不锈钢酸洗污泥是不锈钢酸洗环节产生的含酸废水通过添加石灰乳中和形成的富含Fe、Cu、Zn等多种金属元素、以无机物为主的沉淀物，属于危险废物。酸洗污泥中Zn、Ni、Mn等有价金属含量高达2.67%～12.88%、1.03%～4.12%、0.12%～0.84%。现有的酸洗污泥的处置方法主要为填埋处理、固化稳定化处理、焚烧处理以及资源化利用等，其在实际应用中普遍面临处理成本高、能耗大等问题。嗜酸性氧化硫硫杆菌主要以元素硫和还原态硫化物为底物生物氧化产生硫酸；硫歧化菌是一种无机化能自养菌，同样以元素硫为底物产生硫化物，具有从废弃物中分离回收有价金属的潜力。然而，目前国内外在该技术应用于不锈钢酸洗污泥处理方面的研究报道较少，尤其是在上述生物处理过程中，浸提与回收有价金属的影响因素及形态转化规律尚不明确。为此，本论文在解析酸洗污泥的矿物相组成及其有价金属的化学赋存形态的基础上，通过序批式摇瓶培养和生物反应器实验，探究了嗜酸性氧化硫硫杆菌产酸生物浸出酸洗污泥中有价金属以及硫歧化菌产硫化物沉淀回收浸提液中有价金属的效果及其影响因素，旨在为酸洗污泥中有价金属的选择性回收提供一种新技术原理。论文获得的主要研究结果如下：

（1）通过XRD图谱鉴定出酸洗污泥由白云石（CaMg(CO₃)₂）、蓝铁矿（Fe₃(PO₄)₂）和锰铁橄榄石（FeMnSiO₄）三种矿物相组成，含量分别为89.2%、5.6%、5.2%。污泥抛光表面的EPMA面扫图像以及断裂表面的SEM图像结合分析表明，Zn元素分布集中且含量极高，与钙镁矿物未重叠；As与Mn元素在酸洗污泥中分布比较均匀，含量较高As的分布与钙镁矿物重叠，As元素富集在钙镁矿物内部，Fe元素富集在钙镁矿物表面。改进的BCR连续提取揭示酸洗污泥中有价金属的形态：污泥中结合态的Fe、As元素占比较高（98.9%、70.1%），证实比较难浸出的金属主要结合在钙镁矿物（白云石）中，且矿相对有价金属的结合力较强；反之，结合态的Zn与Mn元素占比较低（41.5%、30.7%），其与矿相结合较弱。

（2）生物硫氧化在促进酸洗污泥中金属离子浸提方面成效显著，其促进过程受到污泥含固率及能源物质投加量的显著影响。污泥含固率越低，生物硫氧化促进酸洗污泥中有价金属浸出的效果越好，低含固率处理组（1%）反应第九天时Zn、Mn、Fe、As的浸出率（98%、85%、40%、24%）优于高含固率处理组（5%）的Zn、Mn、Fe、As的浸出率（1%、2%、0.2%、0.1%）。能源物质投加量适中（6 g/L）时，生物硫氧化促进酸洗污泥中有价金属浸出的效果最佳，反应第九天时Zn、Mn、Fe、As的浸出率分别为95%、88%、35%、23%。随后通过机械力化学二级处理球磨稳定污泥中剩余的有价金属，最佳球磨条件为：转速设定为580 rpm，球磨时长2 h，添加稳定剂硫粉的湿磨。

（3）生物硫歧化促进金属浸提液中金属离子回收受到碳源剂量的影响。最佳培养条件为添加1 g/L NaHCO₃，pH 5.5时，Zn、Mn的回收率在反应第八天时可达到90%以上。生物硫歧化回收的产物经XRD表征、SEM-EDS面扫及TEM-EDS面扫分析可得该物质为纳米级ZnS，经电化学性能测试得到如下结果：纳米ZnS光电流响应效果稳定且光电流强度最高可达11 uA/cm²；在电位为0.5 V时，ZnS的电流密度可以达到6 mA/cm²。

（4）生物硫氧化耦合生物硫歧化的小试实验验证了前述生物硫氧化及生物硫歧化小体系实验在放大规模下较高的稳定性与可行性。在生物硫氧化反应器中，Zn和Mn的浸出量和浸出率均保持稳定上升状态，最高浸出率呈现批次稳定性，分别可达95%和80%以上；同时，Zn与Mn的回收率稳定且高达90%以上。SOB反应器连续运行过程中，将投入0.3 t/t DS硫粉做能源物质，总成本为120元/t DS；在SDB反应器连续运行过程中，仅需投加0.033 t/t DS硫粉作为能源物质，成本为13.2元/t DS；在金属沉淀池阶段需要投加0.05t/t DS NaHCO₃调节pH，产生的成本为60元/t DS。连续运行小试验证实验所需的总药剂成本为193.2元/t DS。

