CN117482892A - Composite material for selectively adsorbing phosphate and preparation method and application thereof - Google Patents
Composite material for selectively adsorbing phosphate and preparation method and application thereof Download PDFInfo
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- CN117482892A CN117482892A CN202311285202.0A CN202311285202A CN117482892A CN 117482892 A CN117482892 A CN 117482892A CN 202311285202 A CN202311285202 A CN 202311285202A CN 117482892 A CN117482892 A CN 117482892A
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- aluminum
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- rare earth
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- mixed solution
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 47
- 239000010452 phosphate Substances 0.000 title claims abstract description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 53
- 239000011259 mixed solution Substances 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 17
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 150000002910 rare earth metals Chemical class 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 239000010865 sewage Substances 0.000 claims description 14
- 150000002603 lanthanum Chemical class 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
- 150000001450 anions Chemical class 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 description 30
- 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 20
- 229910001701 hydrotalcite Inorganic materials 0.000 description 20
- 229960001545 hydrotalcite Drugs 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052746 lanthanum Inorganic materials 0.000 description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 15
- 229940091250 magnesium supplement Drugs 0.000 description 14
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- C02F2101/105—Phosphorus compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of a composite material for selectively adsorbing phosphate, which comprises the following steps: a. mixing magnesium salt, aluminum salt, rare earth metal salt and deionized water to obtain magnesium-aluminum rare earth mixed solution; b. adding the mixed solution of sodium hydroxide and sodium carbonate into the magnesium-aluminum-rare earth mixed solution obtained in the step a, regulating the pH value of the mixed solution to be alkaline, aging, and carrying out solid-liquid separation to obtain a precipitate; c. and c, washing and drying the precipitate obtained in the step b to obtain the composite material. The composite material prepared by the invention has excellent dephosphorization effect, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater and polluted water.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a composite material for selectively adsorbing phosphate and a preparation method thereof, and further relates to application of the composite material for selectively adsorbing phosphate.
Background
The urban domestic sewage is large in water quality and stable, and the sewage can be used as an important supplementary water source of natural water after being treated and utilized as a resource. However, the traditional sewage treatment processes such as A/A/O and oxidation ditch have poor effect on removing phosphorus in sewage, and the high-concentration phosphorus is discharged into water, especially into water in an environment sensitive area, so that eutrophication of the water is easily caused.
Therefore, it is necessary to develop a treatment technology capable of deeply removing phosphorus so as to realize deep reduction of phosphorus concentration of effluent water of a sewage plant, achieve the first-level A standard of total phosphorus emission executed by the sewage plant, and enable phosphorus of the effluent water to be lower than 0.5mg/L.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: current dephosphorization methods include ion exchange, reverse osmosis, chemical precipitation, crystallization and adsorption. Compared with other deep dephosphorization methods, the adsorption method has the advantages of simple operation, low energy consumption, stable operation and the like. The traditional dephosphorization materials such as active carbon, zeolite, dolomite, vermiculite and the like have the defects of low phosphorus adsorption capacity (0.6-6.0 mg/g), high phosphorus in effluent, poor phosphorus selectivity and the like, so that development of novel efficient dephosphorization materials is needed.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a composite material for selectively adsorbing phosphate and a preparation method thereof, wherein the composite material has excellent dephosphorization effect, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater and polluted water.
The preparation method of the composite material for selectively adsorbing phosphate comprises the following steps:
a. mixing magnesium salt, aluminum salt, rare earth metal salt and deionized water to obtain magnesium-aluminum rare earth mixed solution;
b. adding the mixed solution of sodium hydroxide and sodium carbonate into the magnesium-aluminum-rare earth mixed solution obtained in the step a, regulating the pH value of the mixed solution to be alkaline, aging, and carrying out solid-liquid separation to obtain a precipitate;
c. and c, washing and drying the precipitate obtained in the step b to obtain the composite material.
