CN114149063A - Silicate-carbonate composite mineral material, preparation method thereof and application thereof in precipitating heavy metal ions - Google Patents
Silicate-carbonate composite mineral material, preparation method thereof and application thereof in precipitating heavy metal ions Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 60
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 59
- 239000011707 mineral Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 50
- 150000002500 ions Chemical class 0.000 title claims abstract description 35
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 65
- 239000000843 powder Substances 0.000 claims description 41
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 17
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229910001748 carbonate mineral Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010450 olivine Substances 0.000 claims description 11
- 229910052609 olivine Inorganic materials 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 239000002910 solid waste Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000010811 mineral waste Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 abstract description 45
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 21
- 239000011572 manganese Substances 0.000 abstract description 16
- 229910052748 manganese Inorganic materials 0.000 abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 8
- 239000002689 soil Substances 0.000 abstract description 8
- 239000011777 magnesium Substances 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract description 2
- 230000008635 plant growth Effects 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 235000010755 mineral Nutrition 0.000 description 41
- 239000000523 sample Substances 0.000 description 24
- 238000000227 grinding Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 6
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910021532 Calcite Inorganic materials 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 4
- 229910000514 dolomite Inorganic materials 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- XRAOIGDZVAEEED-UHFFFAOYSA-N carbonic acid;silicic acid Chemical compound OC(O)=O.O[Si](O)(O)O XRAOIGDZVAEEED-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- -1 basic carbonate Chemical class 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020091 MgCa Inorganic materials 0.000 description 1
- 101100003996 Mus musculus Atrn gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a silicate-carbonate composite mineral material, a preparation method thereof and application in precipitating heavy metal ions. The silicate-carbonate composite mineral material provided by the invention can efficiently fix heavy metal ions such as cadmium, manganese and the like in a wider pH value range, can achieve the effect of solid-liquid separation by standing and precipitating for a short time, has obvious precipitation effect, small using amount and convenient operation, does not introduce other impurity ions, is green and environment-friendly, does not need acid neutralization treatment when the pH value of the treated solution is in a weak alkaline range, is suitable for water treatment and heavy metal contaminated soil remediation, can slowly release trace/constant elements such as silicon, magnesium, calcium and the like required by plant growth in the process of fixing the heavy metal ions when used for soil remediation, and plays a role of a fertilizer.
Description
Technical Field
The invention belongs to the technical field of solution treatment or purification, and particularly relates to a silicate-carbonate composite mineral material, a preparation method thereof and application thereof in precipitating heavy metal ions.
Background
The discharge of a large amount of wastewater containing heavy metals in the industrial production process can lead to the continuous accumulation of the content of the heavy metals in water and surrounding soil, cause pollution to the ecological environment, and finally threaten the health of human bodies through the transmission of a food chain. Therefore, the removal of heavy metals is of great significance for protecting the water body and the soil ecological environment.
The process for removing heavy metals is numerous, and the alkali precipitation method is a method widely applied in the current industry, and is mainly used for fixing and removing heavy metals by adding strong alkaline substances such as lime, sodium hydroxide, sodium carbonate and the like and adjusting the alkalinity of a water body to convert heavy metal elements into insoluble hydroxides or carbonates, wherein the lime is wide in raw material source and low in price, and is the most widely applied precipitator. However, the method has certain limitations when treating heavy metals, and has the main problems that: (1) when the alkali consumption is insufficient, the heavy metal removal effect cannot be guaranteed, but the use of a large amount of alkali causes the treated water body to have too strong alkalinity (pH)>9) The requirement of emission can be met after further acid neutralization treatment, and the process cost is increased; (2) the sludge taking metal hydroxide as a main component has high water content, large volume, long settling time and difficult solid-liquid separation, and meanwhile, the sludge belongs to dangerous solid waste, and secondary pollution can be caused by re-dissolution of part of heavy metal ions in the stacking process. Particularly, when the waste liquid containing manganese and cadmium heavy metal ions is treated, the manganese and cadmium ions are combined with six water molecules in a water environment to form a stable octahedral shell-core structure (Me (H)2O)6 2+Me-Cd and Mn) is a tetradentate heavy metal ((Me (H) is2O)4 2+) In addition, the hydration energy is higher, namely the energy required for removing the hydrated shell is higher, so that the reaction activity is low; and the cadmium and manganese hydroxides have larger solubility product constants, and the pH value of a water body is required to be adjusted to be more than 12 in the traditional alkali neutralization process to ensure the high enough removal rate of cadmium and manganese, so that the short plate of the alkali precipitation process is more prominent. In addition, when heavy metal polluted soil is treated, the strong alkaline substances are used in a large amount to destroy the acid-base balance of the soil, so that secondary pollution is caused.
