CN101186375B - Material and method for processing water containing heavy metal ion - Google Patents
Material and method for processing water containing heavy metal ion Download PDFInfo
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- CN101186375B CN101186375B CN2007101910822A CN200710191082A CN101186375B CN 101186375 B CN101186375 B CN 101186375B CN 2007101910822 A CN2007101910822 A CN 2007101910822A CN 200710191082 A CN200710191082 A CN 200710191082A CN 101186375 B CN101186375 B CN 101186375B
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Abstract
The invention relates to a material containing heavy metal ions and a handling method thereof, which is characterized in that the material focuses on iron sulfide or manganese sulfide, and by weight percentage, the sulfur content in the material is more than 10 percent; the iron sulfide and manganese sulfide include FeS, MnS, FeS2, Fe3S4, Fe2S3 and Fe1-xS; the heavy metal ions include Cd<2+>, Hg<2+>, Ag<+>, Pb<2+>, Cr<3+>, Cu<2+>, Co<2+>, Ni<2+> and Zn<2+>. The method of the invention makes use of the solubility product difference that the solubility product of iron sulfide or manganese sulfide is far larger than that of the iron sulfide or manganese sulfide of heavy metal ions sulphide, so as to lead to the displacement reaction of the iron sulfide or manganese sulfide and the heavy metal ions in water and remove the heavy metal ions transformed into sulphide from water. The invention does not need solid-liquid separation, has low residual metal concentration in water and wide application range and can recycle polluted heavy metal as resources.
Description
Technical field
The present invention relates to material for water treatment and method, a kind of being used to of more specifically saying so handled the waste water that heavy metal ion content surpasses emission standard, or the overproof all kinds of surface water bodies of heavy metal ion content, phreatic material and method.
Background technology
There is the trade effluent about 40,000,000,000 tons every year in China, and the waste water that wherein contains heavy metal occupies significant proportion, and the distribution of heavy metal wastewater thereby is comparatively extensive, comprises industries such as mine, smelting, electrolysis, plating, agricultural chemicals, medicine, paint, chemical industry, pigment.Water body, especially soil pollution that the heavy metal-containing waste water discharging causes have become the formidable enemy who threatens human body health.
The treatment process of heavy metal wastewater thereby can be divided into two big classes both at home and abroad at present.One class is to make the heavy metal ion that is dissolved state in the waste water change insoluble heavy metal compound into, removes from waste water through precipitation or the floating method that goes up again.Method commonly used has hydroxide precipitation method, sulphide precipitation, ferrite coprecipitation method, redox precipitation method, ion floatation method, electrolytic process, membrane electrolysis, biological process etc.The most frequently used in these methods is hydroxide precipitation method, sulphide precipitation, ferrite coprecipitation method and redox precipitation method.But the problem that exists is jointly, and deposit seeds is tiny, needs settling tank, and newborn fine particle is difficult to separate fully with water, water treatment effect instability, and precipitating sludge belongs to dangerous refuse, and sludge quantity is big, the sludge treatment difficulty.In sulphide precipitation, it is an amount of that precipitation agent is difficult to control, easily causes secondary pollution.Several methods such as ion floatation method, electrolytic process, membrane electrolysis are because of processing cost height, system complex, seldom use difficult in maintenance.
Another kind of method is to adsorb under the condition that does not change the heavy metal ion chemical form, concentrate and separate, concrete grammar has reverse osmosis method, electroosmose process, membrane separation process, evaporation concentration method, absorption method, ion exchange method, solvent extration etc., and wherein extensive concern is absorption method.The material that absorption method processing heavy metal wastewater thereby generally uses is cheap mineral material, as wilkinite, zeolite, sepiolite, attapulgite etc.These mineral materials or modified product are to Cd in the waste water
2+, Pb
2+, Hg
2+, Cr
6+, Cu
2+Deng having stronger adsorption, but loading capacity is limited, and handling sludge moisture content height, the heavy metal content that the back forms only be 1-5%, does not reach the requirement of resource utilization, becomes the refuse of danger on the contrary.
Both at home and abroad heavy metal-containing waste water be studies show that, utilize the sodium sulphite precipitation of heavy metals can reach than hydroxide precipitation method lower go out water concentration, but because during lower concentration, the sulfide of formation is difficult to precipitation, have the solid-liquid separation difficulty, the dosage of vulcanizing agent also is difficult to control simultaneously.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, a kind of material and method of handling water containing heavy metal ion is provided, in the hope of the recovery of the stabilizing treatment, advanced treatment, harmless treatment and the resource that reach heavy metal wastewater thereby.
