CN103641214A - Method for treating heavy metal wastewater by superconductive HGMS (high gradient magnetic separation)-FeOOH coupled technique - Google Patents
Method for treating heavy metal wastewater by superconductive HGMS (high gradient magnetic separation)-FeOOH coupled technique Download PDFInfo
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Abstract
The invention relates to a method for treating heavy metal wastewater by a superconductive HGMS (high gradient magnetic separation)-FeOOH coupled technique, belonging to the fields of resources and environments. The superconductive HGMS-FeOOH coupled technique for treating heavy metal wastewater has the advantages of simpler operation and higher treatment efficiency than the single absorption technique. The result proves that the superconductive HGMS-FeOOH coupled technique has favorable treatment effect under the conditions of the optimal technological parameters; and the removal rate of arsenic ions from high-concentration arsenic wastewater can reach higher than 77.12% under the following conditions: the addition amount of FeOOH is 0.1-0.9 g/ml, the magnetic gradient is 3-5T, the standing time is 1-15 minutes, and the distance i between the reaction tank diameter d/magnetic field generator and the reaction tank wall is not greater than 3. Before the treatment, no pretreatment is needed, and the pH value of the wastewater is not regulated. Under the technological conditions of the superconductive HGMS-FeOOH coupled technique, the saturation adsorption quantity of FeOOH is 6.5-7.5 mg/g, and the technological parameters can be properly regulated according to the arsenic ion concentration characteristic of wastewater.
Description
Technical field:
The invention belongs to resource and environment field, relate to the coupling technique that utilizes superconduction HGMS (High Gradient Magnetic Separation) technology and FeOOH (hydrous iron oxide), can realize the utilization of refuse Treatment and recovery.Be particularly suitable for acid high density containing the treatment and reuse of arsenic heavy metal wastewater thereby.
Background technology:
Heavy metal wastewater thereby is mainly derived from plating, cold-rolled steel and non-ferrous metals smelting works etc., the heavy metal ion such as the chromium containing in waste water (Cr), arsenic (As), cadmium (Cd), zinc (Zn), nickel (Ni) have the features such as difficult degradation, irreversible, toxicity is bioaccumulation greatly and easily, trace can produce toxic effect, very harmful, it is carried out to efficient improvement extremely urgent.
Separated (HGMS) technology of superconducting high-gradient magnetic with its reduced investment, take up an area little, less energy-consumption, low cost, high-level efficiency and show advantage at resource, field of Environment Protection, processing speed is 5 times of ordinary method.But this technology is not good to the separation of high concentration ion state material and removal effect.The introducing of superconductor technology has overcome HGMS method and has only depended on magnetic matrix to improve field gradient, to weak magnetic and the helpless defect of non-magnetic substance.Owing to thering are a large amount of magnetic particles in Wastewater Of Steel Industry, can directly adopt HGMS to remove, simple and convenient.China Shanghai first, Wu Steel Plant and Baosteel all adopted High-gradient Magnetic filter method to process rolling effluent.High-gradient Magnetic is filtered can also, for the steam refrigeration cycle water treatment of power station and other heat power plant, therefrom remove particulate ferromagnetic oxide (Fe
30
4, λ-Fe
20
3and α-Fe
20
3), ferromegnetism or paramagnetism thorium and compound.Heavy-metal ion removal is the research emphasis of High-gradient Magnetic separating treatment trade effluent always.For containing Ni
2+electroplating wastewater, abundant decile two steps of Sun Shui in 2002 have been carried out magnetic kind cohesion/phosphorus isolation technique and have been processed Ni
2+electroplating wastewater test, Ni in processed waste water
2+clearance reach more than 99%, water outlet Ni
2+for 0.42mg/L; Li Suqin in 2012, Wang Qiao etc. are applied to metallurgical dust waste water by superconduction-HGMS technology and process, and SS clearance approaches 100%, by flocculation strengthening effect, can realize removing of magnetic and nonmagnetic pollutent a little less than nano level; Valuable material in separation and Extraction vanadium-extracted residues and dedusting ash, in vanadium slag extract, ferric oxide can reach 56%, V
2o
5reach 4% left and right; In dedusting ash extract, Fe2O3 can reach 56.29%, ZnO reaches 18.61%.
