Efficient desulfurization of gasoline fuel using ionic liquid extraction as a complementary process to adsorptive desulfurization

The extractive desulfurization of a model gaso- line containing several alkyl thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids （ILs）, 1-butyl-3-methylimidazolium tetrachloroaluminate, and 1-octyl-3-methylimidazolium te- trafluoroborate, as extractants. A fractional factorial design of experiments was employed to evaluate the effects and possible interactions of several process variables. Analysis of variance tests indicated that the number of extraction steps and the IL/gasoline volume ratio were of statistically highly significant, but none of the interactions were significant. The results showed that the desulfurization efficiency of the model gasoline by the ILs could reach 95.2 % under the optimal conditions. The optimized conditions were applied to study the extraction of thiophenic compounds in model gasoline and several real gasoline samples; the following order was observed in their separation： benzothio- phenc 〉 thiophcne 〉 3-methylthiophene 〉 2-methylthiophene, with 96.1% removal efficiency for benzothiophene. The IL extraction was successfully applied as a complementary process to the adsorptive desulfurization with acti- vated Raney nickel and acetonitrile solvent. The results indicated that the adsorptive process combined with IL extraction could provide high efficiency and selectivity, which can be regarded as a promising energy efficient desulfurization strategy for production of low-sulfur gasoline.

Separation of Red (Y_2O_3:Eu^(3+)), Blue (BaMgAl_(10)O_(17):Eu^(2+)) and Green (CeMgAl_(10)O_(17):Tb^3) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3：Eu^3＋）, blue（BaMgAl10O17：Eu^2＋） and green （CeMgAl10O17：Tb^3） rare earth fluorescent powders was proposed. At first, the blue powder can be extracted selectively from an aqueous solution using a chelating collector 2-thenoyltrifluoroacetone （TTA） dissolved in heptane at alkaline pH condition, then, chloroform was used for extracting the green powder into organic phase. The red phosphor remains in aqueous phase with potassium sodium tartrate depressant （PST）. Therefore, three phosphors can be separated successfully from their artificial mixtures by liquid/liquid extraction, and grades and recovery of separated products reach respectively as follows： red is 96.9% and 95.2%, blue is 82.7% and 98.8%, green is 94.6% and 82.6%.

Synthesis of 2, 6 Bis(1′-Phenyl- 3′- Methyl-5′-Oxopyrazole- 4′) Pyridinediacyl and Its Solid Liquid Extraction Behavior for Ce(Ⅲ)

diketone type chelating ligands have high coordinative activity and selectivity, and are widely applied in analytical chemistry. In order to obtain profounder understanding to the properties of bis(4 acylpyrazolone 5), A new 4 acylpyrazol 5 one derivative (H 2BPMPP) was syntheszed, which contains a heterocyclic ring between two 1 phenyl 3 methyl 4 acylpyrazol 5 one rings. The new compound was characterized by element analyses, UV, IR and 1H NMR spectra. The equilibrium of the keto enol tautomerism was studied. The results show that a lower dielectric constant of solvent favors the enol form which has a higher λ max . Due to special merits of paraffin wax, the solid liquid extraction behavior of Ce(Ⅲ) with molten paraffin wax as a diluent was also investigated at higher temperature. The value of the pH 1/2 was 3.19 and the value of log K ex was 3.467. The chemical composition of the complex was obtained by the slope analysis method.

Comparison of conventional and supported liquid extraction methods for the determination of sitagliptin and simvastatin in rat plasma by LC-ESI-MS/MS

Three extraction methods were compared for their efficiency to analyze sitagliptin and simvastatin in rat plasma by LC-MS/MS, including （1） liquid-liquid extraction （LLE）, （2） solid phase extraction （SPE） and （3） supported liquid extraction （SLE）. Comparison of recoveries of analytes with different extraction methods revealed that SLE was the best extraction method. The detection was facilitated with ion trap-mass spectrometer by multiple reactions monitoring （MRM） in a positive ion mode with ESI. The transitions monitored were m./z 441.1→325.2 for simvastatin, 408.2→235.1 for sitagliptin and 278.1→260.1 for the IS. The lower limit of quantification （LLOQ） was 0.2 ng/mL for sitagliptin and 0.1 ng/mL for simvastatin. The effective SLE offers enhanced chromatographic selectivity, thus facilitating the potential utility of the method for routine analysis of biological samples along with pharmacokinetic studies.

