CN112354513A - Zn2+-Al3+-CO32-LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling - Google Patents
Zn2+-Al3+-CO32-LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 62
- 239000011737 fluorine Substances 0.000 title claims abstract description 62
- -1 fluorine ions Chemical class 0.000 title claims description 42
- 238000004064 recycling Methods 0.000 title abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 70
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 54
- 238000001179 sorption measurement Methods 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000011069 regeneration method Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
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- 239000000243 solution Substances 0.000 claims description 10
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- 150000002500 ions Chemical class 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 description 8
- 229960001545 hydrotalcite Drugs 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
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- 229910044991 metal oxide Inorganic materials 0.000 description 5
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- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Hydrology & Water Resources (AREA)
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- Water Treatment By Sorption (AREA)
Abstract
The invention discloses Zn2+‑Al3+‑CO3 2The adsorption material takes zinc nitrate and aluminum nitrate as raw materials, urea as a precipitator, and Zn grows in situ on the surface of an aluminum matrix by adopting a homogeneous precipitation method2+‑Al3+‑CO3 2‑LDHs film. Zn of the invention2+‑Al3+‑CO3 2-LDHs @ Al pair F‑Has better adsorption performance, the adsorption quantity is gradually increased along with the rise of the calcination temperature, wherein F is obtained when the calcination temperature is 300 DEG C‑The maximum adsorption capacity is 0.0156mg/cm2The fluorine removal rate was 98.2%. And adsorbing F‑Last Zn2+‑Al3+‑CO3 2the-LDHs @ Al can be regenerated and recycled after being roasted. Zn with increasing cycle number2+‑Al3+‑CO3 2Although the defluorination rate of the-LDHs @ Al is reduced, the defluorination rate of the material gradually tends to be stable after the material is cycled for many times, and the defluorination rate can still reach more than 80 percent after the material is recycled for 12 times, so that the material has important recycling value.
Description
Technical Field
The invention belongs to the technical field of fluoride ion adsorption treatment, and particularly relates to Zn2+-Al3+LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling.
Background
Fluorine is a common halogen element in the nature, and excessive fluorine in water can affect human health, cause fluorosis and cause chronic systemic diseases. The fluorine-containing wastewater mainly comes from the fields of fertilizer production, electroplating, steel and aluminum manufacturing and the like. The discharge of fluorine-containing wastewater seriously pollutes the aboveground biological environment and underground drinking water. The treatment of wastewater containing fluorine is one of the hot spots of research of scientists at present. The method for treating the fluorine-containing wastewater mainly comprises the following steps: adsorption, sedimentation, electrodialysis, electrocoagulation, reverse osmosis, and the like.
The adsorption method is one of the most effective methods for treating the fluorine-containing wastewater, and removes low-concentration fluorine ions in water through super-strong physical and chemical adsorption. The method has the advantages of high removal efficiency, low cost, wide application range and the like. In addition, fluoride ion is an important industrial raw material, and has wide application in the aspects of chemical industry, biology, medicine and the like. Whether the fluorine ions in the wastewater can be recycled is an important research content. Therefore, the preparation of recyclable and reusable high-efficiency adsorbents is a great research hotspot nowadays.
Hydrotalcite materials (LDHs for short) are compounds formed by stacking interlayer anions and plates with positive charges, and the special structure and the physicochemical property of the hydrotalcite materials enable the hydrotalcite materials to show excellent adsorption performance in the aspect of water treatment, thereby causing wide attention to industrial production and scientific research. Research shows that the hydrotalcite material has good adsorption capacity to fluorine ions after being calcined, presents ideal removal rate, good stability and recycling capacity, can better adsorb the fluorine ions, and is a novel sewage treatment adsorbent with wide application prospect. In addition, the adsorption of the fluorine ions with negative charges is beneficial to the regeneration of the hydrotalcite, and the material can be used for treating the fluorine-containing wastewater again after fluorine desorption for cyclic utilization. And (4) enriching the separated and recovered fluorine ions, and converting the fluorine ions into other fluorine-containing products. Therefore, the research on recycling of the hydrotalcite materials has important significance for expanding the functions and reducing the cost.
