CN110386700B - Combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization - Google Patents
Combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 84
- 239000011593 sulfur Substances 0.000 title claims abstract description 83
- 239000002351 wastewater Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000010926 waste battery Substances 0.000 title claims abstract description 37
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 21
- 230000023556 desulfurization Effects 0.000 title claims abstract description 21
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 41
- 239000002699 waste material Substances 0.000 claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims description 38
- 238000007599 discharging Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000000843 powder Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 3
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 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
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Classifications
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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
- 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
Abstract
The invention relates to the field of combined treatment of waste water and waste batteries, and particularly discloses a combined treatment method for waste battery discharge and sulfur-containing waste water desulfurization, wherein a battery pack of a waste lithium ion battery or a battery monomer obtained by disassembly is placed in the sulfur-containing waste water for discharge; separating to obtain a discharged battery pack or battery monomer and the effluent after desulfurization treatment; the sulfur-containing wastewater contains H2S、HS‑、S2‑At least one of (1). The method realizes full utilization of residual energy in the waste lithium batteries, is efficient and clean, overcomes the disadvantages of the traditional method for treating hydrogen sulfide in industrial wastewater, is simple, practical, economical and feasible, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of waste lithium ion battery recovery, and particularly relates to a method for treating hydrogen sulfide in wastewater by gradient utilization of residual energy in waste lithium batteries.
Background
With the rapid development of modern technology, the pollution problem of social energy and environment ecology becomes more and more prominent, and the pollution problem of various waste batteries to the environment and the ecology becomes the focus of social attention. The nickel cobalt lithium manganate ion battery is widely applied to power batteries and energy storage batteries due to the characteristics of high capacity, stable cycle performance, high working platform voltage and the like, and the requirements of the power batteries and the energy storage batteries on battery materials are generally greater than those of conventional small batteries. Therefore, a large amount of waste lithium ion batteries are scrapped in the future 3-5 years, and the recycling of the waste lithium ion batteries has high social value.
However, the waste lithium ion battery still has a considerable amount of voltage, and the residual voltage is reduced to within the safe range by performing discharge operation to ensure the safety of personnel and equipment, the recovery focus of the waste lithium ion battery is mainly focused on the recovery of the rear-stage product, the attention on the discharge treatment of the front stage is low, 5-10% NaCl solution is generally adopted for performing discharge operation, for example, in the 'high-efficiency recovery and separation process based on the lithium ion battery in the waste mobile phone' published by Chinese patent CN 106558739A, the discharge operation is performed before the battery is broken and disassembled, 10% NaCl salt solution is used for soaking for 48h until the residual voltage of the battery reaches the requirement of safe disassembly, 5-10% NaCl salt solution is adopted for performing battery discharge operation to ensure that the residual voltage of the waste battery reaches the requirement of safe disassembly, but the discharge rate is low, the residual voltage is generally soaked for more than 24h to be below 1V, chloride ions which are difficult to remove are introduced into the battery to enter the subsequent impurity removal purification and product recovery stage, and the influence is caused by using OH 633/1 h of NaOH solution before the breaking and OH 633/2 h of the lithium nickel cobalt manganese oxide battery is performed at room temperature, for the battery, for example, CN 104538695A-In aqueous solution to Cl-More difficult discharge adopts the NaOH solution and will reduce the discharge rate and the discharge effect of battery certainly, and NaOH can cause the corruption to the aluminum hull and lead to revealing of electrolyte to pollute quality of water when handling laminate polymer battery.
In summary, in the conventional lithium ion recovery discharge process, the discharge time is long (generally, more than 24 hours), the discharge effect is not ideal, the discharge can only be about 0.7V, and the battery pack is easily corroded in the treatment process, so that the highly toxic electrolyte is leaked into a discharge system, which is very harmful to personnel and environment safety.
In addition, the existing wastewater contains more negative divalent sulfur, for example, hydrogen sulfide belongs to a highly toxic substance, and the industrial wastewater, especially the wastewater generated by the paper industry, contains higher concentration of hydrogen sulfide, which brings great harm to the ecological environment and human health if not treated. The method for treating hydrogen sulfide in wastewater generally comprises a closed collection treatment method, a physical adsorption method, an oxidation method, a biological method and the like, and the methods have the problems of complicated operation, low recovery efficiency and the like and are easy to cause secondary pollution.
