CN103757357A - Leaching method of nickel-cadmium waste battery positive electrode material - Google Patents

Leaching method of nickel-cadmium waste battery positive electrode material Download PDF

Info

Publication number
CN103757357A
CN103757357A CN201310736554.3A CN201310736554A CN103757357A CN 103757357 A CN103757357 A CN 103757357A CN 201310736554 A CN201310736554 A CN 201310736554A CN 103757357 A CN103757357 A CN 103757357A
Authority
CN
China
Prior art keywords
leaching
nickel
positive electrode
electrode material
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310736554.3A
Other languages
Chinese (zh)
Inventor
龙炳清
万旭
陈俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Normal University
Original Assignee
Sichuan Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Normal University filed Critical Sichuan Normal University
Priority to CN201310736554.3A priority Critical patent/CN103757357A/en
Publication of CN103757357A publication Critical patent/CN103757357A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a leaching method of a nickel-cadmium waste battery positive electrode material, which comprises the following steps: adding a positive electrode material subjected to roasting pretreatment separated from nickel-cadmium waste batteries and reed powder into a pressure-resistant sulfuric-acid/nitric-acid-corrosion-resistant reaction kettle, adding a sulfuric acid-nitric acid mixed solution, and carrying out agitation leaching under sealed conditions.

Description

The leaching method of anode material of used nickel cadmium battery
Technical field
The present invention relates to a kind of leaching method of anode material of used nickel cadmium battery.
Background technology
Nickel-cadmium cell is the widely used battery of a class, and this battery will produce a large amount of refuse batteries after using and scrapping.Because this class battery contains plurality of heavy metal, if abandon into environment, will environment be produced to very large direct and potential hazard.The main nickeliferous and cobalt of anode material of used nickel cadmium battery, both total contents are up to 60% left and right, have very much a recovery value.The technique that reclaims at present nickel, cobalt from anode material of used nickel cadmium battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, the nickel that very difficult acquisition is purer and cobalt.Wet processing becomes more readily available purer nickel and cobalt.Leaching is a requisite process in wet processing.The leaching method of anode material of used nickel cadmium battery mainly contains hydrochloric acid leaching process, sulfuric acid leaching, nitric acid lixiviation process and nitration mixture (sulfuric acid adds nitric acid) lixiviation process at present.Hydrochloric acid leaching process, equipment corrosion is large, the large and contaminate environment of acid mist generation.The reductive agent (as hydrogen peroxide etc.) that sulfuric acid leaching consumption is more expensive.The nitric acid consumption of nitric acid lixiviation process is large, and can produce a large amount of oxynitride, contaminate environment.All there is the problem that improves how economically leaching velocity, raising metal leaching rate, reduces acid consumption and other supplementary product onsumption in all wet processings.Although nitric acid processing industry pure oxygen lixiviation process and nitration mixture processing industry pure oxygen lixiviation process have solved the problems referred to above preferably, but leaching plant is more complicated, and the required industrial pure oxygen amount of refuse battery leaching is little, refuse battery is processed enterprise, and manufacture pure oxygen is personal uneconomical on the spot, and the storage of industrial pure oxygen, transportation and use are cumbersome.Development equipment corrosion is little, leaching velocity is fast, leaching yield is high, acid consumes and other supplementary product onsumption is low, easy to use, the leaching method of the anode material of used nickel cadmium battery of basic non-environmental-pollution has larger practical value.
Summary of the invention
