CN111675379A - Method for reducing and catalytically treating composite pollution in water by using clay raw ore - Google Patents
Method for reducing and catalytically treating composite pollution in water by using clay raw ore Download PDFInfo
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- CN111675379A CN111675379A CN202010553857.1A CN202010553857A CN111675379A CN 111675379 A CN111675379 A CN 111675379A CN 202010553857 A CN202010553857 A CN 202010553857A CN 111675379 A CN111675379 A CN 111675379A
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- 239000004927 clay Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 239000002734 clay mineral Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 229910052683 pyrite Inorganic materials 0.000 claims description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011028 pyrite Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- -1 rectorite Chemical compound 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 229940088710 antibiotic agent Drugs 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910052960 marcasite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/30—Organic 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a method for reducing and catalyzing composite pollution in water by using clay raw ore, which comprises the following steps: adding 0.05-20 parts by weight of clay raw ore into 100 parts by weight of wastewater, and adsorbing heavy metals in the wastewater; meanwhile, 0-10 parts by weight of oxidant is added, the oxidant is fully mixed to carry out degradation treatment on organic pollutants in the wastewater, and the treated wastewater is filtered after the reaction is finished; the mixing reaction temperature is 10-45 ℃, the stirring speed is 50-700 rpm, and the reaction time is 0.1-24 h. The wastewater treatment cost of the invention is low and no secondary pollution is caused; the raw clay ore or the low-grade raw ore raw material after mineral separation used in the invention not only has the same adsorption and cation exchange effects as the purified clay mineral, but also can effectively reduce heavy metal pollutants in the wastewater; according to the technical scheme provided by the invention, the organic pollutants in water are effectively degraded while heavy metals are adsorbed, and the heavy metals/organic matters in the composite wastewater are effectively removed.
Description
Technical Field
The invention relates to the technical field of water pollution treatment, in particular to a method for reducing and catalyzing composite pollution in water by using clay raw ore.
Background
The water pollution problem of China is becoming more serious, and the life health safety of human beings is seriously harmed. At present, heavy metals and organic pollutants widely existing in water have the characteristics of high toxicity, strong mobility, wide distribution, difficult degradation and the like, and have potential hazards of teratogenesis, carcinogenesis, mutagenesis and the like.
The clay mineral has the characteristics of high dispersibility, cation exchange property, adsorptivity, adjustability of interlayer hole distance and the like, can effectively remove various pollutants in water, and has been widely researched in the field of water treatment. The raw clay minerals are mostly associated with pyrite, transition metal oxides and the like, and the pyrite, the metal oxides and the like can be used as catalysts to be applied to wastewater treatment. However, the clay mineral separation has the problems of complex process, high economic cost, high difficulty in directly utilizing low-grade raw ores after the clay mineral separation, easy resource waste, secondary environmental pollution and the like. Therefore, it is very important to develop a wastewater treatment method which can efficiently utilize clay minerals to treat wastewater and has high economic benefit and no secondary pollution.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for reducing and catalyzing composite pollution in water by using clay raw ore, which saves the wastewater treatment cost and fully exerts the functions of all components in the raw ore.
The technical scheme of the invention is that a method for reducing and catalyzing and treating composite pollution in water by using clay raw ore comprises the following steps:
the method comprises the following steps: adding 0.05-20 parts by weight of clay raw ore into 100 parts by weight of wastewater, and adsorbing heavy metals in the wastewater; meanwhile, 0-10 parts by weight of oxidant is added, the oxidant is fully mixed to carry out degradation treatment on organic pollutants in the wastewater, and the treated wastewater is filtered after the reaction is finished; the mixing reaction temperature is 10-45 ℃, the stirring speed is 50-700 rpm, and the reaction time is 0.1-24 h.
Preferably, the clay mineral raw ore species comprises one or more of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite, pyrite and beneficiated low-grade raw ore.
Preferably, the effective component in the raw clay mineral ore comprises SiO2、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2And Fe2O3One or more of (a).
Preferably, the mixing method comprises magnetic stirring, electric stirring, shaking table oscillation and aeration and ultrasonic oscillation.
Preferably, the oxidant is any one or more of persulfates, hydrogen peroxide, potassium ferrate, sodium hypochlorite and other oxidants.
Preferably, the persulfate species comprise one or more of potassium peroxymonosulfonate, sodium persulfate, potassium hydrogen persulfate, ammonium persulfate, and potassium persulfate.
Preferably, the contaminants in the wastewater comprise any one or more of organic contaminants and heavy metals.
Preferably, the organic contaminants comprise one or more of azo dyes, antibiotics and pesticides, and the heavy metals comprise one or more of cr (vi), pb (ii), cd (ii) and ni (ii).
