CN205367823U - Fenton method combines high salt industrial waste water electrolysis trough of bipolar membrane technical process - Google Patents
Fenton method combines high salt industrial waste water electrolysis trough of bipolar membrane technical process Download PDFInfo
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Abstract
The utility model relates to an use fenton method combines high salt industrial waste water electrolysis trough of bipolar membrane technical process. The electrolysis trough is cuboid trough - shaped structure, and the electrolysis trough is provided with iron anode, inert anode and inert cathode, and iron anode, inert cathode D. C. Regulated power supply's positive pole and negative pole are connected, be provided with 1~6 high salt industrial wastewater treatment unit of constituteing by bipolar membrane, anion exchange membrane, cation exchange membrane and bipolar membrane between positive pole and the negative pole. For sour room between bipolar membrane and the anion exchange membrane, be the salt room between anion exchange membrane and the cation exchange membrane, be the alkali room between cation exchange membrane and the bipolar membrane. The utility model discloses with fenton technique and bipolar membrane technology integration in a processing apparatus, equipment is compact, gets rid of the COD of salinity, reduction waste water. But generate corresponding acid -base recycle.
Description
Technical field
The present invention relates to the processing technology field of a kind of industrial wastewater, be specifically related to one and utilize Fenton method to process high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting.
Background technology
Along with China's industrial expansion, the discharge capacity of industrial wastewater increases day by day, is wherein high salt industrial wastewater greatly.Such waste water often contains the soluble inorganic salt of higher concentration, such as Cl-, SO4 2-, Na+, Ca2+And difficult degradation or poisonous Organic substance, and its generation amount is the trend of sharp increase, such as untreated direct discharge, ecological environment can cause many harm.High salt industrial wastewater mainly has 2 sources: the 1) waste water that sea water discharges after being directly used in commercial production and life, as industrially, sea water has been used as boiler cooling water.And in urban life, sea water can substitute fresh water as flushing water, the salinity of this type of waste water is generally 2.5 × 104~3.5×104Mg/L (mass concentration, lower same)；2) waste water of discharge in some industrial trade production process, as saponin waste water, petroleum production wastewater and printing and dyeing, papermaking, pharmacy, chemical industry, milk product processing and the waste water of pesticide industry discharge, salinity are typically in about 15% ~ 25%.
High salt industrial wastewater has higher salinity, the toxic and inhibitory action to microorganism, activated sludge also can be caused to be prone to loss of floating, make biochemical treatment system be difficult to properly functioning, so this type of waste water is difficult to direct bioanalysis and processes.At present, industrial, the main method of high salt Industrial Wastewater Treatment has: 1) utilize Efficient salt-tolerant bacterium to process;2) dilute discharge;3) incinerator burning disposal.Efficient salt-tolerant bacterium environmental suitability has certain limit, cultivates difficulty, and operating condition is complicated, and general enterprises is difficult to, and cannot desalination.Major part enterprise adopts dilute discharge, and this had both wasted great lot of water resources (clear water is become waste water), increases the discharge capacity of waste water, can not control again the salt amount entering in environment, it is clear that be the requirement not meeting environmental protection total amount.Adopting incinerator to carry out burning disposal, incineration temperature is up to about 1100 DEG C, and tail gas from incinerator must process, and salinity easily concentrates at furnace wall, need to be rinsed, and the waste water salinity rinsed is high, still can not directly discharge, and also needs to process.Whole complex disposal process, investment is big, and energy consumption is very big, and equipment decay resistance is required height.Therefore, the process of high salt industrial wastewater has become Environmental Protection in China industry urgent need to solve the problem.
Membrane technology is widely used in the process of the sewage such as plating, printing and dyeing, food, papermaking, process hides.Bipolar Membrane (BPM) is a kind of Novel ion exchange composite membrane, is generally composited by anion exchange layer, cation exchange layer.Third layer material can also be added between cavity block layer, anode membrane layer and promote dissociating of water, form the three-decker of anion exchange layer, cation exchange layer, intermediate reaction layer composition.Under the effect of DC electric field, Bipolar Membrane by water decomposition, can produce H in anode membrane layer, cavity block layer both sides respectively+And OH-.Having quickly grown since the eighties succeeds in developing from 20th century, external existing multiple Bipolar Membrane prepare the patent of aspect.Because Bipolar Membrane has the plurality of advantages such as simple to operate, efficiency is high, disposal of pollutants is few, it is used widely at numerous areas such as resource reclaim, Environmental capacity and Chemical Engineerings.
