نوع مقاله : کاربردی

نویسندگان

1 دانشجوی دکتری علوم و مهندسی خاک، دانشکده کشاورزی، دانشگاه شهید باهنر کرمان، ایران

2 استاد گروه علوم و مهندسی خاک، دانشکده کشاورزی، دانشگاه شهید باهنر کرمان، ایران

3 دانشیار گروه علوم و مهندسی خاک، دانشکده کشاورزی، دانشگاه شهید باهنر کرمان، ایران

چکیده

تجمع فسفر در محیط­های آبی باعث به خطر افتادن حیات موجودات زنده می­شود. از این رو، ارائه یک روش موثر جهت حذف فسفر از محلول­های آبی ضروری به نظر می­رسد. مطالعه حاضر با هدف تولید یک کانی هیدروکسید دوگانه لایه­ای منیزیم-آهن و بررسی رفتار آن در جذب فسفر از محلول آبی انجام شد. کانی مورد نظر به روش هم­رسوبی در فاز مایع با ترکیب کلریدمنیزیم و کلریدآهن با نسبت مولی 3 به 1 در pH=10 در آزمایشگاه تهیه و ساختار بلوری آن توسط آنالیز پراش پرتو ایکس مورد مطالعه قرار گرفت. قابلیت جذب فسفر توسط هیدروکسید دوگانه لایه­ای منیزیم-آهن تولید شده با انجام آزمایشات تعادلی در حالت بسته بررسی و اثر عواملی نظیر غلظت اولیه فسفر، pH و زمان تماس مطالعه گردید. نتایج نشان داد که فرآیند جذب فسفر توسط هیدروکسید دوگانه لایه­ای یک فرآیند وابسته به pH بوده و بیشترین جذب در pH=4 اتفاق افتاد. زمان تعادل برای واکنش جذب فسفر 60 دقیقه بود و سینتیک جذب به خوبی توسط مدل شبه رده دوم توصیف گردید. داده­های هم­دمای جذب فسفر به خوبی با مدل لانگمویر برازش یافتند و حداکثر ظرفیت جذب فسفر 96/13 میلی­گرم بر گرم محاسبه شد. مطالعات سینتیکی و اثر pH بر روی جذب فسفر نشان داد که مکانیسم­های احتمالی درگیر در فرآیند جذب فسفر به صورت برهم­کنش الکترواستاتیک، تبادل لیگاندی و تشکیل کمپلکس سطحی بود. نتایج این پژوهش نشان داد که هیدروکسید دوگانه لایه­ای منیزیم-آهن به عنوان یک جاذب کم هزینه و دوست­دار محیط زیست قابلیت موثری در حذف فسفر از محلول­های آبی دارا می­باشد.

کلیدواژه‌ها

موضوعات

عنوان مقاله [English]

Removal of Phosphorus from Aqueous Solution by Mg-Fe Layered Double Hydroxide

نویسندگان [English]

  • Hasan Bolbol 1
  • Majid Fekri 2
  • Majid Hejazi-Mehrizi 3
  • Naser Bromand 3

1 PhD Student, Department of Soil Science, Faculty of Agriculture, Shahid Bahonar University of Kerman, Iran

2 Professor, Department of Soil Science, Faculty of Agriculture, Shahid Bahonar University of Kerman, Iran

3 Shahid Bahonar University of Kerman

چکیده [English]