The calcite mineral and the silicate mineral are two kinds of mineral resources widely existing in nature and are used for environmental managementThe noodle has more applications. Wherein the calcite (contains CaCO)3) Is the main raw material for producing lime, has stable chemical property and weaker adsorption effect on heavy metals. Although the existing research at home and abroad shows that the activated calcite mineral material can directly act on heavy metal ions such as copper, iron, zinc and the like to enable the heavy metal ions to be precipitated in the form of hydroxide or composite salts such as basic carbonate, basic sulfate and the like, the fixed capacity of the calcite mineral material on cadmium and manganese is far lower than that of the metal ions, and the emission requirement cannot be met. Similarly, natural silicate minerals such as montmorillonite, sepiolite, kaolinite, serpentine, talc and the like have been widely studied as heavy metal ion adsorbents, but the adsorption capacities of the raw materials or modified mineral materials are not high, and particularly when heavy metals such as cadmium, manganese and the like are treated, the heavy metal content in the treated solids is only 1-5%. By means of a surface adsorption mechanism with low efficiency, the adsorption capacity of natural minerals to heavy metals cannot achieve the purpose of recycling, and in addition, in order to ensure that the concentration of the heavy metals reaches the standard and is discharged, a large amount of solid slag containing the heavy metals, which is generated by using a large amount of mineral raw materials, needs to be treated urgently.
In the existing research, the precipitant material based on the minerals does not achieve effective fixation of heavy metal elements such as cadmium and manganese, the application provides the carbonate-silicate composite mineral material, the adsorption performance of the carbonate-silicate composite mineral material on heavy metals is enhanced, the preparation and application processes are simple and environment-friendly, the environment is purified, the comprehensive utilization value of non-metal mineral resources is improved, the resource application of related solid wastes is expected to be realized, and the carbonate-silicate composite mineral material has an important industrial application value.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a silicate-carbonate composite mineral material, a preparation method thereof and application in precipitating heavy metal (cadmium, manganese and the like) ions, aiming at the defects in the prior art, wherein the silicate-carbonate composite mineral material can efficiently fix the cadmium and manganese heavy metals under mild conditions, and realizes stable and harmless treatment of heavy metal pollution and recovery of secondary metal resources.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provided is a silicate-carbonate composite mineral material, which is obtained by mixing silicate mineral powder and carbonate mineral powder and performing ball milling activation.
The invention also provides a preparation method of the silicate-carbonate composite mineral material, which comprises the following specific steps: mixing silicate mineral powder and carbonate mineral powder, and putting the mixture into a ball mill for ball milling, wherein the ball-material ratio is 25-50: 1, the ball milling rotation speed is 400-.
According to the scheme, the silicate mineral powder is one or more of natural minerals such as serpentine, olivine, attapulgite and talc, or solid waste containing the minerals, and the particle size is below 158 micrometers.
According to the scheme, the carbonate mineral powder is one of magnesium carbonate, calcium carbonate, basic magnesium carbonate and calcium magnesium carbonate, or natural minerals or solid wastes containing the components, and the particle size is less than 158 micrometers.
According to the scheme, the mass ratio of silicate in the silicate mineral powder to carbonate in the carbonate mineral powder is 1-3: 1.
the invention also comprises the application of the silicate-carbonate composite mineral material in the aspect of precipitating heavy metal ions, and the specific use method comprises the following steps: adding the silicate-carbonate composite mineral material into a solution containing heavy metal ions, oscillating and stirring at a constant speed at normal temperature and normal pressure for reaction, standing after the reaction is finished, and then carrying out solid-liquid separation, wherein the heavy metal is fixed in a form of carbonate and is removed from a liquid phase.
According to the scheme, the heavy metal ions comprise manganese ions and cadmium ions. The invention has good effect of removing the deposition of copper, zinc, nickel and iron ions.
