废锌锰电池制备锰锌铁氧体共沉淀粉料研究.pdf

废锌锰电池制备锰锌铁氧体共沉淀粉料研究 彭长宏 慕思国 白本帅 黄 虹 中南大学冶金科学与工程学院, 湖南长沙 410083 摘要 以废锌锰电池为主要原料, 辅以少量的菱锰矿和废铁屑, 经同时浸出、初步除杂、深度净化和共沉淀等过程, 制 备出纯度高、配比接近 PC30 铁氧体配方且混合均匀的共沉淀粉料。 实验结果表明 在浸出温度 80～ 95℃、搅拌速度 120～ 180 r min、酸用量为理论用量的 1. 2～ 1. 4 倍和浸出时间 3. 0～ 4. 0 h 的条件下, 铁、锰和锌的浸出率分别为 92. 02、96. 14和 98. 34; 共沉淀粉料中铁、锰和锌的平均含量分别为 41. 41、13. 92和 4. 49, 推算出 Fe∶ Zn∶ Mn69. 2∶ 23. 3∶ 7. 5。 完全符合 PC30 对粉料的要求。 本研究既为高档锰锌软磁铁氧体的制备创造了很好的前提条 件, 同时对废锌锰电池的高价值资源化利用具有重要的现实意义。 关键词 废锌锰电池 锰锌铁氧体共沉淀粉料 资源化 1 引言 由于废锌锰电池的主体成分为铁、锌和锰 ,而铁、 锌和锰又都是锰锌软磁铁氧体材料的主体成分。本 研究基于在直接法制取锰锌软磁铁氧体材料领域的 大量研究 [ 1,2] ,初步探索了利用废锌锰电池制备锰锌 铁氧体共沉淀粉的工艺理论和条件 , 制备出纯度高, 铁、 锰和锌含量接近铁氧体 PC30 理论配方且成分混 合均匀的共沉淀粉料 。 2 试验原料 废锌锰电池 ,收集自中南大学垃圾站; 菱锰矿 ,产 自湖南湘潭花桓 ; 废铁屑, -80 目 , 取自中南大学机 械厂 ,其化学成分分析结果见表1 。 表 1 废锌锰电池、菱锰矿和废铁屑化学成分 项目FeZnZnCl2MnMnO2CuMgO CaONH4ClC 废锌锰电池3 . 43 25 . 80 5. 1641 . 57 0 . 5312 . 618 . 60 菱锰矿2 . 3322 . 203 . 70 1. 20 废铁屑90 . 7 辅助试剂 硫化氨、氟化氨和氨水均为化学纯; 碳酸氢铵为农用碳铵; 硫酸锰、硫酸锌和硫酸亚铁为 分析纯; 硫酸为工业硫酸 。 3 工艺流程 实验流程如图 1 所示。 图 1 废锌锰电池制备锰锌铁氧体共沉淀粉原则工艺流程 4 实验操作条件及数据处理 4. 1 浸出过程 套用文献[1,2] 条件 浸出温度 80～ 95℃、搅拌 速度 120～ 180 r min 基础上, 本研究仅对浸出过程的 酸用量和时间进行了条件试验 ,其结果分别如图 2 和 图3 所示。 图 2 硫酸用量与浸出率之间的关系曲线 图 3 浸出时间与浸出率之间的关系曲线 由图 2和图 3 可以看出 铁、锰和锌的浸出率均 随时间和酸用量的增加而增大 ,但锰和锌变化不是非 常剧烈 ,综合三者达到浸出平衡所需的时间和酸用 量,确定其最优实验条件为 浸出温度 80 ～ 95℃、搅 拌速度 120 ～ 180 r min 、酸用量为理论用量的 1. 2 ～ 1. 4 倍,浸出时间 3. 0 ～ 4. 0 h。 在上述优化条件下, 进行了 4 次综合条件试验, 浸出液化学成分分析结果见表 2。由表 2 数据和原 80 环 境 工 程 2005年 10 月第 23卷第 5 期 料用量, 计算出浸出渣率及铁 、 锰和锌 3 种主体成分 的浸出率如表 3 所示 。 表 2 浸出液化学成分 项目 浸出 液体 积 mL 主成分离子浓度 gL- 1 杂质元素离子浓度 mgL- 1 FeMnZnCaMgAlSiCuPbCdNi 11 250 68 . 54 22 . 39 6 . 91890344550191 154546122 . 3 21 230 69 . 01 23 . 50 6 . 45912328312211 023544104 . 5 31 250 68 . 93 22 . 85 7 . 1257227658651 204574245 . 0 41 260 67 . 47 22 . 64 6 . 82775410441101 15460292 . 1 平均 1 250 68 . 49 22 . 85 6 . 83787340472141 134557143 . 5 表 3 铁、锰和锌的渣率与浸出率 项目渣率 浸出率 FeMnZn 120. 4592. 0496. 3299. 35 224. 5190. 7895. 7098. 46 323. 7691. 0595. 4897. 19 420. 1494. 2197. 0598. 37 平均22. 2292. 0296. 1498. 34 由表 2 可知 随着主体金属铁、 锰和锌的浸出 ,其 他杂质元素也被浸入溶液中。如 杂质元素铜的平均 浓度高达 1. 134 g L 、 铅为 0. 557 g L 以上 ,轻金属钙、 镁和铝的浓度都远远高于铁氧体对杂质元素的要求, 因此必须对其净化处理。从表 3 数据可以看出 铁、 锰和锌 均有较高 的浸出率 , 平 均浸出率分 别为 92. 02、 96. 14 和 98. 34。 4. 2 净化过程 套用文献[ 1] 的净化除杂条件 ,进行了硫化沉淀 除重金属离子、氟化沉淀除钙镁和复盐沉淀深度净化 3 个过程的净化试验 。在温度为 85～ 90℃、反应时间 1～ 3 h、 硫化剂用量为理论量 2 ～ 3 倍的条件下 ,进行 了 4 次硫化沉淀除重金属离子试验 。以每次硫化除 重金属离子后的溶液为试液。进行了相对应 4 次氟 化除钙镁试验 。氟化沉淀除钙镁条件为 温度 70 ～ 80℃、 时间 1～ 1. 5 h 和氟化剂用量为理论量 3～ 4 倍。 以氟化沉淀后液体为原料 ,也进行了相对应的 4次复 盐沉淀深度净化试验 。其试验条件为 pH 1. 5～ 2. 5、 复盐沉淀剂的游离浓度为 2. 5～ 3. 5 mol L 、 时间1. 0～ 1. 5 h 。最后将每次的复盐沉淀用蒸馏水溶解, 所得 溶液的体积及其化学成分如表 4 所示 。 由表 4 可知 经硫化沉淀除重金属、氟化沉淀除 钙镁和复盐沉淀深度净化后的复溶液中 Ca 、 Mg 、 Al 、 Si 、 Cu 、 Pb、 Cd 和 Ni 等杂质元素的含量都很低 ,其去除 率分 别 达 到 99. 7 、92. 33、96. 48、63. 64、 99. 86、 98. 51、 53. 0 和 78. 72,为后续共沉淀工 艺提供了合格的溶液 。 表 4 复溶液化学成分 项目 复溶液的 体积 mL 主成分浓度 gL- 1杂质成分浓度 mgL-1 FeMnZnCaMgAlSiCuPbCdNi 11 54045 . 06 14 . 325. 15 0. 9 1813 3. 4 0 . 95 11 6. 30. 4 21 56043 . 94 15 . 