CN104480493A - Method for recycling copper and cadmium and preparing cadmium bronze precursor employing compact biological electrochemical reactor - Google Patents

Abstract

The invention provides a method for recycling copper and cadmium and preparing a cadmium bronze precursor employing a compact biological electrochemical reactor, and belongs to the technical field of bioelectrochemistry. A biological electrochemical reactor is switched into a mode of a microbial fuel cell or a microbial electrolysis cell through a relay switch; external resistors are connected in series in the mode of the microbial fuel cell; small resistors are connected in series in the mode of the microbial electrolysis cell; a power supply is externally connected; a mixed salt solution of Cu(II) and Cd(II) is enclosed into a cathode room of the reactor; a cathode and an anode of the reactor adopt conductive carbon materials; and the cathode room of the reactor is inoculated with sludge of a settling pond of a sewage treatment plant as electrochemical active microbes. The method is clean and efficient in process, compact in reactor, simple in structure and convenient to operate, and has a good application prospect in treatment of copper and cadmium wastewater treatment and preparation of the cadmium bronze precursor.

Description

A kind of compact type bio-electrochemical reactor reclaims copper, cadmium prepare the method for cadmium bronze precursor

Technical field

The invention belongs to bioelectrochemistry technical field, utilize microbiological fuel cell (MFCs) by copper selective separation reclaiming from copper cadmium waste water; Under the prerequisite of not altering reactor main body, MFCs is switched to microorganism electrolysis cell (MECs) pattern, reclaims the cadmium metal in above-mentioned waste water further, there is the features such as structure of reactor is compact, easy to operate.Based on the katalysis of reclaiming copper under MFCs pattern, system original position utilizes copper and realizes the high efficiente callback of cadmium.The copper cadmium mixture generated is precursor and the raw material of the cadmium bronze preparing satisfactory electrical conductivity and thermal conductivity.

Background technology

Heavy metal copper, cadmium are widely used in industrial numerous areas, as alloy, plating, neutron-absorbing control rod, pigment, stabilizer for plastics, fluorescent material, sterilant, sterilant, paint.Therefore, copper cadmium heavy metal containing wastewater treatment is one of focus of paying close attention to of people always.At present, the disposal and recovery patent of cupric cadmium waste water reaches 20 remainders.These methods mainly contain chemical precipitation method, absorption method, ion exchange method, Fe forms method and electrochemical process.Such as, patent CN201310533532, CN201310615806, CN201410111803 etc.The shortcoming of these methods be mainly treatment agent usage quantity large, react wayward, easy secondary pollution, cost is high, Footwall drift is difficult, energy consumption is high.Find copper cadmium that is clean, efficient, nothing/less energy-consumption and reclaim the inevitable requirement that novel method is sustainable society development.

Cadmium bronze be have high-rise electrically, thermal conductivity and have the metallic substance of excellent abrasive resistance, be one of important nonferrous materials being applied to national defence troops' industry.The production of cadmium bronze is generally use cadmium copper alloy, selects certain solid solution temperature and time, form through melting in high-frequency furnace.If can select clean effective means while reclaiming the valuable metal copper in copper cadmium waste water, cadmium, prepare the precursor of cadmium bronze, then can realize the resource utilization of copper cadmium waste water.

Bioelectrochemical system is the new technology of in recent years rising, and when the chemical reaction of anode and negative electrode can spontaneously carry out, this system is MFCs; When the external world needs applying small voltage that anode and cathodic reaction just can be made to carry out, this system is MECs.Carrying out and going deep into along with R&D work, the Application Areas of MFCs and MECs is expanded.Domestic and international 35 MECs just disclosing at present or authorized, 543 MFCs patents, goal in research is from simple treatment of Organic Wastewater and hydrogen manufacturing (WO2014082989, CN201310627011, CN201410209650, CN201310148645, CN201210369997) to fixed co2 (CN201110209149, CN201410169707), denitrogenation desalination (WO2010124079, CN201210550133), produce methane (CN201210240982), sensing and monitoring (CN201410298473, CN201310226890, CN201310214163), contaminated site repairs (CN201420151230), organic products preparation (US2013256149, CN201310212120), the single metal leaching such as cobalt and nickel and recovery (CN201310345579, CN201210153753, CN201210153753, CN201310145779) etc.With regard to the bioelectrochemistry process of hybrid metal waste water and recovery, R&D work is also more rare, and the MECs be only limitted to by applying different voltage reclaims copper, lead, cadmium and zinc (Modin O, Wang X, WuX, Rauch S, Fedje KK.Bioelectrochemical recovery of Cu, Pb, Cd, and Zn fromdilute solutions.J Hazard Mater 2012,235-236:291-297).This research group also once have developed MFCs and drives MECs to reclaim chromium, copper and cadmium (CN201410175987), and Cu (II) promotes the work that Co (III) (201310071793.1) leach.Completely different from the problem that above-mentioned Research Thinking, research contents and principle, goal in research and quasi-solution are determined, the present invention is under not altering reactor agent structure prerequisite, controlled by (automatically) of relay switch, ingenious switching and the power and energy realizing MFCs and MECs, at saving reactor with while saving space, place, reclaim the underpotential deposition cadmium effect of copper under utilizing MFCs pattern, realize the high efficiente callback of cadmium and the preparation of cadmium bronze precursor under MECs pattern.

