Phase equilibrium data prediction and process optimizationin butadiene extraction process

In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.

Development of Extraction and Detection Method for a Chemotherapeutic Drug with Phenytoin in Biological Samples

Dexamethasone is classified as a corticosteroid and is commonly used among cancer patients to decrease the amount of swelling around the tumor. Among patients with cancer, in particular brain tumors, seizures can become a daily routine in their everyday lives. To counteract the seizures, an antiepileptic drug such as phenytoin is administered to act as an anticonvulsant. Phenytoin and dexamethasone are frequently administrated concurrently to brain cancer patients. A previous study has shown that phenytoin serum concentration decreases when administrated concurrently with dexamethasone. Thus, it is important to monitor the concentration of these two drugs in biological samples to ensure that the proper dosages are administrated to the patients. This study aims to develop an effective extraction and detection method for dexamethasone and phenytoin. A reverse-phase high-performance liquid chromatography (HPLC) method with UV/Vis detection has been developed to separate phenytoin and dexamethasone at 219 nm and 241 nm respectively from urine samples. The mobile phase consists of a mixture of 0.01 M KH2PO4, acetonitrile, and methanol adjusted to pH 5.6 (48:32:20) and is pumped at a flow rate of 1.0 mL/min. Calibration curves were prepared for phenytoin and dexamethasone (r2 > 0.99). An efficient solid-phase extraction (SPE) method for the extraction of dexamethasone and phenytoin from urine samples was developed with the use of C-18 cartridges. The percent recovery for phenytoin and dexamethasone is 95.4% (RSD = 1.15%) and 81.1% (RSD = 3.56%) respectively.

Determination of Eleutheroside B and E in Acanthopanax Preparations by High-P erformance Liquid Chromatography with Solid-Phase Extraction

Aim An HPLC method for analyzing eleutheroside B (ELU B) and eleutheroside E(ELU E) , two of the main active substances of Acanthopanax preparations were studied. Methods Thesamples were analyzed on a kromasil ODS column with water-acetonitrile as a gradient mobile phase.The flow rate was 0.8 mL·min^(-1) and detecting wavelengths were 206 nm for ELU B, 220 nm for ELUE, solid phase extraction (SPE) and internal standard-salicin were selected. Results The recoveriesof Acanthopanax tablets and injection were 90.4% - 96.8% and 96.4% - 99.8% for ELU B, 87.7% -93.3%and 95.7% - 98.5% for ELU E, respectively. The linear ranges were 4.45 - 22.25 μg· mL^(-1) (r =0.999 8) and 5.11 - 25.55 μg·mL^(-1) ( r = 0.999 7) respectively. Conclusion This method can savethe time for cleaning the chromatographic system and improve sensitivity for Acanthopanaxpreparations , thus providing a way to evaluate the quality of Acanthopanax preparations.

Synthesis and Solid Phase Extraction Performance Study of NNAL-specific Molecularly Imprinted Polymers Using Dummy Templates

Dummy molecularly imprinted polymers （DMIPs） for 4-（methylnitrosamino）-1-（3-pyridyl）-1-butanol （NNAL） were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-（acetymethylamino）-1-（3-pyridyl）-butanol, 4- （methylamino）-1-（3-pyridyl）-1-butanol, and 1-（3-pyridyl）-1,4,-butanediol. The molecular recognition characteristics of the produced polymers were evaluated by X-ray photoelec- tron spectroscopy （XPS） and Fourier transform infrared spectroscopy （FT-IR）. Interactions between NNAL and methacrylic acid should be cooperative hydrogen bonds while the ni- trogen atom of the pyridine ring and the oxygen atom of the nitroso group in NNAL are two of the hydrogen-bond acceptors. It was further demonstrated that DMIP synthesized by 4-（acetymethylamino）-1-（3-pyridyl）-butanol had the best binding performance by XPS and FT-IR. Then dummy molecularly imprinted solid phase extraction （DMISPE） was developed for the determination of the analyte using the hit polymer as the sorbing material. Under optimal conditions, the recovery of NNAL dissolved in standard solution reached 93%. And the investigated polymer exhibited much higher binding of NNAL when nicotine was acted as the competitive molecule. Also the proposed method was applied to the measurement of NNAL spiked in blank urine samples with recoveries ranging from 87.2% to 101.2%.

Determination of resveratrol in red wine by solid phase extraction-flow injection chemiluminescence method

A sensitive flow injection chemiluminescence method has been developed for the detection of resveratrol in red wine based on the fact that resveratrol can greatly enhance chemiluminescence reaction between KMnO4 and HCHO in sulfuric acid medium. Analytes were pre-concentrated on solid sorbents （C18 solid-phase extraction cartridges）. Under the optimum conditions, the proposed method allows the measurement of resveratrol over the range of 1.32 × 10^-8 to 1.32 × 10^-5 mol/L with a detection limit of 3.30 ×10^-9 mol/L, and the relative standard deviation for 1.32 ×10^-5 mol/L resveratrol （n = 11） is 3.8%. This method has been successfully applied for the determination of the resveratrol in red wine. Furthermore, the possible reaction mechanism was also discussed.