The problem leaching for current anode material of used nickel cadmium battery, the object of the invention is to find a kind of metal leaching rate high, leaching velocity is fast, leaching yield is high, acid consumption and other supplementary product onsumption are low, easy to use, need not expensive reductive agent, the leaching method of the anode material of used nickel cadmium battery of basic non-environmental-pollution, it is characterized in that by positive electrode material isolated from waste nickel-cadmium batteries and that obtain through roasting pretreatment and≤reed powder of 1.5mm adds withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, the mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach.After leaching finishes, carry out liquid-solid separation, obtain required infusion solution.Temperature of reaction is 50 ℃~80 ℃, and the sulfuric acid starting point concentration of leaching is 1mol/L~4mol/L, and the starting point concentration of nitric acid is that 5g/L~10g/L extraction time is 2h~4h, and leaching process stirs, and stirring velocity is 30r/min~120r/min.Sulphuric acid is to add 110%~140% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metals leach.The add-on of reed powder is counted 60%~75% of nickel in positive electrode material, cobalt total mass with butt.
The object of the present invention is achieved like this: airtight and have under the condition that reed powder and nitric acid exists, the anode material of used nickel cadmium battery of sulfuric acid leaching after roasting pretreatment is when (nickel in material and cobalt are metal oxide form), and following main chemical reactions occurs leaching process:
NiO?+?H 2SO 4?=?NiSO 4?+?H 2O
CoO?+?H 2SO 4?=?CoSO 4?+?H 2O
nC 6H 10O 5?+?nH 2SO 4?=n(C 5H 11O 5)HSO 4
n(C 5H 11O 5)HSO 4?+?nH 2O?=?nC 6H 12O 6?+?nH 2SO 4
C 6H 12O 6?+?8HNO 3?=?8NO?+?6CO 2?+?10H 2O
nC 6H 10O 5?+?8nHNO 3?=?8nNO?+?6nCO 2?+?9nH 2O
3Ni 2O 3?+?6H 2SO 4?+?2NO?=?6NiSO 4?+?2HNO 3?+?5H 2O
3Co 2O 3?+?6H 2SO 4?+?2NO?=?6CoSO 4?+?2HNO 3?+?5H 2O
Ni 2o 3and Co 2o 3total reaction be:
12nNi 2O 3?+?nC 6H 10O 5?+?24nH 2SO 4?=?24nNiSO 4?+?6nCO 2?+?29nH 2O
12n?Co 2O 3?+?nC 6H 10O 5?+?24nH 2SO 4?=?24nCoSO 4?+?6nCO 2?+?29nH 2O
Other organism in reed powder also generates NO, CO with nitric acid reaction 2and H 2o, the NO of generation and Ni 2o 3and Co 2o 3by previous reaction, generate NiSO 4, CoSO 4, HNO 3and H 2o.
Because the speed of response of nitric acid and reed powder is very fast, the NO of generation and Ni 2o 3and Co 2o 3reaction also very fast, accelerate thus whole leaching process, and realize Ni 2o 3and Co 2o 3leach more completely.NO can thoroughly destroy the laminate structure of high oxide in positive electrode material, improves the leaching yield of valuable metal.
With respect to existing method, outstanding advantages of the present invention is to adopt reed powder to make reductive agent, and nitric acid is made to leach accelerator and leached anode material of used nickel cadmium battery, and speed of response is fast, and such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and reed powder is cheap; In positive electrode material, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; In leach liquor subsequent disposal, do not need to neutralize a large amount of acid, cost is lower; The waste amount producing in leach liquor subsequent disposal is few, has reduced pollution abatement costs, has obvious economic benefit and environmental benefit; Process is carried out in confined conditions, the environmental pollution of having avoided NO to overflow and produce.
specific implementation method
embodiment 1: the anode material of used nickel cadmium battery (nickeliferous 55.2% by 100g through roasting pretreatment, cobalt 3.8%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm reed powder 35.5g, adding sulfuric acid concentration is the mixed acid solution 800ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 50 ℃~60 ℃, stir (stirring velocity 80r/min) and leach 4h, after leaching finishes, carry out liquid-solid separation, obtain 770ml infusion solution (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.1% and 99.0%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).
Embodiment 2: the anode material of used nickel cadmium battery (nickeliferous 55.2% by 500g through roasting pretreatment, cobalt 3.8%) it is in the lining titanium pressure reaction still of 5L that≤1.5mm reed powder 220g adds volume, adding sulfuric acid concentration is mixed acid solution 2500 ml that 3.0mol/L, concentration of nitric acid are 10g/L, at 70 ℃~80 ℃, stir (stirring velocity 70r/min) and leach 2h, after leaching finishes, carry out liquid-solid separation, obtain 2300 ml infusion solutions (not containing leached mud washing water).The leaching yield of nickel and cobalt be respectively 99.4% and 99.1%(by entering nickel in infusion solution and leached mud washings and cobalt, calculate).