Disclosure of Invention
In order to solve the technical problems of long discharge time, unsatisfactory discharge effect, sulfur pollution of industrial wastewater and the like of the conventional discharge method for recycling the lithium ion battery, the invention innovatively provides a brand-new combined treatment idea, and low-price sulfur in the industrial wastewater is removed on the premise of full discharge.
A combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization comprises placing a battery pack of a waste lithium ion battery or a battery monomer obtained by disassembly in sulfur-containing wastewater for discharge; separating to obtain a discharged battery pack or battery monomer and the effluent after desulfurization treatment;
the sulfur-containing wastewater contains H2S、HS-、S2-At least one of (1).
According to research, the invention discovers that the discharge is carried out in the sulfur-containing wastewater, and the discharge of the residual electric quantity of the waste lithium ion battery is realized by an oxidation-reduction method. The method can realize high-efficiency discharge, and researches show that the method not only obviously shortens the discharge time, but also is beneficial to achieving complete discharge (discharge to 0V), and has obvious advantages compared with the existing method which can only achieve the discharge effect of 0.7V. The method of the invention can not corrode the battery pack (or single battery) device, can not cause leakage of highly toxic electrolyte (such as methyl carboxylate) in the discharging process, and can not cause adverse effects on personnel and environment. In addition, the method is a brand-new idea for removing the sulfur-containing wastewater, and harmful sulfur components in the wastewater are removed by utilizing the residual electricity of the waste batteries. The method realizes the combined treatment of the waste water and the waste battery for the first time.
Preferably, the sulfur-containing wastewater is pretreated by the following steps before being used for discharging:
carrying out first solid-liquid separation on sulfur-containing wastewater to be treated to obtain first filtrate; adding an adsorbent into the first filtrate, performing second solid-liquid separation after adsorption to obtain a second filtrate, and taking the second filtrate as the medium for discharging the sulfur-containing wastewater.
Preferably, the adsorbent is one or more of activated carbon, polyacrylamide, wheat germ powder and carbon molecular sieve.
It has been found that controlling the concentration of low-valent sulfur (negative divalent sulfur) in a suitable solution helps to further increase the discharge efficiency and further improve the discharge effect.
Preferably, the concentration of the negative divalent total sulfur in the sulfur-containing wastewater is not less than 5 wt%; preferably 5 to 20 wt%. At this preferred concentration, discharge to 0V is possible, with a shorter time to discharge to 0V. In addition, the treatment of the high-concentration sulfur-containing wastewater can be realized.
The inventor also finds that the discharging effect can be further improved, the discharging time can be shortened, and the discharging effect can be improved by controlling the pH value in the discharging process, the temperature in the discharging process, adding a conductive material in the sulfur-containing wastewater and the like in the discharging process.
Preferably, the pH value of the sulfur waste water is 1-10.5.
Further preferably, the pH of the sulfur waste water is 1 to 6. The sulfur-containing wastewater is acidic, the negative divalent sulfur in the system mainly exists in the form of H2S, the H2S in the wastewater is removed by the combined treatment method, and in addition, the full discharge of waste batteries is realized.
Preferably, the sulfur-containing wastewater contains H2S, and after discharge, H2 and sulfur are collected.
Further preferably, the pH value of the sulfur waste water is 8-10.5. The sulfur-containing wastewater is alkaline, and the negative divalent sulfur in the system mainly comprises HS-、S2-Exist in the form of (1). Research shows that the discharge effect and the wastewater desulfurization effect are better under the alkaline condition, the discharge in the treatment process is more thorough, and H2S is not generated in the treatment process.
Preferably, theContaining HS in the sulfur-containing wastewater-、S2-After the discharge, sulfur was also collected.
Preferably, in the discharging process, the temperature of the sulfur-containing wastewater is controlled to be 25-35 ℃; preferably 25-30 ℃. The temperature of the sulfur-containing wastewater is also the temperature of the discharging process. Controlling at the preferred discharge temperature can further improve the discharge efficiency, further improve the discharge effect, and also contribute to improving the desulfurization effect.
Through adding conductive material in the sulphur-containing waste water of discharge process, can further improve the effect of discharging, promote discharge efficiency.
