CN104480493B - 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 bio-electrochemical reactor reclaims copper, cadmium and prepares cadmium bronze precursor Method

Technical field

The invention belongs to bio electrochemistry technical field, using microbiological fuel cell (mfcs) by copper from copper cadmium waste water Selective Separation simultaneously reclaims；On the premise of not changing reactor body, mfcs is switched to microorganism electrolysis cell (mecs) mould Formula, reclaims the cadmium metal in above-mentioned waste water further, have structure of reactor compact, easy to operate the features such as.Based on mfcs mould The catalytic action of copper is reclaimed, system original position using copper and realizes the high efficiente callback of cadmium under formula.The copper cadmium complex generating is to prepare The precursor of the cadmium bronze of satisfactory electrical conductivity and heat conductivity and raw material.

Background technology

Heavy metal copper, cadmium are widely used in industrial numerous areas, such as alloy, plating, neutron-absorbing control rod, face Material, stabilizer for plastics, fluorescent material, insecticide, antibacterial, paint.Therefore, copper cadmium heavy metal containing wastewater treatment is always people's concern One of focus.At present, the process of cupric cadmium waste water reaches 20 remainders with reclaiming patent.These methods mainly have chemical precipitation method, Absorption method, ion exchange, ferrum oxidizing process and electrochemical process.For example, patent cn201310533532, cn201310615806, Cn201410111803 etc..The shortcoming of these methods predominantly inorganic agent usage amount is big, react wayward, easily secondary dirt Dye, high cost, recovery metal hardly possible, energy consumption height etc..Find cleaning, efficient, no/low energy consumption copper cadmium recovery new method is sustainable The inevitable requirement of social development.

Cadmium bronze is the metal material having high-rise electrical, heat conductivity and having excellent abrasive resistance, is to be applied to defence and military One of important nonferrous materials of industry.The production of cadmium bronze usually uses cadmium copper alloy, selects certain in high frequency furnace Solid solution temperature and the time, smelting form.If can select to clean effective method having in reclaiming copper cadmium waste water While valency metallic copper, cadmium, prepare the precursor of cadmium bronze, then enable the resource of copper cadmium waste water.

Bioelectrochemical system is the new technique in recent years rising, when the chemical reaction of anode and negative electrode can spontaneous be carried out, This system is mfcs；When the external world needs applying small voltage that anode and cathode reaction just can be made to carry out, this system is mecs.With The development of R＆D work and deeply, the application of mfcs and mecs is expanded.Just disclosed at present or authorize domestic and international For 35 mecs, 543 mfcs patents, goal in research from simple treatment of Organic Wastewater and hydrogen manufacturing (wo2014082989, Cn201310627011, cn201410209650, cn201310148645, cn201210369997) arrive fixing co₂ (cn201110209149, cn201410169707), denitrogenation desalination (wo2010124079, cn201210550133), production first Alkane (cn201210240982), sensing and monitoring (cn201410298473, cn201310226890, cn201310214163), Contaminated site repairs (cn201420151230), organic productss prepare (us2013256149, cn201310212120), cobalt and nickel Etc. single metal leaching with reclaim (cn201310345579, cn201210153753, cn201210153753, Cn201310145779) etc..For the bio electrochemistry of hybrid metal waste water processes and reclaims, R＆D work is also fewer See, and be only limitted to reclaim copper, lead, cadmium and zinc (modin o, wang x, wu x, rauch by applying the mecs of different voltages s,fedje kk.bioelectrochemical recovery of cu,pb,cd,and zn from dilute solutions.j hazard mater 2012,235-236:291-297).This research group also once have developed mfcs and drove Mecs reclaims chromium, copper and cadmium (cn201410175987), and cu (ii) promotes co (iii) (201310071793.1) to leach Work.With the studies above thinking, research contents and principle, goal in research and the problem that intends to solve is entirely different, the present invention exists Under the premise of not changing reactor body structure, by (automatic) control of relay switch, the ingenious switching realizing mfcs and mecs And power and energy, while saving reactor and save place space, using the underpotential deposition reclaiming copper under mfcs pattern Cadmium effect, realizes the preparation of the high efficiente callback of cadmium and cadmium bronze precursor under mecs pattern.

