Lithium-rich geothermal waters are considered as an alternative source, and further concentration of lithium is required for its effective recovery. In this work, we have simulated a three-stage lithium recovery process including the brine softening by precipitation Ca²⁺/Mg²⁺ cations with sodium carbonate (calculated in PHREEQC), followed by an integrated system consisting of membrane distillation unit (water evaporation), crystallizer (NaCl precipitation), and membrane extraction (Li⁺ recovery), which was simulated in Simulink/MATLAB. It was shown that the deterioration of membrane performance in time due to scaling/fouling plays a critical role in the performance of the system resulting in the dramatic increase of the replaced membrane modules by a factor of 5. Low cost membranes are required. The process simulation based on the experimental and literature data on the high salinity solutions with the membrane distillation revealed that the specific productivity can be achieved in the range of 9.9–880 g (Li⁺) per square meter of membranes in the module used before its replacement. The increase of energy efficiency is needed. The mass-flow-rate of saline solution circulated to the crystallizer was set at its almost minimum value as 6.5 kg/min to enable its successful operation at the given parameters of the membrane distillation unit. In other words, the operation of the integrated system having 140 kg of saline solution in the loop and a membrane module of 2.5 m² for concentration of lithium presence from 0.11 up to 2.3 g/kg would be associated with the circulation of about of 259 tons of saline solution per month between the distillation unit (60 °C) and the crystallizer (15 °C) to yield of up to 1.4 kg of lithium ions. The comprehensive summary and discussion are presented in the conclusions section.

For the first time, the effect of the side-chain in polyalkylmethylsiloxane towards pervaporative removal of methyl tert-butyl ether (MTBE) from water was studied. The noticeable enhancement of separation factor during the pervaporation of 1 wt.% MTBE solution in water through the dense film (40–50 µm) can be achieved by substitution of a methyl group (separation factor 111) for heptyl (161), octyl (169) or decyl (180) one in polyalkylmethylsiloxane. Composite membrane with the selective layer (~8 µm) made of polydecylmethylsiloxane (M10) on top of microfiltration support (MFFK membrane) demonstrated MTBE/water separation factor of 310, which was 72% greater than for the dense film (180). A high separation factor together with an overall flux of 0.82 kg·m⁻²·h⁻¹ allowed this M10/MFFK composite membrane to outperform the commercial composite membranes. The analysis of the concentration polarization modulus and the boundary layer thickness revealed that the feed flow velocity should be gradually increased from 5 cm·s⁻¹ for an initial solution (1 wt.% of MTBE in water) to 13 cm·s⁻¹ for a depleted solution (0.2 wt.% of MTBE in water) to overcome the concentration polarization phenomena in case of composite membrane M10/MFFK (T_exp = 50 °C).

This article describes a new technique for the preparation of hollow fiber (HF) membrane samples using an automatic manipulator unit. The manipulator uses a syringe needle to form a HF of a given geometry. The needle in automatic mode is sequentially immersed, first into the polymer solution and then into the coagulation bath. The possibility of using a manipulator to obtain HF samples was studied on the known polysulfone (PSf)/N-methylpyrrolidone (NMP)/pore-forming additive system. A series of HF membrane samples were made within 29 h from twelve 1 mL PSf casting solutions. This was 15 times faster than obtaining samples of HF membranes at the multifunctional research laboratory facility. From the point of view of the consumption of the components of the casting solution, the use of the manipulator was 30 times more economical, and the consumption of water for precipitation and washing was 8000 times less. The developed method made it possible to study samples of HF by scanning electron microscopy (SEM), ultrafiltration, and evaluate its mechanical properties without spinning the membranes. Using the new technique, the optimal composition of the casting solution for the wet spinning of HF PSf membranes was selected during two weeks. Thus, the manipulator makes it possible to significantly reduce the time of the new membrane preparation, reduce the volume of used polymer, and thus makes it promising to study expensive or new membrane materials.

