CN110386700A - A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization - Google Patents
A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization Download PDFInfo
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- CN110386700A CN110386700A CN201810370963.9A CN201810370963A CN110386700A CN 110386700 A CN110386700 A CN 110386700A CN 201810370963 A CN201810370963 A CN 201810370963A CN 110386700 A CN110386700 A CN 110386700A
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- waste water
- sulfur
- old
- containing waste
- battery
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 55
- 239000011593 sulfur Substances 0.000 title claims abstract description 54
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 238000011284 combination treatment Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 12
- 238000011282 treatment Methods 0.000 claims abstract description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 34
- 239000000706 filtrate Substances 0.000 claims description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 34
- 239000005864 Sulphur Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 230000000295 complement effect Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 10
- 238000004064 recycling Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carboxylate methyl ester Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to waste water and old and useless battery Combined Treatment fields, the combination treatment method for specifically disclosing a kind of electric discharge of old and useless battery and sulfur-containing waste water desulfurization by the battery pack of waste and old lithium ion battery or is disassembled obtained battery cell and is placed in sulfur-containing waste water and discharged；Battery pack or battery cell after isolated electric discharge and the water outlet after desulfurization process；Contain H in the sulfur-containing waste water2S、HS‑、S2‑At least one of.The method achieve complementary energy in waste lithium cell to make full use of, high-efficiency cleaning, overcomes the disadvantage for vulcanizing hydrogen methods in conventional process industrial wastewater, simple and practical, economically feasible, is suitble to industrialized production.
Description
Technical field
The invention belongs to waste and old lithium ion battery recycling field, it is related specifically to complementary energy echelon benefit in a kind of waste lithium cell
With the method for hydrogen sulfide in processing waste water.
Background technique
With the high speed development of modernization science and technology, social energy and environment ecological pollution problem becomes increasingly conspicuous, various discarded
Battery is to the pollution problem of environment and ecology at the focus of social concerns.And nickle cobalt lithium manganate ion battery is due to capacity
The features such as height, stable cycle performance, high workbench voltage, is widely used in power battery and energy-storage battery, and power and storage
It can the typically larger than conventional compact battery of demand of the battery to battery material.Therefore, in the following 3-5, will have a large amount of useless
Old lithium ion battery is scrapped, and recycling is carried out to it has very high social value.
However, waste and old lithium ion battery still remains substantial portion of voltage, in order to ensure personnel and equipment safety must be into
Row discharge operation is down to residual voltage within safe range.The recycling focus of waste and old lithium ion battery is concentrated mainly at present
Less to leading portion discharge treatment attention rate on back segment Product recycling, the NaCl solution for generalling use 5-10% carries out discharge operation.
It is mentioned in " based on the lithium ion battery high efficiente callback separating technology in waste mobile phone " announced such as 106558739 A of Chinese patent CN
And discharge operation is carried out before battery crushing dismantling, 48h, which is impregnated, using 10% NaCl salting liquid reaches to battery residual voltage
To the requirement disassembled safely.Carrying out battery discharge operation using the NaCl salting liquid of 5-10% can be such that old and useless battery residual voltage reaches
To the requirement disassembled safely, but discharge rate is slower, and generally to impregnate more than for 24 hours makes the near 1V of residual voltage hereinafter, and can draw
Enter the chloride ion for being difficult to remove and enter in leachate and subsequent impurity and purification and Product recycling stage are affected.In for another example
" method for recycling metal in useless nickle cobalt lithium manganate battery and preparing nickle cobalt lithium manganate " that 104538695 A of state patent CN is announced,
Carry out the discharge operation of 1-3h, OH to battery at room temperature using the NaOH solution of 0.1-1mol/L before battery crushing dismantling-
Compare Cl in aqueous solution-It is more difficult to discharge, will certainly reduces the discharge rate and discharge effect of battery using NaOH solution, and
Water quality is polluted in the leakage that NaOH can cause corrosion to lead to electrolyte to aluminum hull when handling soft-package battery.
To sum up, in existing lithium ion recycling discharge process, also generally existing discharge time is long (it is generally necessary to more than for 24 hours),
And discharge effect is undesirable, is only capable of being discharged to 0.7V or so, and in treatment process, easily corrode battery pack, leads to the electricity of severe toxicity
Solution liquid leaks in electric discharge system, totally unfavorable to personnel and Environmental security.