Effect of Temperature on Phase and Alumina Extraction Efficiency of the Product from Sintering Coal Fly Ash with Ammonium Sulfate

A new developed technology for extracting alumina from coal fly ash was studied in this paper. In this technology, coal fly ash is first sintered with ammonium sulfate, forming ammonium aluminum sulfate in the resultant product, where alumina can be easily leached without using any strong acid or alkali. The products obtained under different sintering conditions were characterized by X-ray diffractometry. Alumina extraction efficiency of these products was also investigated. The results show that the sintering temperature and time substantially influence the phase composition and alumina extraction efficiency of sintered products, while the heating rate has little influence. The optimal sintering condition is 400 °C for 3 h in air with a heating rate of 6 °C·min-1.Under the optimal sintering condition, the alumina extraction efficiency from as-sintered coal fly ash can reach 85% or more.

Influences of solid particles on the formation of the third phase crud during solvent extraction

The influences of solid particles in leach solution on the formation of the third phase crud during solvent extraction of copper were studied. Analyzed from the point of view of pH value and surface tension, the study results showed that the solid particle is one of the most important contributors for the formation of the third phase crud. During solvent extraction, if the pH value was greater than 2.30, the number of solid particles in the mother solution increased, in which case the possibility of forming the third phase crud could also increase, and the interface tension value might grow in pace with the quantity of the third phase crud.

Solid Phase Extraction Chemiluminescence Determination of Methamidaphos on Vegetables

The determination of the methamidaphos pesticide residue on vegetables with a simple solid phase extract（SPE） flow injection（FI） -chemiluminescence（CL） method is described. The method is based on the enhancing effect of methamidaphos on the CL reaction of luminol with hydrogen peroxide in an alkaline solution. Under the optimal conditions, the CL intensity is linear to the methamidaphos mass concentration in a range of 0. 2-13μg/mL （ r= 0. 9992）. The detection limit（3σ） is 0. 047μg/mL. The relative standard deviations for the analysis of three samples are 1.8%, 2.5% and 3.7% （ n = 5 ）, respectively. The recovery is in a range of 90%-109% by the method. In this work, this method was successfully applied to the determination of the methamidaphos residue on some vegetable samples.

Determination of volatile organic compounds in river water by solid phase extraction and gas chromatography

A simple, rapid, and reproducible method is described employing solid phase extraction(SPE) using dichloromethane followed by gas chromatography(GC) with flame ionization detection(FID) for determination of volatile organic compound(VOC) from the Buriganga River water of Bangladesh. The method was applied to detect the benzene, toluene, ethylbenzene, xylene and cumene(BTEXC) in the sample collected from the surface or 15 cm depth of water. Two hundred ml of n hexane pretreated and filtered water samples were applied directly to a C 18 SPE column. BTEXC were extracted with dichloromethane and average concentrations were obtained as 0 104 to 0 372 μg/ml. The highest concentration of benzene was found as 0 372 μg/ml with a relative standard deviation(RSD) of 6 2%, and cumene was not detected. Factors influencing SPE e.g., adsorbent types, sample load volume, eluting solvent, headspace and temperatures, were investigated. A cartridge containing a C 18 adsorbent and using dichloromethane gave better performance for extraction of BTEXC from water. Average recoveries exceeding 90% could be achieved for cumene at 4℃ with a 2 7% RSD.

A novel surface molecularly imprinted polymer as the solid-phase extraction adsorbent for the selective determination of ampicillin sodium in milk and blood samples

Surface molecularly imprinted polymers （SMIPs） for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological characteristics of the polymers were investigated by scanning electron microscope （SEM）, Fourier transform infrared spectroscopy （FT-IR）, thermogravimetric analysis （TGA）, elemental analysis and nitrogen adsorption-desorption test. The obtained results showed that the SMIPs displayed great adsorption capacity （13.5 lag/mg）, high recognition ability （the imprinted factor is 3.2） and good binding kinetics for ampicillin sodium. Finally, as solid phase extraction adsorbents, the SMIPs coupled with HPLC method were validated and applied for the enrichment, purification and determination of anapicillin sodium in real milk and blood samples. The averages of spiked accuracy ranged from 92.1% to 107.6%. The relative standard deviations of intra- and inter-day precisions were less than 4.6%. This study provides a new and promising method for enriching, extracting and determining ampicillin sodium in complex biological samples.

