CN113249794A - Preparation method of zirconium-loaded calcium sulfate whisker - Google Patents
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
The invention relates to a preparation method of zirconium-loaded calcium sulfate whiskers, belonging to the technical field of treatment of fluoride ions in water. The invention aims to provide a preparation method of zirconium-loaded calcium sulfate whiskers, which is simple in process. The method comprises the steps of placing calcium sulfate hemihydrate whiskers in a zirconium oxychloride solution, uniformly mixing, carrying out ultrasonic treatment for 5-25 min, adjusting the pH to 4-9, standing overnight, carrying out solid-liquid separation, washing solids, and drying to obtain the zirconium-loaded calcium sulfate whiskers. The method takes the calcium sulfate hemihydrate crystal whisker as a raw material, and adopts a simple ultrasonic auxiliary method to load metal Zr on the surface of the calcium sulfate crystal whisker, so as to obtain the zirconium-loaded calcium sulfate crystal whisker. The method is simple and environment-friendly, and has low cost. The obtained zirconium-loaded calcium sulfate whisker has good adsorption effect on fluorine ions, the removal rate of fluorine can reach more than 90%, and the zirconium-loaded calcium sulfate whisker can be used for treating fluorine-containing wastewater or fluorine-polluted water sources, provides a new choice for fluorine adsorption, and widens the application of the calcium sulfate whisker in the field of environmental treatment.
Description
Technical Field
The invention relates to a preparation method of zirconium-loaded calcium sulfate whiskers, belonging to the technical field of treatment of fluoride ions in water.
Background
Fluorine (VIIA) is the most electronegative (4.0) element in nature, has small ionic radius and high charge density, is the most active nonmetal element, and therefore, the fluorine-containing compound has wide application. High-concentration fluorine pollution in water is from both nature (dissolution of fluorine-containing minerals or soil, volcanic eruption) and human activities (industrial manufacturing processes, such as glass, semiconductor, steel industry and the like), and the water pollution caused by the high-concentration fluorine attracts great attention. Studies have shown that low concentrations of fluorine are beneficial to the teeth and bones of the human body, but long-term consumption of water containing high concentrations of fluorine can lead to fluorine or skeletal fluorosis. For human health considerations, the World Health Organization (WHO) stipulates a limit of 1.5mg/L for fluorine content in drinking water. Therefore, it is important for human beings to reduce the concentration of fluorine in the water body.
The adsorption method has the advantages of simple operation, economy, high efficiency and the like, and is widely applied to the field of reducing the concentration of the fluorine ions. In recent years, researches show that the zirconium (IV) -containing material has strong affinity with high electronegativity fluorine ions, and can greatly improve the adsorption capacity of the material, so that the fluorine ions in the water body can be efficiently removed.
The calcium sulfate whisker is an inorganic fiber material, and is regarded as an environment-friendly material with wide prospect due to the advantages of good toughness, no toxicity, high strength and modulus and the like. The calcium sulfate crystal whisker has wide sources, and industrial byproducts such as phosphogypsum, flue gas desulfurization gypsum and the like and calcium salt can be used for preparing the material. At present, the calcium sulfate whisker is mainly used as a mechanical property regulator of cement or asphalt, an antiwear agent in rubber and plastics, a paper toughness reinforcing agent and the like. Recently, calcium sulfate whiskers have been found to be an adsorbent material for adsorbing and removing pollutants, including heavy metals as (v), pb (ii), cr (vi), Hg, and inorganic phosphate.
Patent CN201910648179.4 discloses a preparation method of a calcium sulfate whisker supported porous oxide fluorine removal material, in the method, calcium sulfate dihydrate whisker is added into oxychlorination product solutions such as zirconium oxychloride and the like for reaction, and a precursor is obtained by filtering the product; and then carrying out heat treatment on the precursor (by adopting a microwave heating mode, wherein the heating temperature is 160-220 ℃ and the time is 2-5 h) to obtain the calcium sulfate whisker supported porous zirconia fluorine removal material. Although the zirconium-loaded calcium sulfate whisker can be obtained by the method, the method is complex, heat treatment is required to be carried out at a high temperature, and the energy consumption is high.
