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

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.

Seawater purification from cesium and strontium radionuclides

The article deals with the study of sorption (under batch conditions) of cesium and strontium radionuclides from sea water with ferrocyanidic sorbents based on hydrated titanium and zirconium dioxides (Т-35, NPF-HTD), glauconite and clinoptilolite natural aluminum silicates (NPF-G, NPF-C), zirconium phosphate (Т-3А), modified hydrated zirconium dioxide (Т-3К), and manganese dioxide based on hydrated titanium dioxide (MD-HTD). We have obtained the sorption isotherms, defined the cesium and strontium distribution coefficients. Dependences of the cesium distribution coefficient by the sorbents in seawater saline content have been obtained. The authors recommend NPF-G and NPF-HTD sorbents for treatment of liquid radioactive waste based on seawater with various salt content. Coefficients of the cesium distribution between solid and liquid phases were 1,0∙105 and 1,0∙104 mg/l, respectively, even at solutions with the salt content of 100 g/l. In the process of strontium sorption from seawater, the strontium distribution coefficients do not exceed 1,9·102 ml/g, this is connected with big proportion (34±7 %) of stable colloidal forms of strontium in the simulated seawater.

Electrodialytic whey demineralization involving polymer-inorganic membranes, anion exchange resin and graphene-containing composite

Electrodialysis of cheese whey was performed using polymer membranes modified with zirconium hydrophosphate (cation exchange separator) and hydrated zirconium dioxide (anion exchange material). Both neutral and acidic solutions were used as a concentrate. As found, a 0.1 M HCl solution is preferable: the current efficiency towards mineral components and desalination degree reach 75-81 % and 90 % respectively, when the current does not exceed limiting current for cations. Anion exchange resin, as well as the composite containing zirconium dioxide and oxidized graphene, were involved in desalination. The composite adsorbs preferably cations, adsorption of anions is depressed. Its adsorption capacity is 1.2 (K+) and 0.25 (CL-) mmol g-1. Whey passed subsequently through the electrodialysis cell and beds of these materials. This approach allowed us to achieve the demineralization degree of 99%, and minimize losses of organic substances. Adsorption materials can be used repeatedly. The advantage of the composite over ion exchange resins is facile regeneration.

Whey desalination using polymer and inorganic membranes: Operation conditions

Electrodialytic desalination of cheese whey was carried out using a pair of polymer cation exchange (Nafion 117) and inorganic membranes. The ceramic separator was modified with nanocomposite containing hydrated zirconium dioxide and basic bismuth nitrate. This amphoteric filler provides anion exchange ability of the composite membrane. This property is realized when at least one side of the membrane is in contact with an acidic solution. Ion transport through the membranes was shown to be determined by current, whey acidity, and also by composition of the solution in the concentration compartment of the electrochemical cell. It was shown that whey desalination occurred under overlimiting current. Acidification of whey and decrease of the acid content in the concentrate suppress ion transport. The electrodialysis of whey and nanofiltration permeate allowed removal of up to 80% of the mineral components in 5 h and 40 min, respectively. Preliminary ozonation of the permeate increased the rate of desalination.