Preferably, the conductive material is at least one of graphite, graphite oxide and conductive polyaniline.
Preferably, in the sulfur-containing wastewater, the volume fraction of the conductive material is 5-20%.
Preferably, the waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery and a lithium iron phosphate battery.
Preferably, the residual voltage of the battery pack and the battery unit is not lower than 1V, and preferably 3.8V-3.85V.
The discharge time of the invention can be controlled according to the sulfur content of the actual wastewater, when the discharge capacity of the waste battery reaches 0V, the waste battery to be treated can be replaced, when the sulfur content in the wastewater reaches the discharge standard, the treated effluent is discharged, and the new sulfur-containing wastewater to be treated is replaced.
A preferable combined treatment method (a method for treating hydrogen sulfide in wastewater by gradient utilization of residual energy in waste lithium batteries) comprises the following steps:
1) carrying out primary filtration on the industrial hydrogen sulfide-containing wastewater to remove large-particle suspended matters with the particle size of more than 0.5mm to obtain primary filtrate;
2) adding an adsorbent into the primary filtrate, stirring, and carrying out solid-liquid separation to obtain a secondary filtrate;
3) pouring the secondary filtrate into a device filled with waste lithium batteries for discharge reaction, and then performing secondary filtration to respectively obtain discharged waste lithium batteries and elemental sulfur,
the device provided with the waste lithium battery is a closed container with a gas collecting device, and is also provided with a hydrogen sulfide concentration detector for detecting the concentration of H2S in water;
in the discharging process, hydrogen is obtained in the gas collecting device, wherein the waste lithium battery is sent to a battery recovery process;
4) measuring the concentration of hydrogen sulfide in the wastewater before and after treatment, wherein the concentration of hydrogen sulfide in the wastewater (the effluent after desulfurization treatment) after sufficient time reaction can meet the requirement of industrial wastewater discharge on the concentration of hydrogen sulfide; recycling the treated effluent which does not meet the discharge standard to the step 1) for recycling treatment.
The large-particle suspended matter in the step 1 means particles having a particle size of 0.5mm or more.
The adsorbent in the step 2 is one or more of activated carbon, polyacrylamide, wheat germ powder and a carbon molecular sieve.
The device in the step 3 is a closed system provided with a gas collecting device, and the gas purity is obtained by analyzing with a gas purity analyzer.
And (4) measuring the concentrations of the hydrogen sulfide before and after the treatment in the step (4) by using a hydrogen sulfide concentration detector, wherein the sufficient reaction time means that the time is more than 12 hours.
The method disclosed by the invention realizes hydrogen production and sulfur fixation of hydrogen sulfide in the wastewater by using simple chemical and electrochemical methods, realizes echelon utilization of the residual energy of the waste lithium battery, and greatly reduces the cost and has no secondary pollution compared with other methods for treating the hydrogen sulfide in the wastewater.
The invention has the beneficial effects that:
the invention utilizes the residual energy in the waste lithium battery to be applied to the treatment of negative divalent sulfur (such as hydrogen sulfide) in industrial wastewater to realize sulfur fixation, the hydrogen sulfide can also realize hydrogen production, the generated sulfur and the prepared hydrogen can be recycled, and a reliable path with environmental protection and low cost is provided for waste regeneration.
The reacted waste lithium battery has a thorough discharging effect and short discharging time; the treated wastewater is sent to a battery recovery process, discharge operation is not needed before disassembly, the concentration of the hydrogen sulfide in the treated industrial wastewater meets the discharge standard and can be used as industrial water again, and resources are recycled, so that the treatment cost is greatly reduced.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed description of the preferred embodiments
The present invention will now be further described with reference to specific embodiments for the purpose of facilitating a more concise understanding of the invention by those skilled in the art, but it should be understood that the invention is not limited to these embodiments.