FeOOH mainly utilizes its advanced oxidation effect in heavy metal containing wastewater treatment process.FeOOH can ionize out OH free radical, and it has higher oxidizing electrode current potential, has electronegativity or Electron Affinities simultaneously, and addition reaction can occur.In water treatment, can reach in the existing research of effect rapidly and efficiently and point out that working as pH is 3 left and right, when the consumption of iron carbonyl cross-linked rectorite is 13.29g/L, normal temperature vibration absorption 60min, cr
6+clearance can reach 98%, residual cr
6+concentration can be down to below 0.5mg/L.But while using separately, consumption is large, running cost is too high.Research shows that akaganeite is only 80mg/g to the loading capacity of cr (VI).
The water quality characteristics that is acid High Concentration of Arsenic content for above relative merits and heavy metal wastewater thereby, for realizing heavy metal ions in wastewater, efficiently remove, invent a kind of coupling process method, make it little at medicine using dosage, reaction times is short, just can realize the efficient processing of heavy metal wastewater thereby under the simple link of operation of equipment.
Summary of the invention:
The present invention seeks in order to improve high density that the treatment effect containing arsenic heavy metal wastewater thereby, particularly arsenic concentration be greater than 1000mg/L containing arsenic heavy metal wastewater thereby.For heavy metal wastewater thereby water quality characteristics, invent a kind of superconduction HGMS-FeOOH coupling technique, make it, without carrying out pre-treatment, under simple operations condition, can remove plurality of heavy metal ion.Simpler than adopting separately FeOOH technological operation, processing efficiency is high.By many groups orthogonal test, inquired into the impact on heavy metal ion clearance of FeOOH dosage, reaction times and magneticstrength.
Described method is: to adding in heavy metal wastewater thereby after appropriate FEOOH, inject and be placed in the reactive tank of high-gradient magnetic field, standing for some time can remove arsenic 0.3-3810mg/L from high-concentration arsenic-containing wastewater.Before processing, without regulating waste water ph and other any pre-treatment, FEOOH material add-on is 0.1-0.9g/ml, and magneticstrength is 3-5T.
Further, FEOOH material dosage is 0.2-0.4g/ml.
Further, magneticstrength is 4-4.5T.
Further, the time of repose of waste water in magnetic field is 1-15min, more preferably 5-7 minute.
Further, under superconduction HGMS-FEOOH coupling technique condition, the saturated extent of adsorption of FEOOH is the arsonium ion amount of 6.5-7.5mg/g(1gFeOOH absorption).
The device that aforesaid method is used, is characterized in that equipment therefor comprises reactive tank, reactive tank water-in, reactive tank water outlet, is centered around the superconducting high-gradient magnetic field generator outside reactive tank, and wherein magnetic field generator and reactive tank span are not more than 70mm from i.
Reactive tank diameter d/magnetic field generator and reactive tank span are less than 4 from i.
The use step of above-mentioned device, is characterized in that:
Step 1: heavy metal wastewater thereby is not needed to do pre-treatment, FEOOH material is added in a certain amount of waste water and mixed, adjust suitable magneticstrength; Step 2: waste water is injected to the reactive tank (3) be placed in magnetic field, treat that water outlet (2) there are flowing out and stop water filling, and close water outlet (2); Step 3: the waste water in reactive tank after standing staying for some time, is discharged waste water by controlling flow peristaltic pump in magnetic field from reactive tank (3).
In heavy metal wastewater thereby, add appropriate FeOOH material, put into standing for some time of magnetic field and take out.Using superconduction HGMS-FeOOH coupling technique to process in heavy metal wastewater thereby, without waste water is carried out to pre-treatment, the treatment time is short, processes front without regulating waste water ph.Result shows, under optimal processing parameter condition, adopts superconduction HGMS-FeOOH coupling technique treatment effect good.In the former water of heavy metal, arsonium ion concentration is 4940.87mg/l, in 15 minutes, can from high-concentration arsenic-containing wastewater, reach more than 77.12% by arsonium ion clearance.Under superconduction HGMS-FeOOH coupling technique condition, the saturated extent of adsorption of FeOOH is the arsonium ion amount of 6.5-7.5mg/g(1gFeOOH absorption), can be according to waste water containing the suitable adjusting process parameter of arsonium ion concentration feature.
