Abstract: Degradative solvent extraction is the method developed for biomass upgrading by dewatering and fractionation of biomass under the mild condition. However, the conversion mechanism of the degradative solvent extraction method has not been fully understood so far. The rice straw was treated in 1-methylnaphthalene (1-MN) at a different solvent-treatment temperature varied from 250 to 350 oC with the residence time for 60 min. The liquid membrane-Fourier Transform Infrared Spectroscopy (FTIR) technique is applied to study the processing mechanism in-depth without separation of the solvent. It has been found that the strength of the oxygen-hydrogen stretching (3600-3100 cm-1) decreased slightly with increasing temperature in the range of 300-350 oC. The decrease of the hydroxyl group in the solvent soluble suggested dehydration reaction taking place between 300 and 350 oC. FTIR spectra in the carbonyl stretching region (1800-1600 cm-1) revealed the presence of esters groups, carboxylic acid and ketonic groups in the solvent-soluble of biomass. The carboxylic acid increased in the range of 200 to 250 oC and then decreased. The prevailing of aromatic groups showed that the aromatization took place during extraction at above 250 oC. From 300 to 350 oC, the carbonyl functional groups in the solvent-soluble noticeably decreased. The removal of the carboxylic acid and the decrease of esters into the form of carbon dioxide indicated that the decarboxylation reaction occurred during the extraction process.
Abstract: Dysprosium is a rare earth element which is essential for many growing high-technology applications. Dysprosium along with neodymium plays a significant role in different applications such as metal halide lamps, permanent magnets, and nuclear reactor control rods preparation. The purification and separation of rare earth elements are challenging because of their similar chemical and physical properties. Among the various methods, membrane processes provide many advantages over the conventional separation processes such as ion exchange and solvent extraction. In this work, selective extraction and separation of dysprosium from aqueous solutions containing an equimolar mixture of dysprosium and neodymium by emulsion liquid membrane (ELM) was investigated. The organic membrane phase of the ELM was a nanofluid consisting of multiwalled carbon nanotubes (MWCNT), Span80 as surfactant, Cyanex 272 as carrier, kerosene as base fluid, and nitric acid solution as internal aqueous phase. Factors affecting separation of dysprosium such as carrier concentration, MWCNT concentration, feed phase pH and stripping phase concentration were analyzed using Taguchi method. Optimal experimental condition was obtained using analysis of variance (ANOVA) after 10 min extraction. Based on the results, using MWCNT nanofluid in ELM process leads to increase the extraction due to higher stability of membrane and mass transfer enhancement and separation factor of 6 for dysprosium over neodymium can be achieved under the optimum conditions. Additionally, demulsification process was successfully performed and the membrane phase reused effectively in the optimum condition.
Abstract: Samarium as a rare-earth element is playing a growing important role in high technology. Traditional methods for extraction of rare earth metals such as ion exchange and solvent extraction have disadvantages of high investment and high energy consumption. Emulsion liquid membrane (ELM) as an improved solvent extraction technique is an effective transport method for separation of various compounds from aqueous solutions. In this work, the extraction of samarium from aqueous solutions by ELM was investigated using response surface methodology (RSM). The organic membrane phase of the ELM was a nanofluid consisted of multiwalled carbon nanotubes (MWCNT), Span80 as surfactant, Cyanex 272 as mobile carrier, and kerosene as base fluid. 1 M nitric acid solution was used as internal aqueous phase. The effects of the important process parameters on samarium extraction were investigated, and the values of these parameters were optimized using the Central Composition Design (CCD) of RSM. These parameters were the concentration of MWCNT in nanofluid, the carrier concentration, and the volume ratio of organic membrane phase to internal phase (Roi). The three-dimensional (3D) response surfaces of samarium extraction efficiency were obtained to visualize the individual and interactive effects of the process variables. A regression model for % extraction was developed, and its adequacy was evaluated. The result shows that % extraction improves by using MWCNT nanofluid in organic membrane phase and extraction efficiency of 98.92% can be achieved under the optimum conditions. In addition, demulsification was successfully performed and the recycled membrane phase was proved to be effective in the optimum condition.