Separation of Red (Y_2O_3: Eu^(3+)), Blue (Sr,Ca,Ba)_(10)(PO_4)_6Cl_2: Eu^(2+) and Green (LaPO_4:Tb^(3+),Ce^(3+)) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3： Eu^3＋）, blue （Sr, Ca, Ba）10（PO4）6Cl2： Eu^2＋ and green （LaPO4： Tb^3＋, Ce^3＋） fine tricolor phosphor powders was established. First, the green phosphor was extracted and separated from three phosphor mixtures in heptane/DMF（N, N-Dimethylformamide） system using stearylamine or laurylamine （DDA） as the cationic surfactant. Then, after being treated with 99.5% ethanol, the blue and red phosphors could be separated in Heptane/DMF system in presence of 1-octanesulfonic acid sodium salt as the anionic surfactant. Satisfactory separation results have been achieved through two steps extractions with their artificial mixtures. The grades and recovery of separated products reached respectively as follows： red product was 95.3% and 90.9%, blue product was 90.0% and 95.2%, and green product was 92.2% and 91.8%.

Colorimetric determination of nanomolar concentrations of silicate in natural waters after liquid-liquid extraction using methyl isobutyl ketone

A sensitive solvent extraction method for the determination of nonamolar concentrations of silicate in natural waters is developed. According to the traditional aqueous silicate method, silicomolybdenum blue formed by the reaction between silicate and ammoni- um molydate and reduced by metol-sulfite reagent is extracted by methyl isobutyl ketone. The absorbance can be enhanced substantially up to 10-folds. The detection limit of silicate is 8 nmol/dm^3 , which is one tenth smaller than the traditional method, with the precision of 4.0% at a silicate level of 50 nmol/dm^3 and 3.2% at a silicate level of 6 μmol/dm^3. Comparing the calibration curves in the distilled water and seawater, it can be seen that the salt effect also exists in the extraction method. However, the salt effect is a linear function of the salinity and can be corrected by simple calibration. The proposed method is successfully applied to the determination of silicate in natural waters. Natural concentrations of arsenate, arsenite and phosphate cause negligible interference.

Direct injection HILIC-MS/MS analysis of darunavir in rat plasma applying supported liquid extraction

A novel bioanalytical method was developed and validated for the quantitative determination of darunavir（DRV） in rat plasma by employing hydrophilic interaction chromatography and tandem mass spectrometry（HILIC-MS/MS） with supported liquid extraction（SLE）.lrbesartan（IRB） was used as an internal standard（IS）.The analyte in rat plasma（200 μL） was isolated through SLE using ethyl acetate as the eluting solvent.The chromatographic separation was achieved on Luna-HILIC（250 mm × 4.6 mm,5 μm）column with a mobile phase of 0.1% of formic acid in water：acetonitrile（5：95,v/v）,at a constant flow rate of 1.0mL/min.The MS/MS ion transitions for DRV（548.1→392.0） and IS（429.2→207.1） were monitored on an ion trap mass spectrometer,operating in the multiple reaction monitoring（MRM） mode.The lower limit of quantitation（LLOQ） was 0.2 ng/mL and quantitation range was 0.2-5000 ng/mL.The method was validated for its selectivity,sensitivity,carryover,linearity,precision,accuracy,recovery,matrix effect and stability.The method was successfully applied to pharmacokinetic study in rats.

Extraction Behavior of Rare Earths with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 Using Solid-liquid Extraction Technique

The extraction behavior of rare earths was studied by using paraffin with ceresin as a diluent containing 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5.In solid phase,the composition of complexes is REP_3.The equilib- rium extraction constants and pH_(1/2) values of solid-liquid extraction are higher than those of normal liquid-liquid extraction.The extraction efficiency tends to maximum when the ratio of phases is 1:1.When the extraction temperature is higher than the melting point of paraffin and the extraction time is over 10 min,the extraction efficiency keeps constant.Moreover,the relationship among separation factor,equilibrium extrac- tion constant,pH_(1/2) value and atomic number was obtained.The mechanism of solid-liquid extraction is analogous to that of liquid-liquid extraction.

