水合氧化铁负载量对丙烯酸树脂基复合吸附剂的结构及除磷影响

孙健; 徐兆郢; 赵平歌; 张格红; 薛崇灏

doi:10.13801/j.cnki.fhclxb.20201019.002

水合氧化铁负载量对丙烯酸树脂基复合吸附剂的结构及除磷影响

doi: 10.13801/j.cnki.fhclxb.20201019.002

1.
西安工业大学　建筑工程学院，西安 710021
2.
西安热工研究院有限公司，西安 710054

基金项目: 国家自然科学基金(51908439)；陕西省教育厅专项科学研究计划项目(19JK0395)；西安工业大学校长基金(XAGDXJJ18019)

详细信息

通讯作者:
孙健，博士，讲师，研究方向为污水处理、再生水回用　E-mail：201sun@163.com

中图分类号: X703
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出版历程
- 收稿日期: 2020-08-27
- 录用日期: 2020-10-12
- 网络出版日期: 2020-10-19
- 刊出日期: 2021-08-15

Effect of hydrated ferric oxide loadings on structure and phosphate adsorption of acrylic polymer-supported composite adsorbents

1.
School of Civil & Architecture Engineering, Xi’an Technological University, Xi’an 710021, China
2.
Xi’an Thermal Power Research Institute CO. LTD., Xi’an 710054, China

摘要

摘要: 为优化丙烯酸树脂基水合氧化铁(Hydrated ferric oxide，HFO)复合吸附剂的负载量，调节FeCl₃浓度制备出5种复合吸附剂(HFO负载量分别为5.3wt%、8.6wt%、12.1wt%、14.9wt%和18.5wt%，以Fe质量分数计)，分析其结构性能，并考察D213-HFO复合吸附剂对磷的吸附等温线、吸附动力学、pH和共存离子影响及洗脱效果。结果表明，复合吸附剂负载HFO颗粒为纳米无定型HFO，在直径方向呈U型分布。此外，随HFO负载量增加，磷吸附容量先升高后下降，负载量为14.9wt%的复合吸附剂吸附容量最大(19.04 mg·g⁻¹)。复合吸附剂吸附磷在240 min达到平衡，更符合准一级动力学模型(R²>0.99)。磷吸附最佳pH为6~8，当SO₄²⁻≥600 mg·L⁻¹树脂对磷无吸附效果，而负载HFO吸附磷不受影响。在连续4个吸附-洗脱周期内，5wt%的NaOH和5wt%的NaCl溶液对磷的洗脱率均接近100%。实验表明，复合吸附剂的吸附容量随HFO负载量增加先升高后下降，而结构性能、吸附平衡时间、pH适应范围、共存离子影响及洗脱效果无显著差异。
- 吸附剂 /
- 水合氧化铁 /
- 丙烯酸树脂 /
- 磷酸盐 /
- 结构
Abstract: In order to optimize the hydrated ferric oxide (HFO) loadings of acrylic resin-based HFO composite adsorbents, five composite adsorbents were prepared by regulating FeCl₃ concentration, and the HFO loadings were 5.3wt%, 8.6wt%, 12.1wt%, 14.9wt% and 18.5wt% (mass fraction in Fe), respectively. The structure properties of composite adsorbents were analyzed. Furthermore, the adsorption performance of composite adsorbents in removing phosphate were investigated, including adsorption isotherms, adsorption kinetics, effect of pH and coexisting anion, and elution effect. The results show that HFO nanoparticles dispersed into composite adsorbents are amorphous in nature, and the radial distribution of HFO obeys U-type distribution. Moreover, the phosphate adsorption capacity increases with the HFO loadings and then decreases, and the adsorption capacity of the composite adsorbent with HFO loading of 14.9wt% is the maximum (19.04 mg·g⁻¹). The contact time of 240 min is long enough for composite adsorbents to achieve adsorption equilibrium, and the adsorption kinetic curves of the composite adsorbents are fitted well with pseudo-first order kinetic model (R²>0.99). The optimal pH for phosphate adsorption is 6~8. Furthermore, there is no phosphate adsorption by resin when the concentration of SO₄²⁻ is equal or greater than 600 mg·L⁻¹, while it does not pose any noticeable effect on phosphate adsorption by the loaded HFO nanoparticles. The regeneration efficiencies approach 100% by a binary 5wt% NaOH and 5wt% NaCl solution during 4 continuous adsorption-regeneration cycles. The experiments show that the phosphate adsorption capacity of the composite adsorbents increases with the HFO loadings and then decreases, while there is no significant difference in structure property, adsorption equilibrium time, pH range, effect of coexisting anion, and elution effect.
- adsorbent /
- hydrated ferric oxide /
- acrylic resin /
- phosphate /
- structure

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图 1 树脂D213与D213-HFO复合吸附剂的切面SEM图像

Figure 1. SEM images of section of D213 and D213-HFO composite adsorbents((a1)-(f1)) ×150; (a2)-(f2) ×10 000)

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图 2 D213和D213-14.9HFO复合吸附剂的FTIR图谱