According to the scheme, the pH value of the solution containing the heavy metal ions is 3-7.
According to the scheme, the molar ratio of the heavy metal ions in the solution containing the heavy metal ions to the carbonate in the silicate-carbonate composite mineral material is 1: 0.5 to 3.
According to the scheme, the process conditions of uniform-speed oscillation stirring reaction are as follows: stirring with shaking at the rotation speed of 300-500rpm, and reacting for 30-240 minutes.
The invention utilizes a mechanochemical grinding means to mix, grind and activate the silicate mineral and the carbonate mineral, the ball milling can destroy the crystal structure of the primary mineral and improve the reaction activity, in addition, the mixing of the silicate mineral and the carbonate mineral enhances the interface interaction (the load of the carbonate mineral on the surface of the silicate mineral) between the two materials under the specific ball milling condition, and the silicate-carbonate composite material is prepared. In the process of solidifying heavy metal ions, under the synergistic action of silicate minerals and carbonate minerals, the heavy metal ions such as cadmium and manganese ions can form carbonate precipitates on the surfaces of the silicate minerals, solid-liquid separation can be realized through standing precipitation, the reaction can be effectively carried out in the environment with the pH value of 3 or above, high-efficiency fixation of the heavy metal ions such as cadmium and manganese is realized under the extremely low dosage of a fixing agent, and no new impurities are introduced in the process. The basic reaction principle is shown in the following formulas (a) and (b):
X-Si-O(H)+YCO3→YCO3@X-Si-O(H) (a)
YCO3@X-Si-O(H)+Me2+→MeCO3@X-Si-O(H)+Y2++X2+ (b)
the X refers to different metal cation components in silicate minerals, mainly comprising alkali metal and alkaline earth metal elements such as magnesium, calcium, sodium, potassium and the like, and the Y refers to cation components in carbonate minerals, mainly comprising magnesium and calcium.
The solid residue obtained after the precipitation can be leached out by weak acid (pH value is 2), so that heavy metal elements can be dissolved out, and the recovery of heavy metal resources such as cadmium, manganese and the like is realized.
The invention has the beneficial effects that: 1. the silicate-carbonate composite mineral material provided by the invention can efficiently fix heavy metal ions such as cadmium, manganese and the like in a wider pH value range, can achieve the effect of solid-liquid separation by standing and precipitating for a short time, has obvious precipitation effect, small using amount and convenient operation, does not introduce other impurity ions, is green and environment-friendly, does not need acid neutralization treatment when the pH value of the treated solution is in a weak alkaline range, is suitable for water treatment and heavy metal contaminated soil remediation, can slowly release trace/constant elements such as silicon, magnesium, calcium and the like required by plant growth in the process of fixing the heavy metal ions when used for soil remediation, and plays a role of a fertilizer. 2. The mineral raw materials used in the invention have wide sources and low price, the silicate-carbonate composite mineral material is constructed by adopting a mechanical chemical grinding method, the preparation method is simple and convenient, and the industrial production is easy to realize.
Drawings
FIG. 1 is a graph showing the X-ray diffraction contrast of a 600-2.6SP-1CC powder product obtained in example 1 of the present invention with a 600-2.6SP +1CC sample and a ball-milled serpentine sample of a control group;
FIG. 2 is a comparative X-ray diffraction pattern of the 600-2.6SP-1CC powder product obtained in example 1 and the filtered and dried solid residue after Cd treatment;
FIG. 3 is a comparative X-ray diffraction pattern of the control 600-2.6SP +1CC sample and the filtered and dried solid residue after Cd treatment in example 1;
FIG. 4 is an XRD spectrum of a solid residue obtained after the treatment of heavy metal elements (cadmium) with the olivine-calcium carbonate composite material obtained in example 2;
FIG. 5 is a graph showing the removal rate of cadmium in different amounts of calcium carbonate ball-milled samples under different reaction times.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
The serpentine powder used in the examples of the present invention contains Mg as a main active ingredient3Si2O5(OH)4(SP for short), the content of effective component is 95%, and the main effective component Mg in the olivine powder2SiO4(abbreviated as MSi) content of 87%, and MgCa (CO) as main effective component in dolomite powder3)2The (abbreviated as MCC) content was 95%, the main impurity being quartz. All percentages herein refer to mass percent. The particle size of the powder material used in this example was 158 μm or less.