In the method of the embodiment of the invention, magnesium salt, aluminum salt and rare earth metal salt are mixed together to prepare the composite material by a coprecipitation method, so that rare earth metal elements can be successfully doped into aluminum-magnesium hydrotalcite crystal lattice without changing the crystal form of hydrotalcite, the interlayer spacing of the adsorption composite material is increased, and the adsorption effect is improved; 2. the method of the embodiment of the invention is simple, effectively reduces the production cost and is easy for industrial application; 3. the composite material prepared by the method provided by the embodiment of the invention has an excellent phosphorus removal effect, can effectively remove phosphorus pollutants in water, has a removal rate of more than 98%, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater.
In some embodiments, in the step a, M in the magnesium-aluminum-rare earth mixed solution Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2-3:1,M Aluminum (Al) /M Rare earth metals =1:0.3-2, where M Magnesium (Mg) 、M Aluminum (Al) 、M Rare earth metals Respectively refers to the molar weight of magnesium, aluminum and rare earth metal elements in the magnesium-aluminum-rare earth mixed solution;
preferably M Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2:1，M Aluminum (Al) /M Rare earth metals ＝1:0.5；
Preferably M Magnesium (Mg) 、M Aluminum (Al) And M is as follows Rare earth metals The molar ratio of (2) is (6-10): (2-3): (1-2), further preferably 6:2:1;
and/or, in the magnesium-aluminum-rare earth mixed solution, the molar concentration of the magnesium salt is 0.05-0.8mol/L.
In some embodiments, in step a, the magnesium salt comprises at least one of magnesium nitrate, magnesium chloride, magnesium sulfate; the aluminum salt comprises at least one of aluminum nitrate, aluminum chloride and aluminum sulfate; the rare earth metal salt comprises at least one of a lanthanum salt or a cerium salt, preferably the lanthanum salt comprises at least one of lanthanum nitrate or lanthanum chloride, and the cerium salt comprises at least one of cerium nitrate or cerium chloride.
In some embodiments, in the step b, the sodium hydroxide and sodium carbonate mixed solution, the sodium hydroxide concentration is 2-6mol/L, and the sodium carbonate concentration is 0.1-0.5mol/L; and/or, the pH value of the mixed solution is adjusted to 9-11.
In some embodiments, in step b, the aging time is from 8 to 24 hours.
In some embodiments, in the step b, the solid-liquid separation is performed by using a centrifuge, and the rotational speed of the centrifuge is 3500-8000rpm, and the centrifugation time is 3-10min.
In some embodiments, in the step c, the drying temperature is 60-120 ℃ and the drying time is 5-24 hours.
The embodiment of the invention also provides a composite material for selectively adsorbing phosphate, which is prepared by adopting the method of the embodiment of the invention. The composite material provided by the embodiment of the invention has an excellent dephosphorization effect, can effectively remove phosphorus pollutants in water, has a removal rate of more than 98%, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater.
The embodiment of the invention also provides application of the composite material for selectively adsorbing phosphate in wastewater dephosphorization treatment.
The embodiment of the invention also provides a method for dephosphorizing sewage, wherein the composite material for selectively adsorbing phosphate is added into the sewage to be treated, preferably, the adding amount of the composite material is 0.05-0.3g/L, and the phosphorus content in the sewage to be treated is 0.1-20mg/L in terms of phosphate radical.
Drawings
FIG. 1 is an XRD contrast pattern of the adsorbing materials prepared in example 1 and comparative example 1;
FIG. 2 is a FTIR comparison of the adsorption materials prepared in example 1 and comparative example 1;
FIG. 3 is a graph showing the comparison of the dephosphorization effect of the adsorbent materials prepared in example 1 and comparative example 1;
FIG. 4 is a graph showing the comparison of the dephosphorization effect of the adsorbent materials prepared in example 1 and comparative example 2;
FIG. 5 is a graph showing the effect of the coexisting anions of a solution on the removal of phosphorus from the adsorbent material produced in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The preparation method of the composite material for selectively adsorbing phosphate comprises the following steps:
a. mixing magnesium salt, aluminum salt, rare earth metal salt and deionized water to obtain magnesium-aluminum rare earth mixed solution;
b. adding the mixed solution of sodium hydroxide and sodium carbonate into the magnesium-aluminum-rare earth mixed solution obtained in the step a, regulating the pH value of the mixed solution to be alkaline, aging, and carrying out solid-liquid separation to obtain a precipitate;
c. and c, washing and drying the precipitate obtained in the step b to obtain the composite material.