Figure 2. FTIR spectra of D213 and D213-14.9HFO composite adsorbents

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图 3 D213-HFO复合吸附剂的TEM图像和Fe元素径向分布图

Figure 3. TEM images and Fe radial distribution images of D213-HFO composite adsorbents

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图 4 D213-HFO复合吸附剂的XRD图谱

Figure 4. XRD spectra of D213-HFO composite adsorbents

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图 5 D213-HFO复合吸附剂对P的吸附等温线

Figure 5. Adsorption isotherms of P onto D213-HFO composite adsorbents

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图 6 不同磷浓度下D213-HFO复合吸附剂的固液分配系数K_d

Figure 6. Distribution coefficients K_d of D213-HFO composite adsorbents at different phosphate levles

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图 7 D213和D213-HFO复合吸附剂的吸附动力学曲线

Figure 7. Adsorption kinetic curves of D213 and D213-HFO composite adsorbents

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图 8 pH对P在D213-HFO复合吸附剂上吸附效果的影响

Figure 8. Effect of pH on P adsorption by D213-HFO composite adsorbents

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图 9 SO₄²⁻对D213和D213-HFO复合吸附剂吸附P效果的影响

Figure 9. Effect of sulfate on P adsorption by D213 and D213-HFO composite adsorbents

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图 10 连续4个周期内D213-HFO复合吸附剂的 P吸附容量

Figure 10. Adsorption capacity of P by D213-HFO composite adsorbents during 4 continuous cycles

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图 11 连续4个周期内D213-HFO复合吸附剂的P洗脱率

Figure 11. Regeneration efficiency of P by D213-HFO composite adsorbents during 4 continuous cycles

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表 1 不同FeCl₃浓度制备的复合吸附剂

Table 1. Composite adsorbents prepared with various FeCl₃ concentrations

FeCl₃ concentration/(mol·L⁻¹)	HFO loading/wt%	Adsorbent
0.35	5.3	D213-5.3HFO
0.5	8.6	D213-8.6HFO
1.0	12.1	D213-12.1HFO
1.3	14.9	D213-14.9HFO
2.5	18.5	D213-18.5HFO
Note: HFO—Hydrated ferrous oxide.

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表 2 D213和D213-14.9HFO复合吸附剂的孔特征参数

Table 2. Porous characteristics of D213 and D213-14.9HFO composite adsorbents

Adsorbent	D213	D213-14.9HFO
Surface area/(m²·g⁻¹)	4.46	6.51
Pore volume/(cm³·g⁻¹)	0.011	0.008
Mean pore size/nm	9.43	7.67

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表 3 D213-HFO复合吸附剂的Freundlich模型和Langmuir模型拟合参数

Table 3. Isothermal adsorption model fitting parameters of Langmuir and Freundlich model by D213-HFO composite adsorbents

Adsorbents	Langmuir model			Freundlich model
Adsorbents	q_m/(mg·g⁻¹)	b/(L·mg⁻¹)	R²	K_f/(mg^1−1/n·L^1/n·g⁻¹)	n	R²
D213-5.3HFO	8.98	0.10	0.973	1.29	2.30	0.982
D213-8.6HFO	9.20	0.23	0.964	2.24	2.49	0.972
D213-12.1HFO	15.80	0.19	0.946	3.40	2.18	0.976
D213-14.9HFO	19.04	0.16	0.964	3.76	2.33	0.973
D213-18.5HFO	18.55	0.17	0.941	3.74	2.68	0.964
Notes: q_m―Maximum adsorption capacity; b, K_f and n―Isotherm constants.

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表 4 D213和D213-HFO复合吸附剂的吸附动力学拟合参数

Table 4. Kinetic fitting parameters of D213 and D213-HFO composite adsorbents

Adsorbent	Pseudo-first-order			Pseudo-second-order			Intra-particle diffusion
Adsorbent	q_e/(mg·g⁻¹)	k₁/min⁻¹	R²	q_e/(mg·g⁻¹)	k₂/(g·mg⁻¹·min⁻¹)	R²	C	k_d/(mg·g⁻¹·min^−1/2)	R²
D213	15.23	0.028	0.998	17.32	20.9	0.978	2.816	0.842	0.791
D213-5.3HFO	16.92	0.023	0.999	20.26	11.9	0.976	2.248	0.975	0.840
D213-8.6HFO	17.84	0.021	0.999	21.60	10.2	0.979	2.119	1.037	0.853
D213-12.1HFO	19.66	0.017	0.999	24.79	6.54	0.988	1.507	1.163	0.896
D213-14.9HFO	19.65	0.018	0.999	24.49	7.07	0.989	1.719	1.155	0.892
D213-18.5HFO	19.61	0.015	0.999	25.47	5.06	0.993	0.980	1.161	0.925
Notes: k₁―Pseudo-first-order kinetic constant; k₂―Pseudo-second-order kinetic constant; q_e―Phosphate adsorption capacity in equilibrium; k_d―Intra-particle diffusion rate constant; C―Reaction constant.

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