The aluminum element and the fluorine ions in the aluminum hydrotalcite like material can form better coordination, and the selectivity and the adsorption performance to the fluorine ions are greatly improved. However, the aluminum hydrotalcite-like material has no magnetism, which hinders the recycling of the aluminum hydrotalcite-like material.
Disclosure of Invention
The invention aims to provide a method for preparing Zn by loading an aluminum hydrotalcite-like material on the surface of a base aluminum plate through in-situ growth2+-Al3+The LDHs @ Al adsorbing material solves the agglomeration problem of the hydrotalcite-like material and improves the adsorption performance of the material; on the other hand, the aluminum substrate is used for recovering the hydrotalcite-like material, thereby improving the recovery efficiency of the material, reducing the recovery cost of the adsorbent,the recycling performance of the material is improved.
Zn for the above purpose2+-Al3+the-LDHs @ Al adsorbing material is prepared by the following method:
1. pretreatment of aluminum substrates
Cleaning oil stains on the surface of the aluminum matrix with an acetone solution, removing residual substances on the surface of the aluminum matrix with a sodium hydroxide aqueous solution, and cleaning the residual solvent on the surface of the aluminum matrix with deionized water; then the cleaned aluminum substrate is put into an electrolytic bath for anodic oxidation to form an anodic aluminum oxide layer on the surface.
2. Preparation of Zn2+-Al3+-CO3 2-LDHs@Al
Adding zinc nitrate and aluminum nitrate into deionized water by a homogeneous precipitation method, adding urea, performing ultrasonic homogenization, then immersing the aluminum substrate with the surface of the anodized aluminum layer formed in the step 1 into the obtained mixed solution, and performing reflux reaction to enable in-situ Zn growth on the surface of the aluminum substrate2+-Al3+-CO3 2-Taking out the aluminum matrix after the reaction is finished, washing and drying to obtain Zn2+-Al3+-CO3 2-LDHs @ Al adsorbent material.
In step 2 of the method, the ratio of the zinc nitrate to the aluminum nitrate to the urea is 2:1: 6-9.
In step 2 of the above method, it is preferable to control Zn in the obtained mixed solution2+And Al3+The total concentration of (a) is 40-60 mmol/L.
In the step 2 of the method, the reflux reaction is preferably carried out at a temperature of 95-98 ℃ for 8-12 hours.
Zn of the invention2+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions comprises the following specific steps:
1、Zn2+-Al3+-CO3 2calcination of-LDHs @ Al
Zn is added2+-Al3+-CO3 2Calcining the-LDHs @ Al adsorbing material at 200-600 ℃ for 48 hours.
2、Zn2+-Al3+-CO3 2Adsorption of fluoride ions by-LDHs @ Al
Zn calcined in the step 12+-Al3+-CO3 2-The LDHs @ Al adsorbing material is added into a fluorine-containing ion water solution, stirred for 1-2 hours, and adsorbed to remove fluorine ions in water.
3、Zn2+-Al3+-CO3 2Regeneration of the-LDHs @ Al
Zn after absorbing fluorinion2+-Al3+-CO3 2-Putting the LDHs @ Al adsorbing material into a mixed aqueous solution of sodium hydroxide and sodium carbonate, soaking for 1-5 hours, washing and drying the soaked adsorbing material, and calcining at 300-600 ℃ for 2-8 hours to obtain regenerated Zn2+-Al3+And (4) adsorbing the fluorine ions in the fluorine-containing ion aqueous solution again by using an LDHs @ Al adsorbing material.
In step 1 of the above application, Zn is preferably added2+-Al3+-CO3 2And (3) roasting the-LDHs @ Al adsorbing material at 300-400 ℃ for 5 hours.
In step 2 of the above application, the Zn2+-Al3+-CO3 2-Zn per unit area on LDHs @ Al adsorbing material2+-Al3+-CO3 2-The mass ratio of the LDHs to the fluorine ions in the fluorine ion-containing aqueous solution is 0.01-0.03 mg/cm2。
In step 3 of the above application, it is preferable that Zn after adsorbing fluorine ions is subjected to2+-Al3+-CO3 2-The LDHs @ Al adsorbing material is put into a mixed water solution of sodium hydroxide and sodium carbonate to be soaked for 4 hours, and the soaked adsorbing material is calcined for 3-4 hours at 400-500 ℃ after being washed and dried.