Content of the invention

The invention provides a kind of process cleans, structure of reactor are compact, easy to operate, process copper and cadmium waste water synchronously returns Receive copper and cadmium the method preparing cadmium bronze precursor.

The technical solution used in the present invention is as follows: a kind of compact bio-electrochemical reactor reclaims copper, cadmium and prepares cadmium The method of bronze precursor, specifically comprises the following steps that

Relay switch is controlled 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 power supply 0.5-1.0v；

The cathode chamber of bio-electrochemical reactor loads the mixing salt solution of cu (ii) and cd (ii), and bio electrochemistry reacts The negative electrode of device and anode electrode are conductive material with carbon element；

Equipped with electro-chemical activity microorganism and anolyte in the anode chamber of bio-electrochemical reactor；

Will be micro- as electro-chemical activity for the depositing reservoir mud that the anode chamber of bio-electrochemical reactor inoculates sewage treatment plant Biological.

The mixing salt solution of described cu (ii) and cd (ii) is the mixing salt solution of copper sulfate and cadmium sulfate, copper sulfate and The mixed liquor of the mixing salt solution of the mixed liquor of Caddy (Cleary), copper chloride and cadmium sulfate, copper chloride and Caddy (Cleary).

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

Described depositing reservoir mud ph:6.8-7.0；Electrical conductivity: 0.80-0.93ms/cm；Suspension solid content: 30-35g/l； COD: 150-300mg/l.

Described anolyte composition is: 12.0mm sodium acetate；5.8mm nh₄cl；1.7mm kcl；17.8mm nah₂po₄· h₂o；32.3mm na₂hpo₄；Mineral element: 12.5ml/l, consists of mgso₄:3.0g/l；mnso₄·h₂o:0.5g/l；nacl: 1.0g/l；feso₄·7h₂o:0.1g/l；cacl₂·2h₂o:0.1g/l；cocl₂·6h₂o:0.1g/l；zncl₂:0.13g/l； cuso₄·5h₂o:0.01g/l；kal(so₄)₂·12h₂o:0.01g/l；h₃bo₃:0.01g/l；na₂moo₄:0.025g/l； nicl₂·6h₂o:0.024g/l；na₂wo₄·2h₂o:0.024g/l；Vitamin: 12.5ml/l, consists of vitamin b₁:5.0g/ l；Vitamin b₂:5.0g/l；Vitamin b₃:5.0g/l；Vitamin b₅:5.0g/l；Vitamin b₆:10.0g/l；Vitamin b₁₁: 2.0g/l；W factor: 2.0g/l；Para-amino benzoic acid: 5.0g/l；Thioctic acid: 5.0g/l；Aminotriacetic acid: 1.5g/l.

The anode chamber of the reactor of the present invention and cathode chamber need to keep oxygen-free environment in running, can be by being passed through nitrogen Gas is to realize anaerobic condition.

The reactor operation phase flow process of the present invention is: the Organic substance in anolyte anode indoor by microbiological oxidation, The proton that process produces passes through proton to pass through film and enters cathode chamber, and electronics imports negative electrode by external circuit.In cathode electrode surface, Because the standard oxidationreduction potential of cu (ii) and cd (ii) is respectively+0.52v and 0.40v, cu (ii) on electrode for the absorption Under mfcs and mecs pattern, elemental copper or cadmium are reduced to by selectivity respectively with cd (ii).

The operation phase flow process of the raising mecs cadmium response rate of the present invention is: under mfcs pattern, cu (ii) is reduced to list Matter.This copper-plated electrode, according to the underpotential deposition cadmium effect of copper, is catalyzed and high efficiente callback cadmium under mecs pattern, synchronous preparation Cadmium bronze precursor.

Brief description

Fig. 1 is the bio-electrochemical reactor schematic diagram reclaiming copper, cadmium and preparing cadmium bronze precursor.

Fig. 2 be embodiment 1 mfcs pattern under cu (ii), cd (ii) response rate over time.

Fig. 3 is cd (ii) response rate and the hydrogen yield of the mecs mode operation 4h of embodiment 1, and non-copper-plating electrode Comparison.

