Functional material for synchronously stabilizing multiple metals and preparation method thereof, and method for rehabilitating soil or wastewater contaminated by heavy metals (metalloids)
Disclosed are a functional material for synchronously stabilizing multiple metals and a preparation method thereof, and a method for rehabilitating soil or wastewater contaminated by heavy metals (metalloids). The preparation method includes: mixing a ferrous salt, a ferric salt, a manganous salt, water, a dispersing material, and a phosphate to obtain a first mixture, and subjecting the first mixture to a first precipitation reaction to obtain a first reaction mixture containing the phosphate; adjusting a pH value of the first reaction mixture containing the phosphate to 10-12 by adding an alkali thereto to obtain a second mixture, subjecting the second mixture to a second precipitation reaction to obtain a second reaction mixture; and subjecting the second reaction mixture to a solid-liquid separation to obtain a solid, washing the solid, and drying to obtain the functional material for synchronously stabilizing multiple metals.
1. A functional material for synchronously stabilizing multiple metals, comprising a phosphate compound, an iron-manganese oxide, and an iron-manganese hydroxide, wherein the functional material for synchronously stabilizing multiple metals has a pore diameter of 4 nm to 15 nm, a specific surface area of 110 m 2 /g to 190 m 2 /g, and a total pore volume of 0.14 cm 3 /g to 0.44 cm 3 /g, and
wherein the functional material for synchronously stabilizing multiple metals is prepared by a method comprising
(1) mixing a ferrous salt, a ferric salt, a manganous salt, water, a dispersing material, and a phosphate to obtain a first mixture, and subjecting the first mixture to a first precipitation reaction to obtain a first reaction mixture containing the phosphate, wherein a sum of a molar amount of iron element in the ferrous salt and the ferric salt, and manganese element in the manganous salt is stoichiometrically in excess relative to a molar amount of the phosphate;
(2) adjusting a pH value of the first reaction mixture containing the phosphate to 10-12 by adding an alkali thereto to obtain a second mixture, and subjecting the second mixture to a second precipitation reaction to obtain a second reaction mixture; and
(3) subjecting the second reaction mixture to a solid-liquid separation to obtain a solid, washing the solid, and drying to obtain the functional material for synchronously stabilizing multiple metals.
2. The functional material as claimed in claim 1 , wherein in step (1), mixing the ferrous salt, the ferric salt, the manganous salt, water, the dispersing material, and the phosphate comprises steps of
mixing the ferrous salt, the ferric salt, the manganous salt, and water to obtain an aqueous salt solution;
adding the dispersing material to the aqueous salt solution and mixing to obtain a mixed dispersion; and
adding the phosphate to the mixed dispersion.
3. The functional material as claimed in claim 1 , wherein in step (1), the ferrous salt is at least one selected from the group consisting of FeSO 4 , FeSO 4 ·7H 2 O, FeCl 2 , and Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O; the ferric salt is at least one selected from the group consisting of Fe 2 (SO 4 ) 3 ·xH 2 O, FeCl 3 , and NH 4 Fe(SO 4 ) 2 ; the manganous salt is at least one selected from the group consisting of MnSO 4 , MnSO 4 ·H 2 O, and MnCl 2 ·6H 2 O; and the phosphate is at least one selected from the group consisting of NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , and K 2 HPO 4 .
4. The functional material as claimed in claim 1 , wherein in step (1), a ratio of a sum of a molar amount of Fe 2+ in the ferrous salt, Fe 3+ in the ferric salt and Mn 2+ in the manganous salt to a molar amount of PO 4 3− in the phosphate is in the range of (1.4-13):1; and a molar ratio of Fe 2+ , Fe 3+ and Mn 2+ is in the range of (1-5):(1-5):(1-5).
5. The functional material as claimed in claim 1 , wherein in step (1), the dispersing material is at least one selected from the group consisting of kaolin, rectorite, attapulgite, sepiolite, and white carbon black; and
a mass of the dispersing material is 10% to 25% of a sum of masses of iron element in the ferrous salt and the ferric salt, and manganese element in the manganous salt.
6. The functional material as claimed in claim 1 , wherein the first precipitation reaction and the second precipitation reaction each are independently conducted for 30 min to 120 min; and
both of the first precipitation reaction and the second precipitation reaction are conducted with stirring, each independently at a stirring speed of 200 r/min to 500 r/min.
7. The functional material as claimed in claim 1 , wherein in step (3), the drying is conducted at a temperature of 60° C. to 450° C.
8. A method for rehabilitating soil or wastewater contaminated by heavy metals and/or metalloids, comprising steps of
mixing the soil or wastewater contaminated by heavy metals and/or metalloids with a rehabilitation material for stabilization, and conducting rehabilitation, wherein the heavy metals and/or metalloids comprise at least one selected from the group consisting of Cd, Pb, Cu, Zn, Ni, Cr, As, and Sb; and
the rehabilitation material for stabilization is the functional material for synchronously stabilizing multiple metals as claimed in claim 1 .