Comparison of liquid-liquid extraction-thin layer chromatography with solid-phase extraction-high-performance thin layer chromatography in detection of urinary morphine

Liquid-liquid extraction-thin layer chromatography （LLE-TLC） has been a common and routine combined method for detection of drugs in biological materials. Solid-phase extraction （SPE） is gradually replacing the tra- ditional LLE method. High performance thin layer chromatography （HPTLC） has several advantages over TLC. The present work studied the higher efficiency of a new SPE-HPTLC method over that of a routine LLE-TLC method, in extraction and detection of urinary morphine. Fifty-eight urine samples, primarily identified as mor- phine-positive samples by a strip test, ＇were re-screened by LLE-TLC and SPE-HPTLC. The results of LLE-TLC and SPE-HPTLC were then compared with each other. The results showed that the SPE-HPTLC detected 74% of total samples as morphine-positive samples whereas the LLE-TLC detected 48% of the same samples. We further discussed the effect of codeine abuse on TLC analysis of urinary morphine. Regarding the importance of morphine detection in urine, the present combined SPE-HPTLC method is suggested as a replacement method for detection of urinary morphine by many reference laboratories.

Solid-liquid Extraction Spectrophotometric Determination of Copper with 2,9-dimethyl-1,10-phenanthroline

Solid liquid extraction of copper ion (I) with 2, 9-dimethyl-1, 10-phenanthroline (neo-cuproine, DMP) into molten naphthalene followed by chloroform spectrophotometric determination has been studied experimentally. The ternary complex Cu(I)-DMP-ClO4 was extracted quantitatively into molten naphthalene in the range of pH from 5 to 6 at 85 C-. Absorbance was spectrophotometrically determined at 459 nm against the reagent blank after the solid naphthalene layer was anhydrously dissolved in chloroform. Beer's law is obeyed over a concentration range of 0.5-70 mug/mL. The molar absorptivity and Sandell's sensitivity are 1.0x10(4) L/(mol(.)cm) and 0.0099 mug(.)cm(2) respectively. In addition, the various conditions on determination and the interference of coexisted ions were discussed, and the method was applied to the determination of copper ion both in tea samples and cadmium sulfate reagents. The results are in good agreement with those obtained by ICP AES method.

Determination of 16 Species of OCPs in Water by Liquid-liquid Extraction-GC

[Objective] The research aimed to study the determination of 16 kinds of OCPs in water by liquid-liquid extraction -GC. [Method] The new method for determining 16 kinds of OCPs in water by liquid-liquid extraction -GC was established, and the influencing factors such as nitrogen pressure and water bath temperature were discussed. [ Result] Detection limit of the method was from 3.2 to 14.1 ng/L, the relative standard deviation was between 4.0% and 9.6%, and the average recovery ranged from 80.8% to 106.0%. By optimizing nitrogen pressure and water bath temperature in the sample pretreatment process, when nitrogen pressure was ＋0.087 kPa, and water bath temperature was ±36 ℃, recovery effect of this method was better. [ Conclusion] The determination method had accurate qualitative and quantitative results, and met detection requirement of 16 kinds of OCPs in water.

Sinomenine Purification by Continuous Liquid-Liquid Extraction Process with Centrifugal Extractors

Continuous manufacturing is considered as one of the future trends of pharmaceutical engineering. In this work, continuous liquid-liquid extraction for sinomenine purification was realized with the usage of centrifugal extractors. Chloroform was used as the extractant because of the high distribution coefficient (>100). Higher extraction ratio can be obtained when using the centrifugal extractor of Model CWL50-N. The extraction ratio of the second-stage extraction was higher than that of the first-stage extraction. The extraction ratio of the second-stage countercurrent extraction was higher than that of second-stage cross-flow extraction. When chloroform phase was recycled for liquid-liquid extraction, the extraction ratio was also higher than 95%. This work can also be an example of continuous liquid-liquid extraction for the separation of other Chinese medicine components.