In the preparation method of the composite material for selectively adsorbing phosphate, disclosed by the embodiment of the invention, magnesium salt, aluminum salt and rare earth metal salt are mixed together and prepared into the composite material by a coprecipitation method, so that rare earth metal elements can be successfully doped into aluminum-magnesium hydrotalcite crystal lattices without changing the crystal form of hydrotalcite, the interlayer spacing of the adsorption composite material is increased, and the adsorption effect is improved; the method of the embodiment of the invention is simple, effectively reduces the production cost and is easy for industrial application; the composite material prepared by the method provided by the embodiment of the invention has an excellent phosphorus removal effect, can effectively remove phosphorus pollutants in water, has a removal rate of more than 98%, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater.
In some embodiments, in the step a, M in the magnesium-aluminum-rare earth mixed solution Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2-3:1,M Aluminum (Al) /M Rare earth metals =1:0.3-2, where M Magnesium (Mg) 、M Aluminum (Al) 、M Rare earth metals Respectively refers to the molar weight of magnesium, aluminum and rare earth metal elements in the magnesium-aluminum-rare earth mixed solution; preferably M Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2:1，M Aluminum (Al) /M Rare earth metals =1:0.5. Preferably M Magnesium (Mg) 、M Aluminum (Al) And M is as follows Rare earth metals The molar ratio of (2) is (6-10): (2-3): (1-2), more preferably 6:2:1. In the embodiment of the invention, the proportion of the magnesium salt, the aluminum salt and the rare earth metal is further optimized, which is favorable for effectively doping the rare earth metal into the aluminum-magnesium hydrotalcite, improves the loading quantity of the rare earth element and is favorable for improving the adsorption dephosphorization effect.
In some embodiments, preferably, the molar concentration of the magnesium salt in the magnesium aluminum rare earth mixed solution is 0.05-0.8mol/L.
In some embodiments, in step a, the magnesium salt comprises at least one of magnesium nitrate, magnesium chloride, magnesium sulfate; the aluminum salt comprises at least one of aluminum nitrate, aluminum chloride and aluminum sulfate; the rare earth metal salt comprises at least one of a lanthanum salt or a cerium salt, preferably the lanthanum salt comprises at least one of lanthanum nitrate or lanthanum chloride, and the cerium salt comprises at least one of cerium nitrate or cerium chloride.
In some embodiments, in the step b, the sodium hydroxide concentration is 2-6mol/L, preferably 3-4mol/L, and the sodium carbonate concentration is 0.1-0.5mol/L, preferably 0.2-0.3mol/L; and/or, the pH of the mixed liquor is adjusted to 9-11, preferably 10.
In some embodiments, in step b, the aging time is 8-24 hours, preferably 10-12 hours. In the embodiment of the invention, aging treatment is carried out after the coprecipitation reaction, which is favorable for the growth of crystal particles in the precipitate, reduces the impurity content in the precipitate and improves the stability and purity of the adsorbent.
In some embodiments, in step b, the solid-liquid separation is performed using a centrifuge having a rotational speed of 3500-8000rpm, preferably 5000-6000rpm, and a centrifugation time of 3-10min, preferably 5-7min.
In some embodiments, in step c, a plurality of water washes, preferably 3-5, are used, the pH of the supernatant being neutral.
In some embodiments, in step c, the drying temperature is 60-120 ℃, preferably 80-100 ℃ in an oven, and the drying time is 5-24 hours, preferably 10-12 hours.
In some embodiments, in step c, the precipitate is subjected to a grinding treatment after drying, and the particle size of the ground composite material is 60-200 mesh, preferably 100-120 mesh.
The embodiment of the invention also provides a composite material for selectively adsorbing phosphate, which is prepared by adopting the method of the embodiment of the invention. The composite material provided by the embodiment of the invention has an excellent dephosphorization effect, can effectively remove phosphorus pollutants in water, has a removal rate of more than 98%, is not interfered by other anions, has good phosphate selectivity, and can be used for treating phosphorus-containing wastewater.