Fig. 4 is the electric current density under the mecs pattern of embodiment 1, and the comparison of non-copper-plating electrode.

Fig. 5 is the cyclic voltammetry curve under the mecs pattern of embodiment 1, and the non-copper facing of non-copper-plating electrode, electrode-no cd (ii), the comparison of electrode copper facing-no cd (ii).

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

6 cation exchange membranes；7 anode chambers；8 cathode chambers；9 power supplys；Extrernal resistance under 10mfcs pattern；

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

Specific 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 anode chamber 7 and cathode chamber 8 are lucite material, anode Room liquor capacity is 15ml, and cathode chamber solution volume is 25ml, is separated with ion exchange membrane (cmi-7000) 6, under mfcs pattern Connect 200 ω extrernal resistances 10, connect during mecs 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 anode In room 7 and cathode chamber 8.Carbon-point (Beijing three industry material with carbon element company) apparent size is , carbon felt (Beijing Three industry material with carbon element companies) apparent size be 3.0cm × 2.0cm × 1.0cm).Access reference electrode 2 in reactor cathode chamber, lead to Cross computer and collect resistance 11 both end voltage calculating current with data collecting system；Collect the negative electrode of reactor according to reference electrode Potential.

Step 3: add 15ml culture fluid in reactor anode chamber, consisting of 12.0mm sodium acetate；5.8mm nh₄cl；1.7mm kcl；17.8mm nah₂po₄·h₂o；32.3mm na₂hpo₄；Mineral element: 12.5ml/l (mgso₄: 3.0g/l；mnso₄·h₂o:0.5g/l；nacl:1.0g/l；feso₄·7h₂o:0.1g/l；cacl₂·2h₂o:0.1g/l； cocl₂·6h₂o:0.1g/l；zncl₂:0.13g/l；cuso₄·5h₂o:0.01g/l；kal(so₄)₂·12h₂o:0.01g/l； h₃bo₃:0.01g/l；na₂moo₄:0.025g/l；nicl₂·6h₂o:0.024g/l；na₂wo₄·2h₂o:0.024g/l)；Dimension life Element: 12.5ml/l (vitamin b₁:5.0g/l；Vitamin b₂:5.0g/l；Vitamin b₃:5.0g/l；Vitamin b₅:5.0g/l；Dimension Raw element b₆:10.0g/l；Vitamin b₁₁:2.0g/l；W factor: 2.0g/l；Para-amino benzoic acid: 5.0g/l；Thioctic acid: 5.0g/l；Aminotriacetic acid: 1.5g/l).Anode chamber inoculation sewage treatment plant depositing reservoir mud 10g is (at the Ling Shuihe sewage of Dalian Reason factory).Anolyte seals after exposing nitrogen 20min.

Step 4: add the deionized water of 25ml in reactor cathode chamber.

Step 5: circuit general switch is closed, the switch of electromagnetic relay is placed under mfcs pattern.Device is placed in room temperature Tame under (20-25 DEG C) and run.When electric current drops to below 0.02ma, that is, complete a cycle, and add above-mentioned culture Based 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/l₄Cdso with 50mg/l₄Mixed liquor, Medium is 0.1m Sodium Acetate Trihydrate-hac buffer (ph=4.6), exposes nitrogen 20min.

Step 7: electromagnetic relay switch is placed under mfcs pattern, periodically samples, cu (ii) and cd in analysis liquid phase (ii) content, calculates its response rate.

Step 8: this recovery of cuprio in mfcs mode operation 21h, electromagnetic relay switch is placed under mecs pattern, Periodically sample, hydrogen content in cd (ii) in analysis liquid phase, gas phase.

Step 9: characterize mecs pattern copper-plating electrode and non-copper facing blank electrode, have or not the circulation of cd (ii) comparison etc. Volt-ampere curve；Calculate mecs pattern under based on cadmium, the negative electrode coulombic efficiency of hydrogen, additional electric energy efficiency, system total energy efficiency, Cadmium yield, hydrogen yield.

Following table be embodiment 1 mecs pattern under based on cadmium, the negative electrode coulombic efficiency of hydrogen, additional electric energy efficiency, system Total energy efficiency, cadmium yield, hydrogen yield.