The equipment used in the following examples is as follows:
the ball mill is a German flying planetary mill Pulverisette 7 type; constant temperature magnetic stirrer: shanghai Mei Yipu Instrument manufacturing Limited Chivenen model 524G; measuring the concentration of metal ions in the solution by using an atomic absorption spectrophotometer, model AA-6880 of Shimadzu corporation, Japan; the pH of the solution before and after the reaction was measured by a pH meter, FE20-FiveEasy, MdTMMolding; the phase of the product obtained by the grinding treatment and of the solid residue after treatment of the heavy metals was characterized by means of a rotary X-ray diffractometer (XRD), model D/MAX-RB, RIGAKU, Japan.
Example 1
A silicate-carbonate composite mineral material is prepared by the following steps:
weighing four groups of serpentine powder and calcium carbonate powder (CaCO)3Abbreviated CC, analytical pure): 1.6933+0.3067g (mass ratio SP: CC ═ 5.2:1), 1.4681+0.5319g (mass ratio SP: CC ═ 2.6:1), 1.2958+0.7042g (mass ratio SP: CC ═ 1.7:1), and 1.1597+0.8403g (mass ratio SP: CC ═ 1.3:1) were placed in 45mL zirconium dioxide grinding pots, and 70g of zirconium dioxide balls with a diameter of 15mm were added to each of the groups, at a ball-to-feed ratio of 35: 1, setting the rotation speed of a mill to 600rpm, and collecting each group of powder samples after grinding for 60min to obtain 4 serpentine-calcium carbonate composite fixing agents which are respectively marked as 600-5.2SP-1CC, 600-2.6SP-1CC, 600-1.7SP-1CC and 600-1.3SP-1 CC.
Control group: respectively taking 2g of serpentine and calcium carbonate, respectively putting the serpentine and the calcium carbonate into a 45mL zirconium dioxide grinding tank, adding 70g of zirconium dioxide balls with the diameter of 15mm, wherein the ball-to-material ratio is 35: 1, setting the rotating speed of a mill to 600rpm, collecting a powder sample after grinding for 60min to obtain ground activated serpentine and activated calcium carbonate, weighing two kinds of activated powder according to the mass ratio of SP to calcium carbonate in the serpentine of 2.6:1, and simply mixing to obtain a serpentine and calcium carbonate mixed sample, wherein the label is 600-2.6SP +1 CC.
Using cadmium sulphate (CdSO)4·8/3H2O) preparation containing Cd2+100mL of each 100mg/L solution was placed in a series of beakers with CO3 2-With Cd2+Mole ofThe ratio of 0.5-2: 1 as a standard, adding the four composite fixatives obtained in the embodiment and the powder sample 600-2.6SP +1CC obtained in the control group respectively into a solution containing cadmium to perform a shaking stirring reaction at a speed of 400rpm for 1-4h, standing for 10min after the reaction, taking the supernatant to determine the concentration and pH value of Cd ions in the solution, and the experimental results are shown in the following table 1.
TABLE 1 influence of the ratio of serpentine to calcium carbonate mineral and the amount of different fixatives added on cadmium removal
As can be seen from Table 1, under the conditions of different silicate-carbonate ratios, the serpentine-calcium carbonate composite material can fix cadmium within 4 hours by adjusting the dosage of the composite material, the removal rate of cadmium is above 98%, and the treated solution is weakly acidic to weakly alkaline. In addition, a comparison of experimental groups 3 and 6 shows that under the same treatment time and dosage conditions, the composite material prepared in the embodiment has a cadmium fixing efficiency far higher than that of a simple mineral mixed material of a control group, which indicates that the silicate mineral-carbonate mineral composite material constructed by the invention has a reaction activity far higher than that of the control group obtained by simple physical mixing.
