CN108796531A - The method that a kind of organic composite waste of clean thorough processing tungsten synchronizes recycling metal and by-product hydrogen - Google Patents
The method that a kind of organic composite waste of clean thorough processing tungsten synchronizes recycling metal and by-product hydrogen Download PDFInfo
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- CN108796531A CN108796531A CN201810685425.9A CN201810685425A CN108796531A CN 108796531 A CN108796531 A CN 108796531A CN 201810685425 A CN201810685425 A CN 201810685425A CN 108796531 A CN108796531 A CN 108796531A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to technical field of waste water processing, disclose the method that a kind of organic composite waste of clean thorough processing tungsten synchronizes recycling metal and by-product hydrogen.The cartridge type microorganism electrolysis cell formed with anode and cathode；Anode and cathode electrode is the carbon-based materials such as carbon felt, carbon fiber；Anode and cathode electrode is spaced apart by stainless (steel) wire respectively, and by stainless (steel) wire as electronics export/introduction part；Solution is the organic mixed solution of metal that tungsten and organic matter form in reactor, and a concentration of 1~2500mg/L, pH are 3.0~8.0, and conductivity is 0.3~3mS/cm；Anode and cathode electrode is connected by external resistance with data gathering system and external power, and dispatch from foreign news agency resistance value is 10~1000 Ω.The present invention provides the new method that a kind of cleaning thoroughly removes tungsten organic wastewater while by-product hydrogen, whole process clean environment firendlies.
Description
Technical field
The invention belongs to technical field of waste water processing, more particularly to it is a kind of using microorganism electrolysis cell thoroughly handle tungsten with
The method that organic composite waste synchronizes recycling valuable metal and by-product hydrogen.
Background technology
Tungsten, molybdenum are the widely used rare metals in the fields such as chemical industry, metallurgy, material.Exploitation, smelting in tungsten associated minerals
Refining and product prepare, will produce the composite waste containing tungsten and organic matter during use, not only to environment and ecology
Risk and hidden danger are brought, and causes the waste of resource.On the other hand, tungsten resource is not only resulted in from mining tungsten
Exhaustion, and the energy of recovery process consumption is much larger than the energy that recycling waste product is consumed.Therefore, the resource of tungsten is recycled
Valuable metal has important environment and ecology and social and economic implications in the spent process water exploiting, produce, using etc..
The main methods of tungstenic molybdenum waste water include at present：The precipitation method (CN201010165455.0, CN98123639.1,
CN200710053864.X etc.), solvent extraction (CN201210350518.9, CN200910043895.6,
CN201610252191.X etc.), ion-exchange (CN201110315011.5, CN201610014324.X,
CN201611104581.9 etc.).For heavy metal and organic composite waste, the physical chemistry sides such as treatment technology mainly adsorbs
Method (CN201610894710.2, CN201510738031.1, CN201620925008.3 etc.)；Can also be physico-chemical process and biology
Method is combined (CN201610374914.3, CN201710665161.6, CN201710565332.8 etc.).For example, patent
CN201710665161.6 use including pretreatment, coagulating sedimentation, physical absorption, redox reaction, bio anaerobic and
The group technology of aerobic process handles the composite wastes such as organic pollution and nickel, lead, chromium, manganese.The above method have at
This height, energy consumption be big, complex process, efficiency are low, secondary pollution, more by-product the shortcomings of.Seek to clean effective processing tungsten with
Organic composite waste synchronizes the concern that recycling valuable metal is just causing people.