Summary of the invention

The invention provides that a kind of process cleans, structure of reactor are compact, easy to operate, process copper and cadmium waste water synchronously reclaim copper and cadmium prepare the method for cadmium bronze precursor.

The technical solution used in the present invention is as follows: a kind of compact type bio-electrochemical reactor reclaims copper, cadmium prepare the method for cadmium bronze precursor, and concrete steps are as follows:

Control relay switch by time electromagnetic relay, bio-electrochemical reactor is switched to microbiological fuel cell or microorganism electrolysis cell pattern;

When bio-electrochemical reactor is in MFCs pattern, the extrernal resistance of series connection 100-500 Ω;

When bio-electrochemical reactor is in MECs pattern, the resistance of series connection 5-50 Ω, and external source 0.5-1.0V;

The cathode compartment of bio-electrochemical reactor loads the mixing salt solution of Cu (II) and Cd (II), and the negative electrode of bio-electrochemical reactor and anode electrode are the carbon material of conduction;

Electrochemical activity microorganism and anolyte are housed in the anolyte compartment of bio-electrochemical reactor;

Using the settling pond mud of inoculation sewage work of the anolyte compartment of bio-electrochemical reactor as electrochemical activity microorganism.

Described Cu (II) and the mixing salt solution of Cd (II) are the mixed solution of the mixing salt solution of the mixed solution of the mixing salt solution of copper sulfate and Cadmium Sulphate, copper sulfate and Cadmium chloride fine powder, cupric chloride and Cadmium Sulphate, cupric chloride and Cadmium chloride fine powder.

Described carbon material is carbon cloth, carbon-point or carbon felt.

Described settling pond sludge pH: 6.8-7.0; Specific conductivity: 0.80-0.93mS/cm; Suspension solid substance: 30-35g/L; Chemical oxygen demand (COD): 150-300mg/L.

Described anolyte composition is: 12.0mM sodium acetate; 5.8mM NH ₄cl; 1.7mM KCl; 17.8mM NaH ₂pO ₄h ₂o; 32.3mM Na ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.

The anolyte compartment of reactor of the present invention and cathode compartment need to keep oxygen-free environment, by passing into nitrogen to realize anaerobic condition in operational process.

Reactor operation phase flow process of the present invention is: the organism in anolyte is by microbiological oxidation in anolyte compartment, and the proton that process produces enters cathode compartment through proton through film, and electronics imports negative electrode by external circuit.At cathode electrode surface, because the standard oxidationreduction potential of Cu (II) and Cd (II) is respectively+0.52V and – 0.40V, be adsorbed on Cu (II) on electrode and Cd (II) and under MFCs and MECs pattern, elemental copper or cadmium will be reduced to by selectivity respectively.

The operation phase flow process of the raising MECs cadmium rate of recovery of the present invention is: under MFCs pattern, Cu (II) is reduced to simple substance.This copper-plated electrode is according to the underpotential deposition cadmium effect of copper, and catalysis under MECs pattern high efficiente callback cadmium, interlock system is for cadmium bronze precursor.

Accompanying drawing explanation

Fig. 1 reclaims copper, cadmium prepare the bio-electrochemical reactor schematic diagram of cadmium bronze precursor.

Fig. 2 be Cu (II) under the MFCs pattern of embodiment 1, Cd (II) rate of recovery over time.

Fig. 3 is Cd (II) rate of recovery and the hydrogen yield of the MECs mode operation 4h of embodiment 1, and the contrast of non-copper-plating electrode.

Fig. 4 is the current density under the MECs pattern of embodiment 1, and the contrast of non-copper-plating electrode.

Fig. 5 is the cyclic voltammetry curve under the MECs pattern of embodiment 1, and non-copper-plating electrode, the non-copper facing of electrode-without Cd (II), electrode copper facing-without the contrast of Cd (II).