The 600-2.6SP-1CC powder product obtained in this example (mixed ball milling) was subjected to X-ray diffraction analysis with a control 600-2.6SP +1CC sample (physical mixing), a ball-milled serpentine sample (serpentine powder was separately ball-milled using the ball milling process of this example) and a serpentine raw material, and the comparison results are shown in FIG. 1. As can be seen from FIG. 1, the intensity of the characteristic diffraction peak of the serpentine mineral is obviously reduced after ball milling, which indicates that the serpentine crystal structure is damaged by grinding, so that the serpentine crystal structure is close to amorphization, and the reaction activity of the serpentine mineral is favorably improved. In addition, the characteristic diffraction peak intensity of the calcium carbonate phase in the 600-2.6SP-1CC sample is obviously lower than that of the 600-2.6SP +1CC sample, the sizes of the crystal grains of the main crystal plane (104) are different, the former is obviously larger than the latter, which shows that the damage degree of the crystal structure of the calcium carbonate is larger and the reaction activity is higher under the condition of mixing and ball milling, and the interface interaction of two materials in the sample mixed by ball milling is stronger.
The calcium carbonate powder used in the example was ball milled alone by the ball milling process of the example to obtain a calcium carbonate ball milled sample, and the cadmium sulfate reagent was used to prepare a sample containing Cd2+100mL of each 100mg/L solution was placed in a set of beakers, and different amounts of calcium carbonate, CaCO, were added to each beaker to ball mill the samples3With Cd2+The molar ratios are respectively 0.5, 1, 1.5, 2, 2.5 and 3, and the removal rate of cadmium in the calcium carbonate ball-milled sample is tested. Fig. 5 is a graph of the removal rate of cadmium of calcium carbonate ball-milled samples with different dosages under different reaction times, and it can be seen that when the molar ratio of activated calcium carbonate to cadmium is 1: when 1, the cadmium removal rate is still not high even if the reaction is carried out for 24 hours. The cadmium removal rate of more than 90 percent can be obtained only by increasing the dosage of the medicament and long-time reaction conditions.
The 600-2.6SP-1CC powder product (mixed ball milling) obtained in the embodiment and the filtered and dried solid residue after Cd treatment are subjected to X-ray diffraction analysis, the comparison result is shown in figure 2, the comparison result is shown in figure 3, the comparison group 600-2.6SP +1CC sample (physical mixing) and the filtered and dried solid residue after Cd treatment are subjected to X-ray diffraction analysis, and obvious cadmium carbonate (CdCO) can be observed in the sample after the sample is treated in figure 23) The characteristic diffraction peak and the serpentine and calcium carbonate characteristic diffraction peaks with lower intensity show that the serpentine-calcium carbonate composite material and Cd are subjected to chemical reaction to form stable cadmium carbonate precipitate on the surface of the serpentine, so that the aim of fixing cadmium is fulfilled. Furthermore, it is particularly noted that, after solidification of cadmium, the crystal plane of calcium carbonate (104) at 2 θ ═ 29.5 ° is clearly shifted towards high angles, indicating that a cation exchange action has taken place and that cadmium ions with smaller ionic radius (ionic radius ═ 0.95pm) replace calcium ions in the original crystal structure of calcium carbonate (ionic radius ═ 1 pm). Although cadmium carbonate can be observed in fig. 3, a large amount of calcium carbonate phase remains and no diffraction peak shift occurs, indicating that the process of curing cadmium in the physically mixed sample is a simple carbonate dissolution-precipitation process, and the reaction path is long and inefficient.
Different from the conventional mechanism of physical adsorption on the mineral surface and liquid phase dissolution-precipitation reaction, the action mechanism of the silicate-carbonate composite mineral material and cadmium provided by the invention is that Cd is fixed on the mineral surface in a carbonate form through the interface cation exchange effect, so that the efficiency is higher; meanwhile, the solid-liquid separation efficiency can be greatly improved, and secondary pollution caused by redissolving of cadmium is avoided.
Example 2
A silicate-carbonate composite mineral material is prepared by the following steps:
weighing 1.5g of olivine powder and 0.5g of calcium carbonate powder (mass ratio MSi: CC ═ 2.6:1), putting into a 45mL zirconium dioxide grinding tank, adding 70g of zirconium dioxide balls with diameter of 15mm, wherein the ball-to-material ratio is 35: 1, setting the rotating speed of a mill to be 600rpm, collecting a powder sample after grinding for 60min, and obtaining the olivine-calcium carbonate composite fixing agent which is marked as 600-2.6MSi-1 CC.