Microorganism electrolysis cell (microbial electrolysis cells, MECs) is incited somebody to action under smaller applied voltage
Electronics in the organic matter of anode electrochemical active microorganism extraction, is transmitted to cathode, by electronics on cathode by external circuit
Receptor such as O2、NO3 -、H+, metal ion etc. restores and recycles the cleaning effective technology of price product (hydrogen, metal etc.).Currently,
The metal of MECs recycling includes Cu (II), Ag (I), Zn (II), Hg (II), Cd (II), Ni (II), Cr (VI), Cd (II), Sn
(II) or (CN201310345579.0 such as Sn (IV), Fe (II) or Fe (III)；CN201410175987.0；
201710316396.4；Jiang et al.,Inter J Hydrogen Energy 2014,39:654-663；Luo et
al.,J Hazard Mater 2014,270:153-159；Xin et al.,Bioresour Technol 2009,100:
6163-6169；Cheng et al.,Bioresour Technol2013,147:332-337；Zhang et al.,J Power
Sources 2015,273:1103-1113 etc.).For the removal of tungsten metal and recycling, also there is patent
201611002755.0,201610031987.2 and Huang et al (327 (2017) 584-596 of Chem Eng J；J
Hazard Mater 353 (2018) 348-359) and Wang et al (Electrochimica Acta 247 (2017) 880-
890) report, but above-mentioned Reporting is to remove metal using the two-compartment reactor cathode that amberplex separates, and go
Except the pH value of solution of metal is all very low.Due to the electron donor feature of organic matter, cannot be degraded by the cathode with reproducibility.Cause
This, the organic composite waste of metal cannot simultaneously be removed in dual chamber MECs cathode chambers；Especially it is not too low or too high (such as to pH
3.0<pH<8.0), for the organic composite waste of metal that meets electro-chemical activity microbe survival, single chamber MECs has very big
Advantage.Although also having report (Abourached the et al., Water of a small amount of single chamber MECs processing metal organic compounds
Res 2014,51:228-233；Wu et al.,Bioresour Technol 2018,253:372-377；CN106757117
Deng), but metal concentration all relatively low (such as 12.5mg/L Cu (II), 22.4mg/L Cd (II) or the 26mg/L Zn handled
(II))；And it is defined in the mixture of organic matter and single metal.Skill is handled in conjunction with the single chamber MECs of the organic composite waste of tungsten
The report of art and effluent quality qualified discharge all yet there are no.
The present invention is using MECs for recycling the organic composite waste of tungsten while recycling valuable metal and by-product hydrogen.Pass through
It circulates completely, add organic substrates sodium acetate and stream plus acid for adjusting pH mode, use underwater gold and belong to equal with organic concentration
Reach discharge standard：COD concentration reaches country-level emission standard A (GB18918-2002), and tungsten concentration is less than direct emission
Waste strength limit value (GB21/1627-2008).The present invention overcomes dual chamber MECs handle it is organic with tungsten or other metals it is mixed
Close the limitation (CN201610031987.2 of waste water；CN201611002755.0；Huang et al.,Chem Eng J 327
(2017)584-596；J Hazard Mater 353(2018)348-359；Wang et al.,Electrochimica Acta
247(2017)880-890；CN201310345579.0；CN201410175987.0；Jiang et al.,Inter J
Hydrogen Energy 2014,39:654-663；Luo et al.,J Hazard Mater 2014,270:153-159；
Xin et al.,Bioresour Technol 2009,100:6163-6169；Cheng et al.,Bioresour
Technol2013,147:332-337；Zhang et al.,J Power Sources 2015,273:1103-1113 etc.), and
And valuable metal, organics removal and by-product hydrogen can be thoroughly recycled, it is the recycling and energy of the organic composite waste of tungsten
Provide practicable new way.
The technical principle of the present invention：The oxidation-reduction potential of W (VI) and Mo (VI) are respectively 0.386V and 0.606V, usually
With WO4 2-And MoO4 2-In the presence of.For tungsten and organic (being indicated with sodium acetate) composite waste, the electrochemistry of anode electrode surface
Electronics, for " fuel " (reaction equation (1)), is transmitted to cathode by active microorganism with sodium acetate by external circuit, meanwhile, at one
Under small voltage driving, the WO with higher oxygen reduction potential4 2-And MoO4 2-And the proton hydrogen that microbial metabolism generates is in the moon
Pole electrode surface or cathode electrochemical Iy active microorganism catalysis issue raw reduction reaction (reaction equation (2)-(4))：
2H++2e-→H2 (4)
Invention content
The present invention provides a kind of clean utilization MECs processing organic composite wastes of tungsten to recycle valuable metal simultaneously simultaneously
The new method of by-product hydrogen.Specifically, it is extracted in conjunction with tungsten reduction reaction and electro-chemical activity microorganism catalysis organic matter
Electronics and proton hydrogen and the multi-efficiency of catalysis W (VI) and Mo (VI) reduction, design single chamber MECs reactors, pass through change
Hydraulic detention time adds organic carbon, a small amount of acid stream plus the collective effect mode for adjusting pH, and it is organic mixed to reach thoroughly processing tungsten
Close the purpose that waste water recycles tungsten metal and by-product hydrogen simultaneously.