This enforcement example reclaims copper, cadmium and prepares the cadmium bronze precursor of definite composition.In mfcs pattern, negative electrode occurs React for formula (1), the reaction that negative electrode is carried out in mecs pattern is formula (2) and (3).Negative electrode coulomb based on cadmium during mecs pattern Efficiency (ce_cd), the negative electrode coulombic efficiency (ce based on 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 (4)-(11) shown in.

cu²⁺+2e^-→cu(s) (1)

cd²⁺+2e^-→cd(s) (2)

2h⁺+2e^-→h₂(g) (3)

${\mathrm{ce}}_{cd}=\frac{96485\×b_1\×{\mathrm{\δc}}_{{\mathrm{cd}}^{2+}}\×v_{ca}}{1000\×m_{cd}\×\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i}\×100\%---\left(4\right)$

${\mathrm{ce}}_{h_2}=\frac{96485\×b_2\×n_{h_2}}{\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i}\×100\%---\left(5\right)$

${\mathrm{\η}}_{e,cd}=\frac{96485\×b_1\×{\mathrm{\δc}}_{{\mathrm{cd}}^{2+}}\×v_{ca}\×e_{{\mathrm{cd}}^{2+}}}{1000\×m_{cd}\×e_{ap}\×\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i}\×100\%---\left(6\right)$

${\mathrm{\η}}_{e,h_2}=\frac{n_{h_2}\×{\mathrm{\δh}}_{s,h_2}}{e_{ap}\×\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i}\×100\%---\left(7\right)$

${\mathrm{\η}}_{e+s,cd}=\frac{96485\×b_1\×{\mathrm{\δc}}_{{\mathrm{cd}}^{2+}}\×v_{ca}\×e_{{\mathrm{cd}}^{2+}}}{1000\×m_{cd}\×(e_{ap}\×\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i-n_s{g}_s)}\×100\%---\left(8\right)$

${\mathrm{\η}}_{e+s,h_2}=\frac{n_{h_2}\×{\mathrm{\δh}}_{s,h_2}}{e_{ap}\×\underset{i=1}{\overset{n}{\σ}}{i}_i{\mathrm{\δt}}_i-n_s{g}_s}\×100\%---\left(9\right)$

$y_{cd}=\frac{{\mathrm{\δc}}_{{\mathrm{cd}}^{2+}}\×v_{ca}}{1000\×m_{cd}\×\frac{\mathrm{\δ}cod\×v_{an}}{m_{o_2}}}---\left(10\right)$

$y_{h_2}=\frac{n_{h_2}}{\frac{\mathrm{\δ}cod\×v_{an}}{m_{o_2}}}---\left(11\right)$

The changing value (mg/l) of the concentration of cadmium ions of initial and final state, b is reacted in mecs pattern₁And b₂It is respectively Also original unit's cadmium and the electron number producing required for Unit of Hydrogen；v_ca、v_anBe reactor cathode and anode liquid amass (l)；e_cd2+It is Theoretical reduction electrode potential (v) of cd (ii), e under experiment condition_apIt is additional voltage (v), n_h2And n_sIt is that reaction is initial respectively Consume the amount (mol) of the material of substrate, g to the amount of the material of final state hydrogen, anode_sIt is the Ji of sodium acetate oxidation under experiment condition Buss free energy (j/mol), δ h_s,h2It is the combustion heat (j/mol) of hydrogen, the change of COD in δ cod reactor anode Change value (g/l), i is electric current (a) in loop, and t is reactor run time (s), m_cdAnd m_o2It is the phase of simple substance cadmium and oxygen respectively To molecule (g/mol), 96485 is Faraday constant, (c/mol e^-)；1000 is dimension conversion unit (mg/g).