In the step 1 of the application, the mass concentration of NaOH in the mixed aqueous solution of sodium hydroxide and sodium carbonate is 8-15%, and the concentration of sodium carbonate is 1-2 mol/L.
The invention has the following beneficial effects:
1. the invention takes an aluminum plate as a base body, and the aluminum plate is put into placeIn-situ vertical growth of Zn on the surface of substrate by growth method2+-Al3+-CO3 2—LDHs film, Zn2+-Al3+-CO3 2-The LDHs film grows on the surface of the aluminum matrix uniformly and compactly, has a typical layered structure of LDHs materials, and the edge of the LDHs laminate with adsorption activity can be fully exposed, so that Zn is enhanced2+-Al3+-CO3 2-The LDHs has the capability of adsorbing fluorine ions, and meanwhile, the LDHs material is recycled through the aluminum substrate, so that the recycling cost of the adsorbent is effectively reduced, and the recycling performance of the material is improved.
2. Zn of the invention2+-Al3+-CO3 2--LDHs @ Al pair F-Has better adsorption performance. First adsorption process, Zn2 +-Al3+-CO3 2-Maximum adsorption of-LDHs @ Al after calcination at 300 ℃ and unit area of Zn2+-Al3+-CO3 2-The fluorine ion adsorption capacity of-LDHs @ Al is 0.0156mg/cm2. Zn grown in situ on Al matrix2+-Al3+-CO3 2-After ion exchange for desorbing fluorine, the LDHs has better recycling value, and after calcining for 4 hours at 400 ℃, the regeneration effect tends to be stable, thereby achieving the condition of recycling and reusing Zn2+-Al3+-CO3 2--LDHs @ Al adsorption F-The number of cycles can reach 100.
3. The invention utilizes Zn2+-Al3+The LDHs @ Al adsorbs the fluorine ions in the water body, so that the problem of promoting and strengthening the capability of comprehensively treating wastewater by multistage cyclic utilization of the LDHs material while recycling the fluorine ions is solved, the application value and the application range of the LDHs material are improved, and a new idea is provided for the development, design and application of the LDHs material.
Drawings
FIG. 1 is Zn2+-Al3+-CO3 2--XRD pattern of powder scraped with LDHs @ Al.
FIG. 2 is Zn2+-Al3+-CO3 2-FT-IR chart of scraped-off powder of-LDHs @ AlSpectra.
FIG. 3 is Zn2+-Al3+-CO3 2--CO3 2-SEM pictures of LDHs @ Al, numbers (a), (b), (c) and (d) correspond to SEM pictures with the magnification from low to high respectively.
FIG. 4 is Zn2+-Al3+-CO3 2--CO3 2-Element surface distribution analysis diagram of LDHs @ Al.
FIG. 5 is Zn2+-Al3+-CO3 2--XRD patterns of thermal decomposition products of LDHs at different temperatures: (a)100 ℃; (b)200 ℃; (c)300 ℃; (d)400 ℃; (e)500 ℃ in which diamond-solid represents a composite metal oxide; t. represents spinel.
FIG. 6 is Zn2+-Al3+-CO3 2-FT-IR diagram for different calcination temperatures of LDHs: (a) not calcined; (b)100 ℃; (c)200 ℃; (d)300 ℃; (e)400 ℃; (f) at 500 ℃.
FIG. 7 is Zn2+-Al3+-CO3 2-LDHs @ Al pair F-The change curve of the adsorption quantity along with the roasting temperature.
FIG. 8 is Zn2+-Al3+-CO3 2-LDHs @ Al pair F-The change curve of the adsorption amount along with the addition amount.
FIG. 9 is Zn2+-Al3+-CO3 2-LDHs @ Al adsorption F-The subsequent element surface distribution analysis chart.
FIG. 10 is the calcination temperature vs. Zn2+-Al3+-CO3 2-Influence of LDHs @ Al regeneration effect.