Technical scheme of the present invention：
The method that a kind of organic composite waste of clean thorough processing tungsten synchronizes recycling metal and by-product hydrogen, step is such as
Under：
For the present invention using single chamber tubular MECs, anode and cathode is all made of carbon felt as electrode material, stainless (steel) wire support
Electronics is exported or is imported while with separation anode, cathode circuit, anode and cathode electrode spacing is 1.0cm；The organic mixing of tungsten
Waste water is mixed solution manually preparing, being formed with sodium acetate and tungstates, molybdate, and pH is 3.0~8.0, and conductivity is
0.3~3mS/cm；MECs is connected by external resistance with data collecting system；0.3~1.2V of applied voltage, external resistance be 10~
1000 Ω, cathode potential are -1.50~-0.46V.
It needs to keep anaerobic environment in the single chamber MECs reactor operational process of the present invention, can be detested with realizing by being passed through nitrogen
Oxygen condition.
The water outlet of the organic composite waste of single chamber MECs reactor for treatment tungstens of the present invention needs to add organic carbon source (such as second
Sour sodium or glucose) complete circular flow afterwards.
The water outlet of the organic composite waste of single chamber MECs reactor for treatment tungstens of the present invention, after adding organic carbon source completely
While circular flow, need to flow acid adding (such as sulfuric acid or hydrochloric acid) adjusting inlet flow-patterm.
It is sodium acetate or glucose that organic matter is added in reactor water outlet, and additive amount is 50~1000mg/L, complete circulating
While row, stream plus a small amount of sulfuric acid or hydrochloric acid, additive amount are 2.6~47.4 μM.
The present invention composite waste be into water constituent：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,
1200mg/LCH3COONa,383mg/L(NH4)2SO4,13.6mg/L KH2PO4；12.5mL/L mineral elements；12.5mL/L dimension life
Element；Wherein, mineral element includes 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；
0.1g/LCaCl2·2H2O；0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/LCuSO4·5H2O；0.01g/LKAl
(SO4)2·12H2O；0.01g/LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes
5.0g/L vitamin B1；5.0g/L vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；
2.0g/L vitamin B11；2.0g/L biotin；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；Three second of 1.5g/L amino
Acid.
Bacterium source of the MECs inoculation sewage treatment plant's clarifying basin sludge as domestication electro-chemical activity microorganism.It is described clear
The pH of clear pond sludge is 7.0~8.0；Conductivity is 1.0~2.0mS/cm；Suspension solid content is 10~20g/L；Chemical oxygen demand
Amount is 100~1000mg/L.
MECs operation phase flow of the present invention is：Organic matter in the organic composite waste of tungsten is in anode surface by electrochemistry
Active microorganism aoxidizes (reaction equation (1)), and the proton generated in the process reaches cathode surface outside plus under the driving of small voltage, together
When microbial metabolism organic matter generate electrons pass through external circuit import cathode, on the cathode electrode, WO4 2-、MoO4 2-And
The electronics generation reduction reaction (reaction equation (2)-(4)) that proton hydrogen can receive cathode or electro-chemical activity microorganism provides, generates
The tungsten and molybdenum oxide of lower valency simultaneously deposit, while generating clean H2。
In single chamber MECs of the present invention solution be tungstenic molybdate organic wastewater, by add organic matter (such as sodium acetate or
Glucose) after circulate completely operation, stream acid adding (such as sulfuric acid or hydrochloric acid) adjust pH collective effect mode, make in water outlet
Tungsten content and COD concentration reach discharge standard (GB21/1627-2008, GB18918-2002).The present invention has good
Actual application prospect has both environment and ecological benefits, Social benefit and economic benefit.
