Comparison and mechanism of ammonia nitrogen and phosphorus adsorption properties of six mineral-based fillers
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摘要:
为高效去除污染水体中的氨氮（${\mathrm{NH}}_4^+ $-N）和磷酸盐（${\mathrm{PO}}_4^{3-} $-P），筛选生态修复工程中吸附性能优异的矿物基填料，选取了3种天然填料（沸石、蛭石、火山岩）和3种加工型填料（陶粒、生物滤料、除磷滤料）开展${\mathrm{NH}}_4^+ $-N、${\mathrm{PO}}_4^{3-} $-P的吸附动力学和等温线试验，结合X射线衍射、电子扫描显微镜等表征手段，对不同矿物基填料的吸附特性与作用机制进行对比和分析。结果表明：6种矿物基填料的${\mathrm{NH}}_4^+ $-N和${\mathrm{PO}}_4^{3-} $-P吸附动力学过程均符合伪二级动力学方程，吸附速率主要受化学吸附过程控制。Langmuir和Freundlich方程都能很好地拟合不同矿物基填料的等温吸附曲线，${\mathrm{NH}}_4^+ $-N的理论吸附容量排序为沸石（5.941 6 mg/g）>蛭石（3.695 3 mg/g）>生物滤料（3.250 0 mg/g）>除磷滤料（3.138 9 mg/g）>火山岩（1.000 0 mg/g）>陶粒（0.857 1 mg/g），${\mathrm{PO}}_4^{3-} $-P的吸附容量大小为除磷滤料（4.242 4 mg/g）>生物滤料（2.791 7 mg/g）>蛭石（1.625 0 mg/g）>陶粒（1.210 5 mg/g）>火山岩（1.157 9 mg/g）>沸石（0.562 5 mg/g）。矿物基填料对${\mathrm{NH}}_4^+ $-N和${\mathrm{PO}}_4^{3-} $-P的吸附特性与其比表面积、微孔结构、矿物组成和金属元素含量等因素相关，其中沸石的比表面积和阳离子交换量最大，对${\mathrm{NH}}_4^+ $-N的吸附能力最强，生物滤料和除磷滤料中含有托贝莫来石、Ca、Fe等与磷结合能力较强的成分，对${\mathrm{PO}}_4^{3-} $-P的去除效果明显。综合来看，沸石和蛭石可用于${\mathrm{NH}}_4^+ $-N污染水体的治理，生物滤料和除磷滤料可用于处理含磷污水，而治理同时含有${\mathrm{NH}}_4^+ $-N和磷的污染水体时，可组合使用多种矿物基填料。对比其他填料，自主开发制备的生物滤料和除磷滤料在同步脱氮除磷方面具有明显优势，可作为氮、磷污染水体生态修复工程的优选基质。
Abstract:In order to efficiently remove ammonia nitrogen (${\mathrm{NH}}_4^+ $-N) and phosphates (${\mathrm{PO}}_4^{3-} $-P) from contaminated water and screen mineral-based fillers with excellent adsorption performance used in ecological restoration projects, three natural fillers (zeolite, vermiculite, volcanic rock) and three artificial fillers (ceramsite, biological filter, phosphorus removal filter) were selected to carry out experiments on the adsorption kinetics and isotherm of ammonia nitrogen and phosphorus. The adsorption properties and mechanisms of different mineral-based fillers were compared and analyzed by characterization methods such as X-ray diffraction and scanning electron microscopy. The results showed that the adsorption kinetics of ${\mathrm{NH}}_4^+ $-N and ${\mathrm{PO}}_4^{3-} $-P of the six mineral-based fillers complied with the pseudo-second-order kinetic equation, and the chemisorption process mainly controlled the adsorption rates. Both Langmuir and Freundlich equations could well describe the isothermal adsorption curves, and the theoretical adsorption capacity of ${\mathrm{NH}}_4^+ $-N was ranked as zeolite (
5.9416 mg/g) > vermiculite (3.6953 mg/g) > biological filter (3.2500 mg/g) > phosphorus removal filter (3.1389 mg/g) > volcanic rock (1.0000 mg/g) > ceramsite (0.8571 mg/g). The adsorption capacity of ${\mathrm{PO}}_4^{3-} $-P was as follows: phosphorus removal filter (4.2424 mg/g) > biological filter (2.7917 mg/g) > vermiculite (1.6250 mg/g) > ceramsite (1.2105 mg/g) > volcanic rock (1.1579 mg/g) > zeolite (0.5625 mg/g). The adsorption properties of different mineral-based fillers for ${\mathrm{NH}}_4^+ $-N and ${\mathrm{PO}}_4^{3-} $-P were related to their specific surface area, micropore structure, mineral composition and metal element content, etc. Among them, zeolite had the largest specific surface area and cation exchange capacity, thus exhibiting the strongest adsorption capacity for ${\mathrm{NH}}_4^+ $-N. The biological filter and phosphorus removal filter contained tobermolite, calcium, iron and other components with strong phosphorus binding ability, which removed ${\mathrm{PO}}_4^{3-} $-P from contaminated water obviously. On the whole, zeolite and vermiculite could be used for the treatment of ammonia nitrogen contaminated water, and biological filter and phosphorus removal filter could be chosen to remove phosphorus. When treating contaminated water containing both ammonia nitrogen and phosphorus, a variety of mineral-based fillers could be combined. Compared with other mineral fillers, the self-developed biological and phosphorus removal filters had obvious advantages in the simultaneous removal of nitrogen and phosphorus, and could be used as the optimal substrate fillers for ecological restoration projects of contaminated water.-