Abstract: The high purity rare earth elements (REEs) have been vastly used in the field of chemical engineering, metallurgy, nuclear energy, optical, magnetic, luminescence and laser materials, superconductors, ceramics, alloys, catalysts, and etc. Neodymium is one of the most abundant rare earths. By development of a neodymium–iron–boron (Nd–Fe–B) permanent magnet, the importance of neodymium has dramatically increased. Solvent extraction processes have many operational limitations such as large inventory of extractants, loss of solvent due to the organic solubility in aqueous solutions, volatilization of diluents, etc. One of the promising methods of liquid membrane processes is emulsion liquid membrane (ELM) which offers an alternative method to the solvent extraction processes. In this work, a study on Nd extraction through multi-walled carbon nanotubes (MWCNTs) assisted ELM using response surface methodology (RSM) has been performed. The ELM composed of diisooctylphosphinic acid (CYANEX 272) as carrier, MWCNTs as nanoparticles, Span-85 (sorbitan triooleate) as surfactant, kerosene as organic diluent and nitric acid as internal phase. The effects of important operating variables namely, surfactant concentration, MWCNTs concentration, and treatment ratio were investigated. Results were optimized using a central composite design (CCD) and a regression model for extraction percentage was developed. The 3D response surfaces of Nd(III) extraction efficiency were achieved and significance of three important variables and their interactions on the Nd extraction efficiency were found out. Results indicated that introducing the MWCNTs to the ELM process led to increasing the Nd extraction due to higher stability of membrane and mass transfer enhancement. MWCNTs concentration of 407 ppm, Span-85 concentration of 2.1 (%v/v) and treatment ratio of 10 were achieved as the optimum conditions. At the optimum condition, the extraction of Nd(III) reached the maximum of 99.03%.
Abstract: In the present work, emulsion liquid membrane (ELM) technique was applied for the extraction of cadmium(II) present in aqueous samples. Aliquat 336 (Chloride tri-N-octylmethylammonium) was used as carrier to extract cadmium(II). The main objective of this work is to investigate the influence of various parameters affected the ELM formation and its stability and testing the performance of the prepared ELM on removal of cadmium by using synthetic solution with different concentrations. Experiments were conducted to optimize pH of the feed solution and it was found that cadmium(II) can be extracted at pH 6.5. The influence of the carrier concentration and treat ratio on the extraction process was investigated. The obtained results showed that the optimal values are respectively 3% (Aliquat 336) and a ratio (feed: emulsion) equal to 1:1.
Abstract: The conversion of lignocellulosic waste materials, such as sugar cane bagasse, to biofuels such as ethanol has attracted significant interest as a potential element for transforming transport fuel supplies to totally renewable sources. However, the refractory nature of the cellulosic structure of lignocellulosic materials has impeded progress on developing an economic process, whereby the cellulose component may be effectively broken down to glucose monosaccharides and then purified to allow downstream fermentation. Ionic liquid (IL) treatment of lignocellulosic biomass has been shown to disrupt the crystalline structure of cellulose thus potentially enabling the cellulose to be more readily hydrolysed to monosaccharides. Furthermore, conventional hydrolysis of lignocellulosic materials yields byproducts that are inhibitors for efficient fermentation of the monosaccharides. However, selective extraction of monosaccharides from an aqueous/IL phase into an organic phase utilizing a combination of boronic acids and quaternary amines has shown promise as a purification process. Hydrolysis of sugar cane bagasse immersed in an aqueous solution with IL (1-ethyl-3-methylimidazolium acetate) was conducted at different pH and temperature below 100 ºC. It was found that the use of a high concentration of hydrochloric acid to acidify the solution inhibited the hydrolysis of bagasse. At high pH (i.e. basic conditions), using sodium hydroxide, catalyst yields were reduced for total reducing sugars (TRS) due to the rapid degradation of the sugars formed. For purification trials, a supported liquid membrane (SLM) apparatus was constructed, whereby a synthetic solution containing xylose and glucose in an aqueous IL phase was transported across a membrane impregnated with phenyl boronic acid/Aliquat 336 to an aqueous phase. The transport rate of xylose was generally higher than that of glucose indicating that a SLM scheme may not only be useful for purifying sugars from undesirable toxic compounds, but also for fractionating sugars to improve fermentation efficiency.
