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金属加工液广泛应用于金属材料的加工、切割、研磨、钻孔和锻造等制造过程。除了冷却和润滑功能外,金属加工液还能起到减少摩擦、控制传热、防止腐蚀和提高加工效率[1]的作用,有助于提高加工工具的使用寿命和功能,成本约为加工费用的15%[2]。据统计,金属加工液的全球使用量超过1×107 t·a−1[3]。在金属加工液的使用过程中需要加水稀释,故实际废水排放量是加工液使用量的十倍以上。由于专利问题及加工工艺存在的差异,金属加工液废水不仅组成复杂,而且不同厂家排放的废水成分差异很大,因此,金属加工液废水的处理及其资源化是工业废水处理中的难点。
切削液是一种金属加工液,通常由油、表面活性剂和各种添加剂组成。切削液废水包含大量乳化油、金属屑、有机物等,其COD、总有机碳(TOC)和油浓度都很高[4]。若未经处理的切削液废水排入自然水体,会在水面形成油膜,导致水体缺氧,威胁水中生物的生长。此外,切削液废水中的油脂具有较强的渗透能力,还会透过土壤进入地下水层,进而污染地下水源。废水中的添加剂和金属屑进入水循环后,会通过食物链进入人体,引发患癌风险,危害人类健康[5-10]。2016年,我国发布《国家危险废物名录》,将切削液废水列入HW09废液的一种[11]。因此,以切削液为代表的废乳化液的处理是机械和装备制造领域亟待解决的问题。
由于切削液废水具有成分复杂、浓度高及危害性强的特点,所以需要针对不同行业产生的切削液废水个性化地研发有效的水处理单元或组合工艺。气浮、混凝、过滤、氧化和生物处理等技术已应用于废切削液处理。废水组成的复杂性使得单一处理单元都存在局限性,而组合工艺能够更好地实现废切削液的有效处理,如混凝与过滤联用、氧化与生物法联用等。本文综述了近年来切削液废水处理技术的研究进展,介绍了切削液废水处理过程的难点和新的发展方向,并提出了相关建议,以期为切削液废水的处理提供参考。
切削液废水处理技术研究进展
Progresses in the treatment processes and techniques for cutting fluid wastewater
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摘要: 在机械加工和制造业中,切削液被广泛应用于工件的冷却、清洗、防锈和润滑,产生大量废切削液。切削液废水中含有大量乳化油、添加剂(表面活性剂、缓蚀剂、消泡剂),以及废油、粉尘和金属屑等杂质,排放前需经过严格的处理。切削液废水处理大致分为物理、化学和生物法3大类。不同的处理方法有各自的优缺点。物理法中的膜分离技术具有效率高、占地小、无二次污染等优点,是处理切削液废水的有效技术;但膜污染问题限制了膜过滤技术的大规模引用,开发机械强度高、亲水性的新型膜材料是重要的研究方向。传统的混凝法处理成本较低,然而混凝产生的大量矾花沉淀还需进行二次处理。氧化法能够将污染物矿化为无害无机物,但处理成本很高。由于切削液废水的成分复杂,具有生物毒性,无法对其进行单独的生物处理;可将生物处理单元与氧化过程联用,先通过氧化法提高废水的可生化性,再进行成本低廉的生物处理;这样既能够节约氧化剂用量,也可完成切削液废水的深度处理。本文在综述切削液废水处理技术的研究进展基础上,提出了现有处理工艺中存在的问题,探讨了解决的思路,可为切削液废水处理技术的发展提供参考。Abstract: In machining and manufacturing, cutting fluids are widely used for cooling, cleaning, rust prevention and lubrication of workpieces, resulting in a great amount of waste cutting fluids. Cutting fluid wastewater contains emulsified oil, additives (surfactants, corrosion inhibitors, defoamers), and impurities such as waste oil, dust, and metal chips, which must be appropriately treated prior to environmental discharge. Cutting fluid wastewater treatment could be divided into three main approaches: physical, chemical and biological methods. Different treatment methods have distinct advantages and disadvantages. Membrane separation is a typical physical treatment approach, carrying the advantages of high efficiency, small area, and no secondary pollution, among others, which has been regarded as an effective technology for handling cutting fluid wastewater. Nonetheless, the problem of membrane pollution limits the large-scale application of membrane filtration technology. The development of high mechanical strength, new hydrophilic membrane materials are an important research direction. The traditional coagulation method is a chemical method, and the treatment cost is relatively low. Nevertheless, a large amount of alum precipitation produced by coagulation needs to be processed twice. The oxidation method can mineralize pollutants into harmless inorganic substances, but the processing cost is high. Because the composition of cutting fluid wastewater is complex and toxic, it cannot be subjected to separate biological treatment. The biological treatment unit can be combined with the oxidation process, and the biodegradability of the wastewater can be improved by the oxidation method, and then the low-cost biological treatment can be carried out. This can not only save the amount of oxidant but also complete the advanced treatment of cutting fluid wastewater. Based on the state-of-the-arts of cutting fluid wastewater treatment technology, this article puts forward the existing problems in current treatment processes, and discusses potentials to optimize cutting fluid wastewater treatment technology.
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Key words:
- waste cutting fluid /
- emulsified oil /
- demulsification /
- wastewater treatment
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表 1 含油废水处理技术的优缺点
Table 1. Advantages and disadvantages of each oily wastewater treatment technique
方法 优点 缺点 重力分离 可有效去除游离油和悬浮颗粒,成本低 不能有效去除小油滴和乳化油 酸析 操作简单,能去除大部分乳化油 腐蚀设备,需要加碱中和,增加额外成本 溶解气浮 除油率高,污泥量少 投资高,运行成本高 混凝 成本低 腐蚀设备和管道,产生大量絮体 生物处理 投资和运行成本低 难以处理难降解的有机物,占地大,耐受性差 吸附 处理效率高,无需添加剂 吸附剂不易再生,受吸附容量限制,不能处理高浓度含油废水 膜过滤 无需化学添加剂,成本低,占地小,处理效率高 易污染,需要频繁的反洗,通量难以完全恢复 -
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