Introduction Phosphorus (P) is an essential nutrient for all forms of life on the earth, but in excess concentrations, it can act as a serious water pollutant through eutrophication. Thus, it is very important to remove P from aqueous solutions before their release into natural water resources. Among the various P removal techniques that have been developed, the sorption process is widely accepted to be an effective water treatment technique because of low cost, ease of operation, simplicity of design, and high sorption capacity in dilute solutions. Layered double hydroxides (LDHs) are a type of two-dimensional nanostructure anionic clays with high capacities to sorption of anions. These non-silicate clays consist of positively charged brucite-like octahedral sheets which neutralize by a negatively charged interlayer containing relatively weak bonded anions and water molecules. The positive charges generated by the isomorphous substitution of trivalent cations for divalent cations are balanced by interlayer anions that can be exchanged by other anions making them good anion-exchangers with high selectivity. LDHs have been widely used as environmental sorbents because of their high charge density, large interlayer areas, good thermal stability, and high anion exchange capacities of the interlayer anions. The aim of the present study was to synthesize a Mg-Fe LDH as a sorbent for P removal from aqueous solution.
Materials and Methods The Mg-Fe LDH was synthesized using the co-precipitation method. In brief, a mixture solution containing 0.03 mol MgCl2. 6H2O, and 0.01 mol FeCl3. 6H2O was added dropwise into a flask containing 100 ml of 1 M NaOH solution under vigorous stirring at pH=10. The obtained slurry was filtered and washed repeatedly with DW until the filtrate pH reached neutral. Mg-Fe LDH particles were then obtained by drying the filtrate at 70 °C in an oven overnight. The crystallinity of the sample was studied using X-ray diffraction (XRD) analysis. In order to investigate the performance of the synthesized LDH as a P sorbent, batch experiments were carried out in polyethylene centrifuge tubes. The suspensions were shaken for 24 hours at 250 rpm, and the supernatant was then separated by centrifugation at 4000 rpm for 10 minutes and were filtered by Whatman ashless grade 42 filtration papers. Equilibrium P concentration was determined according to the ascorbic acid method using UV-vis spectrophotometer at the wavelength of 880 nm. The effects of pH, initial P concentration, and contact time on P sorption were investigated in the ranges of 2-10, 0-300 mg/L and 0-1440 min, respectively.
Results and Discussion The XRD pattern of the LDH sample showed typical structure of hydrotalcite-like compounds with sharp and reflection peaks corresponding to the (003), (006), (012), (015), and (110) crystal planes which are characteristic planes of hydrotalcite-like compounds. The efficiency of LDH to remove P decreased with the increasing of initial P concentration and the maximum removal efficiency of LDH occurred in the range of 5-20 mg/L of initial P concentration. With increasing of initial P concentration from 20 to 300 mg/L, the P removal efficiency of LDH decreased from 98.7 to 24.6 %. The P removal efficiency was increased with time and reached equilibrium at 60 min. The P removal rate of LDH in this time was about 66 % and no significant decrease in residual P concentration was observed after 60 min. The sorption of P on LDH was highly pH dependent, and the maximum P removal was found at pH of 4. The sorption kinetic and isotherm data were well described by pseudo-second-order and Langmuir equations, respectively. According to the Langmuir equation, the maximum P sorption capacity (Qmax) of LDH was obtained as 13.96 mg/g.
Conclusion It was found from the results of this study that the mechanisms involved in the P sorption onto LDH included electrostatic attraction, ligand exchange, and surface complex formation. In addition, the results suggested that the synthesized Mg-Fe LDH can be potentially used as an effective sorbent for the removal of P from aqueous solutions. Further research is needed on the regeneration of the LDH after P sorption and the evaluation of desorption behavior of P from LDH under different conditions.

کلیدواژه‌ها [English]

