CN111001374A - Preparation method and application of strontium-doped hydroxyapatite heavy metal adsorption material - Google Patents
Preparation method and application of strontium-doped hydroxyapatite heavy metal adsorption material Download PDFInfo
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- CN111001374A CN111001374A CN201911331221.6A CN201911331221A CN111001374A CN 111001374 A CN111001374 A CN 111001374A CN 201911331221 A CN201911331221 A CN 201911331221A CN 111001374 A CN111001374 A CN 111001374A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
- B01J20/048—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 phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
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Abstract
The invention discloses a preparation method and application of a strontium-doped hydroxyapatite heavy metal adsorption material. Calcium nitrate is used as a calcium source, diammonium phosphate is used as a phosphorus source, strontium nitrate with different volumes is doped in the calcium source, and the strontium-doped hydroxyapatite is prepared through hydrothermal homogeneous precipitation reaction. The doping of strontium can change the performance defect of hydroxyapatite to a certain extent and improve the adsorption capacity of the hydroxyapatite to heavy metal wastewater. The invention adopts hydrothermal homogeneous precipitation method for synthesis, has good reaction controllability, simple preparation process, convenient operation, larger yield and no pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of heavy metal sewage treatment, and particularly relates to a preparation method and application of a strontium-doped hydroxyapatite heavy metal adsorption material.
Background
Heavy metals are one of the main pollutants in water environment, and the heavy metals in the water mainly include mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr), arsenic (As), manganese (Mn), copper (Cu), zinc (Zn), cobalt (Co), nickel (Ni), and the like. With the development of economy and society in China, the problems of water resource shortage and water pollution are becoming more and more serious. Statistics shows that metal wastewater in China accounts for about 10% of the total wastewater discharge amount, human factors such as mining, smelting, electroplating, sewage irrigation and use of products with heavy metals exceeding the standard are main sources of heavy metal wastewater, potential harmfulness is achieved, particularly heavy metals such as mercury, cadmium, lead and chromium have obvious biotoxicity, toxicity can be generated due to trace concentration, and the heavy metals can be converted into organic metal compounds (such as methyl mercury) with stronger toxicity under the action of microorganisms or are biologically enriched and enter human bodies through food chains to cause chronic poisoning. The typical facts that heavy metal pollution brings harm to human health and environment are water guarantee disease caused by mercury poisoning in Japan, pain disease caused by cadmium in Shentong river basin, "blood lead event caused by lead pollution in Shanxi Fengxiang and other places in China," copper pollution caused by leakage accidents of Fujian Zijin mining industry "and the like. Heavy metal wastewater is highly toxic, difficult to metabolize in the environment and difficult to repair. Therefore, a new technical research on treatment and recycling of heavy metal wastewater is actively developed, and it is imperative to effectively remove and recover heavy metal resources in wastewater.
In the aspect of restoration and treatment of heavy metal pollution of water bodies, chemical precipitation methods, ion exchange methods, solvent extraction methods, electrolysis methods, biological methods and the like are mainly adopted at home and abroad at present, but the methods are generally expensive, high in cost, difficult to master in technology and easy to cause secondary pollution, so that the methods are not ideal. At present, the adsorption method is considered to be a more effective method, and commonly used adsorbents are activated carbon, biological adsorbent, mineral materials and the like. Activated carbon is the first and most widely used adsorbent, but has the greatest disadvantages of high price and short service life. The research of removing heavy metals in wastewater by using the biological adsorbent is more and more focused, but the application range is limited in the treatment of low-concentration and single-component heavy metal wastewater due to the certain capacity and high selectivity of the biological adsorbent. The environmental mineral material has strong adsorption capacity, good adsorption effect and small secondary pollution, is easier to gather heavy metal ions compared with a biological method, is not easy to decompose and convert in the environment, can thoroughly treat heavy metal pollution in water, and is valued by various scholars.
Hydroxyapatite is a kind of environmental mineral material with excellent performance and structure, and attracts wide attention of scholars at home and abroad. At present, natural hydroxyapatite, artificially synthesized hydroxyapatite and modified hydroxyapatite are greatly researched at home and abroad, but the characteristics of relatively complex artificial synthesis, small adsorption quantity and low adsorption rate limit the wide application of the hydroxyapatite. The existing methods for preparing hydroxyapatite mainly comprise a precipitation method, a microemulsion method, a self-combustion method and the like, and the methods have the defects of high cost, complex preparation process, long period, harsh conditions and the like. The strontium and calcium elements belong to the same main group in the periodic table of the elements, and the strontium element can replace calcium in hydroxyapatite in the crystal to form a replacement solid solution. In view of the difference of ionic radius and property between strontium and calcium, strontium can distort the crystal lattice of hydroxyapatite, thereby changing the crystallinity and biodegradability of hydroxyapatite. In order to refine, homogenize and activate the hydroxyapatite, improve the adsorption performance of the hydroxyapatite, improve the harsh adsorption conditions of the hydroxyapatite, simplify the preparation process of the hydroxyapatite and enlarge the application range, a simple preparation process of the strontium-doped hydroxyapatite is needed to be improved or sought.
