CN116119680A - Method for solidifying nonferrous metal tailings by using 4A zeolite and solidified body thereof - Google Patents
Method for solidifying nonferrous metal tailings by using 4A zeolite and solidified body thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 130
- 239000002184 metal Substances 0.000 title claims abstract description 130
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 57
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010457 zeolite Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- -1 sodium silicate pentahydrate Chemical class 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010899 nucleation Methods 0.000 claims description 5
- 230000006911 nucleation Effects 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000012013 faujasite Substances 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 5
- 238000007711 solidification Methods 0.000 abstract description 10
- 230000008023 solidification Effects 0.000 abstract description 10
- 238000002386 leaching Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000007259 addition reaction Methods 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
- 239000010426 asphalt Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
- C01B39/16—Type A from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica but seeds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Materials Engineering (AREA)
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Abstract
The invention provides a method for solidifying nonferrous metal tailings by using 4A zeolite and a solidified body thereof. The method comprises the following steps: uniformly mixing a siliceous raw material, an aluminum raw material and nonferrous metal tailings, adding water, and stirring to obtain a 4A zeolite-nonferrous metal tailing complex; or mixing a siliceous raw material, an aluminum raw material and water and then injecting the mixture into nonferrous metal tailings to obtain a 4A zeolite-nonferrous metal tailings complex; the 4A zeolite-nonferrous metal tailing complex reacts to obtain a 4A zeolite-nonferrous metal tailing solidified body. The solidified body comprises a 4A zeolite-nonferrous metal tailing solidified body solidified by the method. The beneficial effects of the invention include: the method for solidifying the nonferrous metal tailings by the in-situ forming 4A zeolite has simple and convenient process and can effectively reduce the preparation cost; the nonferrous metal tailings have good solidification performance and low leaching rate of heavy metals.
Description
Technical Field
The invention relates to the technical field of tailing solidification, in particular to a method for solidifying nonferrous metal tailings by using 4A zeolite and a solidified body thereof.
Background
As the demand for nonferrous metal minerals increases, a large amount of nonferrous metal tailings are produced. The nonferrous metal tailings are used as solid waste after dressing and smelting, and have the advantages of small particle size, low particle cohesion and multiple heavy metal biotoxicity. Is often accumulated outdoors to cause environmental pollution such as atmospheric pollution, soil pollution, water pollution and the like. Heavy metals in nonferrous metal tailings are easy to migrate from the tailings to the surrounding environment through the geochemistry effect, so that the surrounding soil and water source are polluted by the heavy metals, and huge pressure is brought to the ecological environment restoration around the mining area. The heavy metal pollutants in the nonferrous metal tailings are mainly Fe, mn, pb, zn, cd, cu, ni, sr and the like. In conclusion, the nonferrous metal tailings serve as a special environment medium, and the treatment of the nonferrous metal tailings needs to be carried out by simultaneously considering the restoration of heavy metals and the consolidation of nonferrous metal tailings particles.
At present, a solidification/stabilization technology is often adopted to carry out in-situ restoration on nonferrous metal tailings, and main solidification stabilizers are cement, natural minerals, asphalt, polypropylene, ferrous sulfate, phosphate and the like. However, the method has high energy consumption, high cost, easy secondary pollution generation and failure in repairing the heavy metal pollution caused by the nonferrous metal tailings. There is a need for a method that has low energy consumption and can repair the problem of heavy metal pollution caused by nonferrous metal tailings.
Disclosure of Invention
The invention aims to solve at least one of the defects in the prior art, and one of the aims of the invention is to provide a method for solidifying nonferrous metal tailings.
In order to achieve the above purpose, the invention provides a method for solidifying nonferrous metal tailings by using 4A zeolite.
The method comprises the following steps: uniformly mixing a siliceous raw material, an aluminum raw material and nonferrous metal tailings, adding water, and stirring to obtain a 4A zeolite-nonferrous metal tailing complex; or mixing a siliceous raw material, an aluminum raw material and water and then injecting the mixture into nonferrous metal tailings to obtain a 4A zeolite-nonferrous metal tailings complex; the 4A zeolite-nonferrous metal tailing complex reacts to obtain a 4A zeolite-nonferrous metal tailing solidified body.
According to an exemplary embodiment of the present invention, an auxiliary agent is further added in the step of obtaining the 4A zeolite-nonferrous metal tailing complex.
According to an exemplary embodiment of the present invention, the auxiliary agent may include sodium hydroxide.
According to an exemplary embodiment of the present invention, the mixture of the siliceous raw material, the aluminum raw material, the auxiliary agent and the nonferrous metal tailings may have a mass ratio of 0.01 to 0.5:1, mixing uniformly.