Development trend and prospect of solid phase extraction technology

Solid phase extraction is widely used in sample pretreatment,concentration and analysis processes due to high selectivity and suitability for low concentration sample system.In this review,we systematically summarized and discussed the development trends of solid phase extraction by bibliometrics method.By analyzing papers output scale,the research and development direction of solid phase extraction technology is prospected.We also give an overview on current strategies of novel solid phase extraction from the separation medium and separation technology.The paper aims to describe the global research profile and the development trends of solid phase extraction,to help researchers to accurately grasp the research trend and to provide support for scientific research institutions to formulate scientific policies and strategic plans.Furthermore,the prospect of the development and application of solid phase extraction is also discussed.

Phase separation in solvent extraction of cobalt from acidic sulfate solution using synergistic mixture containing dinonylnaphthalene sulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester

Phase separation rate is a critical character in determining the usefulness of a solvent extraction system in hydrometallurgy. A survey of the synergistic mixture containing dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexly 4-pyridinecarboxylate ester (4PC) for the extraction of cobalt from acidic single metal sulfate solution was carried out to suggest how the physicochemical properties and the morphology of the reverse micelles in the loaded organic phase affect the phase separation. The results show that effective parameters affecting the phase separation are the viscosity and the excess water uptake of the loaded organic phase. It is obvious that the specific settling rate (SSR) decreases with the apparent increase of these two parameters. The measurement of small angle X-ray scattering (SAXS) proves that the morphology of the reversed micelles in the loaded organic phase changes evidently with the change of the specific settling rate (SSR).

Prediction of dispersed phase holdup in pulsed disc and doughnut solvent extraction columns under different mass transfer conditions

Using experimental data from a number of pulsed disc and doughnut solvent extraction columns, a unified correla- tion for the prediction of dispersed phase holdup that considers the effects of mass transfer is presented. Pulsed disc and doughnut solvent extraction columns （PDDC） have been used for a range of important applications such as ura- nium extraction and nuclear fuel recycling. Although the dispersed phase holdup in a PDDC has been presented by some researchers, there is still the need to develop a robust correlation that can predict the experimental dispersed phase holdup over a range of operating conditions including the effects of mass transfer direction. In this study, dis- persed phase holdup data from different literature sources for a PDDC were used to refit constants for the correlation presented by Kumar and Hartland lind. Eng. Chem. Res.,27 （1988）,131-138] which did not consider the effect of col- umn geometry. In order to incorporate the characteristic length of the PDDC （i.e. the plate spacing）, the unified cor- relation for holdup proposed by Kumar and Hartland based on data from eight different types of columns [Ind. Eng. Chem. Res.,34 （1995） 3925-3940] was refitted to the PDDC data. New constants have been presented for each hold- up correlation for a PDDC based on regression analysis using published holdup data from PDDCs that cover a range of onerating conditions and nhwical nronerties and consider the direction of mass transfer.

Hollow fiber-based liquid phase microextraction followed by analytical instrumental techniques for quantitative analysis of heavy metal ions and pharmaceuticals

Hollow-fiber liquid-phase microextraction(HF-LPME)and electromembrane extraction(EME)are miniaturized extraction techniques,and have been coupled with various analytical instruments for trace analysis of heavy metals,drugs and other organic compounds,in recent years.HF-LPME and EME provide high selectivity,efficient sample cleanup and enrichment,and reduce the consumption of organic sol-vents to a few micro-liters per sample.HF-LPME and EME are compatible with different analytical in-struments for chromatography,electrophoresis,atomic spectroscopy,mass spectrometry,and electrochemical detection.HF-LPME and EME have gained significant popularity during the recent years.This review focuses on hollow fiber based techniques(especially HF-LPME and EME)of heavy metals and pharmaceuticals(published 2017 to May 2019),and their combinations with atomic spectroscopy,UV-VIS spectrophotometry,high performance liquid chromatography,gas chromatography,capillary elec-trophoresis,and voltammetry.

Preconcentration of copper with multi-walled carbon nanotubes pretreated by potassium permanganate cartridge for solid phase extraction prior to flame atomic absorption spectrometry

A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1–100 ng/mL (R(2) = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.