Disclosure of Invention
The invention aims to provide a preparation method and application of a strontium-doped hydroxyapatite heavy metal adsorption material.
According to the method, calcium nitrate is used as a calcium source, diammonium phosphate is used as a phosphorus source, strontium nitrate with different volumes is doped into the calcium source and the diammonium phosphate, and the strontium-doped hydroxyapatite is prepared through hydrothermal reaction. The phase, structure, composition and morphological characteristics of the water are characterized, and the water is applied to the removal of heavy metals in water.
The preparation method of the strontium-doped hydroxyapatite heavy metal adsorption material comprises the following specific steps:
0.2mol/L calcium nitrate (Ca (NO) is prepared respectively3)2·4H2O solution, 0.2mol/L ammonium hydrogen phosphate ((NH)4)2HPO4) Solution and 0.2mol/L strontium nitrate (Sr (NO)3)2) A solution; uniformly mixing the prepared calcium nitrate solution and strontium nitrate solution according to the molar ratio of 5-95: 95-5, adding diammonium phosphate solution according to the molar sum of calcium nitrate and strontium nitrate being 1.67 times of diammonium phosphate, adding ammonia water to adjust the pH value of the mixed solution to 10-11, and rapidly stirring the mixed solution to obtain milky turbid liquid; magnetically stirring the obtained milky white suspension for 30 minutes, and aging for 24-120 hours under the water bath condition of 50 ℃; and (3) centrifugally washing the white precipitate after the aging is finished for three times by using ethanol and water, drying the white precipitate for 24 hours in an oven at the temperature of 80 ℃ to obtain a white solid, and grinding the obtained white solid and sieving the ground white solid with a 100-mesh sieve to obtain the strontium-doped hydroxyapatite heavy metal adsorption material.
The molar ratio of calcium nitrate to strontium nitrate is preferably 50: 50. The strontium-doped hydroxyapatite heavy metal adsorption material prepared at the moment is uniform in size and regular in shape, and has the best effect of removing heavy metal ions in wastewater.
The pH value of the ammonia water adjusting mixed solution is preferably 10.5.
The aging time is preferably 24 hours.
The prepared strontium-doped hydroxyapatite heavy metal adsorption material is used for removing heavy metal ions in wastewater, the heavy metal ions are one or more of copper, cadmium, zinc, lead, cobalt and nickel, the dosage of the strontium-doped hydroxyapatite heavy metal adsorption material in the wastewater is 0.8-6.0 g/L, the pH value is preferably 4-7 under the room temperature condition, and the adsorption time is preferably 120-240 minutes.
The invention has the advantages that: the invention uses the hydrothermal homogeneous precipitation method with simple operation, and uses cheap calcium nitrate, strontium nitrate and diammonium phosphate as precursor solution to prepare the strontium-doped hydroxyapatite heavy metal adsorbing material. The obtained material has low crystallinity, good micropore development, uniform particles, good dispersibility, large specific surface area and strong surface activity. The invention has high removal rate to heavy metal ions, and the removal rate of the strontium-doped hydroxyapatite heavy metal adsorption material to heavy metal ions such as lead, cadmium, cobalt and the like exceeds 98 percent through experimental verification. Compared with other common chemical adsorbents, the product of the invention is suitable for natural water and underground water, is convenient to use, achieves high-efficiency removal of heavy metal ions, and provides a new way for improving the treatment effect of heavy metal wastewater.
Drawings
Fig. 1 is an XRD spectrogram of the strontium-doped hydroxyapatite heavy metal adsorbing material prepared in the embodiment of the present invention.
Fig. 2 is an SEM image of the strontium-doped hydroxyapatite heavy metal adsorbing material prepared in the embodiment of the present invention.
FIG. 3 is a diagram showing the effect of the strontium-doped hydroxyapatite heavy metal adsorbing material on Cd (II) removal under different pH values in the embodiment of the present invention.
Detailed Description
Example (b):
(1) preparing a precursor solution: 0.2mol/L calcium nitrate (Ca (NO) is prepared respectively3)2·4H2O), 0.2mol/L diammonium hydrogen phosphate ((NH)4)2HPO4) And 0.2mol/L strontium nitrate (Sr (NO)3)2) (ii) a Respectively taking prepared calcium nitrate and strontium nitrate solutions250mL of the mixture was mixed well.
