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全球锌生产在很大程度上依赖于混合锌矿的加工。全球 95% 以上的锌都产自这一矿源。在通过湿法冶金或火法冶金方法回收金属锌之前,须消除精矿中的硫。具体方法是在高温下加热硫化锌(ZnS),将其转化为活性更强的氧化锌(ZnO)。

在此过程中产生的二氧化硫随后被转化为硫酸。然而,矿石中的硫化铁会产生问题,因为它在与氧化锌反应时会变成铁氧体锌(ZnO-Fe2O3)。为确保生产出高质量的锌,溶解溶液在电解之前需要经过净化阶段。

本工艺应用说明详细介绍了锌、硫酸和铁含量等关键参数的在线分析。瑞士万通过程分析公司的 2060 TI 过程分析仪可提供准确效率高的测量,减少时间、人力和人为误差。

More than 95% of the world's zinc comes from zinc blende (ZnS) [1]. Before obtaining metallic zinc, which can be done using hydrometallurgical or pyrometallurgical techniques, the sulfur in the concentrate must be removed.

This is accomplished by roasting or sintering at high temperatures (>900 °C), causing zinc sulfide (ZnS) to change into the more reactive zinc oxide (ZnO) (Equation 1). The acquired sulfur dioxide is converted into sulfuric acid within a nearby plant connected to the smelter.

Equation 1.

If there is any iron sulfide in the ore, it will be transformed into iron(III) oxide (Fe2O3), which then reacts with zinc oxide (ZnO) to produce zinc ferrite (ZnO·Fe2O3). This zinc compound is challenging to recover, making ores with low iron content more desirable.

In the leaching step (hot acid leach) shown in Figure 1, zinc oxide is isolated from the other calcines formed in the roasting process. The isolation is done by using sulfuric acid (spent electrolyte) to create zinc sulfate (ZnSO4) and water (Equation 2).

Figure 1. An illustrated diagram showing the major steps in the zinc refining process.
Equation 2.

Zinc dissolves and iron precipitates, while other metals like lead and silver remain undissolved. However, the resulting solution also contains impurities, like trace metals, which must be removed to produce high-purity zinc.

First- and second-stage purification prior to electrolysis is carried out by zinc dust precipitation or cementation. The resulting purified neutral zinc sulfate solution is then subjected to electrolysis in the cell room to create zinc metal.

In the complex process of zinc refining, efficient and accurate analysis of key parameters such as zinc, sulfuric acid, and iron is crucial to maintaining optimal process conditions and ensuring high-quality zinc production. Traditional laboratory analysis methods have long been used to determine these parameters, but they are often time-consuming, labor-intensive, and prone to human error. This is where online analysis systems come into play, revolutionizing the way these critical measurements are made in the zinc refining industry.

In several stages of the zinc refining process, online process analyzers are used to determine the acid, zinc, and ferric concentrations for completion rate monitoring. Metrohm Process Analytics offers a multi-parameter process analyzer solution for the simultaneous analysis of such analytes over a wide concentration range: the 2060 TI Process Analyzer (Figure 2). Other combinations of measurements (e.g., pH), as well as measurement points taken from multiple streams, can be realized with this process analyzer.

Figure 2. 2060 TI Process Analyzer with preconditioning panel in a zinc refining plant.

The acid concentration is measured by a straightforward acid/base titration while the zinc concentration is analyzed by a complexometric titration. The ferric iron is analyzed by redox titration. Another common impurity, cobalt, can be measured with photometry, and other trace metals can be measured by voltammetry (Table 1).

Besides the chemical analysis, sample preconditioning is a crucial factor for the success of online analysis. Figure 2 shows a 2060 TI Process Analyzer with a customized preconditioning panel able to handle this type of slurry sample. Due to the acidic environment and high sample temperature, all parts are made (or coated) with perfluoroalkoxy (PFA) or polytetrafluoroethylene (PTFE).

Table 1. Parameters to monitor in the zinc refining process. Different measurement techniques are suggested based on the concentration range.

Parameter Concentration range Technique
Zn2+ 0–2 mg/L Photometry
Zn2+ 10–90 g/L Titration
H2SO4 50–200 mg/L Titration
Cobalt 0.01–1.5 mg/L Photometry
Trace metals <0.05 mg/L Voltammetry

It is necessary to also measure impurities like nickel, cobalt, copper, cadmium, antimony, and germanium for product quality control, process efficiency, environmental compliance, health, and safety reasons. Additionally, measurement of these impurities is crucial for troubleshooting process issues and potentially recovering valuable resources.

These impurities can be monitored with a dedicated voltammetric process analyzer in the purification filtrates and reactor trains (Figure 1). This process analyzer can also be applied to monitor trace metals in the effluent of the zinc plant for environmental purposes.

In conclusion, zinc production from zinc blende involves removing sulfur, recovering zinc oxide, and purifying the solution. Online analysis systems like the 2060 TI Process Analyzer play a vital role in monitoring various parameters and ensuring high-quality zinc production. They also help measure impurities for quality control and process optimization. These tools have revolutionized the zinc refining industry, improving efficiency and environmental compliance.

  1. Production - Zinc.Org India. http://zinc.org.in/why_zinc/production/

AN-PAN-1019 Online and atline analysis of acids and iron in pickling baths
AN-PAN-1034 Analysis of Bayer aluminate liquors using thermometric titration

  • Guarantee compliance with governmental regulations
  • Safer working environment for employees (e.g., no exposure of the operator to dangerous environments)
  • Enhanced control of chemical dosing (H2SO4) of the zinc refining process
  • Monitor multiple parameters for more savings per measurement point and results
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