Result: reactor prolongation with run time under mfcs pattern, cu (ii) response rate improves constantly, in 21h Cu (ii) response rate reach 96.8 ± 1.6% (Fig. 2)；And the minimizing (10.6 ± 1.3% (Fig. 2)) of cd (ii) is main in whole process Will be owing to the adsorption of electrode.When reactor is switched to mecs pattern, during 4h the response rate of cd (ii) be 46.6 ± 1.3% (Fig. 3)；And the non-copper facing negative electrode contrast experiment under similarity condition shows, cd (ii) response rate is only 26.1 ± 1.1% (Fig. 3), thus the cadmium organic efficiency of copper-plating electrode improves 78.5%.Electric current density under the conditions of copper facing, non-copper-plating electrode is respectively For 1.52 ± 0.09a/m²With 0.31 ± 0.01a/m²(Fig. 4), illustrate that the copper of deposition under mfcs pattern passes through to improve in mecs pattern Electric current density promote cd (ii) recovery and reduction.Cyclic voltammetric analysis shows (Fig. 5), copper facing under mecs pattern, do not plate The reduction spike potential of the cadmium of cathode respectively appears in 0.57v and 0.61v, and the former shuffles compared with the current potential of the latter, shows electrode The copper of Surface Creation has catalytic action to the reduction of follow-up cd (ii)；Correspondingly, the reduction peak current of the cadmium of copper-plating electrode Also larger, illustrate that the copper of mfcs schema creation accelerates the electrode reaction speed under mecs pattern.

Under mecs pattern (upper table), compared with not copper-plated reference electrode, the system total energy efficiency of copper-plating electrode and Cadmium yield all increases；And the negative electrode coulombic efficiency based on cadmium and additional electric energy efficiency are all relatively low；Negative electrode coulomb effect based on hydrogen Rate, additional electric energy efficiency, system total energy efficiency and hydrogen yield all increase.These results indicate that negative electrode is right after copper facing The reduction efficiency of cadmium improves, and also increases the effusion of hydrogen simultaneously, and produces the reduction that hydrogen has competed cadmium.

To sum up, using mfcs by copper Selective Separation reclaiming from copper cadmium waste water, the response rate of cu (ii) reaches 96.8 ± 1.6%；On the premise of not changing reactor body, mfcs is switched to mecs pattern, reclaims the metal in waste water further Cadmium.Compared with blank not copper-plated on electrode, copper-plating electrode improves 78.5% to the response rate of cd (ii), thus realizing mfcs The cd (ii) reclaiming under copper situ catalytic and high efficiente callback mecs pattern under pattern.Copper cadmium ratio example in the cadmium bronze precursor of preparation For 4.16 ± 0.07g/g.Control cd (ii) the also commercial weight under mecs pattern by time electromagnetic relay, copper can be adjusted further The content of cadmium in cadmium product, foundation needs to prepare the cadmium bronze precursor of different proportion composition.This process cleans is pollution-free, has ring concurrently Border and ecological benefits, Social benefit and economic benefit.

Claims (8)

1. a kind of compact bio-electrochemical reactor reclaim copper, cadmium and prepare cadmium bronze precursor method it is characterised in that

Relay switch is controlled by time electromagnetic relay, bio-electrochemical reactor is switched to microbiological fuel cell or micro- Biological electrolysis pool mode；

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 power supply 0.5-1.0v；

The cathode chamber of bio-electrochemical reactor loads the mixing salt solution of cu (ii) and cd (ii), bio-electrochemical reactor Negative electrode and anode electrode are conductive material with carbon element；

Equipped with electro-chemical activity microorganism and anolyte in the anode chamber of bio-electrochemical reactor；

The anode chamber of bio-electrochemical reactor is inoculated the depositing reservoir mud of sewage treatment plant as electro-chemical activity microorganism.

2. method according to claim 1 is it is characterised in that the mixing salt solution of described cu (ii) and cd (ii) is sulfur The mixing salt solution of the mixed liquor of the mixing salt solution of sour copper and cadmium sulfate, copper sulfate and Caddy (Cleary), copper chloride and cadmium sulfate, chlorine Change the mixed liquor of copper and Caddy (Cleary).

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

4. method according to claim 1 and 2 is it is characterised in that described depositing reservoir mud ph:6.8-7.0；Electrical conductivity: 0.80-0.93ms/cm；Suspension solid content: 30-35g/l；COD: 150-300mg/l.

