Optimization of fluorine mine water treatment and fluorine removal mechanism using response surface methodology
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摘要: 地表水或地下水流经富氟岩石易导致水中氟超标。水中氟超标易导致地方性氟中毒、生态环境的破坏，制约水资源综合利用。基于研制的一种高效除氟药剂，通过响应曲面分析中的Box-Behnken设计除氟试验，优化了pH值、除氟药剂投加量和快速搅拌时间对除氟效果的影响，并通过X射线光电子能谱(XPS)、X射线粉末衍射(XRD)、傅里叶红外光谱(FT-IR)等分析手段对除氟药剂及处理后产生的污泥进行表征分析，探讨了除氟药剂去除氟离子的机理。试验结果表明：最佳除氟条件为pH值6.11，药剂投加量4.15 mL，快速搅拌时间10.90 min，此时可使F-从初始的20 mg/L降至0.453 mg/L，与模型预测的0.445 mg/L基本吻合。除氟机理为，药剂在含氟矿井水中形成铁铝硅氧的多核多羟基络合物，通过氟离子与羟基发生交换、取代羟基，将氟离子固定在多核多羟基络合物中，形成铝硅氧四面体结构的氟化物，实现除氟效果。对比现用的羟基磷灰石吸附为主体的处理工艺，本研究制备的除氟药剂具有处理工艺简单、处理效果稳定、处理成本低等优点。Abstract: Surface water or groundwater flowing through fluorine-rich rocks can easily lead to excessive fluorine in water.Excessive fluoride in water can cause endemic fluorosis, damage of the ecological environment and restrict comprehensive utilization of water resources.In this study, based on a highly effective fluoride removal agent developed by the research group earlier, the box-Behnken method of response surface analysis was applied to design fluoride removal experiments where the influences of pH value, dosage of defluoridation reagent and fast stirring time on fluoride removal effect were optimized.This paper used X-Photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Fourier transform infrared spectrum (FT-IR) to characterize the defluoridation reagent and the sludge produced after treatment, and discussed the mechanism of fluoride ion removal.The experimental results showed that F-could be reduced from the initial 20 mg/L to 0.453 mg /L under the optimal conditions of fluoride removal (pH value 6.11, dosage 4.15 mL, fast stirring time 10.90 min), which was basically consistent with the predicted value 0.445 mg /L of the model.The defluoridation reagent was mainly through the formation of Fe, Al, Si and O polynuclear polyhydroxyl complex, fluorine-ion exchange with hydroxyl and replace hydroxyl, then fluorine-ion was fixed in the polynuclear polyhydroxyl complex.Meanwhile, fluoride forms a tetrahedral structure of aluminum, silicon and oxygen, and locks fluorine ions in the tetrahedral structure to achieve fluoride removal.Compared with the current main treatment process using hydroxyapatite adsorption, the defluoridation reagent in this study has the advantages of simple treatment process, stable treatment effect and low treatment cost.
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图 2 上清液氟离子浓度真实值与预测值的关系
Figure 2. Relationship between experimental value and predicted value of fluorine ion removal rate
图 3 pH值、快速搅拌时间和除氟药剂投加量对上清液氟离子浓度影响的响应曲面和等高线
Figure 3. The response surface and contour lines of pH, rapid stirring time and dosage of fluoride removal agent on fluoride ion concentration in supernatant
图 4 高效除氟药剂处理含氟矿井水的中试实验结果
Figure 4. Pilot test results of fluorine-containing mine water treated with high efficiency fluorine-removing agent