Disclosure of Invention
Aiming at the defects, the technical problem to be solved by the invention is to provide a preparation method of the zirconium-loaded calcium sulfate whisker with simple process.
The preparation method of the zirconium-loaded calcium sulfate whisker comprises the following steps:
and (3) placing the calcium sulfate hemihydrate crystal whisker into a zirconium oxychloride solution, uniformly mixing, carrying out ultrasonic treatment for 5-25 min, adjusting the pH to 4-9, standing, carrying out solid-liquid separation, washing the solid, and drying to obtain the zirconium-loaded calcium sulfate crystal whisker.
In one embodiment of the invention, the sonication time is 10 min.
In one embodiment of the invention, the pH is adjusted to 6 to 7.
In one embodiment of the invention, the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is 1: 1-5, wherein the zirconium oxychloride has a molecular formula of ZrOCl2·8H2And (4) measuring O.
Preferably, the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is 1: 1-2.
In one embodiment of the invention, NaOH/HCl is added to adjust the pH.
Drying methods conventional in the art are suitable for use in the present invention. In a specific embodiment of the invention, the drying is drying at 70-90 ℃ for 6-10 h. Preferably, the drying is drying at 80 ℃ for 8 h.
Compared with the prior art, the invention has the following beneficial effects:
the method takes the calcium sulfate hemihydrate crystal whisker as a raw material, and adopts a simple ultrasonic auxiliary method to load metal Zr on the surface of the calcium sulfate crystal whisker, so as to obtain the zirconium-loaded calcium sulfate crystal whisker. The method is simple and environment-friendly, does not consume heat and pressure, is low in cost, and the obtained zirconium-loaded calcium sulfate whisker has a good effect of adsorbing fluorine ions, has a fluorine removal rate of over 90 percent, can be used for treating fluorine-containing wastewater or fluorine-polluted water sources, provides a new choice for fluorine adsorption, and widens the application of the calcium sulfate whisker in the field of environmental treatment.
Drawings
Figure 1 is an XRD diffraction pattern of calcium sulfate whisker raw material and zirconium-loaded calcium sulfate whisker of example 1.
Figure 2 is an SEM-EDS image of calcium sulfate whisker raw material and zirconium-loaded calcium sulfate whiskers from example 1.
Detailed Description
The preparation method of the zirconium-loaded calcium sulfate whisker comprises the following steps:
and (3) placing the calcium sulfate hemihydrate crystal whisker into a zirconium oxychloride solution, uniformly mixing, carrying out ultrasonic treatment for 5-25 min, adjusting the pH to 4-9, standing overnight, carrying out solid-liquid separation, washing the solid, and drying to obtain the zirconium-loaded calcium sulfate crystal whisker.
According to the method, the calcium sulfate hemihydrate crystal whisker is used as a raw material, and the metal Zr is loaded on the surface of the calcium sulfate crystal whisker by a simple ultrasonic auxiliary method, so that the zirconium-loaded calcium sulfate crystal whisker is obtained. The method is simple and environment-friendly, does not need to be heated, does not consume heat and pressure, and can save energy. In the obtained zirconium-loaded calcium sulfate whisker, zirconium loaded on the calcium sulfate whisker exists in a form of zirconium oxide, and fluorine can be well adsorbed. After adsorption, the fluorine ion concentration in the solution can be lower than 0.5mg/L for 10mg/L of fluorine ions, and the maximum adsorption capacity reaches 258.40 mg/g.
In one embodiment of the invention, the sonication time is 10 min.
In one embodiment of the invention, the pH is adjusted to 6 to 7.
The mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is related to the zirconium-carrying amount of the zirconium-carrying calcium sulfate hemihydrate crystal whisker, and in order to improve the fluorine removal performance of the zirconium-carrying calcium sulfate and save cost as much as possible, the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is preferably 1: 1-5, wherein the zirconium oxychloride has a molecular formula of ZrOCl2·8H2And (4) measuring O.
Preferably, the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is 1: 1-2. At the moment, the prepared zirconium-loaded calcium sulfate whisker has the best fluorine removal effect.
