廢鎳氫電池中鎳、鈷和稀土金屬回收工藝研究

1、廢鎳氫電池中鎳、鈷和稀土金屬回收工藝研究34?j?71?(Vol134j?No11?j?Hj?j?CHINESEJOURNALOFRAREMETALS2010?1?CJan12010j?r?w?(:2009-04-10;?(:2009-05-15j?3?/?L?1?,?v?C?h?8?2(6)j?o?cj?(),?,?,?M?(;?M?A?1?23(f63)?,?v?d?j3?(?r?M?cj?,?6?m?3(?2?.?O?(?E?,?113001)?:?V?l?,?v?d?j3?j3?(RE)?r,?1?j3?j3?;?h?P?6?j3?j3?(?;?pHj3?c?O?dRE3+?M?j3?

2、h?P?6?(?r?j4?:?j3?j3?(?8?d?a?2?(?(?J?a?2?j4?O,?a?2?B:?B3.8h,?B15,?;?B1.8mol?L-1,?h?80)1j4?8?a?2?E,?96.8%,?97.3%,?(?94.6%j4?(?J?a?2?B:?pH?B2.0,?c?O?dRE3+?M?B4,?h?B60)1j4?8?E,RE?r?B96.7%j4?i?:?,?v?;?;?;?(doi:10.3969/j.issn.0258-7076.2010.01.016?d?l?:TG139j?j?i?N?3:Aj?j?2?:0258-7076(2010)01-0079-06Reco

3、veryofNi,Co,RareEarthfromWasteMH2NiBatteryWuWei,ZhangHonglin3(CollegeofEnvironmentandBioengineering,LiaoningShihuaUniversity,Fushun113001,China)Abstract:TherecoveryofNi,Co,REfromMH2Nibatterywithwettreatmentwasintroduced,theimpactofleachingtime,liquid2solidratio,sulfuricacidinitialconcentrationandlea

4、chingtemperatureontheleachingrateofNi,Co,REandtheimpactofsolutionpH,themolarratioofNa2SO4andleachingsolutionwithRE3+,reactiontemperatureandotherfactorsontherecoveryrateofREwerestudied.Bytheorthogonaltest,theoptimizedsulfuricacidleachingconditionsforNi,Co,REandtheoptimizedprecipitationcondi2tionsforr

5、areearthdoublesaltwereidentified.Theresultsshowedthattheoptimizedsulfuricacidleachingconditionswereleachingtimeof3.8h,liquid2solidratioof15,initialconcentrationofsulfuricacidof1.8mol?L-1,andleachingtemperatureof80)1.TheleachingrateofNi,CoandREwas96.8%,97.3%and94.6%respectively.Theoptimizedprecipitat

6、ionconditionsforrareearthdoublesaltweresolutionpHof2.0,themolarratioofNa2SO4andleachingsolutionwithRE3+of4,reactiontemperatureof60)1.Undertheseconditions,therecoveryofREreachedto96.7%.Keywords:MH2Nibattery;nickel;cobalt;rareearthj?j?q?,?v?8?,?+?J?A?1?1,2j4?,?v?d?%?.?(j4?2?C?J?H?,?B?Q?83j4?2,?/?Bj3?8

7、?M?j3?Z?H?,?/?Aj3?j3?Z?4?v?j4?,?,?v?r?H?U?P4j4?,?1?,?v?d?j3?j3?(?r?u?H?j4?:?h?,?1?l?2j4?s?J?r?d?(?k?6?r?j3?M?.j4?:?8?H?B?K?1?Q?V?lj4?h?j3?0?j3?J?(?H?M?j3?r?j4?6?,?v?V?l?/,?:?8?(?l?V?l?Uj4?V?l?K?j3?z?E?M?J?Kj4:200404009:1984-:E-mail:80j?j?j?j?Hj?j?34?l?,?v?V?l?M?:?A?j4?8?7?d,?X?l?v?(?Q?B?l,?8?,?:?d?c