The embodiment of the invention also provides application of the composite material for selectively adsorbing phosphate in wastewater dephosphorization treatment.
The embodiment of the invention also provides a wastewater dephosphorization treatment method, wherein the composite material for selectively adsorbing phosphate is added into the wastewater to be treated and is subjected to adsorption treatment, and the adsorption time is preferably 0.2-6h. Preferably, the adding amount of the composite material is 0.05-0.3g/L; the phosphorus content of the phosphorus-containing sewage to be treated is 0.1-20mg/L, and the initial pH value of the phosphorus-containing sewage is 3-12 based on phosphate radical.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
1. 0.06mol of magnesium chloride hexahydrate, 0.02mol of aluminum chloride hexahydrate and 0.01mol of lanthanum chloride hexahydrate are dissolved in 150mL of deionized water, and the mixture is stirred for 3 hours to prepare a magnesium aluminum lanthanum salt mixed solution, namely the molar ratio of magnesium, aluminum and lanthanum elements in the mixed solution is 6:2:1, the molar concentration of magnesium salt in the mixed solution is 0.4mol/L.
2. Preparing 100ml of sodium hydroxide and sodium carbonate mixed solution, wherein the concentration of sodium hydroxide is 4mol/L, the concentration of sodium carbonate is 0.2mol/L, dropwise adding the sodium hydroxide and sodium carbonate mixed solution into the magnesium aluminum lanthanum salt mixed solution obtained in the step 1, regulating the pH value to 10.0, continuously stirring for 3 hours, closing a magnetic stirrer, aging for 12 hours, carrying out solid-liquid separation of the solution by using a centrifugal machine, and obtaining a precipitate, wherein the rotating speed of the centrifugal machine is 6000rpm, and the time is 5 minutes;
3. washing the precipitate obtained in the step 2 with water for 5 times until the pH value of the supernatant is 7, collecting the precipitate, drying the precipitate in an oven at 80 ℃ for 10 hours, and grinding the precipitate until the particle size is not more than 120 meshes to obtain the phosphate adsorption material.
Example 2
The same procedure as in example 1 is followed, except that in step 1, the molar ratio of magnesium, aluminum and lanthanum elements in the mixed solution is 10:3:2.
example 3
The same procedure as in example 1 is followed, except that in step 1, the molar ratio of magnesium, aluminum and lanthanum elements in the mixed solution is 9:2:1.
example 4
The same procedure as in example 1 is followed except that in step 1, the rare earth metal salt added to the mixed solution is cerium chloride.
Example 5
The same procedure as in example 1 was followed except that in step 1, the molar concentration of magnesium salt in the mixed solution was 0.1mol/L.
Example 6
The same procedure as in example 1 was followed except that in step 1, the molar concentration of magnesium salt in the mixed solution was 0.8mol/L.
Comparative example 1
The same procedure as in example 1 was followed except that lanthanum salt was not added in step 1, and the molar ratio of magnesium to aluminum in the mixed solution was 2:1.
Comparative example 2
The same procedure as in example 1 was followed except that lanthanum chloride hexahydrate was replaced with an equivalent amount of zirconium oxychloride octahydrate in step 1 to produce a zirconium doped magnesia alumina hydrotalcite composite.
Performance analysis test of examples and comparative examples
1. The adsorption materials prepared in example 1 and comparative example 1 were subjected to X-ray diffraction (XRD) analysis to analyze the change in crystal structure of magnesium aluminum hydrotalcite before and after lanthanum doping, and the analysis results are shown in fig. 1.