The technical scheme that technical solution problem of the present invention is adopted is:
The characteristics that the present invention handles the material of water containing heavy metal ion are:
Described material is based on iron and/or manganese sulfide, and by weight percentage, sulphur content is greater than 10% in the material; Described iron, manganese sulfide comprise FeS, MnS, FeS
2, Fe
3S
4, Fe
2S
3And Fe
1-xS.
Described heavy metal ion comprises Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+, the concentration of heavy metal ion of described water containing heavy metal ion is 0.5～1000mg/L.
The characteristics of material of the present invention also are:
The source of described iron and manganese sulfide comprises: iron and manganese sulfide that desulfurization produces, synthetic iron and manganese sulfide, natural sulphur manganese ore and pyrrhotite.
The characteristics of the method for material processing water containing heavy metal ion of the present invention are to utilize iron or manganese sulfide solubility product much larger than heavy metal ion Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+The solubility product difference of sulfide solubility product makes heavy metal ion generation replacement(metathesis)reaction in iron or manganese sulfide and the water, with heavy metal ion Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+Changing sulfide into removes from water.
Described heavy metal ion comprises Cd
2+, Hg
2+, Ag
+, Pb
2+, Cu
2+, Co
2+, Ni
2+, Zn
2+, ionic concn is 0.5～1000mg/L.
The characteristics of the inventive method also are:
Described replacement(metathesis)reaction is that described iron and/or manganese sulfidic materials are ground into particle diameter is particle below the 0.5mm, directly puts in the water that contains heavy metal ion, finishes replacement(metathesis)reaction in the process that stirs, and post precipitation is removed heavy metal.
Described replacement(metathesis)reaction is that iron and/or manganese sulfidic materials are ground into particle diameter is the following particle of 0.5mm, and adding adhesive preparation, to become particle diameter be the pellet of 1～10mm, and described pellet is loaded into the filter post, and the control filtering velocity is 1-10m/h; Or described pellet formed the infiltration wall on processed osmosis path of underground water, control seepage velocity is 0.01～0.9m/h, finishes replacement(metathesis)reaction in the process of filtering or permeating.
Described binding agent comprises cement, water glass, sodium metaaluminate, and the consumption of described iron and/or manganese sulfide and caking agent is by weight: iron and/or manganese sulfide are that 80-95, caking agent are 5-20.
Find after deliberation, the sulfide that iron, Mn oxide desulfurization form, iron, manganese sulfide that various chemical industries produce, iron, manganese sulfide that wastewater treatment produces, synthetic iron, manganese sulfide all have higher chemically reactive.The sulfide intergranular pore is grown, help heavy metal ion infiltration, diffuse into granule interior.The sulfide material specific surface area that iron, Mn oxide desulfurization form is big, has very high chemically reactive.When the aqueous solution that contains heavy metal ion passes through iron, manganese sulfide grain filter bed, quick replacement(metathesis)reaction takes place in heavy metal ion in the waste water and iron, manganese sulfide, heavy metal in the waste water forms sulfide and is fixed on iron and/or manganese sulfide grain surface, thereby the heavy metal in the removal waste water prevents the heavy metal environmental pollution.Discharge nontoxic iron, the mn ion of lower concentration, because of oxygen in water to iron, mn ion oxidation, further impel iron, mn ion hydrolysis to form precipitation and dammed by particulate matter.
Though heavy metal sulfide is an insoluble compound, different sulfide solubility products has the solubility product of very big difference (seeing Table 1), especially iron, manganese sulfide more much bigger than the solubility product of other harmful heavy metal sulfide.When the aqueous solution that contains heavy metal ion passes through iron, manganese sulfide grain, if arranged suitable duration of contact, replacement(metathesis)reaction completely takes place in heavy metal ion in the waste water and iron, manganese sulfide, heavy metal in the waste water forms sulfide and is fixed on iron, manganese sulfide grain surface, discharge nontoxic iron, the mn ion of lower concentration, thereby the heavy metal in the removal waste water prevents the heavy metal environmental pollution.The present invention has utilized the difference of iron, manganese sulfide and other harmful heavy metal sulfide solubility products, can remove heavy metal in the waste water effectively by the replacement(metathesis)reaction of heavy metal ion and iron, manganese sulfide, thereby prevent heavy metal contamination.