Fenton technology is collaborative treatment technology electrochemical process and Fenton technology combined.Its ultimate principle is O2It is H in cathodic reduction2O2(or anode directly drips H2O2) and and Fe2+(can sacrifice iron anode to generate) reacting generates OH free radical, and OH free radical has extremely strong oxidability (oxidizing potential is only second to fluorine, up to 2.80V).Additionally, hydroxyl radical free radical has significantly high electronegativity or electrophilicity (electron affinity energy power reaches 569.3kJ), very strong additive reaction characteristic, can be CO without selecting oxidation operations most of in water2And H2O or small organic molecule, be particularly well-suited to bio-refractory or general chemical oxidation is difficult to the oxidation processes of the organic wastewater proved effective.
This patent adopts Fenton method to process high salt industrial wastewater in conjunction with Bipolar membrane water splitting, while reducing the COD of waste water and salinity, the salinity in waste water is converted into corresponding acid, alkali is recycled, it is achieved the recycling of waste water salinity.
Summary of the invention
It is an object of the invention to design a kind of employing combine with Fenton method while of double; two Bipolar Membrane, can efficiently process the electrolysis bath of high salt industrial wastewater.Salinity in waste water can be converted into corresponding acid by this electrolysis bath, alkali is recycled, it is achieved the recycling of waste water salinity, meanwhile, reduces the COD of waste water.
The technical scheme is that electrolysis bath is cuboid groove-like structure for realizing the purpose of this patent, the left end head of electrolysis bath is provided with iron anode and inert anode, the right end of electrolysis bath is provided with inert cathode, iron anode, inert cathode are connected with the positive pole of D.C. regulated power supply and negative pole respectively, and inert anode, inert cathode are connected with the positive pole of another D.C. regulated power supply and negative pole respectively；1～6 high salt Industrial Wastewater Treatment unit being made up of Bipolar Membrane, anion exchange membrane, cation exchange membrane and Bipolar Membrane it is provided with between anode and negative electrode.Space residing for iron anode and inert anode is anode chamber, and the space residing for negative electrode is cathode chamber, is acid room between Bipolar Membrane and anion exchange membrane；It it is salt room between anion exchange membrane and cation exchange membrane；It it is alkali room between cation exchange membrane and Bipolar Membrane.
When 1～6 described high salt Industrial Wastewater Treatment unit is provided only with 2 unit, from anode electrolytic cell end, the arrangement of film is followed successively by: Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane and Bipolar Membrane.
When 1～6 described high salt Industrial Wastewater Treatment unit is provided only with 3 unit, from anode electrolytic cell end, the arrangement of film is followed successively by: Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane and Bipolar Membrane.
When 1～6 described high salt Industrial Wastewater Treatment unit is provided only with 4 unit, from anode electrolytic cell end, the arrangement of film is followed successively by: Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane, Bipolar Membrane, anion exchange membrane, cation exchange membrane and Bipolar Membrane.
As it has been described above, when described high salt Industrial Wastewater Treatment unit has 5 or 6, carry out also according to above-mentioned arrangement regulation.
Described anode chamber, is connected with H above it2O2Hopper, hopper passes through conduit with certain flow velocity by H2O2Being added drop-wise in anode chamber, now iron anode loses electronics when energising, generates Fe2+, with H2O2React generation OH free radical, oxidative degradation Organic Pollutants in Wastewater, so that the COD of industrial wastewater reduces.