Comparison sample: weighing 2g of olivine and calcium carbonate respectively, and putting the olivine and the calcium carbonate into a 45mL zirconium dioxide grinding tank for ball milling, wherein 70g of zirconium dioxide balls with the diameter of 15mm are added in the ball milling process, and the ball-material ratio is 35: 1, setting the rotating speed of a mill to 600rpm, collecting powder samples after grinding for 60min to obtain ground activated olivine and activated calcium carbonate, respectively taking 1.5g and 0.5g of two kinds of activated powder according to the mass ratio of MSi to calcium carbonate in the olivine of 2.6:1, and simply mixing to obtain mixed powder of the olivine and the calcium carbonate, wherein the mixed powder is marked as 600-2.6MSi +1 CC.
Using cadmium sulphate (CdSO)4·8/3H2O) preparation containing Cd2+100mL of each 100mg/L solution was placed in a beaker according to CO3 2-With Cd2+The molar ratio of the fixing agent to the control sample is 1:1, 0.0355g of each fixing agent and control sample obtained in the embodiment are added into a cadmium-containing solution to perform oscillation stirring reaction, the oscillation stirring speed is 400rpm, the reaction time is 2h, the reaction is performed for 10min after standing, the supernatant is taken to determine the concentration and the pH value of Cd in the solution, and the experimental results are shown in the following table 2.
TABLE 2 comparison of the cadmium removal effectiveness of the olivine-calcium carbonate composite with that of a simple blend
As can be seen from table 2, the removal rate of cadmium of the olivine-calcium carbonate composite material prepared in this example is more than 92%, the solution after the reaction is weakly acidic, and the removal effect of cadmium of the sample simply mixed with the comparative sample is only 26.5%. In practical application, better treatment effect can be achieved by properly increasing the using amount of the composite material or prolonging the reaction time.
The solid residue obtained after removing cadmium from the sample of this example was filtered, dried and analyzed by X-ray diffraction, and the results are shown in fig. 4. From fig. 4, a large number of cadmium carbonate characteristic diffraction peaks and partial short olivine and calcium carbonate characteristic diffraction peaks can be seen, which indicates that the olivine-calcium carbonate composite material and cadmium ions undergo chemical reaction to form stable cadmium carbonate precipitates on the surface of the olivine, thereby realizing efficient fixation of cadmium.
Example 3
A silicate-carbonate composite mineral material is prepared by the following steps:
weighing 1.5g of serpentine powder and 0.5g of dolomite powder (mass ratio SP: MCC: 3:1), putting into a 45mL zirconium dioxide grinding tank, and simultaneously adding 70g of zirconium dioxide balls with the diameter of 15mm, wherein the ball-material ratio is 35: 1, setting the rotating speed of a mill to be 600rpm, and collecting a powder sample after grinding for 60min to obtain the serpentine-dolomite composite material fixing agent which is marked as 600-3SP-1 MCC.
Using cadmium sulphate (CdSO)4·8/3H2O) preparation containing Cd2+100mL of the solution with the concentration of 100mg/L is placed in a beaker according to the CO3 2-With Cd2+The molar ratio of 1:1 is a standard, 0.0346g of the fixing agent obtained in the embodiment is added into a cadmium-containing solution to perform a shaking stirring reaction, the shaking stirring speed is 400rpm, the reaction time is 2 hours, the solution is kept stand for 10min after the reaction, the supernatant is taken to determine the concentration and the pH value of Cd in the solution, and the experimental results are shown in the following table 3.
TABLE 3 Serpentine-dolomite composite for cadmium removal
As is clear from Table 3, the removal rate of cadmium was 94.8% or more, and the solution after the reaction was weakly alkaline. When in application, better treatment effect can be achieved by properly increasing the dosage of the fixing agent or prolonging the reaction time.
Example 4
The silicate-carbonate composite mineral material 600-2.6SP-1CC prepared in example 1 was tested for its effect of removing manganese ions from the solution.
Using manganese sulfate (MnSO)4·H2O) preparation containing Mn2+100mL of the solution with the concentration of 100mg/L is placed in a beaker according to the CO3 2-With Mn2+Adding 0.0684g of fixing agent 600-2.6SP-1CC into a manganese-containing solution according to the molar ratio of 1:1, carrying out oscillation stirring reaction at an oscillation stirring speed of 400rpm for 2h, standing for 10min after reaction, taking supernatant to measure the concentration and pH value of Mn element in the solution, and obtaining the experimental results shown in the following table 4.