In figure: 1 carbon-point; 2 reference electrodes; 3 carbon cloths; 4 Hydrogen collection pipes; 5 negative electrode mixed solutions;

6 cationic exchange membranes; 7 anolyte compartments; 8 cathode compartments; 9 power supplys; Extrernal resistance under 10MFCs pattern;

Resistance under 11MECs pattern; 12 time electromagnetic relays; 13 inlet and outlets.

Embodiment

Below in conjunction with accompanying drawing and technical scheme, further illustrate the specific embodiment of the present invention.

Embodiment 1

Step one: build reactor, as shown in Figure 1: reactor anolyte compartment 7 and cathode compartment 8 are synthetic glass material, anolyte compartment's liquor capacity is 15mL, cathode chamber solution volume is 25mL, separate with ion-exchange membrane (CMI-7000) 6, to connect during 200 Ω extrernal resistance 10, MECs pattern of connecting under MFCs pattern 10 Ω resistance 11 and 0.5V voltage.

Step 2: respectively reactor anode electrode (carbon-point and carbon felt) and cathode electrode (carbon cloth) are placed in reactor anolyte compartment 7 and cathode compartment 8.Carbon-point (Beijing three industry carbon material company) apparent size is 0.8cm × 3.5cm, carbon felt (Beijing three industry carbon material company) apparent size is 3.0cm × 2.0cm × 1.0cm).At reactor cathode compartment access reference electrode 2, collect resistance 11 both end voltage and calculating current by computer and data collecting system; The cathode potential of reactor is collected according to reference electrode.

Step 3: add 15mL nutrient solution in reactor anolyte compartment, it consists of 12.0mM sodium acetate; 5.8mM NH ₄cl; 1.7mM KCl; 17.8mM NaH ₂pO ₄h ₂o; 32.3mM Na ₂hPO ₄; Mineral element: 12.5mL/L (MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L); VITAMIN: 12.5mL/L (vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L).Anolyte compartment's inoculation sewage work settling pond mud 10g (Dalian Ling Shuihe sewage work).Anolyte exposes to the sun after nitrogen 20min and seals.

Step 4: the deionized water adding 25mL at reactor cathode compartment.

Step 5: closed by circuit general switch, under the switch of electromagnetic relay is placed in MFCs pattern.Tame under device being placed in room temperature (20-25 DEG C) and run.When electric current drops to below 0.02mA, namely complete one-period, and add above-mentioned medium component.Continuous five cycles domestication and enrichment anode electrochemical active bacteria.

Step 6: negative electrode deionized water in step 4 is changed to the CuSO of 100mg/L ₄with the CdSO of 50mg/L ₄mixed solution, medium is 0.1M sodium-acetate-hac buffer (pH=4.6), and expose to the sun nitrogen 20min.

Step 7: under electromagnetic relay switch being placed in MFCs pattern, regularly sample, analyzes Cu (II) and Cd (II) content in liquid phase, calculates its rate of recovery.

Step 8: copper reclaims substantially when MFCs mode operation 21h, under electromagnetic relay switch being placed in MECs pattern, regularly samples, hydrogen content in Cd (II), gas phase in analysis liquid phase.

Step 9: characterize MECs pattern copper-plating electrode and non-copper facing blank electrode, cyclic voltammetry curve with or without Cd (II) contrast etc.; Based on the negative electrode coulombic efficiency of cadmium, hydrogen, additional electric energy efficiency, system total energy efficiency, cadmium yield, hydrogen yield under calculating MECs pattern.

Following table is based on the negative electrode coulombic efficiency of cadmium, hydrogen, additional electric energy efficiency, system total energy efficiency, cadmium yield, hydrogen yield under the MECs pattern of embodiment 1.

This enforcement example reclaims copper, cadmium prepare the cadmium bronze precursor of definite composition.The reaction that negative electrode occurs when MFCs pattern is formula (1), and the reaction that negative electrode carries out when MECs pattern is formula (2) and (3).Based on the negative electrode coulombic efficiency (CE of cadmium during MECs pattern _cd), based on the negative electrode coulombic efficiency (CE of hydrogen _h2), additional electric energy efficiency (η _{e, Cd}, η _{e, H2}), system total energy efficiency (η _{e+S, Cd}, η _{e+S, H2}), cadmium yield (Y _cd), hydrogen yield (Y _h2) calculating such as formula shown in (4)-(11).