Description of the drawings
Fig. 1 is the organic composite waste of single chamber MECs processing tungsten of the present invention while recycling metal and the flow chart of by-product hydrogen
(A) with structure of reactor schematic diagram (B)；
Fig. 2 be tungsten recovery rate when the organic composite waste of tungsten of embodiment 1 is run for 24 hours through the single chamber MECs residence times,
Molybdenum recovery, COD removal rates (A), hydrogen output, water outlet metal separation (B), electrode potential and loop current density (C) go out
Water pH and water outlet conductivity (D)；
Fig. 3 is the organic composite waste of tungsten of embodiment 1 after the single chamber MECs residence times run for 24 hours, supplements sodium acetate
And operation, the system closed circuit (A) under stream acid adding adjusting condition and open circuit (B) are circulated completely, the tungsten rate of recovery is compared；
Fig. 4 is the organic composite waste of tungsten of embodiment 1 after the single chamber MECs residence times run for 24 hours, supplements sodium acetate
And operation, the system closed circuit (A) under stream acid adding adjusting condition and open circuit (B) are circulated completely to water outlet COD removal rates and production
Hydrogen amount compares；
Fig. 5 is the organic composite waste of tungsten of embodiment 1 after the single chamber MECs residence times run for 24 hours, supplements sodium acetate
And operation, the system closed circuit (A) under stream acid adding adjusting condition and open circuit (B) are circulated completely to water outlet pH and Conductivity Ratio
Compared with；
Fig. 6 is the organic composite waste of tungsten of embodiment 1 after the single chamber MECs residence times run for 24 hours, supplements sodium acetate
And circulate completely operation, stream acid adding adjusting condition under system closed circuit (A) and open circuit (B) to water outlet metal separation with
Free biomass compares.
In figure：1 nitrogen；The organic composite waste of 2 tungstens；The organic composite waste of tungsten of 3 reflux；The organic mixing of 4 tungstens is useless
Water is intake；5 water pumps；6 fluid flowmeters；7 water inlets；8MECs reactors；9 water outlets；10 outside small power supplies；11 data acquire
System；12 resistance；13 reference electrodes；14 cathode stainless (steel) wires；15 anode stainless (steel) wires；16 Hydrogen collection bags；17 carbon felt cathodes；
18 carbon felt anodes.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
Embodiment 1
Step 1：It builds and assembles single chamber tubular MECs, as shown in Figure 1：Tubular MECs is organic glass material, outside packet
One layer of tinfoil is wrapped up in, for being protected from light.Wherein, outer diameter 34.0cm, high 45.0cm, total volume 40.8L.Reactor is equipped with internal diameter
The head space of 18.0cm, high 2.0cm, volume 0.5L；The collection airbag that maximum volume is 1.0L is installed at head space；In cylindrical base
Water inlet pipe equipped with internal diameter 1.0cm is equipped with the outlet pipe of internal diameter 1.0cm at top.Anode carbon felt be 69.2cm × 40cm ×
1cm, cathode carbon felt are 56.6cm × 40cm × 1cm, and carbon felt is removed with the immersion of 1.0M NaOH and 1.0M HCl solutions for 24 hours successively
Surface impurity is removed, is in neutrality later with deionized water cleaning and dipping to water；Anode conducting stainless (steel) wire (304,14 mesh) size is
69.2cm × 40cm, cathode stainless (steel) wire size are 56.6cm × 40cm.MECs effective working volumes after installation are 38L.
Step 2：External power is connected to by the small extrernal resistances of 10 Ω in circuit, and electricity is collected by computer and data collecting system
Hinder two groups of voltage and calculating current；Cathode potential is collected according to reference electrode, and anode electricity can be calculated according to cathode potential
Gesture.
Step 3：Prepare water inlet：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,1200mg/
LCH3COONa,383mg/L(NH4)2SO4,13.6mg/LKH2PO4, 12.5mL/L mineral elements and 12.5mL/L vitamins；Its
In, mineral element includes 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；0.1g/
LCaCl2·2H2O；0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/L CuSO4·5H2O；0.01g/LKAl
(SO4)2·12H2O；0.01g/LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes
5.0g/L vitamin B1；5.0g/L vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；
2.0g/L vitamin B11；2.0g/L biotin；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；Three second of 1.5g/L amino
Acid.38L nutrient solutions are persistently exposed into nitrogen, are pumped into MECs, while being inoculated with sewage treatment plant clarifying basin sludge 100g (Dalian Ling Shui
River sewage treatment plant).
Step 4：Reactor is placed under room temperature (20-25 DEG C) to the enrichment and domestication for carrying out electro-chemical activity bacterium, applies electricity
0.5V is pressed, 100 Ω of extrernal resistance is connected, solution is not pumped into during domestication.When electric current drops to 0.02mA or less, that is, complete a week
Phase, and add above-mentioned nutrient solution, when continuous three periodic systems electric current is stable and repeats, show the domestication of electro-chemical activity bacterium at
Work(.