  • adsorption
  • anionic clays
  • eutrophication
  • isotherm
  • kinetic
  • phosphorus
  1. Cai, P. H., Zheng, C., Wang, H., Ma, J., Hu, Pu, Y., and Liang, P. 2012. Competitive adsorption characteristics of fluoride and phosphate on calcined MgAl-CO3 layered double hydroxides. Journal of Hazardous Materials, 213: 100- 108.
  2. Cheng, X., Huang, X., Wang, X., Zhao, B., Chen, A., and Sun, D. 2009. Phosphate adsorption from sewage sludge filtrate using zinc-aluminum layered double hydroxides. Journal of Hazardous Materials, 169(1-3): 958-964.
  3. Chubar, N. and Szlachta, M. 2015. Static and dynamic adsorptive removal of selenite and selenate by alkoxide-free sol-gel-generated Mg-Al-CO3 layered double hydroxide: Effect of competing ions. Chemical Engineering Journal, 279: 885-896.
  4. Eaton, A., Clesceri, L. S., Rice, E. W., Greenberg, A. E., and Franson, M. 2005. APHA: standard methods for the examination of water and wastewater. Centennial Edition., APHA, AWWA, WEF, Washington, DC.
  5. Goh, K. H., Lim, T. T., and Dong, Z. 2008. Application of layered double hydroxides for removal of oxyanions: a review. Water Research, 42(6-7): 1343- 1368.
  6. Goh, K. H., Lim T. T., and Dong Z. 2010. Removal of arsenate from aqueous solution by nanocrystalline Mg/Al layered double hydroxide: sorption characteristics, prospects, and challenges. Water Science and Technology, 61(6): 1411-1417.
  7. Ho, Y. S. 2006. Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods. Water Research, 40(1): 119- 125.
  8. Hosni, K., and Srasra, E. 2010. Evaluation of phosphate removal from water by calcined-LDH synthesized from the dolomite. Colloid Journal, 72(3): 423-431.
  9. Jiang, J. Q., and Ashekuzaman, S. 2015. Preparation and evaluation of layered double hydroxides (LDHs) for phosphate removal. Desalination and Water Treatment, 55(3): 836-843.
  10. Jung, K. W., Jeong, T. U., Hwang, M. J., Kim, K., and Ahn K. H., 2015. Phosphate adsorption ability of biochar/Mg-Al assembled nanocomposites prepared by aluminum-electrode based electro-assisted modification method with MgCl2 as electrolyte. Bioresource Technology, 198: 603-610.
  11. Lalley, J., Han, C., Li, X., Dionysiou, D. D., and Nadagouda, M. N. 2016. Phosphate adsorption using modified iron oxide-based sorbents in lake water: kinetics, equilibrium, and column tests. Chemical Engineering Journal, 284: 1386-1396.
  12. Liu, H., Sun, X., Yin, C., and Hu, C. 2008. Removal of phosphate by mesoporous ZrO2. Journal of Hazardous Materials, 151(2-3): 616-622.
  13. Loganathan, P., Vigneswaran, S., Kandasamy, J., and Bolan, N. S. 2014. Removal and Recovery of Phosphate From Water Using Sorption. Critical Reviews in Environmental Science and Technology, 44(8): 847-907.
  14. Long, F., Gong, J. L., Zeng, G. M., Chen, L., Wang, X. Y., Deng, J. H., Niu, Q. Y., Zhang, H. Y., and. Zhang, X. R. 2011. Removal of phosphate from aqueous solution by magnetic Fe-Zr binary oxide. Chemical Engineering Journal, 171(2): 448-455.
  15. Lu, H., Zhu, Z., Zhang, H., Zhu, J., and Qiu, Y. 2015. Simultaneous removal of arsenate and antimonate in simulated and practical water samples by adsorption onto Zn/Fe layered double hydroxide. Chemical Engineering Journal, 276: 365- 375.
  16. Lǚ, J., Liu, H., Liu, R., Zhao, X., Sun, L., and Qu, J. 2013. Adsorptive removal of phosphate by a nanostructured Fe-Al-Mn trimetal oxide adsorbent. Powder Technology, 233: 146-154. 17. Lu, S., Bai, S., Zhu, L., and Shan, H. 2009. Removal mechanism of phosphate from aqueous solution by fly ash. Journal of Hazardous Materials, 161(1): 95- 101.
