RESUMO
A new interpretation of the mechanism of the polyvinylidene fluoride (PVDF) membrane formation using the nonsolvent-induced phase separation (NIPS) method based on an analysis of the complete experimental phase diagram for the three-component mixture PVDF-dimethyl acetamide (DMAc)-water is proposed. The effects of the precipitation bath's harshness and thermodynamic affinity of the polymer's solvent on the morphology, crystalline structure, transport and physical-mechanical properties of the membranes are investigated. These characteristics were studied via scanning electron microscopy, wide-angle X-ray scattering, liquid-liquid porosimetry and standard methods of physico-mechanical analysis. It is established that an increase in DMAc concentration in the precipitation bath results in the growth of mean pore size from ~60 to ~150 nm and an increase in permeance from ~2.8 to ~8 L m-2 h-1 bar-1. It was observed that pore size transformations are accompanied by changes in the tensile strength of membranes from ~9 to ~11 and to 6 MPa, which were explained by the degeneration of finger-like pores and appearance of spherulitic structures in the samples. The addition of water to the dope solution decreased both the transport (mean pore size changed from ~55 to ~25 nm and permeance reduced from ~2.8 to ~0.5 L m-2 h-1 bar-1) and mechanical properties of the membranes (tensile strength decreased from ~9 to ~6 MPa). It is possible to conclude that the best membrane quality may be reached using pure DMAc as a solvent and a precipitation bath containing 10-30% wt. of DMAc, in addition to water.
RESUMO
Membrane gas-liquid contactors have great potential to meet the challenges of amine CO2 capture. In this case, the most effective approach is the use of composite membranes. However, to obtain these, it is necessary to take into account the chemical and morphological resistance of membrane supports to long-term exposure to amine absorbents and their oxidative degradation products. In this work, we studied the chemical and morphological stability of a number of commercial porous polymeric membranes exposed to various types of alkanolamines with the addition of heat-stable salt anions as a model of real industrial CO2 amine solvents. The results of the physicochemical analysis of the chemical and morphological stability of porous polymer membranes after exposure to alkanolamines, their oxidative degradation products, and oxygen scavengers were presented. According to the results of studies by FTIR spectroscopy and AFM, a significant destruction of porous membranes based on polypropylene (PP), polyvinylidenefluoride (PVDF), polyethersulfone (PES) and polyamide (nylon, PA) was revealed. At the same time, the polytetrafluoroethylene (PTFE) membranes had relatively high stability. On the basis of these results, composite membranes with porous supports that are stable in amine solvents can be successfully obtained to create liquid-liquid and gas-liquid membrane contactors for membrane deoxygenation.
RESUMO
Desalination and treatment of wastewater has become critical for Asia regions with water scarcity. In this work, the concept of thin-film distillation equipped with a porous condenser (FDPC) was considered for its implementation in a tropical climate of Vietnam. It was found that samples with a concentration of biocide of 0.5 wt.% possessed lower biofouling, in contrast to the neat membranes. The FD-PC module was developed and water desalination experiments were conducted in Russia and Vietnam. The experiments showed high reproducibility of the results; in particular, the evaporation rate was (4.9/3.0) kg/m2h in Russia and (4.1/2.0) kg/m2h in Vietnam. In addition, as part of this work, the optimal configuration of the installation was calculated using solar collectors as the main energy source. The calculation showed high energy efficiency: specific energy consumption 0.1-0.5 kWh/m3.
RESUMO
Amine CO2 solvents undergo oxidative degradation with the formation of heat stable salts (HSS). These HSS reduce the sorption capacity of amines and lead to intense corrosion of the equipment. In our work, we propose a membrane-supported liquid-liquid extraction of the HSS from alkanolamines. For this purpose, a hollow fiber membrane contactor was used for the first time. A lab-scale extraction system on the basis of a hollow-fiber liquid-liquid membrane contactor with hollow fiber ultrafiltration polyvinylidenefluoride and polysulfone membranes has been studied. The extraction of the HSS-ions from a 30 wt.% solution of monoethanolamine was carried out using a 0.25-1 M solution of OH-modified methyltrioctylammonium chloride in 1-octanol as an extractant. It has been shown that >90% of HSS ions can be extracted from the alkanolamine solvent within 8 h after extraction. The results obtained confirm the possibility of using membrane extraction with a liquid-liquid membrane contactor for the reclaiming of amine CO2 solvents to increase the general efficiency of carbon dioxide capture.
RESUMO
In this work, perspective polymeric materials were developed for membrane contactor applications, e.g., for the dissolved oxygen removal from amine CO2 capture solvents. Several polymeric blends based on poly[1-trimethylsilyl-1-propyne] (PTMSP) and poly[vinyltrimethylsilane] (PVTMS) were studied. The gas and water vapor sorption and permeability coefficients for the PTMSP/PVTMS blend membranes at different PVTMS contents (0-100%) were obtained under temperatures of 30 and 60 °C for the first time. As the PVTMS content increases, the O2 and CO2 permeabilities decrease by 160 and 195 times at 30 °C, respectively. The fractional accessible volume of the polymer blends decreases accordingly. The transport of the CO2 capture solvent vapors through the PTMSP/PVTMS blend membranes were determined in thermo-pervaporation (TPV) mode using aqueous monoethanolamine (30%), N-methyldiethanolamine (40%), and 2-amino-2-methyl-1-propanol (30%) solutions as model amine solvents at 60 °C. The membranes demonstrated high pervaporation separation factors with respect to water, resulting in low amine losses. A joint analysis of the gas permeabilities and aqueous alkanolamine TPV data allowed us to conclude that the polymer blend composition of PTMSP/PVTMS 70/30 provides an optimal combination of a sufficiently high oxygen permeability and the pervaporation separation factor at a temperature of 60 °C.
RESUMO
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.