034. 49 1. 3 3517 2. 9 0 . 42 8. 5 6. 81. 2 31 54044 . 35 14 . 025. 10 2. 2 21 8. 9 8. 8 1. 6 3. 9 5. 10. 6 41 57042 . 61 14 . 094. 82 1. 9991. 4 2. 2 3. 4 3. 00. 1 平均1 55243 . 99 14 . 374. 89 1. 6 2112 4. 1 1. 3 6. 7 5. 30. 6 4. 3 共沉淀过程 套用文献[ 3] 共 沉淀过程的条件 沉淀剂中 NH4HCO3为其 理论 用 量的 1. 2 倍、液 氨 用量 为 [CO 2- 3] [NH3] 2. 8～ 4. 8、终点 pH 7. 4 ～ 7. 7、搅拌 速度为140～ 180 r min、温度 45～ 60 ℃ 及时间 2 h ,先 根据 PC30 理论配方 ,结合表 4 中铁 、 锰及锌主体成分 含量 ,偏离配方的成分, 可配入分析纯 MeSO4 Me 代 表Fe 、 Mn 或 Zn 调整 ,然后进行了 4 次对应的共沉淀 试验 。所得共沉淀粉料中主体元素和杂质元素含量 检测结果见表 5。 表 5 共沉淀粉化学成分 项目 主成分杂质成分10- 6 FeMnZnCaMgAl SiO2 CuPbCdNi 140 . 36 13 . 455 . 231553841211256 242 . 03 14 . 304 . 0817255218418 4 341 . 52 13 . 684 . 2623164223516 40. 1 441 . 71 14 . 234 . 3928294399315 平均 41 . 41 13 . 924 . 49213155167. 32350 从表 5可以看出 Fe∶ Zn∶ Mn 的平均比值为 69. 2∶ 23. 3∶ 7. 5, 与 PC30 的理论配方 Fe∶ Zn∶ Mn 67. 3∶ 24. 4∶ 8. 3 误差分别为 1. 5、-1. 1及 -0. 8, 均 在铁氧体制备允许的 2误差范围之内; 共沉淀粉 料中各杂质元素含量很低, 其平均含量分别为 Ca 0. 002 1、Mg 0. 003 1、Al 0. 005 5、SiO2 0. 001 6、Pb 0. 002 3、Cu 0. 000 73、Cd 0. 000 5,完全符合 PC30 对粉料的要求 。尤其是对 低功耗铁氧体磁性能影响较大的杂质元素硅 ,完全达 到了传统“陶瓷法”和“共沉淀法”对铁氧体粉料中硅 含量的要求 。 81 环 境 工 程 2005年 10 月第 23卷第 5 期 5 结论 1 利用废锌锰电池可以直接生产锌锰铁氧体共 沉淀粉,该技术具有原料廉价 、 产品纯度高、 生产成本 低等特点 ,提高了产品的市场竞争力。 2 较传统的“陶瓷法和共沉淀法” , 本工艺没有 铁氧体主体成分铁 、 锌和锰的相互分离的难题 ,而是 在同一溶液中进行提纯, 缩短了生产流程和周期, 容 易推广实施。 3 本项目的研究充分实现了废锌锰电池中铁、 锰和锌 3 种成分的综合利用 , 消除了污染, 治理了环 境,具有显著的社会和经济效益。 参考文献 1 彭长安, 唐谟堂等. 直接法制备低功耗软磁铁氧体扩大实验研究. 湿法冶金, 2003 3 142～ 146. 2 Tang Motang , Peng Changhong and Yang Shenghai. Pilot Experiment on Mn - Zn soft magnetic ferrite made by direct s. Proceeding of ⅦRussian - China Symposium New Materials and Technologies. 2003. 9. Krasndar Region, Russia . 3 李自强, 李春等. 软磁材料锰锌铁氧体共沉粉料的研制. 四川联合 大学学报, 1997. 5 23～ 29. 作者通讯处 彭长宏 410083 湖南长沙 中南大学冶金科学与环 境学院 电话 0731 8830923 2004- 10-12 收稿 水解-生物接触氧化-化学投药工艺 处理肉类加工废水 古利坚 惠东县环境科学研究所, 惠东 516300 林世光 中山大学, 广州 510089 罗国维 华南师范大学化学系, 广州 510631 摘要 采用优势菌投入水解-生物接触氧化-化学投药法应用于肉类加工厂废水处理, 通过工程实例, 运行结果表明, 处理出水水质能稳定达标, 而且还具有投资费用少, 运行费用低, 管理方便等优点。 关键词 屠宰废水 优势菌 水解 生物接触氧化 化学投药 1 引言 惠东县东进保鲜肉类有限公司主要从事生猪屠 宰和肉类保鲜, 年屠宰生猪 20 万头 。该厂废水主要 来自圈栏冲洗、淋洗 、屠宰及其它厂房地坪冲洗、烫 毛、 剖解、胴修、付食品加工、 洗油和油脂加工等,以及 少量生活污水。废水含有大量的血污 、 油脂和油块、 毛、 肉屑、 内脏杂物 、 未消化的食料和粪便等污染物。 此外 ,废水中还含有大量危害人体健康的微生物。根 据屠宰废水的特点 , 采用优势菌投入水解-生物接触 氧化-化学投药法处理工程, 获得满意效果。 2 废水水量 、 水质及处理要求 惠东县东进保鲜肉类有限公司排放废水量约为 300 m 3 d,其中生产废水 250 m3 d, 生活污水 50 m3 d。 经多次采样分析 ,废水水质如表1 所示。 处理后排放水执行广东省地方标准水污染物 排放限值 DB44 26 2001 一级标准 。 表 1 废水水质mg L pH、色度除外 项目pH 值色度 度SSCODCrBOD5磷酸盐氨氮 废水水质 7. 8～7. 864～ 128410～ 460620～ 1 400190～ 4505. 5～ 8. 344～ 46 排放标准6～9406070200. 510 3 处理工艺流程 由于该厂已对毛、油脂和油块进行回收利用, 排 放废水悬浮物较少。该厂废水可生化性较好 ,宜用生 化法处理, 采用经筛选培驯优势菌挂膜固定化技术, 结合水解-好氧工艺对该厂屠宰废水进行处理 。处理 工艺流程如附图所示 。 废水先经格栅筛网除去悬浮物再经初沉池将泥 砂沉淀进入集水池混匀, 用提升泵泵入水解池, 经水 解产酸菌和降解作用下, 使难溶物质或难降解物质降 解为可溶性小分子物质 。