8、?,?(?(?R?J?j4?(?J?8?v?S?r?h?8j4?d?8?1?Q?l?j4?8?j?v?u?.?(?d5j41j?j?1.1j?,?v?R?%?l?,?v?u?R?1?q?B6j4?,?v?/?q?,?I?K?s?,?.?2?j3?.?2?j3?C?K?v?K?P?C?R?u?.?;?(?/?i?,?C?,?R?l?o?j3?(j3?j3?j?87j4?,?v?u?%?l?2j41.2j?K?q?8?K?x?B?l?j4AA6000?t?r?l?P?P?:?I?h?H?(?/?);8522?h?o?:?t?v?H?;722S?l?P?P?:?I?H?;DZF26020?(?:?I

9、?N?H?;D/Max2A?X?V?V(XRD)?:?7?l?j41.3j?1?,?v?dNi,Co,RE?l?l?u?N?/?m?1j?,?v?u?RTable1j?MajorcomponentsofwasteMH2NibatteryNameWeight/gAccountingfortheweightofbattery/%Plasticshellpackaging0.91.18Ironshell16.521.59Non2wovendiaphragmmaterial3.24.19Batterypositiveplate27.836.39Batterynegativeplate22.229.06

10、Water,Binder,Electrolyte5.87.60Total76.4100.00?2j?%?l?Table2j?MetalcontentanalysisMNFMRMf%555336?j4?r?2?B?O,?l?O?,?8?Q?j4?y?s?o?%?Ni,Co?(?P?H?R?v?%,?j3?v?Z?j3?j3?P?C?R?8j4?1?,?v?%?O,?.?:?2?R?F?c?NiSO4,CoSO4,RE2(SO4)3?P9,?O?O?l?d?V?k?6?%?j4?8?d?c?O?(?RRE?J?,?U?BRE2(SO4)3+Na2SO4+xH2O)?RE2(SO4)3?Na2SO4

11、?xH2O(1)?O?u?%Ni,Co,?8P507?Q?1?l?10j41.4j?1?,?v?dNi,Co,RE?l?z?E?1?,?v?dNi,Co,RE?l?z?E?1j4?j?z?E?Fj?SfainelementsiCoenEasspercentageoelements/2.18.88.7.2818.21ig.1chematicdiagramothetestprocess1?(?cj?Pj?,?v?d?j3?(?r?M?81j?j?j?1.5j?8?V?l?v?r?,?H?m?,?H?B?R?lj4?8?(46m?s-1?(?670mm)?U?c?B?c?v?,?U?c?B?H?B2

12、0mm?:?Z?j4?B?:?,?q?8?A?c?B?cj4?O?,?80.5mm?Q?;?10g?,?v?%,?H?H?a?2?,?500ml,?Y?d?11j3?j3?(12?%?j4?d?50ml?200ml?d,?c?,?,?j4?250ml,?Y?d?j3?j3?(?%?,?j3?r?d?(?u?,?(?l?X?13j4?d?u?%?j3?,?8P507?Q?1?l?j41.6j?l?Ni,Co?%?8?t?r?P?s?Y?;RE?%?8GB/T12690.1222003jI?i?)?l?P?P?jE?Y?;pH?8?b?B?Y?;RE?J?8RE?J?XRD?s?ONaLa(SO4

13、)2?H2O?N?XRD?s?j42j?O?2.1j?V?6?j3?j3?(?B?v?%?d?j3?j3?(?a?2?,?4?m?j4?v?%?B15g,?)?8500ml?d?j4?v?%?3?8,?s?5?,?V?6?j3?j3?(?r?.?U?B:A>B>C>Dj4?s?6?8?l?j3?j3?(?r?u?j42.2j?j3?j3?(?x?s?4?j?J?S?E?j3?j3?(?x?2?q?Bj4?3j?6?c?Table3j?FactorleveloforthogonaltestLevelFactorsALeachingtime/hBLiqui

