Sorption Properties of ZrO2-Analcime Composites in Relation to Cs(I) and Sr(II)

Composite zeolite sorbents based on analcime with inclusions of hydrated zirconium dioxide (ZrO2-analcime) have been obtained by hydrothermal treatment of coal fly ash cenospheres with a high glass phase content in the presence of a zirconium compound and an alkaline activating agent at 150 °C and different stirring modes of the reaction mixture. The synthesis products were characterized by XRD, SEM-EDS, STA and low-temperature nitrogen adsorption; their sorption properties with respect to Cs+ and Sr2+ were studied in the pH range of 2–10. It was found that the ZrO2-analcime compositions surpass unmodified analcime by 2–5 times in terms of sorption of Cs+ and Sr2+ and by two orders of magnitude in terms of the distribution coefficient value (KD ~106 ml/g). The process of high-temperature solid-phase transformation of Cs+/Sr2+-exchanged forms of the compositions was studied, which simulates the process of conversion of water-soluble forms of Cs‑137 and Sr‑90 radionuclides into a mineral-like form. It was shown that at 1000 °C the ZrO2-analcime compositions with sorbed Cs+ and Sr2+ undergo the phase transformation resulting in polyphase systems of similar composition based on nepheline, tetragonal ZrO2, and glass phase

COMPOSITE ION-EXCHANGES FOR THE RECYCLING OF LIQUID WASTE OF DAIRY INDUSTRY

The method of directed formation of particles of hydrated zirconium and titanium oxides into anion exchange resins has been developed. The approach based on the Ostwald-Freundlich thermodynamic equation is applied. Such approach, in particular, connects the size of particles with the solubility of the compound, volume and concentration of reagents. Less soluble zirconium dioxide is deposited as non-aggregated nanoparticles, the size of which does not exceed 10 nm. The composition of such composites is the most reproducible. In the case of more soluble titanium dioxide, aggregates of nanoparticles (up to 70 nm) are formed. When the concentration of the solution of metal salts in the polymer increases, the particles of micron size are deposited, the composition of this type of material is less reproduced. Non-aggregated nanoparticles increase the exchange capacity of the polymer. This leads to an increase in its electrical conductivity in 1.4-1.8 times. This is due to an increase in the concentration of mobile charge carriers in the polymer matrix that is caused by reducing its swelling. Other reason is a contribution of the counter-ions of the functional groups of inorganic component to ion transport. On the contrary, the aggregates of nanoparticles amplify the polymer swelling, resulting in a reduction of exchange capacity and electrical conductivity. Ion-exchangers were used for the ion exchange processing of nanofiltration permeate of milky whey, and for electromembrane desalination of protein concentrate.

MEMBRANES MODIFIED BY NANOCOMPOSITES OF HYDRATED ZIRCONIUM DIOXIDE AND OXIDIZED GRAPHENE

Organo-inorganic membranes were obtained by impregnating ultrafiltration membranes with a composite modifier - zirconium (IV) hydroxide, containing oxidized graphene (0.5 wt.%). The modifier was precipitated in the active layer of the membrane, thus forming a "secondary active layer". The layer thickness calculated according to the Kozeny-Carman equation is 0.66-1.38 μm. A thinner layer is formed in the membrane with smaller pore size. The diffusion coefficients of Li+ and Na+ ions were found. The effect of the modifier on the retention ability relative to hardness ions (10-14%) and to protein compounds (95-98%) during filtration is determined. Mathematical modeling of the dependence of the permeate flux via time showed that the presence of ion exchanger particles in the polymer active layer prevents the accumulation of organic substances in the pores. Therefore, only the outer surface of the membrane is contaminated, and the precipitate can be easily removed mechanically. It was shown that insertion of a carbon component into pores of the membranes, in addition to the inorganic ion-exchangers, is advisable only in the case of a finely porous active layer. In particular, the performance of the initial polymer membrane (20 dm3/m3.h)) and the selectivity to the calibration substance with a molecular weight of 40 kDa (99%) serve as expediency criteria. In comparison with a membrane modified only with inorganic ion exchanger, selectivity is increased, the rate of filtration of protein solutions is higher, and resistance to contamination by organic substances is achieved. The results are discussed from the view of the hydrophobic-hydrophilic properties of oxidized graphene.