By structure as above, after D.C. regulated power supply is energized, DC electric field is formed between anode and negative electrode, water decomposition is there is between Bipolar Membrane yin, yang rete, generate hydrion and hydroxide ion, under the driving of yin, yang two interpolar electric potential difference, migrating to yin, yang the two poles of the earth respectively, also there is directional migration in each anions and canons simultaneously in a cell.Its result is Bipolar Membrane water decomposition produces in acid room and alkali room hydrion and the anions and canons that hydroxide ion and migration come forms acid, alkali, it is achieved reclaim purpose sour, alkali.Waste water after anode chamber's process is adjusted pH value to neutral, can discharge further after sedimentation.
Described electrolysis bath iron anode can adopt tabular, column or netted.
Described cell inert anode and negative electrode or be Ti electrode or for titanium alloy electrode or for graphite electrode, its configuration or be tabular, or be column, or be cellular.
The voltage that described D.C. regulated power supply adopts is 10～20V.
Utilize Fenton method of the present invention to process high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting, can efficiently process high salt industrial wastewater.Its processing procedure is as follows:
First time processes
High salt industrial wastewater injects the salt room in each unit, and after energising under the effect of DC electric field, the anions and canons of the high-salt wastewater in salt room enters in acid room and alkali room respectively through anion exchange membrane and cation exchange membrane, dissociates the H that water generates with Bipolar Membrane+And OH-In conjunction with, generate corresponding acid or alkali.Thus the salinity removed in high-salt wastewater, the acid of generation, alkali can be recovered utilization, it is achieved the purpose of waste water salinity recycling.
Second time processes
After desalination, the waste water in salt room, regulate pH value and pump into, after between 3～5, the anode chamber being provided with iron anode, the H that anode chamber is connected2O2Hopper passes through conduit by H2O2Being added drop-wise in anode chamber, carry out degrading and flocculating under the effect of Fenton reagent, the waste water after process is adjusted pH value and can discharge to neutral sedimentation further.
In second time processing procedure, Fenton reagent can produce molten iron complex in anode chamber's processing procedure, catabolite carries out absorption parcel sedimentation, has good flocculating function, reduce waste water COD further.
Electrolysis bath adopts two anodes (be ferrum anelectrode, be inert electrode) to be connected with cathode chamber negative electrode respectively through two D.C. regulated power supplies, to there being the Fe of q.s in guarantee2+While generating, properly increase electric current density when processing device electrodialysis.
Acid room of the present invention, alkali room need to pass into certain density diluted acid or diluted alkaline, to reduce the solution resistance of system；The acid, the alkali that pass into are the corresponding bronsted lowry acids and bases bronsted lowry of waste water salinity, and its concentration is 0.1～1.5mol/L.
Cathode chamber of the present invention need to pass into certain density electrolyte, can be sodium sulfate, or potassium sulfate, or sodium nitrate, or potassium nitrate, and its concentration is 0.1～2mol/L.
The present invention adopts double; two Bipolar Membrane, arranges multiple processing unit for electrolysis bath and provides possibility.And multiple processing unit can be connected use, so available one group of electrode processes multiple salt room simultaneously, thus improving space availability ratio and the waste water treatment efficiency of electrolysis bath, reduces the generation of electrochemical reaction on electrode and electrode, reduces energy consumption.
There is advantages that
1, Fenton technology and Bipolar membrane water splitting are integrated in one and process in device, facility compact, while desalination, reduces the COD of waste water.
2, desalination, generating corresponding acid, alkali, and is recycled, reaching the purpose that changing waste into resources utilizes, thus reducing processing cost.
3, two anodes (be iron electrode, be inert electrode) are adopted to be connected with negative electrode respectively through two D.C. regulated power supplies, to there being the Fe of q.s in guarantee2+While generating, properly increase the process device electric current density when electrodialysis.
4, by multiple processing units are connected, namely between anode chamber and cathode chamber, replace multiple processing unit being made up of a sour room, a salt room and an alkali room of connecting, reach the purpose adopting one group of yin, yang electrode simultaneously to process multiple salt room, thus improving the space availability ratio of electricity groove, reduce the generation of electrochemical reaction on electrode and electrode, reduce energy consumption.
Accompanying drawing explanation
Fig. 1 is that Fenton method of the present invention processes high salt industrial wastewater cell construction schematic diagram in conjunction with Bipolar membrane water splitting.