14、d2solidratioCSulfuricacidconcentration/(mol?L-1)Dtemperature/)11150.52522101.54533152.56544203.585?4j?Table4j?ResultsoftheorthogonaltestNumberABCDLeachingtime/hLiquid2solidratioSulfuricacidconcentration/(mol?L-1)Temperature/)1LeachingrateofNi/%LeachingrateofCo/%LeachingrateofRE/%1111181.5780.1281.87

15、2122282.3281.3584.123133384.3483.6785.944144484.6384.6285.625212386.5187.7186.326221488.1488.8988.847234186.6387.6590.138243287.3989.2989.399313488.1586.3786.9510324389.5888.8791.5811331293.7993.9490.8912342190.1389.1688.1313414288.3587.9488.3114423191.2492.3192.24535563563333314249.89.279.814419.79

16、.4289.782j?j?j?j?Hj?j?34?5j?l?Table5j?RangeanalysisLeachingrateNiCoREABCDABCDABCDABCDK1332.88344.60356.88349.56329.76342.16356.36349.24337.56343.44350.96352.36K2348.68351.28354.56351.84353.56351.44354.48352.52354.68356.76352.16352.72K3361.64360.36351.12353.80358.36361.52351.64353.68357.56360.56354.5

17、2353.20K4368.56355.52349.16356.48369.96356.48349.08356.16363.52352.52355.64355.00k183.2286.1589.2287.3982.4485.5489.0987.3184.3985.8687.7488.09k287.1787.8288.6487.9688.3987.8688.6288.1388.6789.1988.0488.18k390.4190.0987.7888.4589.5990.3887.9188.4289.3990.1488.6388.30k492.1488.8887.2989.1292.4989.128

18、7.2789.0490.8888.1388.9188.75R8.923.941.931.7310.054.841.821.736.494.281.170.66?6j?Ni?l?Table6j?VarianceanalysisofNileachingrateErrorsourcesDeviationFreedomVarianceFSignificantLeachingtime185.17361.7233.93Liquid2solidratio33.52311.176.14Sulfuricacidconcentration8.8432.951.62Temperature6.4932.161.19E

19、rror5.4631.82Total239.4815?7j?Co?l?Table7j?VarianceanalysisofColeachingrateErrorsourcesDeviationFreedomVarianceFSignificantLeachingtime213.96371.3213.723Liquid2solidratio51.33317.113.29Sulfuricacidconcentration7.6832.560.49Temperature6.1732.060.39Error15.5935.19Total294.7315?8j?RE?l?Table8j?Variance

20、analysisofREleachingrateErrorsourcesDeviationFreedomVarianceFSignificantLeachingtime93.02331.0115.093Liquid2solidratio40.54313.516.58Sulfuricacidconcentration3.4331.140.56Temperature1.0230.340.17Error6.1632.05Total144.1715j?j?s?2?,?83.8?4.0h?1?7?J?,?s?/?,?3.8h?7?I?Kj42.3j?j3?j3?(?x?s?4?j?J?S?E?j3?j3

21、?(?x?3?q?Bj4?s?3?,?815?H?.?j42.4j?;?j3?j3?(?x?s?4?j?J?S?;?E?j3?j3?(?x?4?q?Bj4?s?4?,?j3?x?;?x?S?,?D?(?x?;?x?S?x?j4?81.8mol?L-1?H?,?H?;?81.8mol?L-1?/?4?j42.5j?h?j3?j3?(?x?s?4?j?J?S?h?E?j3?j3?(?x?5?q?Bj4?j?O?j3?j3?(?x?Fj?RffN,R2ig.2elationoleachingtimeandaverageleachingrateoiCoE1?(?cj?Pj?,?v?d?j3?(?r?M