Accompanying drawing explanation:
Reaction unit in Fig. 1 magnetic field, 1 is that water-in, 2 is that water outlet, 3 is that reactive tank, 4 is that left magnetic field, 5 is right magnetic field
Fig. 2. contrast is static without the impact of static technique on treatment effect that be coupled of standing and superconduction HGMS-FeOOH under magnetic field condition,
Fig. 3. FeOOH Electronic Speculum pattern before and after processing.
Embodiment:
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
In design experiment process for waste water arsonium ion concentration used, through a large amount of single factor experiments and each factors combine impact test, determine each factor optimization variables scope, be hydrous iron oxide dosage scope 0.1-0.9g/ml, magneticstrength scope 3-5T, reaction time range 1-15min.Rear design orthogonal test, the i.e. reciprocal effect of three kinds of factors.
| Arsonium ion concentration (mg/L) | Embodiment 1 | |
Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example |
| Before processing (mg/L) | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 | 4940.87 |
| After processing (mg/L) | 3506.5 | 1130.3 | 1284.6 | 1708 | 1338.9 | 1633.5 | 1568.2 | 1338.9 | 1338.9 | 3661.2 |
Embodiment 1:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.1g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 3min in 5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 5 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 3506.5mL/L, reaches 29.03%.
Embodiment 2:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.6g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 15min in 5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 3 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1130.3mL/L, reaches best 77.12%(as shown in Figure 2).
Embodiment 3:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.8g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 8min in 5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 4 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1284.6mL/L, reaches 74%.
Embodiment 4:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.4g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 15min in 3T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 5 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1708mL/L, reaches 65.43%.
Embodiment 5:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.9g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 15min in 3.5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 3 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1338.9mL/L, reaches best 72.9%.
Embodiment 6:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.7g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 15min in 5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 4 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1633.5mL/L, reaches 66.94%.
Embodiment 7:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.2g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 1min in 3.5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 5 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1568.2mL/L, reaches 68.26%.
Embodiment 8:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.6g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 3min in 3.5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 3 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1338.9mL/L, reaches best 72.9%.
Embodiment 9:
Get a certain amount of heavy metal wastewater thereby, the FeOOH that adds 0.8g/ml, by controlling the reactive tank in flow peristaltic pump injection magnetic field, standing 15min in 3.5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 4 from i, survey the arsonium ion concentration in water sample after processing.After processing, arsenic particle concentration is 1338.9mL/L, reaches 72.9%.
Embodiment 10:
Get a certain amount of heavy metal wastewater thereby containing cadmium ion, its concentration of cadmium ions is 4940.87mL/L, the FeOOH that adds 0.5g/ml, by controlling flow peristaltic pump, inject the reactive tank in magnetic field, standing 7min in 3.5T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 4 from i, survey the concentration of cadmium ions in water sample after processing.After processing, cadmium particle concentration is 1390.9mL/L, reaches 71.8%.
Embodiment 11:
Get a certain amount of heavy metal wastewater thereby containing chromium ion, its chromium ion concentration is 4940.87mL/L, the FeOOH that adds 0.6/ml, by controlling flow peristaltic pump, inject the reactive tank in magnetic field, standing 6min in 4T magnetic field, reactive tank diameter d/magnetic field generator and reactive tank span are 3 from i, survey the chromium ion concentration in water sample after processing.After processing, chromium particle concentration is 1377.4mL/L, reaches 71.8%.
Comparative example:
Treatment effect under non-magnetic field condition, gets a certain amount of heavy metal wastewater thereby, adds the FeOOH of 0.6g/ml, standing different time 15min, and arsonium ion clearance reaches 25.90%.
Claims (8)
1. a method of utilizing superconduction HGMS-FeOOH coupling technique to process heavy metal wastewater thereby, it is characterized in that described method is: to adding in heavy metal wastewater thereby after appropriate FeOOH, inject and be placed in the reactive tank of high-gradient magnetic field, standing for some time, process front without regulating waste water ph and other any pre-treatment, FeOOH material add-on is 0.1-0.9g/ml, and magneticstrength is 3-5T.