Cu ²⁺+2e ^-→Cu(s) (1)

Cd ²⁺+2e ^-→Cd(s) (2)

2H ⁺+2e ^-→H ₂(g) (3)

${\mathrm{CE}}_{\mathrm{Cd}}=\frac{96485\×b_1\×\mathrm{\Δ}{C}_{{\mathrm{Cd}}^{2+}}\×V_{\mathrm{ca}}}{1000\×M_{\mathrm{Cd}}\×\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i}\×100\%---\left(4\right)$

${\mathrm{CE}}_{H_2}=\frac{96485\×b_2\×n_{H_2}}{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i}\×100\%---\left(5\right)$

${\mathrm{\η}}_{E,\mathrm{Cd}}=\frac{96485\×b_1\×\mathrm{\Δ}{C}_{\mathrm{Cd}}\×V_{\mathrm{ca}}\×E_{{\mathrm{Cd}}^{2+}}}{1000\×M_{\mathrm{Cd}}\×E_{\mathrm{ap}}\×\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i}\×100\%---\left(6\right)$

${\mathrm{\η}}_{E,H_2}=\frac{n_{H_2}\×{\mathrm{\ΔH}}_{s,H_2}}{E_{\mathrm{ap}}\×\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i}\×100\%---\left(7\right)$

${\mathrm{\η}}_{E+S,\mathrm{Cd}}=\frac{96485\×b_1\×\mathrm{\Δ}{C}_{\mathrm{Cd}}\×V_{\mathrm{ca}}\×E_{{\mathrm{Cd}}^{2+}}}{1000\×M_{\mathrm{Cd}}\×(E_{\mathrm{ap}}\×\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i-n_s{G}_s)}\×100\%---\left(8\right)$

${\mathrm{\η}}_{E+S,H_2}=\frac{n_{H_2}\×{\mathrm{\ΔH}}_{s,H_2}}{E_{\mathrm{ap}}\×\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{I}_i\mathrm{\Δ}{t}_i-n_s{G}_s}\×100\%---\left(9\right)$

$Y_{\mathrm{Cd}}=\frac{\mathrm{\Δ}{C}_{\mathrm{Cd}}\×V_{\mathrm{ca}}}{1000\×M_{\mathrm{Cd}}\×\frac{\mathrm{\ΔCOD}\×V_{\mathrm{an}}}{M_{O_2}}}---\left(10\right)$

$Y_{H_2}=\frac{n_{H_2}}{\frac{\mathrm{\ΔCOD}\×V_{\mathrm{an}}}{M_{O_2}}}---\left(11\right)$

react initial in MECs pattern and the changing value (mg/L) of the concentration of cadmium ions of final state, b ₁and b ₂the electronic number gone back original unit's cadmium and produce required for Unit of Hydrogen respectively; V _ca, V _anthe cathode and anode liquid long-pending (L) of reactor; E _cd2+the theoretical reduction electrode potential (V) of Cd under experiment condition (II), E _apadditional voltage (V), n _h2and n _sthat reaction is initial to the amount of substance of final state hydrogen, the amount of substance (mol) of anode consumption substrate respectively, G _sthe Gibbs free energy (J/mol) of sodium acetate oxidation under experiment condition, Δ H _{s, H2}be the combustion heat (J/mol) of hydrogen, the changing value (g/L) of chemical oxygen demand (COD) in Δ COD reactor anode, I is electric current in loop (A), and t is reactor working time (s), M _cdand M _o2be the average molecular (g/mol) of simple substance cadmium and oxygen respectively, 96485 is Faraday's number, (C/mol e ^-); 1000 is dimension conversion unit (mg/g).

Result: reactor is along with the prolongation of working time under MFCs pattern, and Cu (II) rate of recovery improves constantly, reaches 96.8 ± 1.6% (Fig. 2) in Cu (II) rate of recovery of 21h; And the main adsorption owing to electrode of the minimizing (10.6 ± 1.3% (Fig. 2)) of Cd (II) in whole process.When reactor being switched to MECs pattern, during 4h, the rate of recovery of Cd (II) is 46.6 ± 1.3% (Fig. 3); And the non-copper facing negative electrode contrast experiment under similarity condition shows, Cd (II) rate of recovery is only 26.1 ± 1.1% (Fig. 3), therefore the cadmium organic efficiency of copper-plating electrode improves 78.5%.Current density under copper facing, non-copper-plating electrode condition is respectively 1.52 ± 0.09A/m ²with 0.31 ± 0.01A/m ²(Fig. 4) copper deposited under, MFCs pattern is described promotes recovery and the reduction of Cd (II) by the current density improved in MECs pattern.Cyclic voltammetric analysis shows (Fig. 5), the reduction peak current potential difference Chu Xian – 0.57V of the cadmium of the copper facing under MECs pattern, non-copper facing negative electrode is with – 0.61V, the former shuffles compared with the current potential of the latter, shows that the reduction of copper to follow-up Cd (II) that electrode surface generates has katalysis; Correspondingly, the reduction peak current of the cadmium of copper-plating electrode is also comparatively large, illustrate the copper of MFCs schema creation accelerate MECs pattern under electrode reaction speed.