5. method according to claim 3 is it is characterised in that described depositing reservoir mud ph:6.8-7.0；Electrical conductivity: 0.80-0.93ms/cm；Suspension solid content: 30-35g/l；COD: 150-300mg/l.

6. the method according to claim 1,2 or 5 is it is characterised in that described anolyte composition is: 12.0mm acetic acid Sodium；5.8mm nh₄cl；1.7mm kcl；17.8mm nah₂po₄·h₂o；32.3mm na₂hpo₄；Mineral element: 12.5ml/l, Consist of mgso₄:3.0g/l；mnso₄·h₂o:0.5g/l；nacl:1.0g/l；feso₄·7h₂o:0.1g/l；cacl₂· 2h₂o:0.1g/l；cocl₂·6h₂o:0.1g/l；zncl₂:0.13g/l；cuso₄·5h₂o:0.01g/l；kal(so₄)₂· 12h₂o:0.01g/l；h₃bo₃:0.01g/l；na₂moo₄:0.025g/l；nicl₂·6h₂o:0.024g/l；na₂wo₄·2h₂o: 0.024g/l；Vitamin: 12.5ml/l, consists of vitamin b₁:5.0g/l；Vitamin b₂:5.0g/l；Vitamin b₃:5.0g/ l；Vitamin b₅:5.0g/l；Vitamin b₆:10.0g/l；Vitamin b₁₁:2.0g/l；W factor: 2.0g/l；P-aminophenyl first Acid: 5.0g/l；Thioctic acid: 5.0g/l；Aminotriacetic acid: 1.5g/l.

7. method according to claim 3 is it is characterised in that described anolyte composition is: 12.0mm sodium acetate； 5.8mm nh₄cl；1.7mm kcl；17.8mm nah₂po₄·h₂o；32.3mm na₂hpo₄；Mineral element: 12.5ml/l, composition For mgso₄:3.0g/l；mnso₄·h₂o:0.5g/l；nacl:1.0g/l；feso₄·7h₂o:0.1g/l；cacl₂·2h₂o: 0.1g/l；cocl₂·6h₂o:0.1g/l；zncl₂:0.13g/l；cuso₄·5h₂o:0.01g/l；kal(so₄)₂·12h₂o: 0.01g/l；h₃bo₃:0.01g/l；na₂moo₄:0.025g/l；nicl₂·6h₂o:0.024g/l；na₂wo₄·2h₂o:0.024g/ l；Vitamin: 12.5ml/l, consists of vitamin b₁:5.0g/l；Vitamin b₂:5.0g/l；Vitamin b₃:5.0g/l；Vitamin b₅:5.0g/l；Vitamin b₆:10.0g/l；Vitamin b₁₁:2.0g/l；W factor: 2.0g/l；Para-amino benzoic acid: 5.0g/ l；Thioctic acid: 5.0g/l；Aminotriacetic acid: 1.5g/l.

8. method according to claim 4 is it is characterised in that described anolyte composition is: 12.0mm sodium acetate； 5.8mm nh₄cl；1.7mm kcl；17.8mm nah₂po₄·h₂o；32.3mm na₂hpo₄；Mineral element: 12.5ml/l, composition For mgso₄:3.0g/l；mnso₄·h₂o:0.5g/l；nacl:1.0g/l；feso₄·7h₂o:0.1g/l；cacl₂·2h₂o: 0.1g/l；cocl₂·6h₂o:0.1g/l；zncl₂:0.13g/l；cuso₄·5h₂o:0.01g/l；kal(so₄)₂·12h₂o: 0.01g/l；h₃bo₃:0.01g/l；na₂moo₄:0.025g/l；nicl₂·6h₂o:0.024g/l；na₂wo₄·2h₂o:0.024g/ l；Vitamin: 12.5ml/l, consists of vitamin b₁:5.0g/l；Vitamin b₂:5.0g/l；Vitamin b₃:5.0g/l；Vitamin b₅:5.0g/l；Vitamin b₆:10.0g/l；Vitamin b₁₁:2.0g/l；W factor: 2.0g/l；Para-amino benzoic acid: 5.0g/ l；Thioctic acid: 5.0g/l；Aminotriacetic acid: 1.5g/l.