Homogeneous Liquid-Liquid Extraction (HoLLE) of Palladium in Real Plating Wastewater for Recovery

On the basis of homogeneous liquid-liquid extraction (HoLLE) with Zonyl FSA to plating water containing 1 mg palladium, 96.6% of the palladium was extracted into the sedimented liquid phase. After phase separation, the volume ratio (Va/Vs) of the aqueous phase (Va) and the sedimented liquid phase (Vs) was 556 (50 mL → 0.09 mL). The assessment of the potential implementation of this procedure to wastewater treatment showed that HoLLE was satisfactorily achieved when the volume was scaled up to 1000 mL. Moreover, HoLLE was conducted to real palladium plating wastewater generated in the plating industry. 94.5% of the palladium was extracted into the sedimented liquid phase. After phase separation, the volume ratio (Va/Vs) of the aqueous phase (Va) and the sedimented liquid phase (Vs) was 500 (50 mL → 0.1 mL). In addition, HoLLE could separate palladium from coexisting metals in real plating wastewater. This knowledge is expected to lead to the development of new separation and concentration technologies of rare metals from real plating wastewater.

Determination of brominated diphenyl ethers in atmospheric particulate matter using selective pressurized liquid extraction and gas chromatography–mass spectrometry with a negative chemical ionization

This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers(PBDEs)in atmospheric particulate matter using selective pressurized liquid extraction(SPLE)and gas chromatography–mass spectrometry with a negative chemical ionization(GC-NCI-MS).Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70°C using hexane/dichloromethane(50:50,v/v)as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ngám L^(-1)for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pgám^(-3).

Effective and simple recovery of 1,3-propanediol from a fermented medium by liquid–liquid extraction system with ethanol and K_3PO_4

1,3-Propanediol,traditionally obtained from fossils,has numerous industrial applications,including use in the production of high performance polymers.The microbial production of 1,3-propanediol presents several opportunities,and the final purity grade determines its price and commercial viability.The development of novel separation technology could improve the economic viability of the bioproduction of 1,3-propanediol.Thus,we investigated salting-out extraction as a novel process for 1,3-propanediol recovery from fermentation broth.Initially,a screening for the best salt/solvent combination was conducted and then optimized using the response surface methodology.The solvents studied were methanol,ethanol,isopropanol and acetone,and the salts examined were K_2HPO_4,Na_2CO_3,K_2CO_3,(NH_4)_2SO_4,NaHPO_4,K_3PO_4 and C_6H_5NaO_7.The optimal extraction system consisted of 34 wt%K_3PO_4,28 wt% ethanol,and 38 wt% fermentation broth containing 23.0 g·L^(-1)1,3-propanediol,which gave the highest partition coefficient of 33 and recovery yield of 97%.The results demonstrated that salting-out extraction was a promising method for 1,3-propanediol recovery from fermentation broth.

A highly sensitive SPE-liquid/liquid extraction-RPLC analytical method for the determination of 6β-hydroxycortisol and cortisol in cancer patients' urine

Objective: A highly sensitive SPE-liquid/liquid extraction RPLC method has been developed for the analysis of 6β-hydroxycortisol and cortisol in the urine of cancer patients. Methods: After SPE column purification and liquid-liquid extraction, the sample test solutions were analyzed with RPLC using a C18 analytical column. This improved analytical method has been validated for linearity, accuracy (recovery from urine), repeatability (within-day and between-day precision), specificity, sensitivity, and stability. This SPE-liquid/liquid extraction-RPLC is rapid, simple, accurate and reproducible. The technique is particularly useful for monitoring the CYP3A activity of cancer patients in clinical settings. The results are expressed as the ratio of 6β-hydroxycortisol to cortisol. Results: The CYP3A activity from a total of 153 samples was measured using this improved method. Considerable variation in the CYP3A activity of different cancer patients has been documented. Thus, personalized medical treatment based on the individual metabolic enzyme activity level is necessary. Conclusion: This new analytical method facilitates such individualized medical treatments.