Abstract: Amoxicillin is an antibiotic which is widely used to
treat various infections in both human beings and animals. However,
when amoxicillin is released into the environment, it is a major
problem. Amoxicillin causes bacterial resistance to these drugs and
failure of treatment with antibiotics. Liquid membrane is of great
interest as a promising method for the separation and recovery of the
target ions from aqueous solutions due to the use of carriers for the
transport mechanism, resulting in highly selectivity and rapid
transportation of the desired metal ions. The simultaneous processes
of extraction and stripping in a single unit operation of liquid
membrane system are very interesting. Therefore, it is practical to
apply liquid membrane, particularly the HFSLM for industrial
applications as HFSLM is proved to be a separation process with
lower capital and operating costs, low energy and extractant with
long life time, high selectivity and high fluxes compared with solid
membranes. It is a simple design amenable to scaling up for industrial
applications. The extraction and recovery for (Amoxicillin) through
the hollow fiber supported liquid membrane (HFSLM) using
aliquat336 as a carrier were explored with the experimental data. The
important variables affecting on transport of amoxicillin viz.
extractant concentration and operating time were investigated. The
highest AMOX- extraction percentages of 85.35 and Amoxicillin
stripping of 80.04 were achieved with the best condition at 6 mmol/L
[aliquat336] and operating time 100 min. The extraction reaction
order (n) and the extraction reaction rate constant (kf) were found to
be 1.00 and 0.0344 min-1, respectively.
Abstract: The kinetics of Cu(II) transport through a bulk liquid membrane with different membrane materials was investigated in this work. Three types of membrane materials were used: fresh cooking oil, waste cooking oil and kerosene, each of which was mixed with di-2-ethylhexylphosphoric acid (carrier) and tributylphosphate (modifier). Kinetic models derived from the kinetic laws of two consecutive irreversible first-order reactions were used to study the facilitated transport of Cu(II) across the source, membrane and receiving phases of bulk liquid membrane. It was found that the transport kinetics of Cu(II) across the source phase was not affected by different types of membrane materials but decreased considerably when the membrane materials changed from kerosene, waste cooking oil to fresh cooking oil. The rate constants of Cu(II) removal and recovery processes through the bulk liquid membrane were also determined.
Abstract: The separation of silver ions from medicinal wastewater via hollow fiber supported liquid membrane (HFSLM) was examined to promote the performance of this technique. The wastewater consisting of 30mg/L silver ions and 120mg/L ferric ions was used as the feed solution. LIX84I dissolving in kerosene and sodium thiosulfate pentahydrate solution were used as the liquid membrane and stripping solution, respectively. In order to access the highest performance of HFSLM, the optimum condition was investigated via several influential variables. Final concentration of silver ions in feed solution was obtained 0.2mg/L which was lower than the discharge limit of Thailand’s mandatory.
Abstract: Extraction of Fe(III) from aqueous solution using Trin-
butyl Phosphate (TBP) as carrier needs a highly acidic medium
(>6N) as it favours formation of chelating complex FeCl3.TBP.