Stainless steel pickling sludge is a kind of inorganic precipitate which is rich in Fe, Cu, Zn and other metal elements and formed by adding lime milk to acidic wastewater produced by stainless steel pickling, and belongs to hazardous waste. The content of Zn, Ni, Mn and other valuable metals in pickling sludge is as high as 2.67%~12.88%, 1.03%~4.12%, 0.12%~0.84%. The existing disposal methods of pickling sludge mainly include landfill treatment, solidification stabilization treatment, incineration treatment and resource utilization, etc., which are generally faced with problems such as high treatment cost and high energy consumption in practical applications. Thiobacillus thiosinophilus produces sulfuric acid mainly by biological oxidation of elemental sulfur and reducing sulfide as substrates. Sulfur dismutator is a kind of inorganic chemoautotrophic bacteria, which also produces sulfide from elemental sulfur as substrate, and has the potential to separate and recover valuable metals from waste. However, at present, there are few research reports on the application of this technology in the treatment of stainless steel pickling sludge at home and abroad, especially in the biological treatment process, the influencing factors of the extraction and recovery of valuable metals and the morphological transformation law are not clear. Therefore, on the basis of analyzing the mineral phase composition of pickling sludge and the chemical occurrence forms of valuable metals, this paper explored the effect and influencing factors of the acid-producing bileach of valuable metals from pickling sludge by acidiophilic thiobacillus thiooxidans and the recovery of valuable metals from the leaching solution by sulfur dismutating bacteria through sequencing batch shaker culture and bioreactor experiments. This paper aims to provide a new technical principle for selective recovery of valuable metals from pickling sludge. The main results obtained in this paper are as follows:

(1) The original pickling sludge was identified by XRD pattern as consisting of dolomite (CaMg(CO₃)₂), cyanite (Fe₃(PO₄)₂) and mangano-ferromangineolivine (FeMnSiO₄) with contents of 89.2%, 5.6% and 5.2%, respectively. The combined analysis of EPMA images and SEM images of the polished surface of the sludge showed that Zn was concentrated and high in content, and there was no overlap with calcium and magnesium minerals. As and Mn are evenly distributed in pickling sludge, and the distribution of As with high content overlaps with calcium-magnesium minerals. As is enriched in the interior of calcium-magnesium minerals, and Fe is enriched on the surface of calcium-magnesium minerals. The improved BCR continuous extraction revealed the form of heavy metals in the pickling sludge: the combined Fe and As elements in the sludge accounted for a relatively high proportion (98.9%, 70.1%), which confirmed that the relatively difficult metals were mainly combined in calcium magnesium minerals (dolomite), and the ore had a stronger binding force than the heavy metals. On the contrary, the proportion of Zn and Mn in the combined state is relatively low (41.5%, 30.7%), and the combination with ore is weak.

(2) Biological sulfur oxidation is effective in promoting metal ion extraction from pickling sludge, and its promotion process is significantly affected by the solid content of sludge and the amount of energy substances added. The lower the solid content of sludge, the better the effect of biological sulfur oxidation on promoting the leaching of valuable metals from pickling sludge. The leaching rates of Zn, Mn, Fe and As (98%, 85%, 40%, 24%) in the low solid content treatment group (1%) were better than those of Zn, Mn, Fe and As (1%, 2%, 0.2%, 0.1%) in the high solid content treatment group (5%). On the 9th day of the reaction, the leaching rates of Zn, Mn, Fe and As were 95%, 88%, 35% and 23%, respectively. The remaining heavy metals in the sludge were stabilized by mechanical and chemical secondary milling. The optimal milling conditions were as follows: the rotational speed was set at 580 rpm, the milling time was 2 h, and the stabilizer sulfur powder was added for wet milling.

(3) The recovery of metal ions in metal leaching solution promoted by biological sulfur disproportionation was affected by the dose of carbon source. When 1 g/L NaHCO₃ was added at pH 5.5, the recoveries of Zn and Mn could reach more than 90 % on the eighth day of the reaction. XRD characterization, SEM-EDS surface scan and TEM-EDS surface scan analysis of the recovered products of biological sulfur disproportionation showed that the compounds were nano-scale ZnS. The results of electrochemical performance test were as follows: The photocurrent response of nano-ZnS was stable and the photocurrent intensity was up to 11 uA/cm². At a potential of 0.5 V, the current density of ZnS can reach 6 mA/cm².

(4) The small-scale experimental verification of the coupling of biological sulfur oxidation and biological sulfur disproportionation demonstrated the high stability and feasibility of the aforementioned small-scale biological sulfur oxidation and biological sulfur disproportionation systems when scaled up. In the biological sulfur oxidation reactor, the leaching amounts and leaching rates of Zn and Mn both maintained a stable upward trend, with the highest leaching rates showing batch stability, reaching over 95% and 80% respectively. Meanwhile, the recovery rates of Zn and Mn were stable and exceeded 90%. During the continuous operation of the SOB reactor, 0.3 t/t DS of sulfur powder was added as an energy source, with a total cost of 120 yuan/t DS. In the continuous operation of the SDB reactor, only 0.033 t/t DS of sulfur powder was added as an energy source, with a cost of 13.2 yuan/t DS. In the metal precipitation tank stage, 0.05 t/t DS of NaHCO3 was added to adjust the pH, incurring a cost of 60 yuan/t DS. The total reagent cost for the continuous operation small-scale verification experiment was 193.2 yuan/t DS.

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