The solubility product of the various sulfide of table 1
| Sulfide | Solubility product K SP |
| MnS FeS ZnS CuS HgS PbS NiS CoS CdS Ag 2S | 1.4×10 -13 3.7×10 -18 1.2×10 -22 8.5×10 -36 4.0×10 -53 3.4×10 -28 1.0×10 -24 2.0×10 -25 3.6×10 -25 1.2×10 -49 |
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the replacement(metathesis)reaction of the inventive method in implementation process can be finished in Filter column, thereby, do not need to be provided with settling tank and carry out solid-liquid separation, simplified treatment process greatly;
2, strong to the wastewater pH range accommodation, pH 4～10;
3, when containing various heavy in the waste water, can reclaim various separation of metal ions respectively;
4, because the solubility product of heavy metal sulfide is very little, effluent quality is good, can stablize to reach national I level emission standard (GB8978-1996) Cd
2+0.1mg/L, Hg
2+0.05mg/L, Ag
+0.5mg/L, Pb
2+1.0mg/L, Cr 1.5mg/L, Cu
2+0.5mg/L, Co
2+1.0mg/L, Ni
2+1.0mg/L, Zn
2+2.0mg/L, be particularly suitable for containing the advanced treatment of heavy metal water;
5, be that the removing heavy-metal filtrate of feedstock production is big to the permutoid reaction capacity of heavy metal with iron, manganese sulfide, the cycle of operation is long;
6, after the filter post penetrated, heavy metal content can reach more than 10% in the filtrate, has good recovery value, can be sent to the recovery that non-ferrous metals smelting works carry out heavy metal.
Below the invention will be further described by embodiment:
Embodiment
Embodiment 1:
Get the Mn oxide ore sample, its mineral composition mainly is Mn oxide, ferriferous oxide, clay mineral, quartz, and wherein the manganese mass percent is 28%, iron content 10%.Mn oxide ore reduction is become the particle of 2-5mm, and the The columns of loading into diameter 12mm, high 600mm is used for the desulfurization of H 2 S-containing gas.One of Mn oxide ore desulfurization product main component is MnS, S, FeS, and sulfide sulfur content weight percent is 14%.Desulfurization product is ground to form the powder of 0.1mm, put into pH and be in 4～7 the copper ions waste water, stirring reaction 30～60 minutes, sedimentation 30 minutes, atomic absorption spectrophotometer is surveyed copper ion concentration in the supernatant liquor, obtains copper ion concentration less than 0.5mg/L.
Embodiment 2:
Get the Mn oxide ore sample, its mineral composition mainly is pyrolusite, pyrrhosiderite, rhombohedral iron ore, clay mineral, quartz, and wherein the manganese mass percent is 32%, iron content 8%.Natural Mn oxide ore reduction is become the particle of 2-5mm, and the The columns of loading into diameter 12mm, high 600mm is used for the H 2 S-containing gas desulfurization.One of Mn oxide ore desulfurization product main component is MnS, S, FeS, and sulfide sulfur content weight percent is 12%.Desulfurization product is ground to form the powder of 0.1mm; with water glass as binding agent; being prepared into the particle of 2～3mm in tablets press, in the Filter column of the Glass tubing formation of diameter 20mm, long 1000mm, is the particle packing of preparation 100mg/L with concentration; pH is 5 copper-containing solution; 3m/h is by the filtration experiment post for rate speed, gets the water outlet of filter post, surveys copper ion concentration in the supernatant liquor with atomic absorption spectrophotometer; operation is 10 days continuously, and the water outlet copper ion concentration is less than 0.5mg/L.
Embodiment 3:
Pyrrhotite ore reduction, pyrrhotite content weight percent is greater than 90%, and sulfide sulfur content weight percent is 32%.The particle of 0.1～0.5mm is chosen in screening.The particle packing of preparation in the Filter column of the Glass tubing of diameter 10mm, long 1000mm formation, with concentration is 100mg/L, pH is 5 copper-containing solution, 1m/h is by the filtration experiment post for rate speed, get the water outlet of filter post, survey copper ion concentration in the supernatant liquor with atomic absorption spectrophotometer, move 10 days continuously, the water outlet copper ion concentration is less than 0.5mg/L.