In addition, containing more negative divalent sulfur in existing waste water, for example, hydrogen sulfide category extremely toxic substance, in industrial wastewater especially
It is the hydrogen sulfide that the waste water of paper industry generation contains higher concentration, if can be to ecological environment and human health without processing
Bring significant damage.The processing method of hydrogen sulfide generally has closed collection process, physisorphtion, oxidizing process and life in waste water
The problems such as object method etc., these methods are all low there is complicated for operation or recovery efficiency, and easily cause secondary pollution.
Summary of the invention
Discharge time existing for charging method for the existing lithium ion battery recycling of solution is long, discharge effect is undesirable, with
And industrial wastewater, containing technical problems such as sulphur pollutions, the present invention innovatively proposes a kind of completely new Combined Treatment thinking, reaches
Under the premise of being substantially discharged, and remove the low price sulphur in industrial wastewater.
The combination treatment method of a kind of electric discharge of old and useless battery and sulfur-containing waste water desulfurization, by the battery pack of waste and old lithium ion battery
Or it is disassembled obtained battery cell and is placed in sulfur-containing waste water and discharged；Battery pack or battery cell after isolated electric discharge,
And the water outlet after desulfurization process；
Contain H in the sulfur-containing waste water2S、HS-、S2-At least one of.
The present invention passes through the study found that discharge in sulfur-containing waste water of the present invention, by oxide-reduction method,
Realize the electric discharge of waste and old lithium ion battery residual electricity.By the method for the invention, it can be achieved that efficient discharge, the study found that this hair
Not only discharge time is obviously shortened bright method, additionally aids and reaches thoroughly electric discharge (being discharged to 0V), is only capable of compared to existing method
The discharge effect for reaching 0.7V, has a clear superiority.The method of the present invention will not also corrosion cell group (or battery cell) device, put
Personnel and environment will not be caused unfavorable shadow by electrolyte (such as the carboxylate methyl ester class) leakage that will not make severe toxicity in electric process
It rings, the method for the present invention is truly realized efficiently, cleanly the electric discharge for making waste and old lithium ion battery, is conducive to industrial practical application.This
Outside, the method for the present invention is a kind of removing thinking of completely new sulfur-containing waste water, and by the remaining electric quantity using old and useless battery, removing is useless
Harmful sulphur ingredient in water.The method of the present invention realizes the Combined Treatment of waste water and old and useless battery for the first time.
Preferably, the sulfur-containing waste water before for discharging, carries out following pretreatment in advance:
Sulfur-containing waste water to be processed is separated by solid-liquid separation through first and obtains the first filtrate；Adsorbent is added into the first filtrate,
Second is carried out after absorption to be separated by solid-liquid separation, and obtains the second filtrate, the medium of electric discharge is used as using the second filtrate as the sulfur-containing waste water.
Preferably, adsorbent is active carbon, polyacrylamide, wheat-germ meal, one or more of carbon molecular sieve.
Research also found, controls the concentration in the low price sulphur (negative divalent sulfur) of suitable solution, helps further to be promoted
Discharging efficiency further improves discharge effect.
Preferably, the concentration of negative divalent total sulfur content is not less than 5wt% in sulfur-containing waste water；Preferably 5~20wt%.In
Under the preferred concentration, it can be discharged to 0V, and the time for being discharged to 0V is shorter.Furthermore, it can be achieved that the sulfur-containing waste water of the high concentration
Processing.
The present inventor's research it has also been found that, to the temperature in discharge process, controlling the pH of discharge process, discharge process and
The operation such as conductive material is added in sulfur-containing waste water, can further improve discharge effect, shortens discharge time, improves discharge effect.
Preferably, the pH of the sulphur waste water is 1-10.5.
Further preferably, the pH of the sulphur waste water is 1-6.The sulfur-containing waste water is acidity, the negative divalent in system
Sulphur mainly exists in the form of H2S, and combination treatment method through the invention removes H2S therein, in addition, also achieving useless
Used batteries are substantially discharged.
Preferably, containing H2S, after being discharged, also collecting in the sulfur-containing waste water and obtaining H2 and sulphur.
Further preferably, the pH of the sulphur waste water is 8-10.5.The sulfur-containing waste water is alkalinity, minus two in system
Valence sulphur is mainly with HS-、S2-Form exist.The study found that discharge effect and waste water desulfurization effect are equal under the alkaline condition
More excellent, the electric discharge for the treatment of process is more thorough, and treatment process will not generate H2S.