FIG. 11 is the calcination time vs. Zn2+-Al3+-CO3 2-Influence of LDHs @ Al regeneration effect.
FIG. 12 is Zn2+-Al3+-CO3 2-The effect of the number of regeneration cycles of LDHs @ Al on fluorine removal.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Pretreatment of aluminum substrates
An aluminum sheet (2cm x 2cm) with the purity of more than 90 percent is used as an aluminum matrix. Firstly, cleaning oil stains on the surface of an aluminum sheet by using an acetone solution, then removing residual substances on the surface of the aluminum sheet by using a 1mol/L sodium hydroxide aqueous solution, and finally cleaning the residual solvent on the surface of the aluminum sheet by using deionized water. Putting the cleaned aluminum sheet into an electrolytic bath for anodic oxidation to form an anodic aluminum oxide layer on the surface.
2. Preparation of Zn2+-Al3+-CO3 2-LDHs@Al
4.96g (16.67mmol) Zn (NO)3)2·6H2O、3.13g(8.34mmol)Al(NO3)3·9H2Adding O into a double-neck round-bottom flask, adding 3.75g (62.44mmol) of urea, adding deionized water, performing ultrasonic treatment on the double-neck round-bottom flask in an ultrasonic instrument for 5 minutes to uniformly mix the solution, and controlling Zn in the obtained mixed solution2+And Al3+The total concentration of (a) is 50 mmol/L; then, the aluminum sheet with the surface formed with the anode aluminum oxide layer in the step 1 is immersed into the mixed solution, and the reflux reaction is carried out for 8 hours at the temperature of 98 ℃, so that Zn grows on the surface of the aluminum matrix in situ2+-Al3+-CO3 2-Taking out the aluminum matrix after the reaction of the-LDHs film, washing the aluminum matrix by deionized water, and drying the aluminum matrix at 80 ℃ to obtain Zn2+-Al3+-CO3 2-LDHs @ Al adsorbent material. Calculated Zn loaded on each piece of aluminum matrix2+-Al3+-CO3 2The amount of LDHs is about 0.09g, Zn distributed per unit area of aluminum matrix2+-Al3+-CO3 2The amount of-LDHs is 0.0225g/cm2。
XRD phase analysis is carried out on the powder scraped from the surface of the obtained adsorbing material by adopting a D8 type powder diffractometer manufactured by Brucher company, the scanning range is 2-70 degrees (2 theta), and the scanning speed is 5 degrees/min; adopting a TENSOR 27 type infrared spectrometer of Brucher company in Germany, and scanning the range of 400-4000 cm-1Measuring the infrared spectrum of the powder scraped from the surface by a potassium bromide tabletting method; scanning electrode using field emission of Segma 300 of German ZeissObserving the appearance of the sample by a mirror; and analyzing the element distribution and content of the sample by adopting an Oxford energy spectrometer. The results are shown in FIGS. 1 to 4.
From FIG. 1, the peaks observed are all Zn2+-Al3+-CO3 2-And (4) a characteristic diffraction peak of the LDHs, and no diffraction peak of other mixed phases is observed, so that the synthesis of the ternary component LDHs material with higher purity is proved. Zn2+-Al3+-CO3 2-The characteristic diffraction peaks of the crystal planes of (003), (006), (012), (015), (018), (101), (104), (110) and (113) of the LDHs are strong, the peak forms are symmetrical and sharp, and no sawtooth diffraction peak exists, which indicates that the prepared product has high crystallinity and complete crystal phase structure. The prepared material samples show diffraction peaks of LDHs (003) and (006) crystal planes at about 10 DEG and 20 DEG, and symmetrical and sharp diffraction peaks (003) and (006) show Zn on the surface of an aluminum matrix2+-Al3+-CO3 2-High crystallinity and good lamellar character of LDHs. According to the layer spacing d ═ d003＝2d006Calculating Zn2+-Al3+-CO3 2-The LDHs layer spacing was 0.753 nm.