According to an exemplary embodiment of the present invention, the siliceous raw material may include one or more of sodium silicate pentahydrate, sodium silicate nonahydrate, orthosilicic acid, water glass, white carbon black and fumed silica.
According to an exemplary embodiment of the present invention, the aluminum raw material may include one or more of aluminum hydroxide, aluminum powder, and sodium aluminate.
According to an exemplary embodiment of the present invention, the reaction conditions may be room temperature, normal pressure; wherein, the room temperature is 2-30 ℃ and the normal pressure is 1 atmosphere; the reaction may include a nucleation process having a reaction time of 1 to 7d, a crystallization and curing process having a reaction time of 7 to 60d.
According to an exemplary embodiment of the present invention, siO of the 4A zeolite in the 4A zeolite-nonferrous metal tailing complex 2 、Al 2 O 3 And Na (Na) 2 The molar ratio of O can be 0.5-1.5: 0.5 to 2.0:0.5 to 2.0; h of 4A zeolite in the 4A zeolite-nonferrous metal tailing complex 2 O and Na 2 The molar ratio of O can be 1-200: 0.8 to 1.2.
In another aspect the present invention provides a 4A zeolite-nonferrous metal tailings solidified body comprising a 4A zeolite-nonferrous metal tailings solidified body solidified by the method described above.
According to an exemplary embodiment of the present invention, the crystalline zeolite phase in the solidified body is one or more of 4A zeolite and faujasite, and the particle size is 100 to 600nm; the early product is a spherulitic aggregate, and the 4A zeolite crystal is cubic after crystallization is completed; the solidifying rate of the 4A zeolite-nonferrous metal tailings solidifying body to the cationic heavy metal in the nonferrous metal tailings is more than 90%.
Compared with the prior art, the invention has the beneficial effects that at least one of the following contents is included:
(1) The method for solidifying the nonferrous metal by the 4A zeolite has simple and convenient process and can effectively reduce the preparation cost.
(2) The method can effectively solidify the nonferrous metal tailings, has good solidifying performance and low heavy metal leaching rate, and solves the problem that the nonferrous metal tailings pollute the environment.
(3) The reaction conditions of the method are room temperature and normal pressure, and the method is environment-friendly, saves energy and has important environmental and economic benefits.
(4) The temperature required for synthesizing the 4A zeolite in a laboratory is far higher than the outdoor environment temperature, and the 4A zeolite can be crystallized and molded at the outdoor environment temperature.
Drawings
The foregoing and other objects and features of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows an X-ray diffraction pattern of a 4A zeolite-nonferrous metal tailing solidified body prepared in example 1 of the present invention;
FIG. 2 shows a scanning electron microscope image of a 4A zeolite-nonferrous metal tailing solidified body prepared in example 1 of the present invention;
FIG. 3 shows a schematic view of the solidification rate of the static leaching of heavy metal ions from the 4A zeolite solidified nonferrous metal tailings of example 1 of the present invention;
FIG. 4 shows an X-ray diffraction pattern of a 4A zeolite-nonferrous metal tailing solidified body prepared in example 2 of the present invention;
FIG. 5 shows a schematic view of the solidification rate of the static leaching of heavy metal ions from the 4A zeolite solidified nonferrous metal tailings of example 2 of the present invention;
FIG. 6 shows an X-ray diffraction pattern of a 4A zeolite-nonferrous metal tailing solidified body prepared in example 3 of the present invention;
fig. 7 shows a schematic diagram of the solidification rate of the static leaching of heavy metal ions from the 4A zeolite solidified nonferrous metal tailings of example 3 of the present invention.
Detailed Description
The present invention will be better understood by those skilled in the art by reference to the following detailed description of the present invention taken in conjunction with the accompanying drawings and specific embodiments.
Example embodiment 1
The present exemplary embodiment provides a method for solidifying nonferrous metal tailings with 4A zeolite. The method comprises the following steps:
s1, uniformly mixing a siliceous raw material, an aluminum raw material, an auxiliary agent and nonferrous metal tailings, adding water, and stirring to obtain a 4A zeolite-nonferrous metal tailings complex; or mixing the siliceous raw material, the aluminum raw material, the auxiliary agent and water, and then injecting the mixture into the nonferrous metal tailings to obtain the 4A zeolite-nonferrous metal tailings complex.