As can be seen from FIG. 1, in comparative example 1, lanthanum was not doped, the molar ratio of Mg/Al was 2:1, and the adsorption material exhibited characteristic diffraction peaks near 2θ of 11.6 °, 23.4 °, 34.8 °, 39.4 °, 46.9 °, 60.7 °, 62.1 °, respectively corresponding to hydrotalcite (Mg 0.66 Al 0.333 )(OH) 2 (CO 3 ) 0.167 (H 2 O) 0.5 Typical crystal plane characteristic diffraction peaks of (003), (006), (012), (015), (018), (110) and (113) of (PDF # 89-0460), wherein 11.6 DEG and 23.4 DEG characteristic peaks are hydrotalcite layered structure characteristic peaks, interlayer spacing d 003 And the thickness of the hydrotalcite sample is 0.759nm, carbonate ions are used as interlayer ions of corresponding hydrotalcite, and the prepared magnesium aluminum hydrotalcite sample has complete crystalline phases. In example 1, doped with lanthanum element, the adsorption composite material also exhibits characteristic peaks of pure magnalium hydrotalcite, which indicates that lanthanum doping does not change the crystal form of hydrotalcite, and lanthanum is successfully doped into the crystal lattice of magnalium hydrotalcite. But its diffraction peak intensity is reduced, crystallinity is deteriorated, and layer spacing d of lanthanum-doped adsorption composite material 003 0.804, illustrating a smaller ionic radius of Al 3+ La with larger radius 3+ Instead, lanthanum doping increases the interlayer spacing, facilitating adsorption of phosphate.
2. Fourier infrared transform spectroscopy (FTIR) analysis was performed on the adsorption materials prepared in example 1 and comparative example 1 to analyze the functional group change of the magnesium aluminum hydrotalcite before and after lanthanum doping, and the analysis results are shown in fig. 2.
As can be seen from the FTIR analysis results of FIG. 2, the waveThe number is 3400-3500cm -1 The wave number is 1610-1650cm -1 Bending vibration corresponding to adsorbed water H-O-H in a range of 1350-1380cm -1 Characteristic absorption peaks corresponding to carbonate groups in the range; 500-800cm -1 The characteristic absorption peaks corresponding to the adsorbents M-O (m=mg, al, la) in the range. In example 1 and comparative example 1, the adsorption material exhibited characteristic absorption peaks of hydroxyl groups, carbonate groups and M-O before and after lanthanum doping, indicating that lanthanum doping did not change the functional group species of the adsorption material. This is consistent with the results of XRD of figure 1.
3. The adsorption materials of the examples and comparative examples were subjected to experimental tests of the adsorption effect of phosphate, and the results are shown in Table 1 and FIGS. 3 to 4.
The dephosphorization experimental process of the adsorption material is as follows: respectively preparing 2, 5 and 10mg/L potassium dihydrogen phosphate solution, placing the solution into a beaker, respectively adding 0.3g/L adsorption material, fully reacting for 4 hours, measuring the content of phosphate in the solution, and calculating the removal rate of the phosphate.
TABLE 1
As can be seen from Table 1, the removal rate of phosphate in the adsorption composite materials prepared in examples 1 to 6 of the invention can reach more than 95%. As shown in fig. 3, in comparative example 1, pure magnesium aluminum hydrotalcite was used as the adsorption material because lanthanum was not doped, and although 98% removal rate was achieved at a phosphate concentration of 2mg/L, the removal rate was severely reduced to 53% when the phosphate concentration was increased to 10mg/L, whereas the composite material of example 1 doped with lanthanum was able to achieve 98% removal rate even at a high concentration of 10mg/L, and the phosphorus removal rate was increased by 45%, and it was found that lanthanum doping greatly improved the adsorption performance of phosphate. As shown in fig. 4, although the zirconium-doped magnesium aluminum hydrotalcite prepared in comparative example 2 can achieve a removal rate of 97.1% at a phosphate concentration of 2mg/L, the removal rate is severely reduced to only 59.7% when the phosphate concentration is increased to 10mg/L, and thus, the phosphorus removal effect of the lanthanum-doped magnesium aluminum hydrotalcite composite material of the embodiment of the present application is greatly superior to that of the zirconium-doped magnesium aluminum hydrotalcite composite material of comparative example 2.
4. The effect of coexisting ions on the removal of phosphorus by the adsorbent is studied by using 4 common anions in the water body, and the analysis result is shown in fig. 5.
