高活性多羟基结构态亚铁FHC(Cl-)去除Se(Ⅳ)的性能与机制

doi:10.7503/cjcu20160772

摘要/Abstract

摘要：

通过慢速滴定法合成了高活性的多羟基结构亚铁FHC(Cl^-), 对FHC(Cl^-)去除Se(Ⅳ) 的动力学进行了研究, 并对体系中的投加量、 pH值、溶解氧和氯化钠浓度进行了响应面分析. 研究结果表明, FHC(Cl^-)去除Se(Ⅳ)的表观速率常数k_obs=0.60 min^-1, 约为纳米零价铁的4倍和零价铁的16倍. 由Box-Benhnken设计拟合得出响应值对编码自变量的二次多项回归方程为Y(c/c₀)=0.14-0.20A+0.017B-0.27C-0.019D-0.047AB-0.095AC+0.13AD-0.010BC-0.082BD+0.33A²+0.023B²+0.097C²+0.065D², 最优条件为: FHC(Cl^-)投加量98 mg/L, 溶液的pH=7.5, 氯化钠浓度1 mmol/L, 体系为封闭. 产物XPS分析结果表明, Se(Ⅳ)最终被FHC(Cl^-)还原为Se(0)或Se(-Ⅱ).

关键词: 反应动力学, 高活性, 还原, 响应面法, X射线光电子能谱

Abstract:

The highly active ferrous hydroxyl complex[FHC(Cl^-)] was synthesized by slow titration. The dynamics of Se(Ⅳ) removal by FHC(Cl^-) was investigated, where the impact factors of FHC(Cl^-) dosage, pH, oxygen and sodium chloride concentration were studied with response surface analysis method. The results demonstrated that the apparent rate constant(k_obs) was 0.60 min^-1, which was 4 times as great as that of Nano Zero-Valent Iron and 16 times that of Zero-Valent Iron. In addition, the response value of quadratic multinomial regression equation(designed by Box-Benhnken) for coding the independent variables was Y(c/c₀)=0.14-0.20A+0.017B-0.27C-0.019D-0.047AB-0.095AC+0.13AD-0.010BC-0.082BD+0.33A²+0.023B²+0.097C²+0.065D². The optimum reaction conditions were FHC(Cl^-) dosage 98 mg/L, pH=7.5, the concentration of NaCl 1 mmol/L and closed system. The results of XPS indicated that Se(Ⅳ) was eventually reduced to Se(0) or Se(Ⅱ) by FHC(Cl^-).

Key words: Reaction kinetics, High-reactivity, Reduction, Response surface method(RSM), X-ray photoelectron spectroscopy(XPS)

中图分类号:

O641
O613.52

TrendMD:

张勇, 付茂, 吴德礼, 张亚雷. 高活性多羟基结构态亚铁FHC(Cl^-)去除Se(Ⅳ)的性能与机制. 高等学校化学学报, 2017, 38(5): 830.

ZHANG Yong, FU Mao, WU Deli, ZHANG Yalei. Removal Performance and Mechanism of Selenite with the Highly Active Ferrous Hydroxyl Complex FHC(Cl^-)^†. Chem. J. Chinese Universities, 2017, 38(5): 830.

图/表 12

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Level	Dosage/(mg·L^-1)	O₂	pH	c(NaCl)/(mmol·L^-1)
1	56.0	Aerobic	5.5	0
2	98.0	Closed	7.5	1
3	140.0	Anaerobic	9.5	2