(2) 300mL of the prepared diammonium hydrogen phosphate solution is added, ammonia water is rapidly added to adjust the pH value to 10.5, and the mixed solution is rapidly stirred in the process.
(3) The resulting milky white suspension was magnetically stirred for 30 minutes and then aged in a water bath at 50 ℃ for 24 hours.
(4) And (3) centrifugally washing the white precipitate after the aging is finished for three times by using ethanol and water, drying the white precipitate in an oven at the temperature of 80 ℃ for 24 hours, and grinding the obtained white solid and sieving the ground white solid by using a 100-mesh sieve to obtain the strontium-doped hydroxyapatite heavy metal adsorbing material.
The strontium-doped hydroxyapatite heavy metal adsorbing material prepared by the embodiment is used for carrying out an adsorption experiment on Cd (II) in water. The method comprises the following specific steps:
0.08g of the strontium-doped hydroxyapatite heavy metal adsorbing material prepared in the example is weighed and respectively placed in 50mL of solutions containing 20, 50 and 100 mg/L of Cd (II). After oscillation reaction is carried out for 24 hours at the pH of 1, 2, 3, 4, 5, 6, 7 and 8, the temperature of 25 ℃ and the rotation speed of 180rpm, a filter membrane of 0.22 mu m is used for filtering, and the concentration of the residual Cd (II) in the solution is measured by a flame atomic absorption spectrometer to examine the removal capacity of the Cd (II), and the result is shown in figure 3, so that the strontium-doped hydroxyapatite heavy metal adsorbing material prepared by the invention has good removal capacity on Cd (II) under the condition that the pH = 3-8.
Claims (5)
1. A preparation method of a strontium-doped hydroxyapatite heavy metal adsorption material is characterized by comprising the following specific steps:
respectively preparing 0.2mol/L calcium nitrate solution, 0.2mol/L diammonium phosphate solution and 0.2mol/L strontium nitrate solution; uniformly mixing the prepared calcium nitrate solution and strontium nitrate solution according to the molar ratio of 5-95: 95-5, adding diammonium phosphate solution according to the molar sum of calcium nitrate and strontium nitrate being 1.67 times of diammonium phosphate, adding ammonia water to adjust the pH value of the mixed solution to 10-11, and rapidly stirring the mixed solution to obtain milky turbid liquid; magnetically stirring the obtained milky white suspension for 30 minutes, and aging for 24-120 hours under the water bath condition of 50 ℃; and (3) centrifugally washing the white precipitate after the aging is finished for three times by using ethanol and water, drying the white precipitate for 24 hours in an oven at the temperature of 80 ℃ to obtain a white solid, and grinding the obtained white solid and sieving the ground white solid with a 100-mesh sieve to obtain the strontium-doped hydroxyapatite heavy metal adsorption material.
2. The preparation method of the strontium-doped hydroxyapatite heavy metal adsorbing material as claimed in claim 1, wherein the molar ratio of the calcium nitrate to the strontium nitrate is 50: 50.
3. The preparation method of the strontium-doped hydroxyapatite heavy metal adsorbing material as claimed in claim 1 or 2, wherein the ammonia water is used for adjusting the pH value of the mixed solution to 10.5.
4. A method for preparing a strontium-doped hydroxyapatite heavy metal adsorbing material according to claim 1, 2 or 3, characterized in that the aging time is 24 hours.
5. The application of the strontium-doped hydroxyapatite heavy metal adsorbing material prepared by the preparation method according to claim 1, 2, 3 or 4 is characterized in that the strontium-doped hydroxyapatite heavy metal adsorbing material is used for removing heavy metal ions in wastewater, the heavy metal ions are one or more of copper, cadmium, zinc, lead, cobalt and nickel, and the dosage of the strontium-doped hydroxyapatite heavy metal adsorbing material in the wastewater is 0.8-6.0 g/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569916A (en) * | 2020-05-11 | 2020-08-25 | 四川大学 | Modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN114229819A (en) * | 2021-12-27 | 2022-03-25 | 四川大学 | Strontium-modified hydroxyapatite and synthesis and application method thereof |
| CN114365746A (en) * | 2022-03-01 | 2022-04-19 | 江苏雪豹日化有限公司 | Method for preparing strontium-doped hydroxyapatite bacteriostatic agent by Nafion template method |
| CN114870792A (en) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | Manganese-doped hydroxyapatite material and preparation method and application thereof |
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| CN114365746A (en) * | 2022-03-01 | 2022-04-19 | 江苏雪豹日化有限公司 | Method for preparing strontium-doped hydroxyapatite bacteriostatic agent by Nafion template method |
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Application publication date: 20200414 |