The waste battery is 523 type waste lithium ion battery
Example 1
As shown in FIG. 1, the present invention is a method for treating hydrogen sulfide in waste water by utilizing waste energy in batteries in a gradient manner, and industrial waste water (sulfur in the waste water exists in the form of S)2-And HS-Total sulfur mass fraction of 9.6 wt.%) was previously freed from suspended matter having a particle size of more than 0.5mm by primary filtration; then secondary filtration is carried out, and an adsorbent is added during the secondary filtration to remove suspended matters with the particle size of less than 0.5mm through centrifugal filtration to obtain secondary filtrate. The pH value of the secondary filtrate is about 7.3 (7.3 +/-0.1), the secondary filtrate is sent to a reaction device containing waste lithium batteries (the waste lithium batteries are soaked in the secondary filtrate) for discharge treatment, generated gas is collected in the discharge reaction process to obtain high-purity hydrogen, the high-purity hydrogen is reacted for a sufficient time and then filtered to obtain suspension containing solid sulfur, the suspension is centrifugally filtered to obtain elemental sulfur, and the waste lithium batteries after complete reaction are sent to a recovery process. The specific operation steps are as follows:
1) carrying out primary filtration on the industrial hydrogen sulfide-containing wastewater to remove large-particle suspended matters with the particle size of more than 0.5mm and a part of harmful substances to obtain primary filtrate;
2) adding adsorbent active carbon into the primary filtrate, mechanically stirring for a certain time, and then performing secondary centrifugal filtration to remove suspended matters with the particle size of less than 0.5mm to obtain secondary filtrate;
3) pouring the secondary filtrate into a device (provided with a gas collecting device) filled with waste lithium batteries, carrying out discharge reaction for more than 12 hours, filtering to obtain discharged waste lithium batteries and suspension containing elemental sulfur respectively, carrying out centrifugal filtration on the obtained suspension to obtain high-purity elemental sulfur, and obtaining high-purity hydrogen in the gas collecting device, wherein the waste lithium batteries are sent to a battery recovery process;
4) the concentration of the hydrogen sulfide in the wastewater before and after treatment is measured, and the concentration of the hydrogen sulfide in the wastewater after reaction for sufficient time can meet the requirement of industrial wastewater discharge on the concentration of the hydrogen sulfide. The average residual pressure of the discharged waste batteries is reduced to be below 0.3V, the comprehensive residual energy utilization rate is over 90 percent, and the H of the treated effluent2The content of S can be reduced to less than 0.5 wt.%, H2The comprehensive recovery utilization rate of S is more than 85%.
Example 2
Taking 10L industrial wastewater, obtaining secondary filtrate without suspended matters after primary filtration and secondary adsorption filtration, determining the sulfur content of the secondary filtrate to be 9.6 wt.%, pouring the secondary filtrate into a closed device filled with waste batteries, adjusting the initial voltage of the waste batteries to be 3.8-3.85V, adding sulfuric acid to adjust the pH value of the filtrate to be about 1, and adjusting the pH value of the filtrate to be about 1 by using H in the solution at the moment2S, HS-exists in the form. After 24 hours of discharge, the sulfur content in the waste battery is measured to be 0.73 wt.%, the average residual pressure of the waste battery is about 0.5V, the volume fraction of hydrogen is 73% and the volume fraction of hydrogen sulfide is 25% when gas components in the gas collecting device are analyzed. It can be seen that hydrogen sulfide gas is precipitated and released in an acidic environment.
Example 3
Taking 10L industrial wastewater, obtaining secondary filtrate without suspended matters after primary filtration and secondary adsorption filtration, determining the sulfur content of the secondary filtrate to be 9.6 wt.%, pouring the secondary filtrate into a closed device filled with waste batteries, adjusting the pH value of the filtrate to be about 10 (10 +/-0.1) by adding sodium hydroxide, and adjusting the pH value of the filtrate to be about 10 by using S as sulfur in the solution at the moment2-Exist in the form of (1). The sulfur content in the waste battery is measured to be 0.13 wt.% after 24h of discharge, the average residual pressure of the waste battery is about 0V, the volume fraction of hydrogen is 98 percent after the gas components in the gas collecting device are analyzed, and no sulfur is detectedA hydrogen-oxide gas. Therefore, no hydrogen sulfide gas is precipitated and released in the alkaline environment.
Comparative example 1
Taking 10L industrial wastewater, obtaining secondary filtrate without suspended matters after primary filtration and secondary adsorption filtration, determining the sulfur content of the secondary filtrate to be 9.6 wt.%, adding sodium hydroxide for adjustment, adjusting the pH value of the secondary filtrate to be about 10, adding excessive water-soluble zinc sulfate, stirring, standing for 24h, and filtering to obtain the product without S2-Then will not contain S2-And pouring the filtrate into a discharging device filled with waste batteries, wherein the initial voltage of the waste batteries is 3.8-3.85V. And after 24h of discharge, the average residual pressure of the waste battery is about 3.0V, the gas components in the gas collecting device are analyzed, the volume fraction of the hydrogen is 98%, and no hydrogen sulfide gas is detected.