Infrared spectroscopy is one of the main methods for characterizing anionic functional groups between layers of LDHs materials. From FIG. 2, Zn can be seen2+-Al3+-CO3 2-LDHs at 3470cm-1The absorption band can be attributed to the stretching vibration of O-H bonds on the laminate and O-H bonds in interlayer water molecules; at 2895cm-1The acromion belongs to H2O and CO3 2-Stretching vibration to form hydrogen bond; 1639cm-1The absorption peak is bending vibration in water molecules; at 1375 and 774cm-1The stronger absorption band can be attributed to interlayer CO3 2-Stretching vibration and bending vibration. These information fully indicate the presence of CO between the layers of the resulting samples3 2-And H2And O. FT-IR spectrum at 3700cm-1No amorphous or crystalline metal hydroxide free hydroxyl stretching vibration peak is found, and the existence of the absorption peak is shown, which indicates that Zn2+、Al3+More stable Zn is formed on the aluminum matrix2+-Al3+-CO3 2--LDHs。
From FIG. 3, Zn can be seen2+-Al3+-CO3 2-The LDHs grows vertically on the aluminum substrate, the LDHs film growing on the aluminum sheet has the appearance of a laminated layer, the laminated layer structure has a clear shape, and a plurality of LDHs are tightly aggregated together, so that Zn is ensured2+-Al3+-CO3 2-The active edge of the LDHs layered structure is well exposed. The product was observed to have a typical layered structure of LDHs at high magnification, with a laminate thickness of about 100 nm.
The surface distribution diagram 4 of the elements shows that the zinc and aluminum metal elements appear in the sample, which proves that the zinc and aluminum elements are successfully introduced into the hydrotalcite-like laminate structure, and the zinc and aluminum elements are uniformly distributed on the sample. Furthermore, Zn2+-Al3+-CO3 2-The carbon and oxygen elements in the interlayer region of the LDHs are distributed more uniformly, further illustrating the hydrotalcite interlayer anion CO3 2-And also uniformly distributed, in accordance with the results of the FT-IR analysis. The elemental areal distribution profile further illustrates the dense Zn growth on the aluminum matrix2+-Al3+-CO3 2--LDHs film material.
Example 2
Zn prepared in example 12+-Al3+-CO3 2Application of-LDHs @ Al adsorbing material in adsorbing fluorine ions
1、Zn2+-Al3+-CO3 2Calcination of-LDHs @ Al
Zn is added2+-Al3+-CO3 2And (3) putting the LDHs @ Al adsorbing material into a muffle furnace, heating to 100 ℃, 200 ℃, 300, 400, 500 and 600 ℃ at the heating rate of 1 ℃/min respectively, and calcining at constant temperature for 5 hours.
The XRD pattern of the calcined product is shown in fig. 5. Although the (003) and (006) plane diffraction peaks of the calcined product still exist with the increase of the calcination temperature (100-200 ℃), the diffraction peak of the calcined product becomes wide and moves to the high angle direction, which shows that the layered structure in the calcined product at 200 ℃ still exists, but the crystallinity of the product is deteriorated, the interlayer distance is reduced (0.753nm is reduced to 0.662nm), and the regularity between layers is weakened mainly due to the collapse of interlayer anions and water molecules from the interlayer plate-out part in the calcination process (fig. 5a and 5 b). As the temperature was gradually increased to 300 ℃, the diffraction peaks of the (003) and (006) crystal planes in the XRD pattern of the product disappeared (fig. 5c), indicating that the layered structure of LDHs completely collapsed and began to decompose to form a complex metal oxide. The product obtained from the calcination showed a diffraction peak characteristic of the metal oxide when the calcination temperature reached 400 c (fig. 5d), and showed a spinel phase when the calcination temperature reached 500 c (fig. 5e), indicating that the composite metal oxide had begun to sinter to form spinel.