  17. Luengo, C. V., Volpe, M. A., and Avena, M. J. 2017. High sorption of phosphate on Mg-Al layered double hydroxides: Kinetics and equilibrium. Journal of Environmental Chemical Engineering, 5(5): 4656-4662.
  18. Lv, L., He, J., Wei, M., Evans, D., and Zhou, Z. 2007. Treatment of high fluoride concentration water by MgAl-CO3 layered double hydroxides: Kinetic and equilibrium studies. Water Research, 41(7): 1534-1542.
  19. Peleka, E., and Deliyanni, E. 2009. Adsorptive removal of phosphates from aqueous solutions. Desalination, 245(1-3): 357-371.
  20. Prasanna, S. V., and Vishnu Kamath, P. 2008. Chromate uptake characteristics of the pristine layered double hydroxides of Mg with Al. Solid State Sciences, 10(3): 260-266.
  21. Rahmani, A., Mousavi, H. Z., and Fazli, M. 2010. Effect of nanostructure alumina on adsorption of heavy metals. Desalination, 253(1-3): 94-100.
  22. Rojas Delgado, R., De Pauli, C. P., Carrasco, C. B., and Avena, M. J. 2008. Influence of MII/MIII ratio in surface-charging behavior of Zn-Al layered double hydroxides. Applied Clay Science, 40(1): 27-37.
  23. Rojas R. 2012. Layered double hydroxides applications as sorbents for environmental remediation. In: A. Calixto Carillo and D. Analiz Griego (Eds), Hydroxides: Synthesis, Types and Applications, Nova Science Publishers, Inc, pp: 40-73.
  24. Rojas, R., Bruna, F., de Pauli, C. P., Ángeles Ulibarri, M., and Giacomelli, C. E. 2011. The effect of interlayer anion on the reactivity of Mg-Al layered double hydroxides: Improving and extending the customization capacity of anionic clays. Journal of Colloid and Interface Science, 359(1): 136-141.
  25. Sparks, D. L. 2003. Environmental soil chemistry, New York, Academic Press, Elsevier.
  26. Theiss, F. L., Couperthwaite, S. J., Ayoko, G. A., and Frost, R. L. 2014. A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides. Journal of Colloid and Interface Science, 417: 356-368.
  27. Wan, D., Liu, H., Liu, R., Qu, J., Li, S., and Zhang, J. 2012. Adsorption of nitrate and nitrite from aqueous solution onto calcined (Mg-Al) hydrotalcite of different Mg/Al ratio. Chemical Engineering Journal, 195-196: 241-247.
  28. Wang, Y., and Li, G. 2016. Adsorption behavior of phosphate on Mg-Al layered double hydroxide/montmorillonite composite. Desalination and Water Treatment, 57(38): 17963-17972.
  29. Wang, Z., Nie, E., Li, J., Yang, M., Zhao, Y., Luo, X., and Zheng, Z. 2012. Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon. Environmental Science and Pollution Research, 19(7): 2908-2917.
  30. Wang, Z., Shi, M., Li, J., and Zheng, Z. 2014. Influence of moderate preoxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon. Journal of Environmental Sciences, 26(3): 519-528.
  31. Xing, K., Wang, H., Guo, L., Song, W., and Zhao, Z. 2008. Adsorption of tripolyphosphate from aqueous solution by Mg-Al-CO3-layered double hydroxides. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 328(1-3): 15-20.
  32. Yang, M., Lin, J., Zhan, Y., and Zhang, H. 2014. Adsorption of phosphate from water on lake sediments amended with zirconium-modified zeolites in batch mode. Ecological Engineering, 71: 223-233.
  33. Yao, Y., Gao, B., Inyang, M., Zimmerman, A. R., Cao, X., Pullammanappallil, P., and Yang, L. 2011. Biochar derived from anaerobically digested sugar beet tailings: characterization and phosphate removal potential. Bioresource Technology, 102(10): 6273-6278.
  34. Zamparas, M., Gianni, A., Stathi, P., Deligiannakis, Y., and Zacharias, I. 2012. Removal of phosphate from natural waters using innovative modified bentonites. Applied Clay Science, 62: 101-106.