The mitigation of the physical aging of thin-film composite (TFC) poly[1-trimethylsilyl-1-propyne] (PTMSP) membranes was studied via the simultaneous application of a polymer-selective layer crosslinking and mixed-matrix membrane approach. For the first time, a recently developed highly porous activated carbon material (infrared (IR) pyrolyzed poly[acrylonitrile] (PAN) or IR-PAN-a) was investigated as an additive to a PTMSP-selective layer for the reduction of aging in TFC membranes. The total electric energy spent on the IR irradiation treatment of IR-PAN-a particles was twice lower than conventional heating. The flat-sheet porous microfiltration membrane MFFK-1 was used as a support, and the crosslinked PTMSP/PEI loaded with a porous filler was applied as a selective layer (0.8–1.8 µm thick) to the TFC membranes. The initial IR-PAN-a sample was additionally milled to obtain a milled IR-PAN-aM sample with a monomodal particle size distribution of 500–800 nm. It was shown that IR-PAN-a, as a filler material with a high surface area and pore volume (2450 m²/g and 1.06 cm³/g, respectively) and a well-developed sponge-like structure, leads to the increase of the N₂, O₂, and CO₂ permeance of PTMSP-based hybrid membrane material and the decrease of the aging of PTMSP. The simultaneous effect of crosslinking and the addition of a highly porous filler essentially improved the aging behavior of PTMSP-based TFC membranes. The monomodal and narrow particle size distribution of highly porous activated IR-pyrolyzed PAN is a key factor for the production of TFC membranes with reduced aging. The highest stability was achieved by the addition of a milled IR-PAN-aM sample (10 wt%). TFC membrane permeance was 6300 GPU (30% of initial permeance) after 11,000 h of aging at ambient laboratory conditions.

The influence of hyper-crosslinked polystyrene (HCPS) Macronet^TM MN200 on the gas transport properties and aging of the highly permeable glassy polymer poly(1-trimethylsilyl-1-propyne) (PTMSP) was studied and analyzed in detail. The gas transport characteristics of dense PTMSP membranes containing 0–10.0 wt % HCPS were studied. It was shown that the introduction of a small amount of HCPS into the PTMSP matrix led to a 50–60% increase of the permeability coefficients of the material for light gases (N₂, O₂, CO₂) and slowed down the deterioration of polymer transport properties over time. The lowest reduction in gas permeability coefficients (50–57%) was found for PTMSP containing HCPS 5.0 wt % after annealing at 100 °C for 300 h. It was found that HCPS sorbed residues of tantalum-based polymerization catalyst from PTMSP. In order to investigate the influence of catalysts on transport and physical properties of PTMSP, we purified the latter from the polymerization catalyst by addition of 5 wt % HCPS into polymer/chloroform solution. It was shown that sorption on HCPS allowed for almost complete removal of tantalum compounds from PTMSP. The membrane made of PTMSP purified by HCPS demonstrated more stable transport characteristics compared to the membrane made of the initial polymer. HCPS has a complex effect on the aging process of PTMSP. The introduction of HCPS into the polymer matrix not only slowed down the physical aging of PTMSP, but also reduced chemical aging due to removal of active reagents.

For the first time, membranes based on poly(1-trimethylsilyl-1-propyne) (PTMSP) with 5–50 wt% loading of hyper-crosslinked polystyrene sorbent particles (HCPS) were obtained; the membranes were investigated for the problem of effective removal of volatile organic compounds from aqueous solutions using vacuum pervaporation. The industrial HCPS sorbent Purolite Macronet™ MN200 was chosen due to its high sorption capacity for organic solvents. It has been found that the membranes are asymmetric when HCPS content is higher than 30 wt%; scanning electron microscopy of the cross-sections the membranes demonstrate that they have a clearly defined thin layer, consisting mainly of PTMSP, and a thick porous layer, consisting mainly of HCPS. The transport and separation characteristics of PTMSP membranes with different HCPS loading were studied during the pervaporation separation of binary and multicomponent mixtures of water with benzene, toluene and xylene. It was shown that the addition of HCPS up to 30 wt% not only increases the permeate fluxes by 4–7 times, but at the same time leads to 1.5–2 fold increase in the separation factor. It was possible to obtain separation factors exceeding 1000 for all studied mixtures at high permeate fluxes (0.5–1 kg/m²∙h) in pervaporation separation of binary solutions.