Step 5：Prepare solution：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,
1200mg/LCH3COONa,383mg/L(NH4)2SO4,13.6mg/LKH2PO4, 12.5mL/L mineral elements and
12.5mL/L vitamins；Wherein, 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；
0.1g/LCaCl2·2H2O；0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/LCuSO4·5H2O；0.01g/LKAl
(SO4)2·12H2O；0.01g/LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes
5.0g/L vitamin B1；5.0g/L vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；
2.0g/L vitamin B11；2.0g/L biotin；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；Three second of 1.5g/L amino
Acid.The initial pH for adjusting tungsten organic liquid mixture is 3.0, conductivity 3.0mS/cm, MECs is pumped into after exposing nitrogen, in waterpower
Stop lower operation for 24 hours；
Step 6：Since hydraulic retention cannot completely remove tungsten under for 24 hours, and organic carbon source is insufficient, the raised pH of water outlet
Water outlet is added complete circular flow after 150mg/L sodium acetates by the problems such as reducing the deposition of tungsten, and every 0.5h streams plus H2SO4
(23.7 μM) regulation and control pH.
Step 7：Progress parallel with step 6, runs MECs control reactors in the open circuit condition, and carbon source supplement and stream add
It is sour with closed circuit condition when identical, effect of the comparison loop electric current to reactor runnability accordingly.
Step 8：Every W (VI), Mo (VI) concentration in 2h analysis water outlets, tungsten metal recovery rate is calculated；It analyzes simultaneously
Water pH, conductivity, free biomass；H is analyzed every 12h2Content, water outlet COD contents.Calculate tungsten recovery rate (αW, %), molybdenum return
Yield (αMo, %), tungsten separation (ε), water outlet COD removal rates (α, %), reducing metal energy efficiency (ηMetal, %), production hydrogen
Energy efficiency (ηHydrogen, %) and as shown in formula (5)-(10).
In formula：C0,WWith C0,Mo、Ct,WWith Ct,MoW when respectively the organic composite waste of tungsten is initial and run time t
(VI), Mo (VI) concentration (g/L)；C0,CODWith Ct,CODCOD when respectively the organic composite waste of tungsten is initial and run time t
Concentration (g/L)；nH2For run time t when MECs generate H2It measures (mol)；MW、MMo、MO2Respectively tungsten, molybdenum and oxygen is opposite
Atom or molecular mass (g/mol)；V is the effective working volume (L) of MECs；ΔHH2For H2The combustion heat (J/mol)；ΔGsFor mark
This free energy (J/mol) of the jeep of sodium acetate under the conditions of standard；EW、EMoFor the standard electrode potential (V) of reduction W (VI), Mo (VI)；E is
MECs applied voltages (V)；I is the electric current (A) in the circuits MECs；T is reactor run time (s)；2 be the amount W of unit substance
(VI), the electron number (mol/mol) that Mo (VI) reduction obtains；4 electron number (the mol/ obtained for the oxygen of the amount of unit substance
mol)；96485 be Faraday constant (C/mol e-)。
As a result：MECs descends tungsten recovery rate 66.2-73.7%, the molybdenum recovery 74.1- of stable operation in the residence time for 24 hours
76.5%, water outlet COD removal rates 88.6-92.7% (Fig. 2A)；Hydrogen output 0.003m3/m3/ d, metal separation are 0.38 left
Right (Fig. 2 B)；Corresponding anode potential is 0.03V, and cathode potential is -0.48V, and loop current is stablized in 0.35A/m3(Fig. 2 C)；
It is discharged pH to stablize 6.1, water outlet conductivity is 0.71-0.74mS/cm (Fig. 2 D).