The pH can be adjusted by methods conventional in the art, preferably by the addition of NaOH/HCl. That is, NaOH is added if the pH is to be adjusted to a higher value, and HCl is added if the pH is to be adjusted to a lower value.
And (3) after the pH value is adjusted, standing overnight, fully aging, and then carrying out solid-liquid separation to obtain solid, namely the coarse zirconium-loaded calcium sulfate whisker. And washing the solid by using a conventional washing method, for example, washing the solid by using deionized water, and then drying to obtain the zirconium-loaded calcium sulfate whisker.
Drying methods conventional in the art are suitable for use in the present invention. Preferably, the drying is carried out for 6-10 h at the temperature of 70-90 ℃. Preferably, the drying is drying at 80 ℃ for 8 h.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
The zirconium-loaded calcium sulfate whisker is prepared by the following method:
weighing ZrOCl2·8H2Dissolving O1 g in a 250mL beaker by stirring to obtain a zirconium-containing solution; weighing 2g of calcium sulfate hemihydrate crystal whisker in a zirconium-containing solution, and fully stirring and uniformly mixing; performing ultrasonic treatment in an ultrasonic device for 10 min; taking out, slowly dropwise adding 1M NaOH/HCl under the conditions of room temperature and magnetic stirring to adjust the pH value of the mixed solution to 6.0; standing overnight, and fully aging; performing suction filtration, and fully washing with deionized water; and drying in an oven at 80 ℃ for 8h, taking out, grinding, sealing and storing to obtain the zirconium-loaded calcium sulfate whisker.
The XRD diffraction pattern of the zirconium-loaded calcium sulfate whisker and the calcium sulfate whisker raw material is shown in figure 1, and as is obvious from figure 1, the calcium sulfate whisker raw material used in the invention belongs to calcium sulfate hemihydrate whisker, and after zirconium is loaded, the calcium sulfate hemihydrate whisker is converted into calcium sulfate dihydrate whisker due to hydration.
FIG. 2 is an SEM-EDS diagram of calcium sulfate whisker raw materials and zirconium-loaded calcium sulfate whiskers. The surface of the calcium sulfate hemihydrate crystal whisker is flat and smooth, and becomes rough after being loaded with zirconium. Meanwhile, an EDS map also confirms that metal Zr is loaded on the surface of the calcium sulfate hemihydrate crystal whisker.
Examples 2 to 14
By adopting the preparation method of the example 1, only part of parameters are changed to obtain the zirconium-loaded calcium sulfate whisker, wherein the specific parameters are shown in the table 1.
TABLE 1
Test example 1
Are respectively provided with0.2g of each of the calcium sulfate dihydrate crystal whisker and the zirconium-loaded calcium sulfate crystal whisker prepared in the examples 1 to 14 was weighed, 40mL of a standard solution containing 10mg/L of fluorine ions was weighed and added to the series of zirconium-loaded calcium sulfate crystal whisker material samples, and the mixture was shaken well and subjected to water bath shaking at room temperature for 3 hours (150 r/min). Centrifuging at 3600r/min for 10min, collecting supernatant, and measuring F in the supernatant with fluorine ion selective electrode-The removal rate was calculated from the concentration of (2), and the results are shown in Table 3.
TABLE 3
Test example 2
0.2g of the zirconium-loaded calcium sulfate whisker prepared in example 1 is weighed into a 50mL centrifuge tube, fluorine solutions with different initial concentrations are added, the mixture is shaken well and shaken in a water bath for 24h (150r/min) at the temperature of 25 ℃. Then centrifuging for 10min under the condition of 3600r/min, taking supernatant, and measuring the concentration of fluorine ions by adopting a fluorine ion selective electrode. The removal rate and adsorption capacity were calculated and the results are shown in Table 4.