The Fenton method that Fig. 2 is described in this patent processes cell construction schematic diagram during two the processing unit series connection of high salt industrial wastewater in conjunction with Bipolar membrane water splitting.
Detailed description of the invention
In order to the present invention is better understood from, in conjunction with accompanying drawing 1 or accompanying drawing 2, the present invention is described further.
In Fig. 1,1 is iron anode；2 is inert anode；3 is Bipolar Membrane；4 is anion exchange membrane；5 is cation exchange membrane；6 is Bipolar Membrane；7 is inert cathode；8 is D.C. regulated power supply；9 is hydrogen peroxide hopper；10 is hydrogen peroxide effusion meter.I is the anode chamber residing for iron anode 1；II is acid room；III is salt room；IV is alkali room；V is cathode chamber.
In Fig. 2,1 is iron anode；2 is inert anode；3 is Bipolar Membrane；4 is anion exchange membrane；5 is cation exchange membrane；6 is Bipolar Membrane；7 is anion exchange membrane；8 is cation exchange membrane；9 is Bipolar Membrane；10 is inert cathode；11 is D.C. regulated power supply；12 is hydrogen peroxide hopper；13 is hydrogen peroxide effusion meter.I is anode chamber；II is acid room；III is salt room；It it is alkali room；V is acid room；VI is salt room；VII is alkali room；VIII is cathode chamber.
Embodiment 1
Electrolysis bath is cuboid groove-like structure, the left end head of electrolysis bath is provided with iron anode (1) and inert anode (2), the right end of electrolysis bath is provided with inert cathode (7), iron anode (1), inert cathode (7) are connected with the positive pole of D.C. regulated power supply (8) and negative pole respectively, and inert anode (2), negative electrode (7) are connected with the positive pole of another D.C. regulated power supply (8) and negative pole respectively；1～6 high salt Industrial Wastewater Treatment unit being made up of Bipolar Membrane (3), anion exchange membrane (4), cation exchange membrane (5) and Bipolar Membrane (6) it is provided with between cell inert anode (2) and inert cathode (7).After segmentation, the space residing for iron anode (1) and inert anode (2) is anode chamber I, and the space residing for negative electrode is cathode chamber V, is acid room (II) between Bipolar Membrane and anion exchange membrane；It it is salt room (III) between anion exchange membrane and cation exchange membrane；It it is alkali room (IV) between cation exchange membrane and Bipolar Membrane.
Described anode chamber (I), is connected with H above it2O2Hopper (9), hopper (9) by effusion meter (10) with certain flow velocity by H2O2Being added drop-wise in anode chamber (I), now iron anode (1) loses electronics when energising, generates Fe2+, with H2O2React generation OH free radical, oxidative degradation Organic Pollutants in Wastewater, so that the COD of industrial wastewater reduces.
By structure as above, after D.C. regulated power supply energising, DC electric field is formed between anode and negative electrode, water decomposition is there is between the yin, yang rete of Bipolar Membrane, generate hydrion and hydroxide ion, under the driving of yin, yang two interpolar electric potential difference, migrating to yin, yang the two poles of the earth respectively, also there is directional migration in each anions and canons simultaneously in a cell.Its result is that the hydrion of Bipolar Membrane water decomposition generation and the anions and canons of hydroxide ion and migration form acid, alkali in acid room and alkali room, and reclaims.Waste water after anode chamber's process is adjusted pH value to neutral, can discharge further after sedimentation.
The electrolysis bath iron anode that the present embodiment adopts is tabular.
Cell inert anode and negative electrode described in the present embodiment are Ti electrode, and it is configured as column.
The voltage that D.C. regulated power supply described in the present embodiment (8) adopts is 10V.
Said structure is as shown in Figure 1.