Key words:
- mineral-based fillers /
- ammonia nitrogen /
- phosphorus /
- adsorption /
- ecological restoration
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图 1 不同矿物基填料的XRD图谱
注：C—CaCO3；Q—石英；M—珍珠云母；P—金云母；G—斜方钙沸石；H—片沸石；T—托贝莫来石；Ca—硅钙石。
Figure 1. XRD patten of different mineral-based fillers
图 3 不同矿物基填料对水体中${\bf{NH}}_4^+ $-N的吸附动力学、吸附等温线及拟合结果
Figure 3. Adsorption kinetics and adsorption isotherms of ${\mathrm{NH}}_4^+ $-N on different mineral-based fillers and their fitting lines
图 4 不同矿物基填料对水体中${\bf{PO}}_4^{3-} $-P的吸附动力学、吸附等温线及拟合结果
Figure 4. Adsorption kinetics and adsorption isotherms of ${\mathrm{PO}}_4^{3-} $-P on different mineral-based fillers and their fitting lines
表 1 矿物基填料的比表面积、主要元素组成和阳离子交换量分析
Table 1. Specific surface area, main element composition and cation exchange capacity of mineral-based fillers
矿物基填料 比表面积/(m2/g) 元素组成/% 阳离子交换量/
(cmol/kg)总表面积 微孔内表面积 外表面积 O Si Al Fe Ca K Na Mg 沸石 30.491 6.880 23.611 40.573 35.461 7.846 2.884 5.015 3.937 1.683 1.198 55.983 蛭石 13.045 4.436 8.609 33.075 17.955 7.996 22.393 1.417 6.308 0.415 7.621 15.629 火山岩 4.733 5.029 28.249 26.219 10.268 16.395 8.516 1.926 2.788 3.011 4.967 陶粒 4.372 4.372 29.729 31.489 11.988 13.261 1.873 5.398 1.373 2.516 6.767 生物滤料 13.786 2.192 11.594 33.136 19.809 8.491 13.37 14.524 2.137 1.829 3.534 22.043 除磷滤料 10.003 1.761 8.242 33.123 19.048 8.269 13.621 15.237 2.335 1.759 3.219 20.432 
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表 2 矿物基填料对水体中${\bf{NH}}_4^+ $-N和${\bf{PO}}_4^{3-} $-P的吸附动力学的伪二级动力学方程拟合结果
Table 2. Fitted results of ${\mathrm{NH}}_4^+ $-N and ${\mathrm{PO}}_4^{3-} $-P adsorption kinetics on mineral-based fillers with the pseudo-second-order kinetic equation
矿物基
填料${\mathrm{NH}}_4^+ $-N ${\mathrm{PO}}_4^{3-} $-P k2/
〔g/(mg∙h)〕qe/(mg/g) R2 k2/
〔g/(mg∙h)〕qe/(mg/g) R2 沸石 20.333 7 0.938 1 1.000 0 − 16.1523 0.044 8 0.992 0 蛭石 1.238 5 0.759 4 0.998 7 1.1627 0.169 2 0.973 1 火山岩 −13.309 4 0.259 9 0.998 0 − 8.2869 0.029 9 0.899 9 陶粒 −68.248 9 0.026 6 0.996 1 − 9.0916 0.031 1 0.968 9 生物滤料 −2.236 8 0.234 8 0.990 2 0.3417 0.529 9 0.978 6 除磷滤料 3.872 1 0.156 6 0.985 1 0.1072 0.602 0 0.860 9
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表 3 矿物基填料对水体中${\bf{NH}}_4^+ $-N吸附等温线的Langmuir和Freundlich方程拟合结果
Table 3. Fitted results of ${\mathrm{NH}}_4^+ $-N adsorption isotherms on mineral-based fillers with Langmuir and Freundlich equation
矿物基填料 Langmiur模型 Freundlich模型 qm/(mg/g) KL/(L/mg) R2 KF/(mg/g)·(mg/L)−b b R2 沸石 5.941 6 0.054 8 0.981 2 0.656 7 0.502 0 0.982 7 蛭石 3.695 3 0.012 8 0.992 0 0.173 0 0.523 0 0.993 4 火山岩 1.000 0 0.006 5 0.997 5 0.038 3 0.495 1 0.989 9 陶粒 0.857 1 0.002 1 0.993 1 0.005 8 0.704 3 0.981 1 生物滤料 3.250 0 0.005 6 0.984 3 0.062 6 0.622 8 0.963 4 除磷滤料 3.138 9 0.003 6 0.986 4 0.032 8 0.690 2 0.970 2
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表 4 矿物基填料对水体中${\bf{PO}}_4^{3-} $-P吸附等温线的Langmuir和Freundlich方程拟合结果
Table 4. Fitting results of ${\rm{PO}}_4^{3-} $-P adsorption isotherms on mineral-based fillers with Langmuir and Freundlich equation
矿物基填料 Langmiur模型 Freundlich模型 qm/(mg/g) KL/(L/mg) R2 KF/(mg/g)·(mg/L)−b b R2 沸石 0.562 5 0.001 6 0.969 4 0.001 3 0.868 8 0.962 4 蛭石 1.625 0 0.002 4 0.999 2 0.007 1 0.814 9 0.996 3 火山岩 1.157 9 0.001 9 0.967 7 0.003 2 0.868 7 0.958 5 陶粒 1.210 5 0.001 9 0.957 1 0.003 3 0.873 8 0.946 9 生物滤料 2.791 7 0.004 8 0.988 9 0.031 6 0.724 6 0.996 0 除磷滤料 4.242 4 0.006 6 0.947 4 0.079 4 0.662 2 0.965 1
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