9. The method as claimed in claim 8 , wherein under the condition of rehabilitating the soil contaminated by heavy metals and/or metalloids, a mass of the rehabilitation material for stabilization is 0.1% to 3% of a mass of the soil, and the rehabilitation is conducted at a temperature of 10° C. to 40° C. for 10 days to 35 days; and
under the condition of rehabilitating the wastewater contaminated by heavy metals and/or metalloids, the rehabilitation material for stabilization is added to the wastewater in an amount of 0.2 g/L to 3 g/L, and the rehabilitation is conducted at a temperature of 10° C. to 40° C. for 3 h to 24 h.
10. A method for preparing a functional material for synchronously stabilizing multiple metals, comprising steps of
(1) mixing a ferrous salt, a ferric salt, a manganous salt, water, a dispersing material, and a phosphate to obtain a first mixture, and subjecting the first mixture to a first precipitation reaction to obtain a first reaction mixture containing the phosphate, wherein a sum of a molar amount of iron element in the ferrous salt and the ferric salt, and manganese element in the manganous salt is stoichiometrically in excess relative to a molar amount of the phosphate;
(2) adjusting a pH value of the first reaction mixture containing the phosphate to 10-12 by adding an alkali thereto to obtain a second mixture, and subjecting the second mixture to a second precipitation reaction to obtain a second reaction mixture; and
(3) subjecting the second reaction mixture to a solid-liquid separation to obtain a solid, washing the solid, and drying to obtain the functional material for synchronously stabilizing multiple metals.
11. The method as claimed in claim 10 , wherein in step (1), mixing the ferrous salt, the ferric salt, the manganous salt, water, the dispersing material, and the phosphate comprises steps of
mixing the ferrous salt, the ferric salt, the manganous salt, and water to obtain an aqueous salt solution;
adding the dispersing material to the aqueous salt solution and mixing to obtain a mixed dispersion; and
adding the phosphate to the mixed dispersion.
12. The method as claimed in claim 11 , wherein in step (1), the ferrous salt is at least one selected from the group consisting of FeSO 4 , FeSO 4 ·7H 2 O, FeCl 2 , and Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O; the ferric salt is at least one selected from the group consisting of Fe 2 (SO 4 ) 3 ·xH 2 O, FeCl 3 , and NH 4 Fe(SO 4 ) 2 ; the manganous salt is at least one selected from the group consisting of MnSO 4 , MnSO 4 ·H 2 O, and MnCl 2 ·6H2O; and the phosphate is at least one selected from the group consisting of NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , and K 2 HPO 4 .
13. The method as claimed in claim 11 , wherein in step (1), a ratio of a sum of a molar amount of Fe 2+ in the ferrous salt, Fe 3+ in the ferric salt and Mn 2+ in the manganous salt to a molar amount of PO 4 3− in the phosphate is in the range of (1.4-13):1; and a molar ratio of Fe 2+ , Fe 3+ and Mn 2+ is in the range of (1-5):(1-5):(1-5).
14. The method as claimed in claim 11 , wherein in step (1), the dispersing material is at least one selected from the group consisting of kaolin, rectorite, attapulgite, sepiolite, and white carbon black; and
a mass of the dispersing material is 10% to 25% of a sum of masses of iron element in the ferrous salt and the ferric salt, and manganese element in the manganous salt.
15. The method as claimed in claim 10 , wherein in step (1), the ferrous salt is at least one selected from the group consisting of FeSO 4 , FeSO 4 ·7H 2 O, FeCl 2 , and Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O; the ferric salt is at least one selected from the group consisting of Fe 2 (SO 4 ) 3 ·xH 2 O, FeCl 3 , and NH 4 Fe(SO 4 ) 2 ; the manganous salt is at least one selected from the group consisting of MnSO 4 , MnSO 4 ·H 2 O, and MnCl 2 ·6H 2 O; and the phosphate is at least one selected from the group consisting of NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , and K 2 HPO 4 .
16. The method as claimed in claim 10 , wherein in step (1), a ratio of a sum of a molar amount of Fe 2+ in the ferrous salt, Fe 3+ in the ferric salt and Mn 2+ in the manganous salt to a molar amount of PO 4 3− in the phosphate is in the range of (1.4-13):1; and a molar ratio of Fe 2+ , Fe 3+ and Mn 2+ is in the range of (1-5):(1-5):(1-5).
17. The method as claimed in claim 10 , wherein in step (1), the dispersing material is at least one selected from the group consisting of kaolin, rectorite, attapulgite, sepiolite, and white carbon black; and
a mass of the dispersing material is 10% to 25% of a sum of masses of iron element in the ferrous salt and the ferric salt, and manganese element in the manganous salt.
18. The method as claimed in claim 10 , wherein the first precipitation reaction and the second precipitation reaction each are independently conducted for 30 min to 120 min; and
both of the first precipitation reaction and the second precipitation reaction are conducted with stirring, each independently at a stirring speed of 200 r/min to 500 r/min.
19. The method as claimed in claim 10 , wherein in step (3), the drying is conducted at a temperature of 60° C. to 450° C.