Preferably, containing HS in the sulfur-containing waste water-、S2-In, after being discharged, also collects and obtain sulphur.
Preferably, the temperature for controlling sulfur-containing waste water is 25-35 DEG C in discharge process；Preferably 25-30 DEG C.Described
The temperature of sulfur-containing waste water that is to say the temperature of discharge process.Control can further promote electric discharge under the preferred discharge temp
Efficiency further improves discharge effect, additionally aids improvement desulfurization effect.
It by adding conductive material in the sulfur-containing waste water of discharge process, can further improve discharge effect, promote electric discharge
Efficiency.
Preferably, the conductive material is at least one of graphite, graphite oxide, electrically conductive polyaniline.
Preferably, the volume fraction of the conductive material is 5-20% in the sulfur-containing waste water.
Preferably, the waste and old lithium ion battery is waste and old ternary power battery, cobalt acid lithium battery, LiMn2O4 electricity
Pond, one or more of ferric phosphate lithium cell.
Preferably, the battery pack, battery cell residual voltage be not less than 1V, preferably 3.8V~3.85V.
Discharge time of the invention can be controlled according to the sulfur content of actual waste water, when the discharge capacity of old and useless battery reaches
When 0V, the old and useless battery to be processed that can more renew, when the sulfur content in waste water reaches discharge standard, after emission treatment
Water outlet, and the sulfur-containing waste water to be processed more renewed.
A kind of preferred combination treatment method (in waste lithium cell complementary energy echelon using hydrogen sulfide in processing waste water side
Method), comprising the following steps:
1) primary filter is carried out to industrial sulfide hydrogen waste water and removes the bulky grain suspended matter that partial size is greater than 0.5mm, obtained
Primary filtrate；
2) adsorbent is added into primary filtrate, is separated by solid-liquid separation after stirring, and secondary filtrate is obtained；
3) secondary filtrate is poured into the device equipped with waste lithium cell, carries out exoelectrical reaction, it can through secondary filter after
The waste lithium cell and elemental sulfur being discharged are respectively obtained,
The device equipped with waste lithium cell is the closed container with gas collecting apparatus, and the device is also with useful
The concentration of hydrogen sulfide survey meter of H2S concentration in detection water；
In discharge process, hydrogen is obtained in gas collecting apparatus, wherein waste lithium cell power transmission pond recovery process；
4) concentration of hydrogen sulfide in waste water before and after the processing is measured, waste water is (after desulfurization process after the sufficient time is reacted
Water outlet) in concentration of hydrogen sulfide can reach requirement of the industrial wastewater discharge to concentration of hydrogen sulfide；The place of discharge standard is not reached
Water outlet recycled after the reason circular treatment into step 1).
Bulky grain suspended matter described in step 1 refers to partial size in above particle of 0.5mm.
Adsorbent described in step 2 is active carbon, polyacrylamide, wheat-germ meal, one or more of carbon molecular sieve.
Device described in step 3 is equipped with the closed system of gas collecting apparatus, and the gas purity uses gas purity
Analyzer analysis gained.
The concentration of hydrogen sulfide is all made of concentration of hydrogen sulfide survey meter and is measured before and after the processing described in step 4, sufficiently
Reaction time refers to that the time should be greater than 12h.
Currently preferred method realizes that the hydrogen manufacturing of hydrogen sulfide in waste water is solid using simple chemistry and electrochemical method
Sulphur, while realizing that the echelon of waste lithium cell complementary energy utilizes, substantially compared to other method costs for handling hydrogen sulfide in waste water
It reduces and without secondary pollution.
The beneficial effects of the present invention are:
The present invention is applied to the negative divalent sulfur in processing industrial wastewater using complementary energy in waste lithium cell (for example, vulcanization
Hydrogen), it realizes that solid sulphur, the hydrogen sulfide can also be achieved hydrogen manufacturing, the sulphur of generation and the recyclable recycling of the hydrogen of preparation, is discarded
Object regeneration provides a kind of trusted path of environmental protection low cost.
The discharge effect of waste lithium cell after having reacted is thorough, and discharge time is short；Power transmission pond recovery process, tears open after processing
It no longer needs to carry out discharge operation before solution, the concentration of hydrogen sulfide, which meets discharge standard, in processed industrial wastewater can be re-used as work
Industry water, resource circulation utilization greatly reduce processing cost.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Case is embodied
For the ease of the simpler understanding present invention of those skilled in the art, now in conjunction with specific implementation case to the present invention
It is described further, however, it is to be understood that the present invention is not limited to these embodiments.
