改性天然沸石对煤化工废水中高浓度NH<sub>4</sub> <sup>+</sup>的吸附和再生研究

doi:10.19965/j.cnki.iwt.2023-0682

摘要/Abstract

摘要：

针对目前常用的蒸氨法和吹脱法去除煤化工废水中高浓度氨氮带来的能耗高、处理成本高、操作复杂等实际问题，对天然沸石进行改性，探究改性沸石对煤化工废水中高浓度氨氮的吸附性能和化学再生性能。结果表明，相较于未改性天然沸石，经300 ℃热处理与1.5 mol/L NaCl溶液协同改性后，沸石的比表面积由18.541 m²/g增加至32.198 m²/g，吸附容量提升了74%，NH₄ ⁺去除率达88.94%。吸附动力学和等温线分析表明，改性沸石对煤化工废水中高浓度NH₄ ⁺的吸附过程符合化学多层吸附过程。0.100 mol/L NaClO溶液对改性沸石再生效果最好，再生率高达94.5%，且可将再生NH₄ ⁺转化为无毒、无害的N₂，实现了沸石的高效、可持续再生，且无二次污染。

关键词: 煤化工废水, 沸石, NH₄ ⁺, 改性, 吸附, 再生

Abstract:

In view of the practical problems of high energy consumption, high treatment cost and complicated operation caused by the current high-concentration ammonia nitrogen removal method in coal chemical wastewater, such as the steaming ammonia and stripping method, the natural zeolite was modified to investigate the adsorption and chemical regeneration performance of the modified zeolite on the high concentration of ammonia nitrogen in coal chemical wastewater. The results showed that the specific surface area of zeolite increased from 18.541 m²/g to 32.198 m²/g after the synergistic modification processes by heat treatment at 300 ℃ and brine leaching in 1.5 mol/L NaCl solution. Compared with the natural zeolite, the adsorption capacity increased by 74% and the removal efficiency of NH₄ ⁺ also reached to 88.94%. The adsorption kinetic and isotherm analysis showed that the adsorption process of high-concentration NH₄ ⁺ by modified zeolite in coal chemical wastewater was consistent with the chemical multilayer adsorption process. In addition, 0.100 mol/L NaClO solution had the best regeneration effect for the modified zeolite, with the regeneration rate as high as 94.5%, and the regenerated NH₄ ⁺ was converted into non-toxic and harmless N₂, which realized the prospects of high-efficiency and sustainable regeneration of zeolite without secondary pollution.

Key words: coal chemical wastewater, zeolite, NH₄ ⁺, modification, adsorption, regeneration

中图分类号:

X703

刘磐. 改性天然沸石对煤化工废水中高浓度NH₄ ⁺的吸附和再生研究[J]. 工业水处理, 2024, 44(7): 141-149.

Pan LIU. Adsorption and regeneration performances of the modified zeolite for high-concentration ammonium in real coal chemical wastewater[J]. Industrial Water Treatment, 2024, 44(7): 141-149.

https://www.iwt.cn/CN/Y2024/V44/I7/141

图/表 11

表1 煤化工废水主要水质数据

Table 1 The main water quality of coal chemical wastewater

水质指标	pH	NH₄ ⁺-N	COD	K⁺	Na⁺	Fe³⁺	Mn²⁺
数值	8~9	1 000~1 500	4 000~5 000	1.782	7.124	2.465	4.789

图1 不同方法改性后沸石的吸附效果

Fig.1 Adsorption effects of zeolites modified by different methods

图2 天然沸石和改性沸石的SEM

Fig.2 SEM of natural and modified zeolites

图3 天然沸石和改性沸石的基本物理特性

Fig.3 Basic physical characterizations of natural and modified zeolites

图4 改性沸石的Zeta电位

Fig.4 Zeta potential of modified zeolite

图5 不同影响因素对改性沸石吸附性能的影响

Fig.5 Effects of different interfering factors on adsorption performance of modified zeolite

图6 改性沸石的吸附动力学和等温特性

Fig.6 Adsorption kinetics and isotherm characteristics of modified zeolite

表2 改性沸石吸附高浓度NH₄ ⁺的吸附热力学参数

Table 2 Adsorption thermodynamic parameters of high-concentration NH₄ ⁺ by modified zeolite

温度/K	K _c	ΔG ⁰/ （kJ·mol^-1）	ΔH ⁰/ （kJ·mol^-1）	ΔS ⁰/ （J·mol^-1·K^-1）
288	0.35	-16.13	28.82	39.14
298	1.17	-16.48
308	1.23	-17.13
318	2.42	-17.55

图7 再生试剂对饱和沸石再生率的影响

Fig.7 Effects of regenerants on regeneration efficiency

图8 再生后生成N₂的选择性

Fig.8 The selectivity of produced nitrogen after regeneration

图9 再生条件对改性沸石再生性能的影响

Fig.9 Effect of desorption conditions on regeneration of modified zeolite

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改性天然沸石对煤化工废水中高浓度NH₄ ⁺的吸附和再生研究

Adsorption and regeneration performances of the modified zeolite for high-concentration ammonium in real coal chemical wastewater

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改性天然沸石对煤化工废水中高浓度NH4 +的吸附和再生研究

Adsorption and regeneration performances of the modified zeolite for high-concentration ammonium in real coal chemical wastewater

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改性天然沸石对煤化工废水中高浓度NH₄ ⁺的吸附和再生研究