According to the invention, when the clay mineral adsorbs heavy metals, the oxidant is added, and the ferric sulfate ore and the transition metal oxide in the raw ore are utilized to catalyze and degrade organic pollutants, so that the heavy metals/organic matters in the wastewater are effectively removed. Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the clay raw ore which is not treated by the beneficiation process or the low-grade raw ore subjected to beneficiation is directly used, the wastewater treatment cost is low, and secondary pollution is avoided;
(2) the raw clay ore or the low-grade raw ore after mineral separation used in the invention contains components such as pyrite, transition metal oxide and the like, and can effectively reduce heavy metal pollutants in the wastewater besides the adsorption and cation exchange effects of the raw clay ore and the purified clay ore;
(3) under the condition of adding the oxidant, the low-grade clay raw ore has the catalytic oxidation effect which is not possessed by the purified clay, can catalytically activate the oxidant to generate sulfate radicals and hydroxyl radicals, effectively degrades organic pollutants in water while adsorbing heavy metals, and realizes effective removal of the heavy metals/organic matters in the composite wastewater.
Drawings
FIG. 1 is an XRD pattern of raw and purified rectorite in example 1 of the present invention;
FIG. 2 is an SEM photograph of a rectorite raw ore of example 1 of the present invention;
FIG. 3 is a graph showing the removal effect of rectorite raw ore on different heavy metals according to example 1 of the present invention;
FIG. 4 is a graph showing the effect of the rectorite raw ore and the purified rectorite activated persulfate of example 2 of the present invention in degrading the organic matter activated red X-3B;
FIG. 5 is a graph showing the effect of activated persulfate of rectorite raw ore on degrading tetracycline hydrochloride, which is an organic pollutant, in example 3 of the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The invention relates to a method for reducing and catalytically treating composite pollution in water by using clay raw ore, which comprises the following steps: adding 0.05-20 parts by weight of clay raw ore into 100 parts by weight of wastewater, and adsorbing heavy metals in the wastewater; meanwhile, 0-10 parts by weight of oxidant is added, and the oxidant are fully mixed to degrade organic pollutants in the wastewater; the mixing reaction temperature is 10-45 ℃, the stirring speed is 50-700 rpm, and the reaction time is 0.1-24 h.
The clay mineral raw ore types comprise one or more of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite, pyrite and low-grade raw ore after mineral separation.
The effective component in the raw clay mineral ore comprises SiO2、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2And Fe2O3One or more of (a).
The mixing method comprises magnetic stirring, electric stirring, shaking table oscillation, aeration and ultrasonic oscillation.
The oxidant is any one or more of persulfates, hydrogen peroxide, potassium ferrate, sodium hypochlorite and the like.
The persulfate species include one or more of potassium peroxymonosulfonate, sodium persulfate, oxone, ammonium persulfate, and potassium persulfate.
The pollutants in the wastewater comprise any one or more of organic pollutants and heavy metals.
The organic pollutants comprise one or more of azo dyes, antibiotics and pesticides, and the heavy metals comprise one or more of Cr (VI), Pb (II), Cd (II) and Ni (II).
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the embodiment of the invention, the clay raw ore is rectorite raw ore.
Example 1
A wastewater treatment method based on clay raw ore comprises the following steps:
adding rectorite raw ore into wastewater containing heavy metals of Cr (VI), Pb (II) and Cd (II), wherein the concentration of the heavy metal wastewater is 50mg/L, adding 2 g of rectorite raw ore into 500g of heavy metal wastewater, mixing and reacting at the temperature of 25 ℃, stirring at the speed of 200 rpm, reacting for 18 h, and filtering to obtain the clay raw ore and reclaimed water capable of adsorbing pollutants.
XRD test is carried out on the rectorite raw ore of the embodiment, and the test result is shown in figure 1.
As can be seen from fig. 1, in the XRD spectrum of the raw rectorite, a series of relatively obvious characteristic peaks of rectorite exist at 2 θ =17.90 °, 18.74 °, 19.97 °, 25.37 °, 26.51 °, 27.46 °, 29.09 °, 35.15 ° and 62.61 °; compared with the rectorite after ore dressing and purification, the peaks appearing at 33.06 degrees, 37.11 degrees, 40.77 degrees, 47.42 degrees and 56.28 degrees of the raw rectorite are derived from FeS existing in the raw rectorite2。
SEM test was performed on the raw rectorite ore of this example, and the test results are shown in fig. 2.