The first time of high-salt wastewater processes:
Being introduced by high salt industrial wastewater (sulfur acid sodium: 100g/L, COD:10000mg/L) in the salt room (III) of electrolysis bath as shown in Figure 1, it is the sulfuric acid solution of 4.2 that anode chamber adds pH value, adds 2mol/L metabisulfite solution in cathode chamber.Connect D.C. regulated power supply (8), after energising processes 5 hours, regulating industrial wastewater in salt room to pH with 12mol/L sulphuric acid is after 4.2, introduce anode chamber, start hydrogen peroxide effusion meter (10) simultaneously, controlling hydrogen peroxide flow velocity is 3mL/min, is pumped in salt room (III) by second batch waste water simultaneously.After processing 5 hours, by sulphuric acid or sodium hydroxide, the waste water in anode chamber being regulated pH to 7, natural subsidence was discharged after 30 minutes.
Undertaken recycling (part can be used as adjustment process system pH value and uses) by the acid in acid room and alkali room, alkali.
Above-mentioned processing procedure is to be separately added into sulphuric acid and sodium hydroxide solution in acid room (II) and alkali room (IV), and its concentration is 0.5mol/L.
The high salt industrial wastewater that the present embodiment uses is simulation industrial wastewater.
High salt industrial wastewater is after this device processes, and COD is 32.5mg/L, and waste water sodium sulfate concentration reduces to 0.98g/L.
Example 2
The electrolysis bath that the present embodiment uses is cuboid groove-like structure, and the arrangement of electrode and various film is identical with embodiment 1.But the left end head of electrolysis bath is provided that netted iron anode (1), inert anode (2) adopts Ti electrode, for cellular；The right end of electrolysis bath is provided with negative electrode (7), for the Ti electrode of column.
Electrolysis bath cationic exchange membrane (5) is nafion cation exchange membrane；Anion exchange membrane (4) is chitosan anion exchange membrane；Bipolar Membrane (3) and Bipolar Membrane (6) all adopt BP-1 type Bipolar Membrane.
The voltage that described D.C. regulated power supply (8) adopts is 12V.
The first time of high-salt wastewater processes:
Being introduced by high salt industrial wastewater (sulfur acid sodium: 100g/L, COD:10000mg/L) in the salt room (III) of device as shown in Figure 1, it is the sulfuric acid solution of 4.5 that anode chamber adds pH value, adds 1.5mol/L metabisulfite solution in cathode chamber.Connect D.C. regulated power supply (8), after energising processes 5.5 hours, regulating industrial wastewater in salt room to pH with 12mol/L sulphuric acid is after 4.5, introduce anode chamber, start hydrogen peroxide effusion meter (10) simultaneously, controlling hydrogen peroxide flow velocity is 3.5mL/min, is pumped in salt room (III) by second batch waste water simultaneously.After processing 5.5 hours, by sulphuric acid or sodium hydroxide, the waste water in anode chamber being regulated pH to 7, natural subsidence was discharged after 30 minutes.
Undertaken recycling (part can be used as adjustment process system pH value and uses) by the acid in acid room and alkali room, alkali.
Above-mentioned processing procedure is to be separately added into sulphuric acid and sodium hydroxide solution in acid room (II) and alkali room (IV), and its concentration is into 0.8mol/L.
The high salt industrial wastewater that the present embodiment uses is simulation industrial wastewater.
High salt industrial wastewater is after this device processes, and COD is 25.6mg/L, and waste water sodium sulfate concentration reduces to 0.76g/L.
Example 3
The electrolysis bath that the present embodiment uses is cuboid groove-like structure, and the left end head of electrolysis bath is provided with the iron anode (1) of column, and inert anode (2) adopts Ti electrode, for column；The right end of electrolysis bath is provided with negative electrode (10), for the graphite electrode of column.
Electrolysis bath cationic exchange membrane (5), cation exchange membrane (8) are nafion cation exchange membrane；Anion exchange membrane (4), anion exchange membrane (7) are chitosan anion exchange membrane；Bipolar Membrane (3), Bipolar Membrane (6) and Bipolar Membrane (9) all adopt BP-1 type Bipolar Membrane.
H it is connected with above anode chamber2O2Hopper, hopper conduit is by H2O2It is added drop-wise in anode chamber.
Described iron anode (1) is connected to form independent current path by D.C. regulated power supply (11) with the graphite cathode (10) in cathode chamber；
Described inert anode (2) is connected to form independent current path by D.C. regulated power supply (11) with the negative electrode (10) in cathode chamber；
The voltage that described D.C. regulated power supply (11) adopts is 17V.