In the embodiment, a mixture of siliceous raw materials, aluminum raw materials, auxiliary agents and nonferrous metal tailings is placed in an organic glass tube with the diameter of 20mm and the bottom of the organic glass tube is sealed to obtain a 4A zeolite-nonferrous metal tailings complex, water is added into the mixture for reaction while stirring, or the siliceous raw materials, the aluminum raw materials, the auxiliary agents and the water are mixed and then injected into the nonferrous metal tailings to obtain the 4A zeolite-nonferrous metal tailings complex for reaction.
In this embodiment, the nonferrous metal tailings include one or more of nonferrous metal tailings and solid wastes such as nonferrous metal tailings contaminated soil.
In this embodiment, the siliceous raw material may include one or more of sodium silicate pentahydrate, sodium silicate nonahydrate, silicic acid, water glass, white carbon black and fumed silica. For example, the siliceous material is sodium silicate pentahydrate, the siliceous material is water glass or the siliceous material is orthosilicic acid. The siliceous feedstock provides a source of silicon for the synthesis of the 4A zeolite.
In this embodiment, the aluminum raw material may include one or more of aluminum hydroxide, aluminum powder, and sodium aluminate. For example, the aluminum material is aluminum hydroxide, the aluminum material is aluminum powder, or the aluminum material is sodium aluminate. The aluminum feedstock provides an aluminum source for the synthesis of the 4A zeolite.
In this embodiment, the auxiliary agent may include sodium hydroxide, or no auxiliary agent is added. The function of the auxiliary agent is to provide an alkaline environment for the synthesis of the 4A zeolite.
In the present example, chemical components of siliceous raw materials, aluminum raw materials and auxiliary agents of the 4A zeolite in the 4A zeolite-nonferrous metal tailing complex SiO 2 、Al 2 O 3 And Na (Na) 2 The mol ratio of O is 0.5-1.5: 0.5 to 2.0:0.5 to 2.0. For example, siO 2 、Al 2 O 3 And Na (Na) 2 The molar ratio of O may be 1.0:1.0:2.0, 1.0:0.5:2.0, 1.0:2.0:2.0 or 1.0:0.5:0.75.
in the embodiment, the mass ratio of the mixture of the siliceous raw material, the aluminum raw material and the auxiliary agent of the 4A zeolite to the nonferrous metal tailings in the 4A zeolite-nonferrous metal tailings complex is 0.01-0.5: 1, for example, the mass ratio is 0.5: 1. 0.1: 1. 0.3: 1. 0.01:1.
in this example, the 4A zeolite-nonferrous metal tailing complex is obtained by adding water to a mixture of a siliceous material, an aluminum material, an auxiliary agent and nonferrous metal tailings while stirring to react, or mixing the siliceous material, the aluminum material, the auxiliary agent and water and then injecting the mixture into the nonferrous metal tailings. H of 4A zeolite in 4A zeolite-nonferrous metal tailing complex 2 O and Na 2 The mol ratio of O is 1-200: 0.8 to 1.2. For example, 4.0:1.0, 40:1.0, 50:0.9, 150:1.1, 100:1.0 or 200:1.0.
s2, reacting the 4A zeolite-nonferrous metal tailing complex to obtain a 4A zeolite-nonferrous metal tailing solidified body.
In this example, the reaction temperature is room temperature, and the room temperature is 2 to 30 ℃, for example, 5 ℃, 10 ℃, 25 ℃, or 30 ℃. The reaction pressure is normal pressure, and the normal pressure is standard atmospheric pressure.
In this example, the reaction includes a process of 4A zeolite nucleation, crystallization and solidification of nonferrous metal tailings, wherein the nucleation process reaction time is 1 to 7d, e.g., 3d, 5d, 6d; the reaction time of the process of crystallizing and solidifying the nonferrous metal tailings is 7-60 d, such as 10d, 20d, 28d, 35d, 48d, 55d.
In this example, the method of synthesizing the 4A zeolite-nonferrous metal tailing solidified body may further include a step of aging for 1 to 60d after the water addition reaction, for example, the intermediate product may be aged for 10d, 28d or 60d. Aging can allow the components in the intermediate product to be fully reacted and the nonferrous metal tailings to be fully solidified.
In the present embodiment, siO 2 、Al 2 O 3 、Na 2 O and H 2 The molar ratio of O, the reaction temperature and the reaction time are key parameter ranges for synthesizing the 4A zeolite, and when the molar ratio of O, the reaction temperature and the reaction time are beyond the parameter ranges, the 4A zeolite cannot be synthesized, and the 4A zeolite-nonferrous metal tailing solidified body cannot be obtained.