Claims (14)
1. A joint treatment method for waste battery discharge and sulfur-containing wastewater desulfurization is characterized in that a battery pack of a waste lithium ion battery or a battery monomer obtained by disassembly is placed in the sulfur-containing wastewater for discharge; separating to obtain a discharged battery pack or battery monomer and the effluent after desulfurization treatment;
the sulfur-containing wastewater contains H2S、HS-、S2-At least one of (1).
2. The combined treatment method for discharging waste batteries and desulfurizing sulfur-containing wastewater as claimed in claim 1, wherein the concentration of the negative divalent total sulfur in the sulfur-containing wastewater is not less than 5 wt%.
3. The combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization according to claim 2, wherein the concentration of the negative divalent total sulfur in the sulfur-containing wastewater is 5-20 wt%.
4. The combined process for the discharge of spent batteries and the desulfurization of sulfur-containing wastewater according to claim 1, wherein the pH of the sulfur-containing wastewater is 1 to 10.5.
5. The combined treatment method for discharging waste batteries and desulfurizing sulfur-containing wastewater as claimed in claim 4, wherein the pH of the sulfur-containing wastewater is 8-10.5.
6. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization as claimed in claim 1, characterized in that, during the discharge, the temperature of the sulfur-containing wastewater is controlled to 25-35 ℃.
7. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization as claimed in claim 6, characterized in that, during the discharge, the temperature of the sulfur-containing wastewater is controlled to 25-30 ℃.
8. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization according to claim 1, characterized in that the sulfur-containing wastewater further contains a conductive material, and the conductive material is at least one of graphite, graphite oxide, conductive polyaniline and polypyrrole.
9. The combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization according to any one of claims 1 to 8, wherein the sulfur-containing wastewater is pretreated before being used for discharge as follows:
carrying out first solid-liquid separation on sulfur-containing wastewater to be treated to obtain first filtrate; adding an adsorbent into the first filtrate, performing second solid-liquid separation after adsorption to obtain a second filtrate, and taking the second filtrate as the sulfur-containing wastewater as the discharge medium.
10. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization as claimed in claim 9, wherein the adsorbent is one or more of activated carbon, polyacrylamide, wheat germ powder, carbon molecular sieve.
11. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization as claimed in claim 1, wherein said waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery and a lithium iron phosphate battery.
12. The combined treatment method for discharging waste batteries and desulfurizing sulfur-containing wastewater according to claim 1, wherein the residual voltage of the battery pack and the battery monomer is not lower than 1V.
13. The combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization according to claim 12, wherein the residual voltage of the battery pack and the battery cell is 3.8V to 3.85V.
14. The combined treatment method of waste battery discharge and sulfur-containing wastewater desulfurization according to claim 1, wherein said sulfur-containing wastewater contains H2S, specifically comprising the following steps:
1) carrying out primary filtration on the industrial hydrogen sulfide-containing wastewater to remove large-particle suspended matters with the particle size of more than 0.5mm to obtain primary filtrate;
2) adding an adsorbent into the primary filtrate, stirring, and carrying out solid-liquid separation to obtain a secondary filtrate;
3) pouring the secondary filtrate into a device filled with waste lithium batteries for discharge reaction, then respectively obtaining discharged waste lithium batteries and elemental sulfur through secondary filtration,
the device provided with the waste lithium battery is a closed container with a gas collecting device, and the device is also provided with a device for detecting H in water2A hydrogen sulfide concentration detector of S concentration;
in the discharging process, hydrogen is obtained in the gas collecting device, wherein the waste lithium battery is sent to a battery recovery process;
4) measuring the concentration of hydrogen sulfide in the wastewater before and after treatment, wherein the concentration of hydrogen sulfide in the wastewater after reaction for a sufficient time can meet the requirement of industrial wastewater discharge on the concentration of hydrogen sulfide; recycling the treated effluent which does not meet the discharge standard to the step 1) for recycling treatment.
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