From FIG. 6, Zn can be seen2+-Al3+-CO3 2-LDHs @ Al calcined at 200 ℃ and 1383cm-1Interlayer CO belonging to LDHs3 2-Decrease in absorption peak (FIG. 5c), illustrating interlayer CO3 2-Decomposition is started. When the calcination temperature is further increased to 300 ℃, CO3 2-The vibration absorption peak is obviously reduced, which shows that the interlayer CO of LDHs3 2-Gradually decomposing at 200-300 deg.C, and when the temperature is 400 deg.C, CO3 2-The absorption peak of (A) is completely decomposed, at the same time at 3453cm-1Due to the presence of the layer OH-The absorption vibration peak is obviously reduced and moves to the direction of low wave number, which shows that LDHs are completely converted into LDO, and when the calcining temperature exceeds 500 ℃, 669cm-1And 563cm-1The expansion vibration absorption peaks of Zn-O and Al-O bonds in the metal composite oxide are respectively shown, which indicates that the calcined product generates spinel, and the phenomenon is consistent with the phenomenon observed by XRD.
2、Zn2+-Al3+-CO3 2Adsorption of fluoride ions by-LDHs @ Al
Using a fluoride ion selective electrode method to F-The concentration of (2) is measured by the following specific measurement method: preparing a fluorine ion stock solution with the concentration of 100mg/L by using a polyethylene bottle, measuring 50.00mL of the stock solution, diluting, and preparing a fluorine ion standard solution to enable the concentration of the fluorine ions to be L0 mg/L; 1000mL of a buffer solution of sodium citrate and sodium nitrate was prepared. Drawing a fluorine ion standard curve according to a fluorine ion selective electrode method to obtain a corresponding potential value sumAnd (4) calculating the concentration of the fluorine ions according to the potential value of the standard curve.
Discussing Zn by adding different adsorbent amounts to adsorption experiments to discuss corresponding adsorption amount and adsorption rate2+-Al3+-CO3 2-LDHs @ Al pair F-The adsorption process of (1). The reaction is a static reaction, initially F-The reaction was carried out at a concentration of 10mg/L at 25 ℃ for 1 hour. The adsorption curve is shown in fig. 8. It can be seen from FIG. 8 that as the number of aluminum sheets increases, the pair F-The removal rate of (a) gradually increases. The addition amount is in the range of 20 pieces/L-40 pieces/L, the removal rate is improved fastest, when the addition amount is increased from 40 pieces/L to 90 pieces/L, the removal rate curve gradually tends to be gentle,at this time, the removal rate was about 98%, and it was found that the adsorption amount was close to saturation when the addition amount was 40 pieces, and the result was consistent with the result obtained in FIG. 7.
FIG. 9 shows Zn2+-Al3+-CO3 2-surface scanning analysis of LDHs @ Al after adsorption of fluoride ions after calcination at 300 ℃. From the surface distribution diagram of the elements, zinc and aluminum metal elements and uniformly distributed fluorine elements appear in the sample, and further illustrate that a large amount of fluorine ions are adsorbed between LDHs layers.
3、Zn2+-Al3+-CO3 2Regeneration of the-LDHs @ Al
Because the LDHs has a topological transformation effect, the LDHs can be regenerated under an alkaline condition through roasting recombination and anion exchange reaction and can be repeatedly used, so that the aim of recycling is fulfilled. F is adsorbed by adopting a roasting recombination method and an anion exchange pair-And regenerating the subsequent adsorbing material. The specific method comprises the following steps: taking Zn after absorbing fluorinion2+-Al3+-CO3 2Putting the-LDHs @ Al adsorbing material into a mixed aqueous solution of sodium hydroxide (the mass fraction is 10%) and sodium carbonate (1.5mol/L) to be soaked for 4 hours, washing and drying the soaked adsorbing material, and drying the dried Zn2+-Al3+-CO3 2Putting the-LDHs @ Al into a muffle furnace to be respectively calcined at 100, 200, 300, 400, 500 and 600 ℃ for 4 hours to obtain regenerated Zn2+-Al3+-CO3 2And (4) adsorbing the fluorine ions in the fluorine-containing ion aqueous solution again by using an LDHs @ Al adsorbing material.