The mixture of siliceous and aluminum materials and auxiliary agent reacts very rapidly after meeting water, a small amount of siliceous materials are dissolved, and AlNaO is generated at the dissolution position x Si y ，AlNaO x Si y It should be a zeolite precursor having a different silica to alumina ratio, i.e. a gel containing 4A zeolite nuclei. As the crystallization time is prolonged, the precursor is gradually grown and formed, and if the crystallinity is high, the cubic structure of the 4A zeolite will appear.
In the embodiment, the 4A zeolite-nonferrous metal tailing solidified body has good solidifying performance on heavy metals in nonferrous metal tailings, the leaching rate of the heavy metals in static leaching is low, and the solidifying rate of the 4A zeolite-nonferrous metal tailing solidified body on cationic heavy metals in the nonferrous metal tailings is more than 90%.
The present exemplary embodiment provides a 4A zeolite-nonferrous metal tailings solidified body comprising the 4A zeolite-nonferrous metal tailings solidified body solidified by the method described in exemplary embodiment 1.
In this embodiment, the crystalline zeolite phase in the solidified body is one or more of 4A zeolite and faujasite, and the particle size is 100-600 nm; the early product is a spherulitic aggregate, and the 4A zeolite crystals are cubic after crystallization is completed.
In this example, the microscopic morphology of the 4A zeolite in the 4A zeolite-nonferrous metal tailings solidification body may include spheres and cubes.
In this example, the particle size of the 4A zeolite in the 4A zeolite-nonferrous metal tailing solidified body can reach the nano-scale.
In the embodiment, the particle size of the 4A zeolite in the 4A zeolite-nonferrous metal tailing solidified body is extremely small and can reach the nanometer level, and spherical polymers formed after the nonferrous metal tailings are solidified are covered on the surfaces of nonferrous metal tailing particles, so that the solidification performance of heavy metals in the nonferrous metal tailings is good.
For a better understanding of exemplary embodiments of the present invention, reference is made to the following description in conjunction with specific examples.
Example 1
9.1g of sodium silicate pentahydrate, 7.0g of sodium aluminate and 50g of nonferrous metal tailings are thoroughly mixed and placed in a bottom-closed organic glass tube with the diameter of 20 mm.
200mL of deionized water is added for reaction at 25 ℃ and normal pressure to obtain the 4A zeolite-nonferrous metal tailing complex. Chemical component SiO of 4A zeolite in 4A zeolite-nonferrous metal tailing complex 2 、Al 2 O 3 、Na 2 O and H 2 The molar ratio of O is 1.0:1.0:2.0:40.
aging the composite for 14 days at a constant temperature of 25 ℃ to obtain a 4A zeolite-nonferrous metal tailing solidified body.
Fig. 1 and 2 are an X-ray diffraction pattern and a scanning electron microscope pattern, respectively, of the 4A zeolite-nonferrous metal tailing solidified body synthesized in example 1. As shown in figures 1 and 2, the XRD diffraction peak of the 4A zeolite is sharp, the crystals are complete, the crystals are of a typical 4A zeolite cube structure, the crystals are mutually overlapped and compact, the particle size distribution is between 100 and 600nm, and the 4A zeolite covers the surface of the nonferrous metal tailings. As shown in fig. 3, after 5 static leaches of the 4A zeolite-nonferrous metal tailing solidified body with ph=4 deionized water, mn 2+ And Sr 2 + The curing rate was 99.96%.
Example 2
After thoroughly mixing 2.6g of sodium silicate pentahydrate, 2g of sodium aluminate and 50g of nonferrous metal tailings, the mixture was placed in a bottom-closed organic glass tube with a diameter of 20 mm.
At 25 ℃ and normal pressure, 35mL of deionized water is added for reaction, and the 4A zeolite-nonferrous metal tailing complex is obtained. Chemical composition SiO of 4A zeolite in 4A zeolite-nonferrous metal tailing complex 2 、Al 2 O 3 、Na 2 O and H 2 The molar ratio of O is 1.0:4.0:1.0:20.
aging the composite for 25 days at the constant temperature of 10 ℃ to obtain the 4A zeolite-nonferrous metal tailing solidified body.
FIG. 4 is an X-ray diffraction pattern of the 4A zeolite-nonferrous metal tailing solidified body synthesized in example 2. As shown in fig. 4, no significant diffraction peak of the 4A zeolite was found in the XRD pattern. As shown in fig. 5, after the 4A zeolite-nonferrous metal tailing solidified body is statically leached out by 5 times of deionized water with ph=4, mn 2+ And Sr 2+ The curing rate is kept above 90%.