Similarly, stripping of Iron(III) from loaded organic solvents requires
neutral pH or alkaline medium to dissociate the same complex. It is
observed that TBP co-extracts acids along with metal, which causes
reversal of driving force of extraction and iron(III) is re-extracted
back from the strip phase into the feed phase during Liquid Emulsion
Membrane (LEM) pertraction. Therefore, rate of extraction of
different mineral acids (HCl, HNO3, H2SO4) using TBP with and
without presence of metal Fe(III) was examined. It is revealed that in
presence of metal acid extraction is enhanced. Determination of mass
transfer coefficient of both acid and metal extraction was performed
by using Bulk Liquid Membrane (BLM). The average mass transfer
coefficient was obtained by fitting the derived model equation with
experimentally obtained data. The mass transfer coefficient of the
mineral acid extraction is in the order of kHNO3 = 3.3x10-6m/s > kHCl =
6.05x10-7m/s > kH2SO4 = 1.85x10-7m/s. The distribution equilibria of
the above mentioned acids between aqueous feed solution and a
solution of tri-n-butyl-phosphate (TBP) in organic solvents have been
investigated. The stoichiometry of acid extraction reveals the
formation of TBP.2HCl, HNO3.2TBP, and TBP.H2SO4 complexes.
Moreover, extraction of Iron(III) by TBP in HCl aqueous solution
forms complex FeCl3.TBP.2HCl while in HNO3 medium forms
complex 3FeCl3.TBP.2HNO3
Abstract: Separation of propylene-propane mixture using
immobilized liquid membrane was investigated. The effect of transmembrane
pressure and carrier concentration on membrane
separation performance was studied. It was observed that for 30:70
(vol. %) propylene-propane mixture, at pressure of 120kPa and
carrier concentration of 20wt. %, a separation factor of 474 was
obtained.
Abstract: A double module hollow fiber supported liquid
membrane (HFSLM) was applied to selectively separate lead and
mercury ions from dilute synthetic produced water. The experiments
were investigated on several variables: types of extractants
(D2EHPA, Cyanex 471, Aliquat 336, and TOA), concentration of the
selected extractant and operating time. The results clearly showed
that the double module HFSLM could selectively separate Pb(II) and
Hg(II) in feed solution at a very low concentration to less than the
regulatory discharge limit of 0.2 and 0.005 mg/L issued by the
Ministry of Industry and the Ministry of Natural Resource
Environment, Thailand. The highest extractions of lead and mercury
ions from synthetic produced water were 96% and 100% using 0.03
M D2EHPA and 0.06 M Aliquat 336 as the extractant for the first
and second modules.
Abstract: Extraction of lactic acid by emulsion liquid membrane technology (ELM) using n-trioctyl amine (TOA) in n-heptane as carrier within the organic membrane along with sodium carbonate as acceptor phase was optimized by using response surface methodology (RSM). A three level Box-Behnken design was employed for experimental design, analysis of the results and to depict the combined effect of five independent variables, vizlactic acid concentration in aqueous phase (cl), sodium carbonate concentration in stripping phase (cs), carrier concentration in membrane phase (ψ), treat ratio, and batch extraction time (τ)
with equal volume of organic and external aqueous phase on lactic acid extraction efficiency. The maximum lactic acid extraction efficiency (ηext) of 98.21%from aqueous phase in a batch reactor using ELM was found at the optimized values for test variables, cl, cs, ψ, and τ as 0.06 [M], 0.18 [M], 4.72 (%,v/v), 1.98 (v/v) and 13.36 min respectively.
Abstract: A new supported liquid membrane (SLM) system for
the selective transport of VO2
+ ions was prepared in this present
work. The SLM was a thin porous polyvinylidene difluoride
(PVDF) membrane soaked with Di-(2-ethylhexyl) phosphoric acid
(D2EHPA) as mobile carrier in Xylene as organic solvent.
D2EHPA acts as a highly selective carrier for the uphill transport of
VO2
+ ions through the SLM. The transport of VO2
+ ions reached to
64%. In the presence of P2O7-2 ion as suitable masking agent in the
feed solution, the interfering effects of other cations were eliminated.