Said structure is as shown in Figure 2.
The first time of high-salt wastewater processes:
Being introduced by high salt industrial wastewater (sulfur acid sodium: 100g/L, COD:10000mg/L) in salt room (III) and salt room (VI) of device as shown in Figure 2, it is the sulfuric acid solution of 4.8 that anode chamber adds pH value, adds 2mol/L metabisulfite solution in cathode chamber.Connect D.C. regulated power supply (11), after energising processes 6 hours, regulating industrial wastewater in salt room to pH with 12mol/L sulphuric acid is after 4.8, introduce anode chamber, start hydrogen peroxide effusion meter (13) simultaneously, controlling hydrogen peroxide flow velocity is 4mL/min, is pumped into by second batch waste water in salt room (III) and salt room (VI) simultaneously.After processing 6 hours, by sulphuric acid or sodium hydroxide, the waste water in anode chamber being regulated pH to 7, natural subsidence was discharged after 30 minutes.
Undertaken recycling (part can be used as adjustment process system pH value and uses) by the acid in acid room and alkali room, alkali.
Above-mentioned processing procedure is to be separately added into sulphuric acid and sodium hydroxide solution in acid room (II), acid room (V) and alkali room (IV), alkali room (VII), and its concentration is 0.8mol/L.
The high salt industrial wastewater that the present embodiment uses is simulation industrial wastewater.
High salt industrial wastewater is after this device processes, and COD is 29.3mg/L, and waste water sodium sulfate concentration reduces to 0.58g/L.
Claims (5)
1. a Fenton method processes high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting, it is characterized in that electrolysis bath is cuboid groove-like structure, the left end head of electrolysis bath is provided with iron anode and inert anode, the right end of electrolysis bath is provided with inert cathode, iron anode, inert cathode are connected with the positive pole of D.C. regulated power supply and negative pole respectively, and inert anode, inert cathode are connected with the positive pole of another D.C. regulated power supply and negative pole respectively；1～6 high salt Industrial Wastewater Treatment unit being made up of Bipolar Membrane, anion exchange membrane, cation exchange membrane and Bipolar Membrane it is provided with between anode and negative electrode；Space residing for iron anode and inert anode is anode chamber, and the space residing for negative electrode is cathode chamber, is acid room between Bipolar Membrane and anion exchange membrane；It it is salt room between anion exchange membrane and cation exchange membrane；It it is alkali room between cation exchange membrane and Bipolar Membrane.
2. a kind of Fenton method processes high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting according to claim 1, it is characterized in that also being connected with above described anode chamber H2O2Hopper, hopper conduit is by H2O2It is added drop-wise in anode chamber.
3. a kind of Fenton method processes high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting according to claim 1, it is characterized in that described electrolysis bath iron anode can adopt tabular, column or netted.
4. a kind of Fenton method processes high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting according to claim 1, it is characterized in that described cell inert anode and negative electrode or for Ti electrode, titanium alloy electrode or graphite electrode, its configuration or be tabular, column or cellular.
5. according to claim 3 or 4, a kind of Fenton method processes high salt industrial wastewater electrolysis bath in conjunction with Bipolar membrane water splitting, it is characterized in that the voltage that described D.C. regulated power supply adopts is 10～20V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105329988A (en) * | 2015-11-27 | 2016-02-17 | 福建创源环保有限公司 | Electrolytic bath for treating high-salt industrial waste water by combining Fenton method with bipolar membrane technology |
| CN106517543A (en) * | 2016-11-27 | 2017-03-22 | 杭州水处理技术研究开发中心有限公司 | Device for removing heavy metals in hard waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329988A (en) * | 2015-11-27 | 2016-02-17 | 福建创源环保有限公司 | Electrolytic bath for treating high-salt industrial waste water by combining Fenton method with bipolar membrane technology |
| CN106517543A (en) * | 2016-11-27 | 2017-03-22 | 杭州水处理技术研究开发中心有限公司 | Device for removing heavy metals in hard waste water |
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