As can be seen from fig. 2, in addition to a large amount of small-particle rectorite clay pieces dispersed in the raw rectorite ore, a part of pyrite having a large particle size is present.
The heavy metal content in the solution before and after the reaction was tested, and the test results are shown in fig. 3.
As can be seen from fig. 3, the rectorite raw ore of embodiment 1 of the present invention has good removal effects on cr (vi), pb (ii), cd (ii), and cr (vi), has a removal rate of 100% for cr (vi), an adsorption capacity for pb (ii) of 60%, and an adsorption capacity for cd (ii) of 10%, and has a high practical application value in the field of wastewater treatment.
Example 2
A wastewater treatment method based on clay raw ore comprises the following steps:
adding rectorite raw ore into wastewater containing active red X-3B with the concentration of 50mg/L, respectively adding 0.2 g of rectorite raw ore and 0.2 g of rectorite subjected to mineral separation into two 500g of active red X-3B wastewater, respectively adding 0.2 g of potassium peroxymonosulfonate (oxidant), stirring and reacting at the temperature of 25 ℃, the stirring rate of 500 rpm, sampling at the same time interval during the reaction, and filtering to obtain a clay material adsorbing pollutants and reclaimed water.
The reactive red X-3B in the solution before and after the reaction was detected, and the test results are shown in FIG. 4.
As can be seen from fig. 4, the raw rectorite ore of the embodiment has a better removal effect than the purified rectorite, and has low cost and strong practicability.
Example 3
A wastewater treatment method based on clay raw ore comprises the following steps:
adding rectorite raw ore into wastewater containing tetracycline hydrochloride with the concentration of 50mg/L, adding 0.2 g of rectorite raw ore into 500g of tetracycline hydrochloride wastewater, adding 0.2 g of potassium peroxymonosulfonate (oxidant), stirring at the reaction temperature of 25 ℃, at the stirring speed of 500 rpm, sampling at the same time interval during the reaction, and filtering to obtain a clay material adsorbing pollutants and reclaimed water.
Tetracycline hydrochloride in the solution before and after the reaction was detected, and the test results are shown in fig. 5.
As can be seen from fig. 5, the rectorite raw ore of the present embodiment still has a good effect of removing tetracycline hydrochloride, and can be applied to the treatment of various organic pollutants.
The above-described preferred embodiments of the present invention are not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the claims of the present invention.
Claims (8)
1. A method for reducing and catalyzing composite pollution in water by using clay raw ore comprises the following steps: adding 0.05-20 parts by weight of clay raw ore into 100 parts by weight of wastewater, and adsorbing heavy metals in the wastewater; meanwhile, 0-10 parts by weight of oxidant is added, and the oxidant are fully mixed to degrade organic pollutants in the wastewater; the mixing reaction temperature is 10-45 ℃, the stirring speed is 50-700 rpm, and the reaction time is 0.1-24 h.
2. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the clay mineral raw ore types comprise one or more of montmorillonite, bentonite, rectorite, kaolin, illite, halloysite, palygorskite, sepiolite, attapulgite, vermiculite, chlorite, pyrite and low-grade raw ore after mineral separation.
3. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the effective component in the raw clay mineral ore comprises SiO2、Al2O3、TiO2、CaO、Na2O、K2O、MnO、ZnO、CuO、FeS2And Fe2O3One or more of (a).
4. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the mixing method comprises magnetic stirring, electric stirring, shaking table oscillation, aeration and ultrasonic oscillation.
5. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the oxidant is any one or more of persulfates, hydrogen peroxide, potassium ferrate, sodium hypochlorite and the like.
6. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the persulfate species include one or more of potassium peroxymonosulfonate, sodium persulfate, oxone, ammonium persulfate, and potassium persulfate.
7. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the pollutants in the wastewater comprise any one or more of organic pollutants and heavy metals.
8. The method for reducing-catalyzing composite pollution in water by using clay raw ore according to claim 1, is characterized in that: the organic pollutants comprise one or more of azo dyes, antibiotics and pesticides, and the heavy metals comprise one or more of Cr (VI), Pb (II), Cd (II) and Ni (II).
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| CN113842890A (en) * | 2021-10-28 | 2021-12-28 | 南华大学 | Preparation method and application of clay-mineral-based metal manganese chelate |
| CN113976117A (en) * | 2021-10-28 | 2022-01-28 | 南京大学 | Preparation method and application of zero-valent aluminum/iron-containing clay composite material for catalyzing persulfate to oxidize organic matters |
| CN114433010A (en) * | 2022-02-18 | 2022-05-06 | 内蒙古大学 | Treatment method of waste rectorite, heterogeneous interlayer material, preparation method and application thereof |
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