Old and useless battery is 523 type waste and old lithium ion batteries
Embodiment 1
As shown in Figure 1, the present invention is method of the complementary energy echelon using hydrogen sulfide in processing waste water, Industry Waste in a kind of battery
(in waste water, the existence form of sulphur is S to water2-And HS-, the total mass fraction of sulphur is in 9.6wt.%) and it goes out in advance through primary filter
Partial size is greater than the suspended matter of 0.5mm；Secondary filter is then carried out, adsorbent centrifugal filtration is added when secondary filter, and to remove partial size small
Secondary filtrate is obtained in the suspended matter of 0.5mm.The pH value of secondary filtrate is sent into dress in 7.3 or so (7.3 ± 0.1), secondary filtrate
Have in the reaction unit of waste lithium cell and (waste lithium cell is immersed in secondary filtrate) and carries out discharge treatment, exoelectrical reaction
The gas of generation is collected in journey to obtain high-purity hydrogen, the sufficient time reacted after the suspension of the sulphur containing solid-state is obtained by filtration
Liquid obtains elemental sulfur using centrifugal filtration to suspension, and the waste lithium cell after fully reacting send recovery process.Concrete operations step
It is rapid as follows:
1) primary filter is carried out to industrial sulfide hydrogen waste water and removes bulky grain suspended matter of the partial size greater than 0.5mm and one
Point harmful substance obtains primary filtrate；
2) adsorbent activity carbon is added into primary filtrate through mechanical stirring certain time, the rear secondary centrifugal filtration of progress removes
Suspended matter of the partial size less than 0.5mm is gone to obtain secondary filtrate；
3) secondary filtrate is poured into the device (equipped with gas collecting apparatus) equipped with waste lithium cell through exoelectrical reaction, reaction
Time should be greater than 12h, can respectively obtain the waste lithium cell being discharged by filtering and containing the suspension of sulphur simple substance, hang to gained
Supernatant liquid carries out centrifugal filtration and obtains high purity elemental sulphur, high-purity hydrogen is obtained in gas collecting apparatus, wherein waste lithium cell power transmission pond
Recovery process；
4) concentration of hydrogen sulfide in waste water before and after the processing is measured, concentration of hydrogen sulfide in waste water after the sufficient time is reacted
It can reach requirement of the industrial wastewater discharge to concentration of hydrogen sulfide.Old and useless battery after the electric discharge residual voltage that is averaged is down to 0.3V hereinafter, comprehensive
Utilization rate of complementary energy is closed 90% or more, the H that treated is discharged2The content of S can be down to 0.5wt.% hereinafter, H2The synthesis of S is returned
Utilization rate is received 85% or more.
Embodiment 2
10L industrial wastewater is taken, obtains the secondary filtrate of no suspended substance to it after primary filter and secondary adsorption filtering
Sulfur content is measured as 9.6wt.%.Then secondary filtrate is poured into the obturator equipped with old and useless battery, old and useless battery
Initial voltage be 3.8~3.85V, add sulfuric acid to adjust filtrate pH value to 1 or so, at this time in solution sulphur with H2The form of S, HS-
In the presence of.Wherein sulfur content is measured as 0.73wt.% after electric discharge for 24 hours, old and useless battery is averaged residual voltage in 0.5V or so, right
It is 73% that gas ingredients in gas collecting apparatus, which carry out analysis hydrogen volume score, and hydrogen sulfide volume fraction is 25%.It can be seen that in acid
Property environment under have hydrogen sulfide gas be precipitated release.
Embodiment 3
10L industrial wastewater is taken, obtains the secondary filtrate of no suspended substance to it after primary filter and secondary adsorption filtering
Sulfur content is measured as 9.6wt.%.Then secondary filtrate is poured into the obturator equipped with old and useless battery, old and useless battery
Initial voltage be 3.8~3.85V.Adding sodium hydroxide adjusts filtrate pH value to 10 or so (10 ± 0.1), at this time in solution sulphur with
S2-Form exist.Wherein sulfur content is measured as 0.13wt.% after electric discharge for 24 hours, old and useless battery is averaged residual voltage in 0V
Left and right, carrying out analysis hydrogen volume score to the gas ingredients in gas collecting apparatus is 98%, and hydrogen sulfide gas is not detected.It can be seen that
It is precipitated and discharges without hydrogen sulfide gas under alkaline environment.