图 5 高效除氟药剂及药剂作用后污泥XPS谱图
Figure 5. XPS spectrum of high efficiency fluoride removal agent and sludge after treatment
图 7 除氟药剂合成过程XRD谱图
Figure 7. XRD spectrum of the main synthesis process of defluoridation reagent
图 8 除氟药剂及处理后产生的药剂作用后污泥XRD谱图
Figure 8. XRD spectrum of the fluoride removal reagents and sludge after treated
图 9 除氟药剂及药剂除氟作用后污泥FT-IR谱图
Figure 9. FT-IR spectrum of the fluoride removal reagent and sludge after treated
表 1 实验药剂
Table 1. Experimental reagents
试剂名称 等级 生产厂家 聚合氯化铝 分析纯 德力通净水材料 A 分析纯 国药集团化学试剂有限公司 B 分析纯 德力通净水材料 C 分析纯 福晨化学试剂有限公司 氟化钠 分析纯 上海麦克林生化科技有限公司 盐酸 分析纯 国药集团化学试剂有限公司 氢氧化钠 分析纯 国药集团化学试剂有限公司 聚丙烯酰胺 分析纯 德力通净水材料 
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表 2 实验仪器
Table 2. Experimental instruments
仪器名称 型号 生产厂家 分析天平 BSA124S 德国赛多利斯集团 恒温鼓风干燥箱 DHG-9243A 上海精其仪器有限公司 恒温磁力搅拌器 B11-1 上海司乐仪器公司 超纯水系统 Direct-Pure RO 赛默飞世尔科技公司 pH计 PHS-3C 上海雷磁仪器公司 浊度计 WZS-186 上海雷磁仪器公司 X射线衍射仪 D8 ADVANCE 布鲁克(北京)科技有限公司 傅立叶红外光谱 Nicolet IS 10 赛默飞世尔科技(中国) 有限公司 X射线光电子能谱 ESCALAB 50Xi 日本Hitachi 氟离子计 PXS-270 上海雷磁仪器公司 六联搅拌机 MY-3000-6M 武汉梅宇仪器公司
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表 3 Box-Behnken设计因子及水平
Table 3. Factors and levels of Box-Behnken design
符号 因子 单位 水平 -1 0 +1 a pH值 — 6.0 6.25 6.5 b 药剂投加量 mL 3.5 4.0 4.5 c 快速搅拌时间 min 5 9 13
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表 4 BBD实验设计及结果
Table 4. BBD experimental design and results
运行序号 a b/mL c/min 上清液氟离子
浓度/(mg·L-1)1 6.00 3.50 9.00 1.25 2 6.50 3.50 9.00 2.54 3 6.00 4.50 5.00 0.77 4 6.50 4.50 9.00 1.69 5 6.00 4.00 13.00 1.54 6 6.50 4.00 9.00 2.25 7 6.00 4.00 9.00 0.71 8 6.50 4.00 13.00 1.93 9 6.25 3.50 13.00 2.28 10 6.25 4.50 5.00 1.50 11 6.25 3.50 9.00 1.31 12 6.25 4.50 9.00 0.88 13 6.25 4.00 9.00 0.80 14 6.25 4.00 5.00 0.68 15 6.25 4.00 5.00 0.70 16 6.25 4.00 9.00 0.74 17 6.25 4.00 13.00 0.71
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表 5 二次响应面回归模型的方差分析
Table 5. Analysis of variance for quadratic response surface regression model
方差来源 平方和 自由度 均方 F值 P值 模型 6.46 9 0.72 112.94 < 0.000 1 a 2.14 1 2.14 336.86 < 0.000 1 b 0.81 1 0.81 126.80 < 0.000 1 c 0.94 1 0.94 147.56 < 0.000 1 ab 0.034 1 0.034 5.38 0.053 4 ac 0.065 1 0.065 10.22 0.015 1 bc 0.031 1 0.031 4.82 0.064 3 a2 0.95 1 0.95 149.84 < 0.000 1 b2 0.55 1 0.55 86.16 < 0.000 1 c2 0.69 1 0.69 108.99 < 0.000 1 残差 0.045 7 0.006 4 失拟项 0.036 3 0.012 5.47 0.067 0 误差 0.008 7 4 0.002 2 总离差 6.51 16
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表 6 二次响应面回归模型的可信度分析
Table 6. Credibility analysis of quadratic response surface regression model
参数 数值 相关系数 0.993 2 调整后的相关系数 0.984 4 预测相关系数 0.909 9 信噪比 30.573 标准差 0.080 变异系数/% 6.09
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表 7 二次响应面回归模型预测值验证
Table 7. Verification of prediction values of quadratic response surface regression model
除氟药剂
投加量/mLpH值 快速搅拌
时间/min出水氟离子
浓度/(mg·L-1)4.15 6.11 10.9 0.47 4.15 6.11 10.9 0.44 4.15 6.11 10.9 0.45
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