Under MECs pattern (upper table), compared with not copper-plated reference electrode, system total energy efficiency and the cadmium yield of copper-plating electrode all increase; And based on the negative electrode coulombic efficiency of cadmium and additional electric energy efficiency all lower; All increase based on the negative electrode coulombic efficiency of hydrogen, additional electric energy efficiency, system total energy efficiency and hydrogen yield.These results show, negative electrode improves the reduction efficiency of cadmium after copper facing, too increase the effusion of hydrogen simultaneously, and product hydrogen has competed the reduction of cadmium.

To sum up, utilize MFCs by copper selective separation reclaiming from copper cadmium waste water, the rate of recovery of Cu (II) reaches 96.8 ± 1.6%; Under the prerequisite of not altering reactor main body, MFCs is switched to MECs pattern, reclaims the cadmium metal in waste water further.Compared with blank not copper-plated on electrode, the rate of recovery of copper-plating electrode to Cd (II) improves 78.5%, thus the Cd (II) under the recovery copper situ catalytic realized under MFCs pattern and high efficiente callback MECs pattern.In the cadmium bronze precursor of preparation, copper cadmium ratio example is 4.16 ± 0.07g/g.By the also commercial weight of the Cd (II) under time electromagnetic relay control MECs pattern, the content of cadmium in copper cadmium product can be regulated further, according to needing the cadmium bronze precursor preparing different ratios composition.This process cleans is pollution-free, has environment and ecological benefits, Social benefit and economic benefit concurrently.

Claims (8)

1. compact type bio-electrochemical reactor reclaims copper, cadmium prepare the method for cadmium bronze precursor, it is characterized in that,

Control relay switch by time electromagnetic relay, bio-electrochemical reactor is switched to microbiological fuel cell or microorganism electrolysis cell pattern;

When bio-electrochemical reactor is in MFCs pattern, the extrernal resistance of series connection 100-500 Ω;

When bio-electrochemical reactor is in MECs pattern, the resistance of series connection 5-50 Ω, and external source 0.5-1.0V;

The cathode compartment of bio-electrochemical reactor loads the mixing salt solution of Cu (II) and Cd (II), and the negative electrode of bio-electrochemical reactor and anode electrode are the carbon material of conduction;

Electrochemical activity microorganism and anolyte are housed in the anolyte compartment of bio-electrochemical reactor;

Using the settling pond mud of inoculation sewage work of the anolyte compartment of bio-electrochemical reactor as electrochemical activity microorganism.

2. method according to claim 1, it is characterized in that, described Cu (II) and the mixing salt solution of Cd (II) are the mixed solution of the mixing salt solution of the mixed solution of the mixing salt solution of copper sulfate and Cadmium Sulphate, copper sulfate and Cadmium chloride fine powder, cupric chloride and Cadmium Sulphate, cupric chloride and Cadmium chloride fine powder.

3. method according to claim 1 and 2, is characterized in that, described carbon material is carbon cloth, carbon-point or carbon felt.

4. method according to claim 1 and 2, is characterized in that, described settling pond sludge pH: 6.8-7.0; Specific conductivity: 0.80-0.93mS/cm; Suspension solid substance: 30-35g/L; Chemical oxygen demand (COD): 150-300mg/L.

5. method according to claim 3, is characterized in that, described settling pond sludge pH: 6.8-7.0; Specific conductivity: 0.80-0.93mS/cm; Suspension solid substance: 30-35g/L; Chemical oxygen demand (COD): 150-300mg/L.

6. the method according to claim 1,2 or 5, is characterized in that, described anolyte composition is: 12.0mM sodium acetate; 5.8mM NH ₄cl; 1.7mM KCl; 17.8mM NaH ₂pO ₄h ₂o; 32.3mMNa ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.

7. method according to claim 3, is characterized in that, described anolyte composition is: 12.0mM sodium acetate; 5.8mM NH ₄cl; 1.7mM KCl; 17.8mM NaH ₂pO ₄h ₂o; 32.3mM Na ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.

8. method according to claim 4, is characterized in that, described anolyte composition is: 12.0mM sodium acetate; 5.8mM NH ₄cl; 1.7mM KCl; 17.8mM NaH ₂pO ₄h ₂o; 32.3mM Na ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.