然后流入一氧化池在好氧 82 环 境 工 程 2005年 10 月第 23卷第 5 期 PROTLAND CEMENTZhou Jia et al 63 Abstract It is presented that alkali activatedslag pavement concrete AASPCismade by activating industrial slag such as steel slag , slag and fly ash etc without any Portland cement as binder and using GGBS gravel and GGBS sand in place of natural gravel and sand as the fine and coarse aggregates. The effect of the proportion of alkali solution on the strength of AASPC is studied. The results show thatwith proper workability the 28 d compressive strength of 44 MPa, bending strength of 8. 3 MPa are obtained. Keywords fly ash, pavement concrete, steel slag , slag and alkali -activated THE EXISTING PROBLEMS OF DETERMINING MICRO -AMMONIA BY NASHI REAGENT COLORIMETRY AND THE SUGGESTIONS ON IMPROVEMENTZhang Surong et al 65 Abstract It is discussed the existing problems of determining micro -ammonia by Nashi reagent colorimetry in the determination of micro- ammonia, it is given the path to lower the s detection limit through reducing the volume of absorbing liquid and adding the sampling volume, and the problem of the overhigh detection limit in the determination of micro -ammonia is solved. Keywords Nashi reagent colorimetry , micro -ammonia, problem and suggestion on improvement APPLICATION OF GRAY RELATIONAL ANALYSIS OF PROMOTING CLEAN PRODUCTION IN ECO-INDUSTRIAL PARKLin Jiquan et al 67 Abstract Clean production is the precondition of construction of an eco-industrial park. Full realization of clean production must be promoted step by step in the exising reconstructive eco -industrial parks. The gray relational analysis was applied in the assessment of promoting clean prouction in an existing reconstructive eco -industrial park. The indicator system and criterion of assessment were set up. The present, medium-term and long term schemeswere respectively set down by the gray relational grade. At the same time, the main problems that restrain the improvement of clean production level of every enterprise were found out by gray relational coefficient. Taking coking enterprises in LongmenIndustry Park for example, the results show that the gray relational grade of No. 4 and No. 9 enterprises exceed 0. 8, in which experiments of carrying out clean production were made, that is to say, they are schemes of promoting clean production at present, and the enterprises are selected in the future, which is the scheme of higher cost for the park. The is a very useful one for assessment of guiding clean production promotion in eco -industrial park with the advantages of uncomplicated principle and reliable results. Keywords clean production promotion, eco -industrial park, gray relational grade and gray relational coefficient APPLICATION OF THE COMBINED TRAPEZOID SPRAY TRAY IN REING SOURWATER STRIPPING COLUMNZhang Wenlin et al 71 Abstract This paper introduces the operational perancesof the combined trapezoid spray tray CTST . In the technical reconstruction of the sour water stripping column for oil refineries, this tray was used instead of F1 float