SYNTHESIS AND PROPERTIES OF ION EXCHANGERS DERIVED FROM NON-WOOD CELLULOSE
Abstract
A rational scheme for the processing of large-scale agro-industrial waste – walnut shells Juglans Regia L. and apricot kernels Prunus Armeniaca L. was proposed. At first stage, the raw material was delignificated using liquid ammonia to remove hemicelluloses and lignin. Isolated non-wood pulp is chemically modifying to increase sorption and ion exchange properties. For the synthesis of anion exchangers, cellulose was aminated using pyridine or trimethylamine after preliminary treatment consequentially with formalin and C2H5OH in HCl medium. As a result, we obtained high and weakly-basic ion exchangers with nitrogen content of 10.3–11.5% and high exchange capacity towards various classes of inorganic anions. For synthesis of cation exchangers, cellulose was treated with solution consisting of 20% H3PO4, 40% CO(NH2)2, and 40% H2O. Consequently, we obtained phosphorus-containing high-acidic cation exchangers with exchange capacity towards heavy metal of 5.5–8.6 mmol∙cm–3. Both types of ion exchangers have a high capacity towards uranium: anion exchanger – 4.25 mmol∙cm–3 and cation exchanger – 4.94 mmol∙cm–3, respectively. Average total yield of ion exchangers related to weight of air-dry feedstock was 90%. Synthesized ion exchangers characterized by IR spectroscopy. Presence of amine functional groups –NH2 in aminated cellulose and phosphate ester groups –OPO(OH)2 in phosphorylated cellulose was established. Specific surface area and total static exchange capacity of synthesized ion exchangers were established. An environmentally friendly method for the disposal of spent solutions from the synthesis of cation exchangers was proposed. It allows getting a liquid complex fertilizer containing 17% N and 13.9% P2O5. Usage of this fertilizer for grain crops feeding increases plants length by 40–75%, as well as overall biomass increase by 20–30%.
References
Rubleva N.V., Lebedeva E.O., Afineevskii A.V., Voronova M.I., Surov O.V., Zakharov A.G. Production of cellulose nanocrystals by hydrolysis in mixture of hydro-chloric and nitric acids. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. [Russ. J. Chem. & Chem. Tech.]. 2019. V. 62. N 12. P. 8593. DOI: 10.6060/ivkkt.20196212.5984.
Eletskii P.M., Yakovlev V.A., Parmon V.N. Modern approaches to the production of carbon materials from vegetable biomass. Theor. Exp. Chem. 2011. V. 47. P. 139-154. DOI: 10.1007/s11237-011-9195-9.
Puzii A.M. Methods of production, structure, and physicochemical characteristics of phosphorylated carbon ad-sorbents. Theor. Exp. Chem. 2011. V. 47. P. 277-291. DOI: 10.1007/s11237-011-9216-8.
Kudratov A.M., Salimov Z.S. The elaboration of technol-ogy of preparation of adsorption ion exchange materials in the basis of rice waste. Russ. J. Appl. Chem. 2010. V. 83. P. 562-568. DOI: 10.1134/S1070427210030341.
Efanov M.V., Averin R.Y. Peroxide-Ammonia Delignification of Pine Wood. Chem. Nat. Comp. 2004. V. 40. P. 172-175. DOI: 10.1023/B:CONC.0000033939.81490.d2.
Efanov M.V., Klepikov A.G. Preparation of N-containing lignocarbohydrates. Chem. Nat. Comp. 2001. V. 37. P. 80-82. DOI: 10.1023/A:1017666913519.
Ergozhin E.E., Bektenov N.A., Mekebaeva A.K., Chopabaeva N.N. Preparation of phosphoric-carboxylic cation exchangers from wood cellulose. Chem. Nat. Comp. 2003. V. 39. P. 299-302. DOI: 10.1023/A:1025486922276.
Ubaidullaev B.K., Kudratov A.M., Salimov Z.S. Preparation and ion-exchange properties of P-containing cellulose derivatives from certain plant species. Chem. Nat. Comp. 2004. V. 40. P. 410-411. DOI: 10.1023/B:CONC.0000048261.95951.e1.
Illy N., Fache M., Ménard R., Negrell C., Caillol S., David G. Phosphorylation of bio-based compounds: the state of the art. Polymer Chem. 2015. V. 35. P. 6257-6391. DOI: 10.1039/C5PY00812C.
Obolenskaya A.V., Elnit-skaya Z.P., Leonovich A.A. Laboratory works on the chemistry of wood and cellulose. M.: Ekologiya. 1991. 320 p. (in Russian).
Hegyesi N., Vada R.T., Pukánszky B. Determina-tion of the specific surface area of layered silicates by methylene blue adsorption: The role of structure, pH and layer charge. Appl. Clay Sci. 2017. V. 146. P. 50-55. DOI: 10.1016/j.clay.2017.05.007.
Tanaka Y. Ion exchange membranes: fundamentals and application. Amsterdam: Elsevier Science. 2015. 492 p.
Mather R.R., Wardman R.H. The Chemistry of Textile Fibres. Cambridge: The Royal Society of Chemistry. 2015. 472 p.
Crompton T.R. Organic compounds in soils, sediments & sludges: analysis and determination. Boca Raton: CRC Press. 2013. 268 p.
Nepenin N.N., Nepenin Yu.N. Pulp technology. Volume III. Pulp cleaning, drying and bleaching. Other methods of cellulose producing. M.: Ekologiya. 1994. 592 p. (in Russian).
Mineev V.G. Workshop on agrochem-istry. M.: Izd. dom MGU. 2001. 689 p. (in Russian).
Hassan S.S., Williams G.A., Jaiswal A.K. Emerging technologies for the pretreatment of lignocellulosic biomass. Biores. Tech. 2018. V. 262. P. 310-318. DOI: 10.1016/j.biortech.2018.04.099.
Pugacheva I.N., Karmanov A.V., Zueva S.B., De Michelis I., Ferella F., Molokanova L.V., Vegliò F. Heavy metal removal by cellulose-based textile waste product. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. [Russ. J. Chem. & Chem. Tech.]. 2020. V. 63. N 2. P. 105110. DOI: 10.6060/ivkkt.20206302.6098.
Teixeira S., Delerue-Matos C., Santos L. Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells. Environ. Sci. Pollut. Res. 2012. V. 19. P. 3096-3106. DOI: 10.1007/s11356-012-0853-9.
Karmanov A.P., Derkacheva O.Yu. Applica-tion of IR Fourier spectroscopy for the study of lignins of herbaceous plants. Khimiya Rastit. Syr'ya. 2020. V. 16. P. 61-70 (in Russian).
Kakhramanov N.T., Gadjieva R.Sh., Gahramanly J.N., Arzumanova N.B. Sorption of heavy metals by multi-component foam polymer sorbents. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. [Russ. J. Chem. & Chem. Tech.]. 2019. V. 62. N 5. P. 110117 DOI: 10.6060/ivkkt.20196205.5769.
