or acetate.
4. A method as claimed in claim 3, characterized in that the volume ratio between said raw natural limestone and said modifying agent is such that the ratio between the raw natural limestone: the modifier is (3-5): 1.
5. the method of claim 3 or 4, wherein the modifier is sodium citrate.
6. The production method according to claim 1, wherein in the step (2), the molar ratio among the carbon dioxide gas, the calcium ions in the reaction solution, and the magnesium ions in the reaction solution is the ratio of the carbon dioxide gas: calcium ion in the reaction solution: the magnesium ions in the reaction liquid are (3-6): 1: (2-5).
7. A calcium-magnesium mineralized filter, which is prepared by the preparation method as set forth in any one of claims 1 to 6, and comprises a substrate and a coating layer coated on the outer surface of the substrate, wherein the substrate is modified limestone, the coating layer comprises recrystallized calcite and recrystallized dolomite, and the mass ratio of the modified limestone, the recrystallized calcite and the recrystallized dolomite is the following ratio: the recrystallized calcite: the recrystallized dolomite is (3-10): 1: (2-3); the particle size of the modified limestone is 60 meshes-80 meshes, and the total pore volume of the modified limestone is 1.047 multiplied by 10 -2 ～4.859×10 -2 cm 3 (ii)/g, and the specific surface area of the modified limestone is 4.2m 2 /g～6.7m 2 /g。
8. The calcium-magnesium mineralized filter material according to claim 7, wherein the thickness of the coating layer is 40 μm to 100 μm.
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