Thoroughly to remove and recycling tungsten, makes water outlet metal and content of organics qualified discharge, the residence time is run for 24 hours
Water outlet add after 150mg/L sodium acetates that cycle continues to run with completely, while every 0.5h streams plus a small amount of H2SO4(23.7 μM) tune
Control pH.When proceeding to 36h, tungsten recovery rate is up to 95%, and molybdenum recovery is up to 98% (Fig. 3 A), hydrogen output 0.0028m3/
m3/ d, although water outlet COD removal rates are reduced to 62.5% (Fig. 4 A), but absolute magnitude is increased, until when run time 48h, is gone out
While water tungsten is completely removed and recycled (Fig. 3 A), hydrogen 0.0026m is produced3/m3/ d (Fig. 4 A), COD removal rates (are schemed up to 97.1%
4A)；Energy efficiency for reducing metal is 26.6 ± 0.3%, and the energy efficiency for producing hydrogen is 4.9 ± 0.1%；Again make
With the organic composite waste water inlet of tungsten, reactor (48-96h), the operation result repeated (Fig. 3 A and 4A) are run again.
To sum up, the organic composite waste of tungsten passes through through the postrun water outlet for 24 hours of MECs residence times disposably adds 150mg/L sodium acetates
For 24 hours, process streams add a small amount of acid to adjust for complete circular flow afterwards, and final outflow water tungsten content is only 0.8mg/L and 0.6mg/ respectively
L, COD only remain 30mg/L or so, and organic matter reaches country-level emission standard A (GB18918-2002), and metal concentration is less than
Direct emission waste strength limit value (GB21/1627-2008).In the open circuit control of identical run time 36h, the tungsten rate of recovery
It is only respectively 27.9% and 35.1% (Fig. 3 B), COD removal rates are only 29.6% (Fig. 4 B).The above results clearly show, although
Also acid stream adduction organic carbon source supplement, system no current significantly reduce tungsten metal recovery, organic matter removal and production hydrogen effect
Fruit, show loop current and acid stream plus, supplement organic carbon thoroughly remove that tungsten and organic carbon, by-product hydrogen has simultaneously to system
Important function.In addition, the water outlet pH of 36h is 5.1-5.2, conductivity is 0.48mS/cm (Fig. 5 A), hence it is evident that is less than non-acid adding tune
6.1 and 0.74mS/cm (Fig. 2 D) when section；Water outlet pH is higher than 2.4 in open circuit control, and conductivity is less than open circuit control
3.5mS/cm (Fig. 5 B), be mainly due to it is closed circuit under the conditions of higher tungsten removal rate and liberation of hydrogen consume more proton hydrogen (formula
(2)-(4))；Meanwhile more tungsten is removed from liquid phase, reduces the conductivity of solution naturally.It is closed circuit and open circuit water outlet
Free biomass difference is little, between 5.9-7.6mg/L (Fig. 6), shows MECs electrode biomembrane stable operations.And closed circuit condition
Under separation be zero, show the complete co-deposition (Fig. 6 A) of tungsten.
It is above-mentioned the experimental results showed that, MECs of the invention can thoroughly handle the organic composite waste of tungsten, and to synchronize recycling valuable
Metal and by-product hydrogen.The present invention had both overcome the composite waste that dual chamber MECs handles organic and tungsten or other metals
Limitation, and thoroughly recycle valuable metal, organics removal and by-product hydrogen, be the organic composite waste of tungsten recycling and
Energy provides practicable new way, has preferable environmental pollution improvement, recycling and energy effect, has both ring
Border and ecological benefits, Social benefit and economic benefit.
Claims (10)
1. the method that a kind of organic composite waste of clean thorough processing tungsten synchronizes recycling metal and by-product hydrogen, feature exist
In steps are as follows：
Using single chamber tubular MECs as reactor, anode and cathode is all made of carbon felt as electrode material, and stainless (steel) wire supports and divides
Every anode, cathode, while stainless (steel) wire as electronics export/introduction part, the spacing of cathode and anode is 1.0cm；Reactor
The interior organic composite waste of tungsten, with the mixed solution that sodium acetate and tungstates, molybdate form, pH is 3.0~8.0, conductivity
For 0.3~3mS/cm；Anode and cathode is connected by external resistance with data gathering system and external power；Applied voltage 0.3~
1.2V, external resistance are 10~1000 Ω, and reactor is discharged while complete circular flow after adding organic matter, anode potential
For -0.4~0.2V vs. standard hydrogen electrodes；Cathode potential is -0.9~-0.1V vs. standard hydrogen electrodes；It keeps detesting in reactor
Oxygen environment.
2. according to the method described in claim 1, it is characterized in that, the concentration of tungsten, molybdenum and organic matter is equal in the solution of reactor
For 1~2500mg/L.
