专利资讯

废旧碱性锌锰电池正极材料再生方法；废旧锂离子电池正极材料钻酸锂活化工艺；一种用于废旧电池关键材料回收再生的方法；利用废旧锌锰电池制取复合微量元素肥料的方法；一种利用生物淋滤技术直接溶出废旧电池中金属离子的方法。     

废无汞碱性电池极性材料制备锰锌铁氧体磁性纳米颗粒

以硝酸浸取废无汞碱性电池极性材料,再加入硝酸铁及蔗糖生成前驱体,最后通过焙烧制得锰锌铁氧体磁性纳米颗粒。优化了酸浸和焙烧条件,采用FTIR和DTA-TG技术研究了前驱体的形成和热解过程,采用XRD、FTIR、TEM技术和振动样品磁强计对锰锌铁氧体进行了表征。结果表明:废无汞碱性电池极性材料酸浸的最佳条件为H_2O_2加入量3%(w)、液固比10 mL/g、稀硝酸浓度4 mol/L、浸取温度40℃,该条件下浸取10 min锰和锌的浸出率均可达100%;所得前驱体为葡萄糖酸盐,其最佳焙烧条件为焙烧温度450℃、焙烧时间2 h;最佳条件下所得锰锌铁氧体为尖晶石型Mn_(0.5)Zn_(0.5)Fe_2O_4,其颗粒为球形、大小均匀,且磁性能优良。     

用含锌废催化剂制备纳米氧化锌

以含锌废催化剂为原料，经酸浸、除杂、锌粉置换、合成等工艺制得碱式碳酸锌，再经过滤、洗涤、干燥、煅烧制备纳米氧化锌。考察了酸浸工艺硫酸溶液含量和液固比（硫酸与含锌废催化剂的质量比）对锌浸出率的影响，以及煅烧温度对纳米氧化锌质量的影响。实验结果表明：在硫酸质量分数为30%、液固比为5的最佳酸浸工艺条件下，锌浸出率为92%；在最佳煅烧温度为400 ℃的条件下，氧化锌质量分数大于95%，比表面积大于50 m²/g；纳米氧化锌颗粒大小均匀，平均粒径小于50 nm。     

废旧锌锰电池及其回收过程中汞载体的研究

针对目前一些回收废旧锌锰电池工艺在汞回收处理上存在的问题,集中对废旧锌锰电池中汞的载体以及回收处理废旧锌锰电池过程中汞载体的变化进行了研究,为废旧锌锰电池回收处理中汞的完全回收提供了依据.     

从6-APA和7-ADCA生产废液中回收苯乙酸

采用溶剂萃取、水法提取等方法从6-氨基青霉烷酸和7-氨基-3-去乙酰氧基头孢烷酸生产废液（简称废液）中回收苯乙酸（PAA）,考察了各种因素对回收效果的影响。实验结果表明：以甲苯为萃取剂,在萃取温度30℃、萃取时间15m in、500mL废液中萃取剂加入量130mL的最佳条件下,萃取率为96.5%;在提取温度为65℃左右、结晶温度低于10℃的条件下,PAA收率大于89%,纯度大于99%;所得PAA产品质量好,可用于青霉素G等医药产品的生产。     

萃取法回收钛白水解废酸中的硫酸

提出了以三异辛胺作萃取剂、H2O作反萃取剂从钛白水解废酸中萃取回收硫酸的新工艺。考察了萃取剂浓度、相调节剂浓度、相比及温度对萃取和反萃取的影响，并进行了模拟试验。在以40％三异辛胺、25％仲辛醇和35％航空煤油(均为质量分数)为萃取有机相，相比为2，以H2O为反萃剂，相比为1．5的条件下，质量浓度为146．02g/L的废酸经8级萃取和6级反萃取，硫酸回收率达到91．81％，产品酸质量浓度达119．73g/L。     

萃取回收氯提残液中的氯仿

采用溶剂取法回收氯提残液中溶解和夹带的氯仿，以磺化煤油为萃取剂，萃取设备采用振动筛板柱。萃取氯仿后的磺化煤油，用水蒸汽蒸馏回收。在本实验选取的工艺条件下，氯仿的回收率达到９０％以上。     

从废旧锌锰电池中回收汞和铵的工艺研究

针对废旧锌锰电池中汞分散存在给回收处理废旧锌锰电池工作完全回收汞所带来的困难,利用汞和铵的性质特点,找到了从废旧锌锰电池中集中回收汞和铵的工艺条件,为废旧锌锰电池的资源化和防止二次污染创造了有利条件.     