The experimental procedure was as follows: preparing 2mg/L phosphate solution, respectively adding NaCl and NaHCO with different concentrations (1 mmol/L and 10 mmol/L) 3 、NaNO 3 And Na (Na) 2 SO 4 In a beaker, fully mixing, adding 0.1g/L of the adsorption composite material prepared in the example 1, reacting for 4 hours, measuring the concentration of phosphate in the solution, and comparing the influence of ions with different concentrations on the phosphorus removal of the adsorption composite material.
As can be seen from fig. 5, the removal rate of phosphate from the composite material prepared in example 1 can be maintained between 97.2% and 98.3% even in the presence of coexisting ions. The influence of coexisting ions on the phosphorus removal of the adsorbent is negligible, and therefore, the adsorption material prepared by the embodiment of the invention has excellent selectivity on phosphate.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method for preparing a composite material for selectively adsorbing phosphate, which is characterized by comprising the following steps:
a. mixing magnesium salt, aluminum salt, rare earth metal salt and deionized water to obtain magnesium-aluminum rare earth mixed solution;
b. adding the mixed solution of sodium hydroxide and sodium carbonate into the magnesium-aluminum-rare earth mixed solution obtained in the step a, regulating the pH value of the mixed solution to be alkaline, aging, and carrying out solid-liquid separation to obtain a precipitate;
c. and c, washing and drying the precipitate obtained in the step b to obtain the composite material.
2. The method for preparing a composite material for selectively adsorbing phosphate according to claim 1, wherein in the step a, M is contained in the magnesium-aluminum-rare earth mixed solution Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2-3:1,M Aluminum (Al) /M Rare earth metals =1:0.3-2, where M Magnesium (Mg) 、M Aluminum (Al) 、M Rare earth metals Respectively refers to the molar weight of magnesium, aluminum and rare earth metal elements in the magnesium-aluminum-rare earth mixed solution;
preferably M Magnesium (Mg) /(M Aluminum (Al) +M Rare earth metals )＝2:1，M Aluminum (Al) /M Rare earth metals ＝1:0.5；
Preferably M Magnesium (Mg) 、M Aluminum (Al) And M is as follows Rare earth metals The molar ratio of (2) is (6-10): (2-3): (1-2), further preferably 6:2:1;
and/or, in the magnesium-aluminum-rare earth mixed solution, the molar concentration of the magnesium salt is 0.05-0.8mol/L.
3. The method of claim 1, wherein in step a, the magnesium salt comprises at least one of magnesium nitrate, magnesium chloride, and magnesium sulfate; the aluminum salt comprises at least one of aluminum nitrate, aluminum chloride and aluminum sulfate; the rare earth metal salt comprises at least one of a lanthanum salt or a cerium salt, preferably the lanthanum salt comprises at least one of lanthanum nitrate or lanthanum chloride, and the cerium salt comprises at least one of cerium nitrate or cerium chloride.
4. The method for preparing a composite material for selectively adsorbing phosphate according to claim 1, wherein in the step b, the concentration of sodium hydroxide is 2-6mol/L and the concentration of sodium carbonate is 0.1-0.5mol/L in the mixed solution of sodium hydroxide and sodium carbonate; and/or, the pH value of the mixed solution is adjusted to 9-11.
5. The method for preparing a composite material for selectively adsorbing phosphate according to claim 1, wherein in the step b, the aging time is 8 to 24 hours.
6. The method for preparing a composite material for selectively adsorbing phosphate according to claim 1, wherein in the step b, the solid-liquid separation is performed by using a centrifuge, the rotational speed of the centrifuge is 3500-8000rpm, and the centrifugation time is 3-10min.
7. The method for preparing a composite material for selectively adsorbing phosphate according to claim 1, wherein in the step c, the drying temperature is 60-120 ℃ and the drying time is 5-24h.
8. A composite material for selectively adsorbing phosphate, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. Use of the composite material for selectively adsorbing phosphate according to claim 8 in wastewater dephosphorization treatment.
10. A method for dephosphorizing sewage, characterized in that the composite material prepared by the method of any one of claims 1 to 7 or the composite material of claim 8 is added into the sewage to be treated with phosphorus, preferably, the adding amount of the composite material is 0.05 to 0.3g/L, and the phosphorus content of the sewage to be treated with phosphorus is 0.1 to 20mg/L in terms of phosphate radical.
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