TABLE 4
| Concentration before adsorption (mg/L) | Concentration after adsorption (mg/L) | Removal Rate (%) | Adsorption capacity (mg/g) |
| 20 | 1.14 | 94.3 | 3.77 |
| 40 | 1.67 | 95.8 | 7.67 |
| 60 | 2.06 | 96.57 | 11.59 |
| 100 | 2.77 | 97.23 | 19.45 |
| 300 | 3.45 | 98.85 | 59.31 |
| 500 | 4.91 | 99.02 | 99.02 |
| 800 | 23.68 | 97.04 | 155.26 |
| 1000 | 150.25 | 84.98 | 169.95 |
| 1500 | 436.19 | 70.92 | 212.76 |
| 2000 | 857.81 | 57.11 | 228.44 |
| 2500 | 1280.1 | 48.80 | 243.98 |
| 3000 | 1689.72 | 43.68 | 262.06 |
As can be seen from table 4, the zirconium-loaded calcium sulfate whiskers of the present invention have a good effect of removing fluoride ions, especially in a high-concentration fluoride ion solution. The maximum adsorption capacity of the zirconium-loaded calcium sulfate whisker to fluorine ions is obtained by fitting according to a Langmuir isothermal adsorption model, and the maximum adsorption capacity of the zirconium-loaded calcium sulfate whisker to fluorine ions reaches 258.40 mg/g. Therefore, the zirconium-loaded calcium sulfate whisker can be used for treating fluoride ions in water, provides a new choice for fluorine adsorption, and widens the application of the calcium sulfate whisker in the field of environmental treatment.
Claims (8)
1. The preparation method of the zirconium-loaded calcium sulfate whisker is characterized by comprising the following steps:
and (3) placing the calcium sulfate hemihydrate crystal whisker into a zirconium oxychloride solution, uniformly mixing, carrying out ultrasonic treatment for 5-25 min, adjusting the pH to 4-9, standing, carrying out solid-liquid separation, washing the solid, and drying to obtain the zirconium-loaded calcium sulfate crystal whisker.
2. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 1, wherein: and (5) carrying out ultrasonic treatment for 10 min.
3. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 1, wherein: adjusting the pH value to 6-7.
4. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 1, wherein: the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is 1: 1-5, and the molecular formula of the zirconium oxychloride is ZrOCl2·8H2And (4) measuring O.
5. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 4, wherein: the mass ratio of the zirconium oxychloride to the calcium sulfate hemihydrate crystal whisker is 1: 1-2.
6. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 1, wherein: NaOH/HCl was added to adjust the pH.
7. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 1, wherein: and the drying is carried out for 6-10 h at the temperature of 70-90 ℃.
8. The method for preparing zirconium-loaded calcium sulfate whiskers as recited in claim 7, wherein: the drying is carried out for 8h at the temperature of 80 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275756A (en) * | 2021-12-30 | 2022-04-05 | 中国科学院地球化学研究所 | Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum |
| CN117258763A (en) * | 2023-11-16 | 2023-12-22 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
| CN117813265A (en) * | 2023-11-19 | 2024-04-02 | 广东邦普循环科技有限公司 | Heavy metal capturing agent and preparation method and application thereof |
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| CN103952765A (en) * | 2014-04-30 | 2014-07-30 | 江南大学 | Preparation method of conductive calcium sulfate whisker |
| CN104651945A (en) * | 2015-01-26 | 2015-05-27 | 江苏一夫科技股份有限公司 | Method for modifying calcium sulphate whisker surface |
| CN110433782A (en) * | 2019-07-18 | 2019-11-12 | 北京科技大学 | A kind of calcium sulfate crystal whiskers support the preparation method of porous oxide defluorination material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952765A (en) * | 2014-04-30 | 2014-07-30 | 江南大学 | Preparation method of conductive calcium sulfate whisker |
| CN104651945A (en) * | 2015-01-26 | 2015-05-27 | 江苏一夫科技股份有限公司 | Method for modifying calcium sulphate whisker surface |
| CN110433782A (en) * | 2019-07-18 | 2019-11-12 | 北京科技大学 | A kind of calcium sulfate crystal whiskers support the preparation method of porous oxide defluorination material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275756A (en) * | 2021-12-30 | 2022-04-05 | 中国科学院地球化学研究所 | Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum |
| CN117258763A (en) * | 2023-11-16 | 2023-12-22 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
| CN117258763B (en) * | 2023-11-16 | 2024-02-02 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
| CN117813265A (en) * | 2023-11-19 | 2024-04-02 | 广东邦普循环科技有限公司 | Heavy metal capturing agent and preparation method and application thereof |
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