污泥灰中磷的湿化学法回收技术研究进展

从污泥灰中磷的提取、磷与重金属的分离和磷产品的制备3方面综述了国内外湿化学法回收污泥灰中磷的研究进展,重点分析了磷提取过程中的各种影响因素,并对今后污泥灰中磷的湿化学法回收技术的研究方向进行了展望。指出:利用萃取的方法将提取液中的无机强酸萃取出来并回收重复利用,可大幅降低酸的消耗量;在回收磷的同时可研究回收不同种类金属的方法,尤其是价值较大的重金属,以进一步提高污泥灰资源的回收价值。     

多组分电镀污泥酸浸出液中铁的分离

研究了采用Ｐ５０７－煤油－Ｈ２ＳＯ４萃取体系分离电镀污泥酸浸出液中Ｆｅ＾３＋的工艺，确定了从含有多种上金属组分的硫酸溶液中萃取铁的最佳工艺条件以及负载有机相反萃取较优工艺条件，研究结果表明，以Ｐ５０７为萃取剂，硫酸为洗涤剂，经３级萃取、２级洗涤的分馏萃取后，可以从含有多种金属组分的硫酸溶液中分离出９９．９％的铁，其他金属的流失量小于１％，不影响后者的回收，铁在工艺过程中以ＦｅＣｌ３·６Ｈ２Ｏ的形式     

Hydrometallurgical recycling of cobalt from zinc plants residue

A large amount of hot filter cake (HFC) is annually generated in Iranian zinc plants. It contains 1% zinc, 16–30% manganese, 5–25% calcium and 1–4.5% cobalt. Usually, zinc is selectively leached by an alkaline medium and its residue is known as alkaline leached HFC (ALHFC). In the present study, the possibility of cobalt extraction from ALHFC was investigated using a creative hydrometallurgical process. At the first stage, zinc and cadmium were selectively removed with sulfuric acid. At the second stage, it was deeply focused on the possibility of selective reductive leaching of cobalt by H₂O₂ as a reductant in the presence of manganese. As results, several differences were found between the mechanism of cobalt and manganese leaching. Accordingly, cobalt leaching was more affected by acid concentration and manganese leaching was more affected by reductant concentration. Consequently, with manipulating these important parameters, it was made possible to selectively separate cobalt from manganese. Based on the obtained results, 90.9% of cobalt and only 10.04% of manganese were leached with 1% of H₂O₂. At the third stage, pregnant cobalt solution was successfully purified through a solvent extraction process with D2EHPA. Finally, cobalt hydroxide as our final product with a purity of more than 99% was precipitated from the pure pregnant solution at 70 °C.     

废锂电池放电及正极片分离回收处理

研究了废锂电池放电及正极片分离回收处理工艺。实验结果表明:经质量浓度30 g/L NaCl溶液浸泡9.0 h可实现电池放电,残余电压在0.5 V以下;在60℃恒温水浴振荡、NaOH质量浓度40 g/L、废锂电池质量与NaOH溶液体积的比为15 g/L的优化条件下,集流体完全与活性物质分离,回收得到的黑色粉末为LiCoO2活性材料,未见铝杂质的特征峰;通过硫酸中和的方法回收碱浸溶液中的铝,当体系pH为10.0时,可获得最大量的Al(OH)3沉淀,沉淀物颗粒表面光滑,粒径大小不一。     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.     

Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO₄ solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO_x synthesized in our laboratory.The characterization by XRD, FTIR and XPS reveal the presence of Mn₂O₃ in the EMO and the CMO samples, together with some Mn⁴⁺ cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn₃O₄.The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO₂.The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.     

Metal separation from mixed types of batteries using selective precipitation and liquid-liquid extraction techniques

The purpose of this paper is to study metal separation from a sample composed of a mixture of the main types of spent household batteries, using a hydrometallurgical route, comparing selective precipitation and liquid-liquid extraction separation techniques. The preparation of the solution consisted of: grinding the waste of mixed batteries, reduction and volatile metals elimination using electric furnace and acid leaching. From this solution two different routes were studied: selective precipitation with sodium hydroxide and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphoric acid] as extracting agent. The best results were obtained from liquid-liquid extraction in which Zn had a 99% extraction rate at pH 2.5. More than 95% Fe was extracted at pH 7.0, the same pH at which more than 90% Ce was extracted. About 88% Mn, Cr and Co was extracted at this pH. At pH 3.0, more than 85% Ni was extracted, and at pH 3.5 more than 80% of Cd and La was extracted.     

镀锌钢板废料中锌的碱浸过程影响因素分析

以强碱(NaOH)溶液为浸取剂,采用碱浸法回收镀锌钢板废料中的锌,考察了不同因素(反应温度、反应时间、碱浓度、添加剂)对锌浸出效果的影响,并对添加剂的作用机理进行了分析。实验结果表明:在NaOH质量浓度为250 g/L、反应温度为90℃、反应时间为300 min的最佳工艺条件下,锌的浸出率高达97.89%;添加NaNO_3可提高锌在碱液中的腐蚀电位和腐蚀电流,从而加快镀锌钢板废料中锌的溶解,缩短反应时间;添加KMnO_4对反应速率基本无影响。     

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi_0.5Mn_1.5O₄ materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H₂SO₄ (2 mol L^?1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ?99.8% is recovered in an electrolytic cell with a cathode efficiency of ?85% under the conditions of 37–40 °C and 300 A m^?2. The most of MnO₂ and a small quantity of electrolytic MnO₂ are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi_0.5Mn_1.5O₄ material of lithium-ion battery. The as-synthesized LiNi_0.5Mn_1.5O₄ discharges 118.3 mAh g^?1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO₂. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.     

利用磷化渣配制复合磷化液

采用固体废物磷化渣配制成复合磷化液，并用所配制的复合磷化液对A3钢试件进行磷化处理，形成磷化膜。通过正交实验确定了配制复合磷化液的较佳配方为：磷化液基础液加入量0．2L／L、氧化锌加入量5g／L、碳酸钠加入量6g／L、硝酸加入量12．5mL／L、浓磷酸加入量2．5mL／L、硫酸铜加入量0．3g／L。复合磷化液为浅绿色透明溶液，pH为4．0，总酸度为40，游离酸度为10，磷化温度为65℃，磷化时间为300～600s。所形成的磷化膜厚度为16．0μm，单位质量为26．875g／m^2，粗糙度为1．425μm，维氏硬度为124．27kgf／mm^2。磷化膜硫酸铜点滴时间为35s，耐盐水时间为8h，耐盐雾时间为4h，其物理性质和耐蚀性能均较佳。     

中和—絮凝法回收硝酸型退锡废水中的锡

将传统的中和法和絮凝法相结合,采用中和—絮凝法回收硝酸型褪锡废水中的锡,考察了反应终点体系pH、碱液浓度、絮凝剂浓度等因素对锡回收效果的影响。实验结果表明,在NaOH溶液浓度为6 mol/L、反应终点体系pH为0.8、聚丙烯酰胺溶液质量浓度为3 g/L的工艺条件下,可得到干基锡含量54.6%（w）的高品位锡泥。与传统的单一中和/絮凝法相比,采用中和—絮凝法不仅可以有效提高生产效率,而且减少了碱液和絮凝剂用量,回收锡之后体系中大量的硝酸可进一步回收利用。