22、?83j?j?j?j?j?s?5?E?h?I?x?j80)1?O,?j3?j3?(?J?.,?q?880)1?/?4?j42.6j?C?a?2?B:?3.8h,?B15,?;?B1.8mol?L-1,?h?80)1j4?C?I?,?v?%?,?j?9?q?Bj4?s?9?,?8?a?2?E,?96.8%,?97.3%,?(?94.6%j42.7j?V?6?(?r?E?O?l?10,11j4?11?:?V?6?RE?r?.?U?B:?mZ>X>Yj4?:?a?2?B:?pH?B2.0,?c?O?dRE3+?M?B4,?h?B60)1j4?8?E,RE?r?B96.7%

23、j4?5j?h?O?j3?j3?(?Fig.5j?RelationoftemperatureandaverageleachingrateofNi,Co,RE?9j?C?Table9j?ResultsofcomprehensiveleachingexperimentLeachingtime/hLiquid2solidratioSulfuricacidconcentration/(mol?L-1)Temper2ature/)1Leachingrate/%NiCoRE3.8151.88096.897.394.6?10j?c?6?Table10j?Factorleveloforthogonaltest

24、LevelFactorsX(SolutionpH)Y(ThemolarratioofNa2SO4andleachingsolutionwithRE3+)Z(Temper2ature/)1)11.024022.036033.0480?11j?Table11j?ResultsoftheorthogonaltestNumberXYZSolutionpHMolarratioofNa2SO4andleachingsolutionwithRE3+Temper2ature/)1RecoveryrateofRE/%111176.4212291.3313396.5421293.5522395.3623189.4

25、731378.7832175.8933291.6k188.0782.8780.5333335R636k292.787.4792.1k82.092.90.1710.709.11.084j?j?j?j?Hj?j?34?3j?j?1.?l?v?(?V?l?z?E?,?r?j4?v?%?8?O,?8?c?(,?(?r?96.7%?I,?S?j?l?(?j42.?v?%?8?,?l?6?B:?>?>?;?>?h?j4?a?2?B:?3.8h,?B15,?;?B1.8mol?L-1,?h?80)1j4?8?a?2?E,?96.8%,?97.3%,?(?94.6%j

26、43.?(?8?c?Q?,?l?6?B:?h?>?pH>?c?O?dRE3+?j4?a?2?B:?pH?B2.0,?c?O?dRE3+?M?B4,?h?B60)1j4?8?E,RE?r?B96.7%j4?1?i:1GuoBingkun,LiXinhai,YangSongqing.j?ChemicalPower2Bat2teryPrinciplesandManufacturingTechnologyM.Changsha:CentralSouthUniversityofTechnologyPress,2000.25.(?(,?,?.j?2?v?2M.?:?d?:?.?X

27、?b,2000.25.)2ChengJu.j?Ni2MHbatteryandhydrogenstoragealloysJ.Me2tallicFunctionalMaterials,1996,4(3):118.(?Ej?.j?,?v?,?C?J.?,1996,4(3):118.)3ChenDedi,HuaPichang.j?EnvironmentalHazardsM.Bei2jing:ChinaEnvironmentalSciencePress,1993.58.(?X?f,?T?.j?CM.?0?:?d?X?b,1993.58.)4XiGuoxi.j?Researchonwastedrybatt

28、eriesresourceprogressJ.ChemicalEngineeringProgress,2001,7(1):136.(?d?.j?v?2?M?J.?2?,2001,7(1):136.)5BernardesAM,EspinosaDCR,TenorioJAS.j?Recyclingofbatteries2areviewofcurrentprocessesandtechnologiesJ.PowerSources,2004,130(122):291.6SongWenshun.j?ChemicalPowerTechnologyM.Beijing:ChinaLightIndustryPress,2000.(?(,?,?.j?2?v?2M.?:?d?:?.?X?b,2000.53.)7ZhouBin.j?BasicresearchonwasteNi2CdbatteryrecyclingD.Tianjin:TianjinUniversity,2001.22.(?j?.j?P?v?r?h?8?q?M?D.?h?p:?h?p?.?,2001.22.)8ChenYan,HuXianzhi.j?Recyclingmethodofpreciousmetalsinelectr