3. method according to claim 1 or 2, which is characterized in that it is sodium acetate or Portugal that organic matter is added in reactor water outlet
Grape sugar, additive amount are 50~1000mg/L.
4. method according to claim 1 or 2, which is characterized in that it is sodium acetate or Portugal that organic matter is added in reactor water outlet
Grape sugar, additive amount is 50~1000mg/L, while complete circular flow, stream plus a small amount of sulfuric acid or hydrochloric acid, and additive amount is 2.6~
47.4μM。
5. according to the method described in claim 3, it is characterized in that, it is sodium acetate or grape that organic matter is added in reactor water outlet
Sugar, additive amount is 50~1000mg/L, while complete circular flow, stream plus a small amount of sulfuric acid or hydrochloric acid, and additive amount is 2.6~
47.4μM。
6. according to the method described in claim 1,2 or 5, which is characterized in that the organic composite waste ingredient of the tungsten is：This
The composite waste of invention is into water constituent：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,1200mg/
LCH3COONa,383mg/L(NH4)2SO4,13.6mg/LKH2PO4；12.5mL/L mineral elements；12.5mL/L vitamins；Wherein,
Mineral element includes 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；0.1g/
LCaCl2·2H2O；0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/LCuSO4·5H2O；0.01g/LKAl
(SO4)2·12H2O；0.01g/LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes
5.0g/L vitamin B1；5.0g/L vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；
2.0g/L vitamin B11；2.0g/L biotin；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；Three second of 1.5g/L amino
Acid.
7. according to the method described in claim 3, it is characterized in that, the organic composite waste ingredient of the tungsten is：The present invention
Composite waste be into water constituent：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,1200mg/LCH3COONa,
383mg/L(NH4)2SO4,13.6mg/LKH2PO4；12.5mL/L mineral elements；12.5mL/L vitamins；Wherein, mineral element packet
Include 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；0.1g/LCaCl2·2H2O；
0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/LCuSO4·5H2O；0.01g/LKAl(SO4)2·12H2O；0.01g/
LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes 5.0g/L vitamin Bs1；5.0g/L
Vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；2.0g/L vitamin B11；2.0g/L dimension
Raw element H；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；1.5g/L aminotriacetic acid.
8. according to the method described in claim 4, it is characterized in that, the organic composite waste ingredient of the tungsten is：The present invention
Composite waste be into water constituent：178mg/LNa2WO4·2H2O,266mg/LNa2MoO4·2H2O,1200mg/LCH3COONa,
383mg/L(NH4)2SO4,13.6mg/LKH2PO4；12.5mL/L mineral elements；12.5mL/L vitamins；Wherein, mineral element packet
Include 3.0g/LMgSO4；0.5g/LMnSO4·H2O；1.0g/LNaCl；0.1g/LFeSO4·7H2O；0.1g/LCaCl2·2H2O；
0.1g/LCoCl2·6H2O；0.13g/LZnCl2；0.01g/LCuSO4·5H2O；0.01g/LKAl(SO4)2·12H2O；0.01g/
LH3BO3；0.024g/LNiCl2·6H2O and 0.024g/LNa2WO4·2H2O；Vitamin includes 5.0g/L vitamin Bs1；5.0g/L
Vitamin B2；5.0g/L vitamin B3；5.0g/L vitamin B5；10.0g/L vitamin Bs6；2.0g/L vitamin B11；2.0g/L dimension
Raw element H；5.0g/L p-aminobenzoic acid；5.0g/L lipoic acid；1.5g/L aminotriacetic acid.
9. according to the method described in claim 1,2,5,7 or 8, which is characterized in that it is dirty that MECs is inoculated with sewage treatment plant's clarifying basin
Bacterium source of the mud as domestication electro-chemical activity microorganism；The pH of the clarifying basin sludge is 7.0~8.0；Conductivity be 1.0~
2.0mS/cm；Suspension solid content is 10~20g/L；COD is 100~1000mg/L.
10. according to the method described in claim 6, it is characterized in that, MECs inoculation sewage treatment plant's clarifying basin sludge is as tame and docile
Change the bacterium source of electro-chemical activity microorganism；The pH of the clarifying basin sludge is 7.0~8.0；Conductivity is 1.0~2.0mS/cm；
Suspension solid content is 10~20g/L；COD is 100~1000mg/L.
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