Comparative example 1
10L industrial wastewater is taken, obtains the secondary filtrate of no suspended substance to it after primary filter and secondary adsorption filtering
Sulfur content is measured as 9.6wt.%.The pH value of what filtrate of adding sodium hydroxide adjusting ability is then plus excessive to 10 or so
Water-soluble zinc sulfate stirring is static to be obtained by filtration afterwards without S for 24 hours2-Filtrate, then will be free of S2-Filtrate pour into equipped with waste and old
In the electric discharge device of battery, the initial voltage of old and useless battery is 3.8~3.85V.The old and useless battery residual voltage that is averaged exists after electric discharge for 24 hours
3.0V or so, carrying out analysis hydrogen volume score to the gas ingredients in gas collecting apparatus is 98%, and hydrogen sulfide gas is not detected.
Claims (9)
1. the combination treatment method of a kind of old and useless battery electric discharge and sulfur-containing waste water desulfurization, which is characterized in that by applying waste lithium ionic electricity
The battery pack in pond or the battery cell obtained through dismantling are placed in sulfur-containing waste water and discharge；Battery pack after isolated electric discharge or
Water outlet after battery cell and desulfurization process；
Contain H in the sulfur-containing waste water2S、HS-、S2-At least one of.
2. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that contain
In sulphur waste water, the concentration of negative divalent total sulfur content is not less than 5wt%；Preferably 5~20wt%.
3. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that institute
The pH for the sulphur waste water stated is 1-10.5；Preferably 8~10.5.
4. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that put
In electric process, the temperature for controlling sulfur-containing waste water is 25-35 DEG C；Preferably 25-30 DEG C.
5. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that institute
In the sulfur-containing waste water stated, also contain conductive material, the conductive material is graphite, graphite oxide, electrically conductive polyaniline, polypyrrole
At least one of.
6. the combination treatment method of old and useless battery electric discharge as claimed in any one of claims 1 to 5 and sulfur-containing waste water desulfurization, special
Sign is that the sulfur-containing waste water carries out following pretreatment before for discharging in advance:
Sulfur-containing waste water to be processed is separated by solid-liquid separation through first and obtains the first filtrate；Adsorbent is added into the first filtrate, is adsorbed
Second is carried out afterwards to be separated by solid-liquid separation, obtains the second filtrate, using the second filtrate as the sulfur-containing waste water, is situated between as the electric discharge
Matter.
7. the combination treatment method of old and useless battery electric discharge as claimed in claim 6 and sulfur-containing waste water desulfurization, which is characterized in that inhale
Attached dose is active carbon, polyacrylamide, wheat-germ meal, one or more of carbon molecular sieve.
8. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that institute
The waste and old lithium ion battery stated is waste and old ternary power battery, cobalt acid lithium battery, lithium manganate battery, one in ferric phosphate lithium cell
Kind is several；
Preferably, the battery pack, battery cell residual voltage be not less than 1V, preferably 3.8V~3.85V.
9. the combination treatment method of old and useless battery electric discharge as described in claim 1 and sulfur-containing waste water desulfurization, which is characterized in that institute
Contain H in the sulfur-containing waste water stated2S, specifically includes the following steps:
1) primary filter is carried out to industrial sulfide hydrogen waste water and removes the bulky grain suspended matter that partial size is greater than 0.5mm, obtain primary
Filtrate；
2) adsorbent is added into primary filtrate, is separated by solid-liquid separation after stirring, and secondary filtrate is obtained；
3) secondary filtrate is poured into the device equipped with waste lithium cell, carries out exoelectrical reaction, can distinguishes after through secondary filter
The waste lithium cell and elemental sulfur being discharged,
The device equipped with waste lithium cell is the closed container with gas collecting apparatus, and the device also has for examining
Survey the concentration of hydrogen sulfide survey meter of H2S concentration in water；
In discharge process, hydrogen is obtained in gas collecting apparatus, wherein waste lithium cell power transmission pond recovery process；
4) concentration of hydrogen sulfide in waste water before and after the processing is measured, waste water (going out after desulfurization process after the sufficient time is reacted
Water) in concentration of hydrogen sulfide can reach requirement of the industrial wastewater discharge to concentration of hydrogen sulfide；After the processing for not reaching discharge standard
Water outlet recycled into step 1) circular treatment.
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