Resource mining from stainless steel pickling wastewater to produce metal-organic frameworks
Graphical abstract
Introduction
During the past two decades, metal-organic frameworks (MOFs) have emerged huge potentials in many fields such as catalysis, separation, degradation and chemical sensing (Zeng et al., 2021; Xia et al., 2021; Fathieh et al., 2018; Razavi and Morsali, 2020), whereas relatively higher cost than zeolite and carbon-based materials seriously limits their industry-level use. Raw materials of MOFs involve metal source, organic ligand, solvent, and acid/base modifier agent (if needed), substitution of which by industrial wastes will effectively reduce the cost. In the past years, some industrial metal wastes have been conversed to high value-added MOFs (Perez et al., 2016; Vo et al., 2019; Kabtamu et al., 2020; Song et al., 2021). Therein, the attempts based on metal wastewater were also reported. For example, simulated battery waste liquor and waste hexavalent chromium solution were used to prepare MOFs (Perez et al., 2016; Vo et al., 2019). However, these attempts were commonly carried out based on the simulated wastewater. Up to date, conversion of practical industrial wastewater to highly valuable MOFs was rarely reported.
Stainless steel manufacturing industry is distributed worldwide and exhibits an increasingly huge annual output. The operation unit of oxide skin pickling will produce a mass of wastewater, which contains high concentrations of Fe3+, Cr3+, Ni2+, F−, NO3− and possesses strong acidity (Rögener et al., 2012). The reuse and recovery of the metals and acids in the pickling wastewater can reduce pollution caused by wastewater discharge, and facilitate the resource recycle. Recently, some conversion attempts have been made based on this wastewater (Yi et al., 2021; Yang et al., 2019; Hermose et al., 2005; Zhang et al., 2021), while the added values of the formed products are not very high and importantly, the treatment of the secondary wastewater and formed hazardous waste still faces challenges. Excitingly, we noted that the metal ions, acids (HF and HNO3), and water of the stainless steel pickling wastewater correspond to all the raw materials of MOFs except for organic ligands. Use of this raw-material integration will largely simplify the preparation units and reduce the cost of MOFs.
In this work, a 3R (reduce, reuse, recycle) approach for treating stainless steel pickling wastewater was proposed, based on the selective crystallization reaction with 1,3,5-benzenetricarboxylic acid (H3BTC). Fe3+ and Cr3+ participate preferably to the reaction to form Fe/Cr-mixed MIL-100 materials and meanwhile Ni2+ was largely purified, realizing the reuse and discharge reduction of the pickling wastewater and the recycle of metal/acid resources. The topology structure, porosity, long-term acid/base stability, and water-phase adsorption performances of the obtained MOFs were systematically measured and analyzed. To the best of our knowledge, the conversion of stainless steel pickling wastewater to MOFs is firstly reported by this work. Our work will promote recycle of industrial wastes resource and large-scale use of MOFs.
Section snippets
Materials
The stainless steel pickling wastewater was collected from Sinosteel Stainless Steel Pipe Technology (Shanxi) Co., Ltd. (Fig. S1). The wastewater shows the dark green colour and its compositions are listed in Table S1. 1,3,5-Benzenetricarboxylic acid (H3BTC), N,N’-dimethylformamide (DMF), methylene blue (MB), methyl orange (MO), moxifloxacin hydrochloride (MOX), zirconium oxychloride octahydrate (ZrOCl2·8H2O) were purchased from HWRK Chem. Co., Ltd.
Synthesis of MOFs
Herein, MOFs were synthesized according to a
Preparation and characterization of the products
The preparation process of BTC-X-Y is shown in Scheme 1. The pickling wastewater and H3BTC were used as the total raw materials and on other additional reagents were added. A simple hydrothermal reaction was carried out and the earthy-yellow powders were collected. As an integrated body of metal, solvent and acid, use of the pickling wastewater simplifies the operation units of MOF preparation and promotes the green synthesis of MOFs.
As shown in Fig. 1a–c, the powder XRD patterns of BTC-X-Y
Conclusion
In summary, we show that stainless steel pickling wastewater was easily transformed to Fe/Cr-MIL-100 and meanwhile Ni2+ can be largely purified. The use of raw-material-integrated pickling wastewater simplified the preparation process and decreased the costs of MOFs. The obtained MIL-100 s exhibit high porosity, long-term acid/base stability, and excellent water-phase adsorption performance. The Fe/Cr ratio was found to be controllable through modifying reaction temperature and solid/liquid
CRediT authorship contribution statement
Xudong Zhao: Conceptualization, Investigation, Formal analysis, Writing – original draft, Funding acquisition. Chengwei Zhang: Methodology, Investigation. Baosheng Liu: Investigation, Formal analysis, Writing – review & editing, Funding acquisition. Huifang Zhao: Methodology, Investigation. Xinli Gao: Methodology, Funding acquisition. Yuanyang Wang: Methodology, Formal analysis. Yuezhong Zhang: Methodology, Formal analysis. Dahuan Liu: Conceptualization, Formal analysis, Writing – review &
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by Fundamental Research Program in Shanxi Province (No. 20210302124685 and 202103021223281), National Natural Science Foundation of China (No. 21978005), and Key Scientific Research Project in Shanxi Province (No. 202102050201003).
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