tray in the same column shell. After the technical reconstruction, the treating capacity was increased by more than 80, and the ammonia content of the purified water at the column bottom was lower than 50 mg L. Keywords tray, CTST , stripping column, sour water and technical reconstruction ANALYSIS OF FACTORS AFFECTING PHOSPHORUS REMOVAL EFFICIENCY OF TRIPLE OXIDATION DITCH PROCESSCao Guoping et al 74 Abstract The factor influencing the efficiency of phosphor removal from triple oxidation ditch in Tangshan North Suburb Wastewater Treatment Plant was studied. The result showed that the supernatant reflux from sludge thickener is the main factor causing the low efficiency as well as no anaerobic condition. Some improving processes are also proposed. Keywords triple oxidation ditch, running way, anaerobic phosphorus releasing , aerobic phosphorus absorption and phosphorus removal THE INFLUENCEOFSULFATEREDUCTION ON DENITRIFICATIONUNDER ANOXIC CONDITIONWei Hua et al 76 Abstract It has been conducted an experimental study on the effect of sulfate reduction ondenitrificationunder anoxic condition. The results have demonstrated that the efficiency, the rate and the course of the denitrification processhave been changedby the sulfate reduction process. The efficiency of denitrification decreased from 100 to 81. 4 when the concentration of sulfate was increased. The maximum denitrification rate ranged from 6. 428 mg L min to 4. 04 mg Lmin when the concentration of sulfate solutionwas varied from 0 mg L to 2 000 mg L. Accordingly, the results have shown that the ammonia nitrogen was accumulated during the denitrification process which has been changed by the sulfate reduction process. Keywords sulfate reduction, denitrification stage, ammonium accumulation and anoxic conditions STUDY ONTHE PREPARTION OF MnZn FERRITE CO-PRECIPITATIONPOWDER WITHZn -Mn WASTE DRY BATTERYPeng Changhong et al 80 Abstract Mn -Zn ferrite co -precipitation powder was prepared by the reaction of simultaneous leaching,deep purification and co- 5 ENVIRONMENTAL ENGINEERING Vol. 23, No. 5,Oct. , 2005 precipitation with waste Zn-Mn dry battery, waste scrap iron and pyrolusite as raw materials. The results indicate that the leaching rates of Mn, Zn and Fe were 92. 02, 96. 14 and 98. 34, respectively at the condition of temperature 80～ 95℃, the rotate rate 120～ 180r min, and with the amount of H2SO4being 1. 2～ 1. 4 times of its theoretical consumption and the leaching time 3. 0～ 4. 0 h. The average contents of main elements in the co -precipitation powder are Fe 41. 41,Mn 13. 92 and Zn 4. 49, Fe∶ Zn∶ Mn69. 2∶ 23. 3∶ 7. 