Zn to be regenerated2+-Al3+-CO3 2Re-feeding F for-LDHs @ Al adsorbing material-Adsorbing in 10mg/L solution with 40 Zn tablets2+-Al3+-CO3 2LDHs @ Al adsorbing material, the reaction temperature is 25 ℃, and the reaction time is 1 hour. Regenerated Zn2+-Al3+-CO3 2Adsorbing F again by using-LDHs @ Al adsorbing material-The experimental results are shown in fig. 10. It can be seen from FIG. 10 that the calcination temperature was increased from 100 ℃ to 400 ℃ and Zn was regenerated2+-Al3+-CO3 2-LDHs @ Al pair F-The removal rate of the metal oxide is gradually increased, which shows that the temperature is increased to promote the removal of interlayer impurities of the LDHs and simultaneously increase the adsorption performance of the LDHs, and is beneficial to Zn2+-Al3+-CO3 2Regeneration of LDHs @ Al, Zn at calcination temperatures above 400 ℃2+-Al3+-CO3 2-LDHs @ Al adsorption F-The effect of (A) is reduced, which shows that the higher calcination temperature destroys the layered structure of LDHs and hinders Zn2+-Al3+-CO3 2-regeneration of LDHs @ Al. Furthermore, Zn2+-Al3+-CO3 2Calcination with-LDHs @ Al regeneration gives the highest fluorine removal at 400 ℃ and fresh Zn2+-Al3+-CO3 2The highest fluorine removal rate of-LDHs @ Al at 300 ℃ indicates that Zn2+-Al3+-CO3 2In the process of treating the fluorine-containing wastewater, part of the repeatedly adsorbed anions can be removed at a higher temperature, and the regeneration temperature is increased. Comprehensively considering calcining energy consumption and regeneration effect, Zn2+-Al3+-CO3 2The calcination temperature for regeneration of-LDHs @ Al is preferably 400 ℃.
FIG. 11 is the calcination time vs. Zn2+-Al3+-CO3 2Influence of LDHs @ Al regeneration effect. It can be seen from the figure that the regeneration effect of the adsorbent gradually increases as the calcination time increases. When the calcination time reaches 4 hours, Zn2+-Al3+-CO3 2-LDHs @ Al pair F-The removal rate of (A) is not obviously increased, which shows that Zn is removed after the calcination time is 4 hours2+-Al3+-CO3 2The regeneration effect of-LDHs @ Al tends to be stable, and Zn is achieved2+-Al3+-CO3 2-conditions and criteria for recycling of LDHs @ Al.
The inventors further investigated Zn2+-Al3+-CO3 2Effect of LDHs @ Al cycle number on fluorine removal. Each time Zn2+-Al3+-CO3 2The regeneration conditions of the-LDHs @ Al are in a mixed aqueous solution of sodium hydroxide and sodium carbonateThe intermediate desorption was carried out for 4 hours, and the product was washed and dried, then calcined at 400 ℃ for 4 hours, and then recycled, and the results are shown in FIG. 12. It can be seen from the figure that there is no Zn before regeneration2+-Al3+-CO3 2The fluorine removal rate of-LDHs @ Al is 98.2%, Zn is increased along with the increase of the cycle number2+-Al3 +-CO3 2The defluorination rate of-LDHs @ Al is reduced, and when the cycle number is 12 times, the defluorination rate is reduced to 83.3 percent, and the main reason is Zn2+-Al3+-CO3 2-LDHs @ Al Zn of the outer surface of the aluminum plate during regeneration and recycling2+-Al3+-CO3 2LDHs partially separate from the substrate during regeneration, the performance of adsorbing fluorine is reduced, and Zn is continuously increased2+-Al3+-CO3 2-LDHs @ Al, and Zn when the cycle times are more than 122+-Al3+-CO3 2The defluorination rate of-LDHs @ Al tends to be stable, and the defluorination rate is kept about 80 percent, which indicates that Zn2+-Al3+-CO3 2the-LDHs @ Al has better recycling value, Zn2+-Al3+-CO3 2The memory performance of the-LDHs @ Al is better.