Level	Dosage/(mg·L^-1)	O₂	pH	c(NaCl)/(mmol·L^-1)
1	56.0	Aerobic	5.5	0
2	98.0	Closed	7.5	1
3	140.0	Anaerobic	9.5	2

pH	c(NaCl)/ (mmol·L^-1)	Dosage/ (mg·L^-1)	O₂	c/c₀	pH	c(NaCl)/ (mmol·L^-1)	Dosage/ (mg·L^-1)	O₂	c/c₀
7.5	2	98.0	Aerobic	0.08	7.5	0	98.0	Aerobic	0.11
7.5	1	98.0	Closed	0.14	5.5	1	98.0	Aerobic	0.66
5.5	1	140.0	Closed	0.52	9.5	0	98.0	Closed	0.38
5.5	1	56.0	Closed	0.88	7.5	2	140.0	Closed	0.02
7.5	1	140.0	Aerobic	0.08	5.5	0	98.0	Closed	0.71
7.5	1	98.0	Closed	0.14	7.5	1	98.0	Closed	0.14
7.5	1	56.0	Aerobic	0.59	7.5	1	98.0	Closed	0.14
7.5	0	98.0	Anaerobic	0.17	9.5	1	98.0	Anaerobic	0.14
9.5	2	98.0	Closed	0.22	7.5	0	56.0	Closed	0.48
7.5	1	98.0	Closed	0.14	5.5	1	98.0	Anaerobic	0.84
7.5	1	140.0	Anaerobic	0.01	7.5	2	56.0	Closed	0.53
7.5	0	140.0	Closed	0.01	5.5	2	98.0	Closed	0.74
9.5	1	140.0	Closed	0.02	9.5	1	98.0	Aerobic	0.49
9.5	1	56.0	Closed	0.76	7.5	2	98.0	Anaerobic	0.47
7.5	1	56.0	Anaerobic	0.61

pH	c(NaCl)/ (mmol·L^-1)	Dosage/ (mg·L^-1)	O₂	c/c₀	pH	c(NaCl)/ (mmol·L^-1)	Dosage/ (mg·L^-1)	O₂	c/c₀
7.5	2	98.0	Aerobic	0.08	7.5	0	98.0	Aerobic	0.11
7.5	1	98.0	Closed	0.14	5.5	1	98.0	Aerobic	0.66
5.5	1	140.0	Closed	0.52	9.5	0	98.0	Closed	0.38
5.5	1	56.0	Closed	0.88	7.5	2	140.0	Closed	0.02
7.5	1	140.0	Aerobic	0.08	5.5	0	98.0	Closed	0.71
7.5	1	98.0	Closed	0.14	7.5	1	98.0	Closed	0.14
7.5	1	56.0	Aerobic	0.59	7.5	1	98.0	Closed	0.14
7.5	0	98.0	Anaerobic	0.17	9.5	1	98.0	Anaerobic	0.14
9.5	2	98.0	Closed	0.22	7.5	0	56.0	Closed	0.48
7.5	1	98.0	Closed	0.14	5.5	1	98.0	Anaerobic	0.84
7.5	1	140.0	Anaerobic	0.01	7.5	2	56.0	Closed	0.53
7.5	0	140.0	Closed	0.01	5.5	2	98.0	Closed	0.74
9.5	1	140.0	Closed	0.02	9.5	1	98.0	Aerobic	0.49
9.5	1	56.0	Closed	0.76	7.5	2	98.0	Anaerobic	0.47
7.5	1	56.0	Anaerobic	0.61

Soruces of variation	Quadratic sum	Degree of freedom	F	Level of significance, P
Model	2.18	14	23.38	<0.0001
A-pH	0.46	1	68.57	<0.0001
B-c(NaCl)	0.003	1	0.50	0.4907
C-dosage	0.85	1	127.44	<0.0001
D-DO	0.004	1	0.66	0.4293
AB	0.009	1	1.36	0.2636
AC	0.04	1	5.43	0.0353
AD	0.07	1	10.55	0.0058
BC	0.0004	1	0.06	0.8099
BD	0.03	1	4.09	0.0626
CD	0.002	1	0.30	0.5899
A²	0.69	1	105.09	<0.0001
B²	0.004	1	0.53	0.4783
C²	0.06	1	9.18	0.0090
D²	0.03	1	4.07	0.0634
Residual error	0.09	14	0.007
Lack of fit	0.09	10	0.09
Pure error	0	4	0
Sum	2.27	28