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丁基黄药(C4H9OCS2Me,Me为Na+或K+)是一种捕收能力较强的有机浮选药剂,被广泛应用于各种硫化矿及硫铁矿的混合浮选中。浮选废水中残留的丁基黄药有一定的生物毒性和稳定性[1],并因其自身的还原性极易导致水体COD值超标,若不进行有效处理,将对受纳水体及其周边的生态环境造成严重影响。因此,寻找可有效同步去除丁基黄药及COD的处理技术十分必要。
目前,用于处理丁基黄药废水的工艺方法中,相较于物化法(化学沉淀法、吸附法[2]等)易产生二次污染、生物法[3]反应周期长的缺点,高级氧化法(臭氧[4]、Fenton氧化法[5]等)具有处理效率高、无二次污染等明显优势[6]。臭氧作为高效氧化剂已常见于各类有机废水的降解处理过程中[7],但相关研究结果指出单一臭氧处理是无法进一步将氧化过程中产生的中间产物彻底氧化和矿化,进而导致COD去除率不高[8-9]。与此同时,活性炭 (AC) 工艺因操作简便、成本低及无二次污染等优点在选矿废水处理中得到广泛应用[10-11],但活性炭也存在长时间使用处理效果易下降、吸附饱和后难以分离回收等缺陷[12]。而O3/AC耦合工艺可实现AC吸附和O3氧化在系统中同时进行,在反应过程中有机污染物首先通过吸附作用富集至AC表面,而后通过O3氧化作用得到降解,在提升O3处理的COD去除能力的同时,使得AC吸附能力得到再生以延长其使用周期[13]。因此,O3/AC耦合工艺逐渐受到有机废水处理领域的广泛关注[14],但基于O3/AC耦合工艺处理含丁基黄药的选矿废水尚鲜见报道,且以往同类研究主要关注于对丁基黄药的去除而未进一步研究对COD的同步去除且其降解路径也尚不明确。因此,本文以含丁基黄药废水为研究对象,通过探讨单独O3氧化、AC吸附和O3/AC耦合工艺对丁基黄药及其COD的同步去除效果,并结合反应动力学、傅里叶红外 (FT-IR) 光谱、紫外-可见(UV-vis)光谱及GC-MS鉴定等多角度分析,揭示其表观反应过程及可能的降解路径,以期为今后类似废水的处理提供新的参考。
基于O3/AC耦合工艺对丁基黄药与COD的同步去除性能及降解机理
Performance and mechanism analysis of simultaneous removal of butyl xanthate and COD based on O3/AC combined process
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摘要: 针对臭氧氧化技术处理含丁基黄药废水COD去除率低等问题,提出了O3/AC耦合工艺。在探讨单独、耦合工艺的丁基黄药去除率和COD去除率、反应影响因素和降解路径的基础上,进一步发掘该耦合工艺对丁基黄药及COD的同步去除性能。结果表明:臭氧(O3)及活性炭(AC)的单独作用均对丁基黄药或COD有一定的去除效果,通过O3/AC的耦合作用则可使丁基黄药的去除率达99.9%,亦使COD的去除率由O3单独作用下的42.9%显著提升至77.2%,且实现最高去除率的时间由AC单独处理所需的80 min缩减至30~40 min;拟一级反应动力学分析结果表明,丁基黄药的反应速率常数表现为
$k{_\text{(O3/AC)}}$ >$k{_\text{O3}}$ >kAC,COD的反应速率常数表现为$k{_\text{(O3/AC)}}$ >kAC>$k{_\text{O3}}$ ,O3/AC耦合工艺去除丁基黄药及COD的反应速率常数均大于两种单独处理工艺;紫外-可见(UV-vis)光谱分析表明丁基黄药在O3、O3/AC作用下生成中间有机产物,结合GC-MS对产物的鉴定结果表明其中间有机产物可能为丁酸等物质,并以此对O3/AC耦合工艺同步去除丁基黄药及COD的降解路径进行了初步推测。Abstract: Aiming at low COD removal rate from butyl xanthate-containing wastewater by ozone oxidation process, a combined O3/AC process was proposed for its treatment. On the basis of exploring the removal rates of butyl xanthate and COD, reaction influencing factors and degradation pathway of the single or coupling process, the simultaneous removal performance of the system on butyl xanthate and COD was further explored. The results showed that: ozone (O3) and activated carbon (AC) alone had certain removal effects for butyl xanthate or COD, and the coupling O3/AC process could remove 99.9% of butyl xanthate, and lead to the increase of COD removal rate from 42.9% under O3 alone to 77.2%, and the time to achieve the maximum removal effect decreased from 80 min under AC alone to 30~40 min. The pseudo-first order kinetic analysis showed that the reaction rate constants of butyl xanthate were$k{_\text{(O3/AC)}}$ >$k{_\text{O3}}$ >kAC, and the reaction rate constants of COD were$k{_\text{(O3/AC)}}$ >kAC>$k{_\text{O3}}$ , and the reaction rate constants of the O3/AC coupling process for the removal of butyl xanthate and COD were greater than those of the two processes alone. UV-visible spectroscopy analysis showed that the butyl xanthate produced intermediate organic products under the action of O3 and O3/AC, and the GC-MS analysis showed that the intermediate organic products might be butyric acid and other substances, which was used to make a preliminary speculation on the degradation pathway of simultaneous removal of butyl xanthate and COD by O3/AC coupling process.-
Key words:
- O3/AC process /
- butyl xanthate /
- COD /
- simultaneous removal /
- degradation pathway
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表 1 反应动力学参数表
Table 1. Reaction kinetics parameter table
处理方法 k/min−1 R2 调整后R2 O3 丁基黄药 0.078 0.935 0.919 COD 0.011 0.910 0.887 AC 丁基黄药 0.020 0.889 0.862 COD 0.020 0.914 0.893 O3/AC 丁基黄药 0.165 0.987 0.983 COD 0.026 0.858 0.823 -
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