5, which can meet fully the demands on the preparation of PC30 ferrite. This study intends to provide a theoretical basis for the manufacture process of Mn-Zn ferrite powder; it is also having the important practical significance to the utilization of waste Zn -Mn dry battery. Keywords Zn -Mn waste dry battery; Mn -Zn ferrite co -precipitation powder and reuse of resource TREATMENT OF MEAT -PROCESSING WASTEWATER BY HYDROLYTIC ACIDIFICATION - BIOCONTACT OXIDATION -CHEMICAL PROCESSGu Lijian et al 82 Abstract Meat -processing wastewater is treated by hydrolytic acidification-biocontact oxidation -chemical process with dominant strains. The running results of an actual project show that the water quality of the effluent can meet the standard constantly. The process features less investment, lower cost of running and convenient management etc. Keywords slaughterhouse wastewater, dominant strain, hydrolysis, biocontact oxidation and chemicals CHARACTERISTIC CHANGE AND ANALYSIS OF EXCESS SLUDGE AFTER ULTRASONIC TREATMENTCao Xiuqin et al 84 Abstract Experimental study on characteristic change of excesssludge after ultrasonic treatment is carriedout. The SCOD, BOD, TN andTP in supernatant and OUR of sludge are changed with ultrasonic time and power levels. And the effect of this ultrasonication on sludge disposal is especially analysed. According to this study, either the sludge after ultrasonication is combined with the system of wastewater treatment to be as a new substrate for microbe, then the reduction of biomass will be achieved;or itwill create the good condition for disposal of this sludge. Keywords supernatant, aerobic rate of sludge, ultrasonic time, power level of sonication, sludge disposal and reduction of sludge PILOT STUDY ON TREATMANT OF TURBID CIRCULATION WATER FOR HOT -ROLLING Tang Weijun et al 86 Abstract Hot -rolling circulationwater in an iron and steel plant is treatd by pressure filter tank filling with modified fiber ball media. The pressure filter tank has a capacity of 8 m3 h to treat the water. The results show that this can remove oil and SS in hot-rolling circulation water effectively. The average treating efficiency of oil and SS is 84. 5 and 88. 77. Oil concentration of water can be decreased to 1. 8 ～ 4. 5 mg L, and SS to 1. 0～ 9. 5 mg L, which meet the needs of hot-rolling circulation water, whose oil concentration must be less than 5 mg L, and SS concentration less than 10 mg L. Keywords hot -rolling , oily wastewater, fiber ball media and SS RESEARCH ON TREATMENT OF PESTICIDE WASTEWATER BY Fe 2-H 2O2OXIDATION Wu Qimo et al 88 Abstract The of Fe2-H2O2has been widely adopting in disposing wastewater, especially it is difficult to be as usual, since it was established by Fenton. The way to pesticide wastewater treatment is mainly introduced, which can create a better condition for disposing such wastewater that can be bio -chemical degradation even more deeper. Finally, treatment of such wastewater synthetically is realized and environment pollution is also decreased. Keywords Fe2 -H2O2, oxidation and pesticide wastewater PRACTICE OF DIOXIN ZERO-DISCHARGE IN FLUE GA