Claims (9)
1. Zn2+-Al3+-CO3 2-LDHs @ Al adsorbent material, characterised in that the material is prepared by a process comprising:
(1) pretreatment of aluminum substrates
Cleaning oil stains on the surface of the aluminum matrix with an acetone solution, removing residual substances on the surface of the aluminum matrix with a sodium hydroxide aqueous solution, and cleaning the residual solvent on the surface of the aluminum matrix with deionized water; then putting the cleaned aluminum substrate into an electrolytic bath for anodic oxidation to form an anodic aluminum oxide layer on the surface;
(2) preparation of Zn2+-Al3+-CO3 2-LDHs@Al
Adding zinc nitrate and aluminum nitrate into deionized water by adopting a homogeneous precipitation method, adding urea, performing ultrasonic homogenization, and forming a positive layer on the surface of the step (1)Immersing the aluminum substrate of the aluminum oxide layer into the obtained mixed solution, and carrying out reflux reaction to enable the surface of the aluminum substrate to grow Zn in situ2+-Al3+-CO3 2-Taking out the aluminum matrix after the reaction is finished, washing and drying to obtain Zn2+-Al3+-CO3 2-LDHs @ Al adsorbent material.
2. Zn according to claim 12+-Al3+-CO3 2-LDHs @ Al adsorbing material, characterized in that: in the step (2), the mass ratio of the zinc nitrate to the aluminum nitrate to the urea is 2:1: 6-9.
3. Zn according to claim 12+-Al3+-CO3 2-LDHs @ Al adsorbing material, characterized in that: in the step (2), Zn in the obtained mixed solution is controlled2+And Al3+The total concentration of (a) is 40-60 mmol/L.
4. Zn according to claim 12+-Al3+-CO3 2-LDHs @ Al adsorbing material, characterized in that: in the step (2), the temperature of the reflux reaction is 95-98 ℃, and the time is 8-12 hours.
5. Zn according to any one of claims 1 to 42+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions comprises the following specific steps:
(1)Zn2+-Al3+-CO3 2calcination of-LDHs @ Al
Zn is added2+-Al3+-CO3 2Calcining the-LDHs @ Al adsorbing material at 200-600 ℃ for 4-8 hours;
(2)Zn2+-Al3+-CO3 2adsorption of fluoride ions by-LDHs @ Al
Zn calcined in the step (1)2+-Al3+-CO3 2-Adding the LDHs @ Al adsorbing material into a fluorine-containing ion water solution, and stirring for 1-2 hoursAdsorbing and removing fluorine ions in the water;
(3)Zn2+-Al3+-CO3 2regeneration of the-LDHs @ Al
Zn after absorbing fluorinion2+-Al3+-CO3 2-Putting the LDHs @ Al adsorbing material into a mixed aqueous solution of sodium hydroxide and sodium carbonate, soaking for 1-5 hours, washing and drying the soaked adsorbing material, and calcining at 300-600 ℃ for 2-8 hours to obtain regenerated Zn2+-Al3+And (4) adsorbing the fluorine ions in the fluorine-containing ion aqueous solution again by using an LDHs @ Al adsorbing material.
6. Zn as set forth in claim 52+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions is characterized in that: in the step (1), Zn is added2+-Al3+-CO3 2And (3) roasting the-LDHs @ Al adsorbing material at 300-400 ℃ for 5 hours.
7. Zn as set forth in claim 52+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions is characterized in that: in the step (2), the Zn2+-Al3+-CO3 2-Zn per unit area on LDHs @ Al adsorbing material2+-Al3+-CO3 2-The mass ratio of the LDHs to the fluorine ions in the fluorine ion-containing aqueous solution is 0.01-0.03 mg/cm2。
8. Zn as set forth in claim 52+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions is characterized in that: in the step (3), Zn adsorbed with fluoride ions is taken2+-Al3+-CO3 2-The LDHs @ Al adsorbing material is put into a mixed water solution of sodium hydroxide and sodium carbonate to be soaked for 4 hours, and the soaked adsorbing material is calcined for 3-4 hours at 400-500 ℃ after being washed and dried.
9. Zn according to claim 5 or 82+-Al3+-CO3 2The application of the-LDHs @ Al adsorbing material in the cyclic utilization of adsorbed fluorine ions is characterized in that: in the step (3), the mass concentration of NaOH in the mixed aqueous solution of sodium hydroxide and sodium carbonate is 8-15%, and the concentration of sodium carbonate is 1-2 mol/L.
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