Embodiment 4:
The sulfonium ion that contains higher concentration in the coking chemical waste water adds ferrous sulfate, the precipitated sulfur ion, and the mud main component that obtains is FeS, sulfide sulfur content weight percent is 29%.。The FeS precipitating sludge that produces in the Coking Plant Wastewater processing is added the particle that sodium silicate binder is prepared into 1～5mm.The particle packing of preparation in the Filter column of the Glass tubing of diameter 10mm, long 1000mm formation, with concentration is that 50mg/L, pH are 5 cadmium-containing solution, 1m/h is by the filtration experiment post for rate speed, get the water outlet of filter post, survey concentration of cadmium ions in the supernatant liquor with atomic absorption spectrophotometer, operation is 10 days continuously, and the water outlet copper ion concentration is less than 0.1mg/L.
Embodiment 5:
Industrial synthetic FeS (sulfide sulfur content weight percent is 36%) is added the particle that sodium silicate binder is prepared into 1～5mm.The particle packing of preparation in the Filter column of the Glass tubing of diameter 10mm, long 1000mm formation, with concentration is that 50mg/L, pH are 5 the mercury solution that contains, 1m/h is by the filtration experiment post for rate speed, get the water outlet of filter post, survey ion concentration of mercury in the supernatant liquor with atomic fluorescence spectroscopy, operation is 20 days continuously, and the water outlet ion concentration of mercury is less than 0.05mg/L.
Because of in treating processes, having a spot of iron, mn ion to be discharged in the water.When the inventive method is applied to water treatment, when the ferromanganese ion concentration of water outlet is had strict restriction, can after handling, the sulfide grain media filtration add aeration, and impel the ferromanganese ion oxidation complete, then through manganese sand or the processing of quartz sand filter.
Claims (5)
1. material of handling water containing heavy metal ion is characterized in that:
Described material is based on iron and manganese sulfide, and by weight percentage, sulphur content is greater than 10% in the material; Iron, manganese sulfide comprise FeS, MnS, FeS
2, Fe
3S
4, Fe
2S
3And Fe
1-xS;
Described heavy metal ion comprises Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+, the concentration of heavy metal ion of described water containing heavy metal ion is 0.5～1000mg/L;
The source of described iron and manganese sulfide comprises: iron and manganese sulfide, synthetic iron and manganese sulfide that desulfurization produces.
2. the method for the described material processing water containing heavy metal ion of claim 1 is characterized in that utilizing iron and manganese sulfide solubility product much larger than heavy metal ion Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+The solubility product difference of sulfide solubility product makes heavy metal ion generation replacement(metathesis)reaction in iron and manganese sulfide and the water, with heavy metal ion Cd
2+, Hg
2+, Ag
+, Pb
2+, Cr
3+, Cu
2+, Co
2+, Ni
2+, Zn
2+Changing sulfide into removes from water.
Described heavy metal ion comprises Cd
2+, Hg
2+, Ag
+, Pb
2+, Cu
2+, Co
2+, Ni
2+, Zn
2+, ionic concn is 0.5～1000mg/L.
3. method according to claim 2, it is characterized in that described replacement(metathesis)reaction is that described iron and manganese sulfidic materials are ground into particle diameter is particle below the 0.5mm, directly put in the water that contains heavy metal ion, finish replacement(metathesis)reaction in the process that stirs, post precipitation is removed heavy metal.
4. method according to claim 2, it is characterized in that described replacement(metathesis)reaction is that iron and manganese sulfidic materials are ground into particle diameter is the following particle of 0.5mm, it is the pellet of 1～10mm that the adding adhesive preparation becomes particle diameter, and described pellet is loaded into the filter post, and the control filtering velocity is 1-10m/h; Or described pellet formed the infiltration wall on processed osmosis path of underground water, control seepage velocity is 0.01～0.9m/h, finishes replacement(metathesis)reaction in the process of filtering or permeating.
5. method according to claim 4 is characterized in that described binding agent comprises cement, water glass, sodium metaaluminate, and the consumption of described iron and manganese sulfide and binding agent is by weight: iron and manganese sulfide are that 80-95, binding agent are 5-20.
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|---|---|---|---|
| CN2007101910822A CN101186375B (en) | 2007-12-06 | 2007-12-06 | Material and method for processing water containing heavy metal ion |
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| CN101186375B true CN101186375B (en) | 2010-10-06 |
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| CN115845788B (en) * | 2022-11-25 | 2024-02-23 | 重庆化工职业学院 | Application of natural manganese mineral powder in adsorbing mercury ions, application of removing mercury ions in wastewater and application of removing mercury ions in soil |
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