2. a kind of method of utilizing superconduction HGMS-FeOOH coupling technique to process heavy metal wastewater thereby according to claim 1, is characterized in that FeOOH material dosage is 0.2-0.4g/ml.
3. a kind of method of utilizing superconduction HGMS-FeOOH coupling technique to process heavy metal wastewater thereby according to claim 1, is characterized in that magneticstrength is 4-4.5T.
4. a kind of method of utilizing superconduction HGMS-FeOOH coupling technique to process heavy metal wastewater thereby according to claim 1, is characterized in that the time of repose in magnetic field is 1-15min, preferably 5-7 minute.
5. according to the arbitrary a kind of described method of utilizing superconduction HGMS-FeOOH coupling technique to process heavy metal wastewater thereby of claim 1 to 4, it is characterized in that the saturated extent of adsorption of FeOOH under superconduction HGMS-FeOOH coupling technique condition is 6.5-7.5mg/g.
6. one kind according to the device of the either method described in claim 1 to 5, it is characterized in that equipment therefor comprises reactive tank, reactive tank water-in, reactive tank water outlet, is centered around the superconducting high-gradient magnetic field generator outside reactive tank, wherein magnetic field generator and reactive tank span are not more than 70mm from i.
7. device according to claim 6, is characterized in that reactive tank diameter d/magnetic field generator and reactive tank span are less than 4 from i.
8. according to the use step of the device described in claim 6 or 7, it is characterized in that:
Step 1: heavy metal wastewater thereby is not needed to do pre-treatment, FeOOH material is added in a certain amount of waste water and mixed, adjust suitable magneticstrength;
Step 2: waste water is injected to the reactive tank (3) be placed in magnetic field, treat that water outlet (2) there are flowing out and stop water filling, and close water outlet (2);
Step 3: the waste water in reactive tank after standing staying for some time, is discharged waste water by controlling flow peristaltic pump in magnetic field from reactive tank (3).
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| CN106277173A (en) * | 2016-10-13 | 2017-01-04 | 东华理工大学 | A kind of iron carbonyl combines superconducting magnetic and separates the method for phosphor resource in water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07185214A (en) * | 1993-12-27 | 1995-07-25 | Hitachi Plant Eng & Constr Co Ltd | Waste water treatment method |
| CN101343102A (en) * | 2008-08-15 | 2009-01-14 | 天津理工大学 | Adsorption and magnetic separation coupling method for recycling precious metal ion in precious metal |
| WO2012115814A1 (en) * | 2011-02-23 | 2012-08-30 | Massachusetts Institute Of Technology | Magnetic colloid petroleum oil spill clean-up of ocean surface, depth, and shore regions |
| CN103121770A (en) * | 2013-01-17 | 2013-05-29 | 北京科技大学 | Separate purification device for processing waste by superconductivity high-gradient magnetic separation (HGMS) technology |
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2013
- 2013-12-10 CN CN201310664735.XA patent/CN103641214B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07185214A (en) * | 1993-12-27 | 1995-07-25 | Hitachi Plant Eng & Constr Co Ltd | Waste water treatment method |
| CN101343102A (en) * | 2008-08-15 | 2009-01-14 | 天津理工大学 | Adsorption and magnetic separation coupling method for recycling precious metal ion in precious metal |
| WO2012115814A1 (en) * | 2011-02-23 | 2012-08-30 | Massachusetts Institute Of Technology | Magnetic colloid petroleum oil spill clean-up of ocean surface, depth, and shore regions |
| CN103121770A (en) * | 2013-01-17 | 2013-05-29 | 北京科技大学 | Separate purification device for processing waste by superconductivity high-gradient magnetic separation (HGMS) technology |
Non-Patent Citations (1)
| Title |
|---|
| 黄自力等: ""在水处理中铁氧化物的作用与应用"", 《金属矿山》, no. 329, 30 November 2003 (2003-11-30) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277173A (en) * | 2016-10-13 | 2017-01-04 | 东华理工大学 | A kind of iron carbonyl combines superconducting magnetic and separates the method for phosphor resource in water |
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