Example 3
13g of sodium silicate pentahydrate, 10g of sodium aluminate and 50g of nonferrous metal tailings are thoroughly mixed and placed in a bottom-closed organic glass tube with the diameter of 20 mm.
73mL of deionized water is added for reaction at 20 ℃ and normal pressure to obtain the 4A zeolite-nonferrous metal tailing complex. Chemical component SiO of 4A zeolite in 4A zeolite-nonferrous metal tailing complex 2 、Al 2 O 3 、Na 2 O and H 2 The molar ratio of O is 1.0:1.0:5.0:50.
aging the composite for 32 days at a constant temperature of 20 ℃ to obtain a 4A zeolite-nonferrous metal tailing solidified body.
FIG. 6 is an X-ray diffraction pattern of the 4A zeolite-nonferrous metal tailing solidified body synthesized in example 3. As shown in fig. 6, the XRD pattern diffraction peak of the 4A zeolite can be observed, but the peak form is weak. As shown in fig. 7, after the 4A zeolite-nonferrous metal tailing solidified body is statically leached out by 5 times of deionized water with ph=4, mn 2+ And Sr 2+ The curing rate is kept above 95%.
Although the present invention has been described above by way of the combination of the exemplary embodiments, it should be apparent to those skilled in the art that various modifications and changes can be made to the exemplary embodiments of the present invention without departing from the spirit and scope defined in the appended claims.
Claims (10)
1. A method for solidifying nonferrous metal tailings with 4A zeolite, the method comprising the steps of:
uniformly mixing a siliceous raw material, an aluminum raw material and nonferrous metal tailings, adding water, and stirring to obtain a 4A zeolite-nonferrous metal tailing complex; or (b)
Mixing a siliceous raw material, an aluminum raw material and water, and then injecting the mixture into nonferrous metal tailings to obtain a 4A zeolite-nonferrous metal tailings complex;
the 4A zeolite-nonferrous metal tailing complex reacts to obtain a 4A zeolite-nonferrous metal tailing solidified body.
2. The method for solidifying non-ferrous metal tailings by using zeolite 4A according to claim 1, wherein an auxiliary agent is further added in the step of obtaining the zeolite 4A-non-ferrous metal tailings complex.
3. The method of solidifying nonferrous metal tailings with zeolite 4A of claim 2 wherein the promoter comprises sodium hydroxide.
4. The method for solidifying nonferrous metal tailings by using 4A zeolite according to claim 2, wherein the mass ratio of the mixture of the siliceous raw material, the aluminum raw material and the auxiliary agent to the nonferrous metal tailings is 0.01-0.5: 1, mixing uniformly.
5. The method of solidifying non-ferrous metal tailings with zeolite 4A of claim 1 wherein the siliceous material comprises one or more of sodium silicate pentahydrate, sodium silicate nonahydrate, orthosilicic acid, water glass, white carbon black, and fumed silica.
6. The method of solidifying nonferrous metal tailings with zeolite 4A of claim 1 wherein the aluminum feedstock comprises one or more of aluminum hydroxide, aluminum powder, and sodium aluminate.
7. The method for solidifying nonferrous metal tailings by using 4A zeolite according to claim 1, wherein the reaction condition is room temperature and normal pressure; wherein, the room temperature is 2-30 ℃ and the normal pressure is 1 atmosphere;
the reaction comprises a nucleation process, a crystallization and curing process, wherein the reaction time of the nucleation process is 1-7 d, and the reaction time of the crystallization and curing process is 7-60 d.
8. The method for solidifying non-ferrous metal tailings by 4A zeolite according to claim 1, wherein the SiO of the 4A zeolite in the 4A zeolite-non-ferrous metal tailings complex 2 、Al 2 O 3 And Na (Na) 2 The mol ratio of O is 0.5-1.5: 0.5 to 2.0:0.5 to 2.0;
h of 4A zeolite in the 4A zeolite-nonferrous metal tailing complex 2 O and Na 2 The mol ratio of O is 1-200: 0.8 to 1.2.
9. A 4A zeolite-nonferrous metal tailings solidified body, wherein the solidified body comprises the 4A zeolite-nonferrous metal tailings solidified body solidified by the method of any one of claims 1-8.
10. The 4A zeolite-nonferrous metal tailing solidified body according to claim 9, characterized in that the crystalline zeolite phase in the solidified body is one or more of 4A zeolite and faujasite, and the particle size is 100-600 nm;
the early product is a spherulitic aggregate, and the 4A zeolite crystal is cubic after crystallization is completed;
the solidifying rate of the 4A zeolite-nonferrous metal tailings solidifying body to the cationic heavy metal in the nonferrous metal tailings is more than 90%.
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