TABLE 4 removal of manganese from serpentine-calcium carbonate composites
As can be seen from Table 4, the removal rate of manganese reached 97.88%, and the solution after the reaction was weakly alkaline, so that the purpose of fixing manganese was achieved. When in application, better treatment effect can be achieved by properly adjusting the dosage of the fixing agent.
Example 5
The silicate-carbonate composite mineral material 600-2.6SP-1CC prepared in example 1 was tested for its effect of removing cadmium ions from the solution.
Using cadmium sulphate (CdSO)4·8/3H2O) preparation containing Cd2+100mL of each 100mg/L solution was placed in a beaker, and the pH of the solution was adjusted to 3, 4, 5, respectively, with 5 wt% dilute sulfuric acid, in CO3 2-With Cd2+According to the molar ratio of 1:1, 0.0336g of fixing agent 600-2.6SP-1CC are respectively added into cadmium-containing solutions with different pH values for oscillating stirring reaction, the oscillating stirring speed is 400rpm, and the reaction is carried outThe time is 2h, the reaction is carried out and then is kept stand for 10min, the supernatant is taken to determine the concentration and the pH value of Cd element in the solution, and the experimental results are shown in the following table 5.
TABLE 5 Effect of different initial pH on cadmium removal from serpentine-calcium carbonate composites
As can be seen from table 5, the cadmium removal rate is 82% or more at an initial pH of 3, and the cadmium removal rate is 90% or more at an initial pH of 4, indicating the effectiveness of the composite mineral material prepared in this example in fixing cadmium under a wide pH condition. When in application, better treatment effect can be achieved by properly adjusting the dosage of the fixing agent or prolonging the reaction time.
Claims (10)
1. The silicate-carbonate composite mineral material is characterized by being prepared by mixing silicate mineral powder and carbonate mineral powder and performing ball milling activation.
2. The silicate-carbonate composite mineral material according to claim 1, wherein the silicate mineral powder is a powder of one or more of natural minerals serpentine, olivine, attapulgite, talc, or a solid waste containing the above minerals, and has a particle size of 158 μm or less.
3. The silicate-carbonate composite mineral material according to claim 1, wherein the carbonate mineral powder is one of magnesium carbonate, calcium carbonate, basic magnesium carbonate, calcium magnesium carbonate, or a natural mineral or solid waste containing the above components, and has a particle size of 158 μm or less.
4. The silicate-carbonate composite mineral material according to claim 1, wherein the mass ratio of silicate in the silicate mineral powder to carbonate in the carbonate mineral powder is 1-3: 1.
5. a method for preparing the silicate-carbonate composite mineral material according to any one of claims 1 to 4, characterized by comprising the following steps: mixing silicate mineral powder and carbonate mineral powder, and putting the mixture into a ball mill for ball milling, wherein the ball-material ratio is 25-50: 1, the ball milling rotation speed is 400-.
6. Use of the silicate-carbonate composite mineral material according to any one of claims 1 to 4 for precipitating heavy metal ions, in a specific method of use: adding the silicate-carbonate composite mineral material into a solution containing heavy metal ions, oscillating and stirring at a constant speed at normal temperature and normal pressure for reaction, standing after the reaction is finished, and then carrying out solid-liquid separation, wherein the heavy metal is fixed in a form of carbonate and is removed from a liquid phase.
7. Use of the silicate-carbonate composite mineral material according to claim 6, for precipitating heavy metal ions, wherein the heavy metal ions comprise manganese ions, cadmium ions.
8. The use of the silicate-carbonate composite mineral material according to claim 6, wherein the solution containing heavy metal ions has a pH of 3 to 7.
9. Use of the silicate-carbonate composite mineral material according to claim 6, for precipitating heavy metal ions, wherein the molar ratio of heavy metal ions in the solution containing heavy metal ions to carbonate in the silicate-carbonate composite mineral material is 1: 0.5 to 3.
10. The application of the silicate-carbonate composite mineral material in precipitating heavy metal ions according to claim 6, wherein the process conditions of uniform speed shaking and stirring reaction are as follows: stirring with shaking at the rotation speed of 300-500rpm, and reacting for 30-240 minutes.
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