Chemical constituents and antioxidant activities of waste liquid extract from Apostichopus japonicus Selenka processing

Apostichopus japonicus Selenka is an ideal tonic food that is used traditionally in many Asian countries, and it contains many bioactive substances, such as antioxidant, antimicrobial, and anticancer materials. To convert waste liquid generated during production into a useful resource, extract from waste liquid was isolated by column chromatography and studied by the pyrogallol autoxidation and 1,10-phenanthroline-Fe 2+ oxidation methods. Results show that the extract scavenged about 91% of the superoxide anion radical at a concentration of 1.4 mg/mL and 24% of the hydroxyl radical at 3.3 mg/mL. Four compounds were isolated and identified from the extract:2,4-dihydroxy-5-methyl-1,3-azine;2,4-dihydroxy- 1,3-diazine;3-O-[β-D-quinovopranosyl-(1 2)-4-O-sodium sulfate-β-D-xylopranosyl]-holosta-9(11)-ene- 3β,12α,17α-triol; and 24-ethyl-5α-cholesta-7-ene-3β-O-β-D-xylopyranoside. All of these compounds are known in A. japonicus, and were found in the waste liquid for the first time.

Separation of ^(152+154)Eu,^(90)Sr from radioactive waste effluent using liquid–liquid extraction by polyglycerol phthalate

A new polyglycerol phthalate extractant was prepared and characterized using Fourier transform infrared spectroscopy, proton nuclear magnetic resonance(~1H NMR) spectroscopy, and thermogravimetric analysis. A preliminary study of the extraction of long-lived(^(90) Sr and ^(152+154)Eu) and short-lived(^(90) Y) radionuclides by polyglycerol phthalate was performed. The influence of different diluents, concentration of the acid, type of acid, and various interfering ions was explored. The stripping of ^(152+154)Eu radionuclide was studied by using different acid solutions, and it was found that sulfuric acid was the ideal acid for this purpose. Furthermore,^(152+154)Eu was extracted from the fission products(^(90) Sr) and the extraction% of^(90) Sr was found to improve in the presence of interfering ions.

Preparation of Highly Concentrated Silver Nanoparticles in Reverse Micelles of Sucrose Fatty Acid Esters through Solid-Liquid Extraction Method

Silver nanoparticles were synthesized in reverse micelles consisting of sucrose fatty acid esters by dissolving reactant powder in the water pool of reverse micelles through the solid-liquid extraction. Silver nanoparticles having various sizes and shapes were obtained at high concentration. The size of silver nanoparticles was controlled by reaction temperature. Moreover, the size of silver nanoparticles was dependent upon the average esterification degree of sucrose fatty acid esters forming reverse micelles. The wavelength in the peaks, which corresponded upon the localized surface plasmon resonance of resultant silver nanoparticles, was correlated with their sizes.

Salting-Out Assisted Liquid-Liquid Extraction Combined with HPLC for Quantitative Extraction of Trace Multiclass Pesticide Residues from Environmental Waters

In this study, salting-out assisted liquid-liquid extraction combined with high performance liquid chromatography diode array detector (SALLE-HPLC-DAD) method was developed and validated for simultaneous analysis of carbaryl, atrazine, propazine, chlorothalonil, dimethametryn and terbutryn in environmental water samples. Parameters affecting the extraction efficiency such as type and volume of extraction solvent, sample volume, salt type and amount, centrifugation speed and time, and sample pH were optimized. Under the optimum extraction conditions the method was linear over the range of 10 - 100 μg/L (carbaryl), 8 - 100 μg/L (atarzine), 7 - 100 μg/L (propazine) and 9 - 100 μg/L (chlorothalonil, terbutryn and dimethametryn) with correlation coefficients (R2) between 0.99 and 0.999. Limits of detection and quantification ranged from 2.0 to 2.8 μg/L and 6.7 to 9.5 μg/L, respectively. The extraction recoveries obtained for ground, lake and river waters were in a range of 75.5% to 106.6%, with the intra-day and inter-day relative standard deviation lower than 3.4% for all the target analytes. All of the target analytes were not detected in these samples. Therefore, the proposed SALLE-HPLC-DAD method is simple, rapid, cheap and environmentally friendly for the determination of the aforementioned herbicides, insecticide and fungicide residues in environmental water samples.