Dynamic microwave-assisted extraction combined with liquid phase microextraction based on the solidification of a floating drop for the analysis of organochlorine pesticides in grains followed by GC

A convenient,cost-effective and fast method using dynamic microwave-assisted extraction and liquid phase microextraction based on the solidification of a floating drop was proposed to analyze organochlorine pesticides in grains including rice,maize and millet.Twelve samples can be processed simultaneously in the method.During the extraction process,10%acetonitrile-water solutions containing 110μL of n-hexadecane were used to extract organochlorine pesticides.Subsequently,1.0 g sodium chloride was placed in the extract,and then centrifuged and cooled.The n-hexadecane drops containing the analytes were solidifi ed and transferred for determination by gas chromatography-electron capture detector without any further filtration or cleaning process.Limits of detection for organochlorine pesticides were 0.97–1.01μg/kg and the RSDs were in the range of 2.6%–8.5%.The developed technology has succeeded in analyzing six real grains samples and the recoveries of the organochlorine pesticides were 72.2%–94.3%.Compared with the published extraction methods,the developed method was used to analyze organochlorine pesticides in grains,being more environmentally friendly,which is suitable for the daily determination of organochlorine pesticides.

Rapid analysis of fifteen sulfonamide residues in pork and fish samples by automated on-line solid phase extraction coupled to liquid chromatography–tandem mass spectrometry

The aim of this work was to develop an automated on-line solid phase extraction(SPE)with liquid chromatography-tandem mass spectrometry method for the detection of fifteen sulfonamides in pork and fish samples.Samples were extracted with 0.2%formic acid acetonitrile solution,purified by on-line SPE device with HLB column,then separated by XBridge C18 column,using 0.1%formic acid solution and acetonitrile as the mobile phase.Mass spectrometric data was acquired under multiple reaction monitoring(MRM)mode using positive ionization electrospray.Internal standard method was used in the quantification,good linear relationship was got in range of 0.1–100 ng/mL and correlation coefficient was higher than 0.9990.The limits of detection were in the range of 0.125–2.00g/kg and the limits of quantitation were in the range of 0.250–5.00g/kg.Recoveries of the method were in range of 78.3%–99.3%,relative standard deviation were lower than 10%.The method was simple,sensitivity,and could be used for routine supervision and analysis of fifteen sulfonamides in pork and fish.

Determination of Sulfadimidine in Royal Jelly by C_(18)-functionalized Magnetic Silica Nanoparticles Solid Phase Extraction-High Performance Liquid Chromatography-Tandem Mass Spectrometry

[Objective] This study aimed to develop a method of C_18-functionalized magnetic silica nanoparticles solid phase extraction-high performance liquid chro- matography-tandem mass spectrometry for the determination of sulfadimidine in royal jelly. [Method] The royal jelly samples were pretreated by MCX SPE column and C_18-functionalized magnetic silica nanoparticles, and the purified samples were de- tected by HPLC-MS/MS. [Result] The detection method showed a good linear rela- tionship in the range of 5-80 ugkg （r=0.993 1）. The recovery ranges were between 93%- 104% with the relative standard deviations （RSD） below 11.3%. [Conclusion] Combined with automation equipment, the method is simple, fast, time-saving, and easy to real- ize the automation of sulfadimidine in the royal jelly samples before determination.

Degradation Dynamics and Residue Analysis of Flubendiamide in Cabbage and Soil by Liquid Chromatography-Tandem Mass Spectrometry with Dispersive Solid Phase Extraction

To formulate a scientific basis for a reasonable spray dose and safe interval period of 20% flubendiamide water dispersible granule (WDG) on controlling vegetable pests, degradation dynamics of flubendiamide in cabbage and soil was analyzed in this study. Dissipation and residue of flubendiamide in 20% flubendiamide WDG in cabbage and soil under field conditions were investigated by liquid chromatography-tandem mass spectrometry with dispersive solid phase extraction. Results showed that the degradation dynamic equations of flubendiamide in cabbage and soil were based on the first-order reaction dynamic equations. The half-lives of the degradation of flubendiamide were 3.51 d to 3.96 d and 3.43 d to 3.87 d in the cabbage of Yangzhou and Jingzhou, respectively, and 4.42 d to 5.13 d and 4.37 d to 4.99 d in the soil of Yangzhou and Jingzhou, respectively. The terminal residues of flubendiamide in the cabbage of Yangzhou and Jingzhou were 0.0247 mg·kg-1 to 0.0393 mg·kg-1 and 0.0225 mg·kg-1 to 0.0273 mg·kg-1, respectively, when 20% flubendiamide WDG was applied at a dose of0.050g·m-2. Flubendiamide is safe to be applied in cabbage fields at the recommended dose.

Extraction Mechanism of Rare Earths with Sec-Octylphenoxy Acetic Acid by Two-Phase Titration Technique

The compositions of the extracted complexes of La, Gd, Er and Y with sec octyl phenoxy acetic acid in heptane and the related apparent extraction equilibrium constants K M were determined using two phase titration technique. The stoichiometric compounds for La, Gd, Er and Y should be LaA 3·2.5HA, GdA 3·3HA, ErA 3·3.1HA and YA 3·4.3HA respectively. And their p K M are 3.43, 3.46, 3.08 and 2.58 respectively.