Claims (1)

1. the leaching method of a nickel anode material of used nickel cadmium battery, it is characterized in that by positive electrode material isolated from waste nickel-cadmium batteries and that obtain through roasting pretreatment and≤reed powder of 1.5mm adds withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, the mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, temperature of reaction is 50 ℃~80 ℃, the sulfuric acid starting point concentration leaching is 1mol/L~4mol/L, the starting point concentration of nitric acid is that 5g/L~10g/L extraction time is 2h~4h, leaching process stirs, stirring velocity is 30r/min~120r/min, sulphuric acid is to add 110%~140% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metals leach, the add-on of reed powder is counted nickel in positive electrode material with butt, 60%~75% of cobalt total mass.
CN201310736554.3A 2013-12-29 2013-12-29 Leaching method of nickel-cadmium waste battery positive electrode material Pending CN103757357A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310736554.3A CN103757357A (en) 2013-12-29 2013-12-29 Leaching method of nickel-cadmium waste battery positive electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310736554.3A CN103757357A (en) 2013-12-29 2013-12-29 Leaching method of nickel-cadmium waste battery positive electrode material

Publications (1)

Publication Number Publication Date
CN103757357A true CN103757357A (en) 2014-04-30

Family

ID=50524671

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310736554.3A Pending CN103757357A (en) 2013-12-29 2013-12-29 Leaching method of nickel-cadmium waste battery positive electrode material

Country Status (1)

Country Link
CN (1) CN103757357A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN1357938A (en) * 2000-12-08 2002-07-10 同济大学 Comprehensive recovery and utilization method of waste NiCd battery
CN101665872A (en) * 2009-06-23 2010-03-10 四川师范大学 Leaching method of anode material of used nickel cadmium battery
JP2010174366A (en) * 2009-02-02 2010-08-12 Sumitomo Metal Mining Co Ltd Method of recovering metal from used nickel-metal hydride battery
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery
WO2012011205A1 (en) * 2010-07-21 2012-01-26 住友金属鉱山株式会社 Method for separating nikel and cobalt from active materials contained in spent nickel-hydrogen battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN1357938A (en) * 2000-12-08 2002-07-10 同济大学 Comprehensive recovery and utilization method of waste NiCd battery
JP2010174366A (en) * 2009-02-02 2010-08-12 Sumitomo Metal Mining Co Ltd Method of recovering metal from used nickel-metal hydride battery
CN101665872A (en) * 2009-06-23 2010-03-10 四川师范大学 Leaching method of anode material of used nickel cadmium battery
WO2012011205A1 (en) * 2010-07-21 2012-01-26 住友金属鉱山株式会社 Method for separating nikel and cobalt from active materials contained in spent nickel-hydrogen battery
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using failed lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李进中等: "氧化锰矿还原浸出工艺技术研究进展", 《中国锰业》, vol. 29, no. 4, 30 November 2011 (2011-11-30), pages 1 - 7 *

Similar Documents

Publication Publication Date Title
CN103757263B (en) The leaching method of anode material of used nickel cadmium battery
CN103757322A (en) Method for leaching positive pole material of waste nickel-metal hydride battery
CN103757317A (en) Method for leaching positive pole material of waste nickel-metal hydride battery
CN103757336A (en) Leaching method of nickel cobalt lithium manganate waste battery positive-negative electrode mixed material
CN103757357A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757339A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757242A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757350A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757338A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757332A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757356A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757331A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757347A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757349A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757358A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757362A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757348A (en) Leaching method of nickel-cadmium waste battery positive electrode material
CN103757361A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757337A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757343A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757385A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757334A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757359A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757352A (en) Leaching method of nickel-cadmium waste battery positive-negative electrode mixed material
CN103757327A (en) Method for leaching positive pole material of waste nickel-metal hydride battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20140430

RJ01 Rejection of invention patent application after publication