A Study on Stoichiometry of Complexes of Tributyl Phosphate and Methyl Isobutyl Ketone with Lithium in the Presence of FeCl_3

To study the characteristic of liquid-liquid extraction equilibrium of lithium from brine sources, the complexes formed from tributyl phosphate （TBP） and methyl isobutyl ketone （MIBK） with lithium were investi- gated using FeCl3 as coextracting agent. Liquid-liquid extraction reaction mechanisms were proposed and the stoichiometry of tetrachloroferrate（III） complex with lithium was obtained by regressing the experimental data. It is found that the stoichiometry of tetrachloroferrate（III） to lithium in the complex is 1 ： 1 with either TBP or MIBK as extractant in kerosene. The stoichiometry of the complex of TBP with Li was 1 ： 1 and that of MIBK with Li was 2 ： 1. The formed complexes of TBP and MIBK with lithium are determined to be LiFeCla-TBP and LiFeC14.2MIBK, respectively, according to the rule of neutralization.

Synthesis of Methyl Isopropyl Ketone and Diethyl Ketone over Ni-Na/ZrO_2-MnO_2-ZnO Catalyst

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.

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.

Condensation Reaction of 5,6-Dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-dione, Ethyl Orthoformate and Substituted Anilines

Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid. Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5, 6-dihydro-6-methyl-6-piperonyl-2H-pyran-2, 4-dione was prepared, which reacted with substituted anilines in the presence of ethyl orthoformate to obtain 3-anilinomethylene-5, 6- dihydro- 6-methyl-6-piperonyl-2H-pyran-2, 4-diones. Their structures were confirmed by 1HNMR and elemental analysis.

Equilibrium and kinetic data of adsorption and separation for zirconium and hafnium onto MIBK extraction resin

The equilibrium and kinetics of methyl isobutyl ketone(MIBK) extraction resin for adsorption and separation of zirconium and hafnium were studied under the different conditions of acidity,initial total concentrations of zirconium and hafnium and temperature.The equilibrium data of both zirconium and hafnium are found to follow the Freundlich adsorption isotherm,and the Freundlich isotherm constants(KF) are 3.53 and 0.64 mg/g,respectively.The equilibrium data of zirconium also fit the Langmuir adsorption isotherm,and the saturation adsorption capacity(Qmax) and the Langmuir isotherm constant(KL)are 75.93 mg/g and-0.012 7 L/g,respectively.The obtained kinetic data of both zirconium and hafnium are found to fit the HO pseudo-second-order kinetic model,and the rate constants of pseudo-second-order equation(k2) are-0.019 and 0.41 g/(mg·min),respectively.Column tests show that the MIBK extraction resin could be used as efficient adsorbent material for separating hafnium from zirconium.

Fabrication of Pd-based metal-acid-alkali multifunctional catalysts for one-pot synthesis of MIBK

The one-pot synthesis of methyl isobutyl ketone（MIBK） from acetone using multifunctional catalysts is an important sustainable organic synthesis method with high atom and energy efficiency.Herein. we report a series of Pd supported on mixed metal oxide（MMO） catalysts with controllable acidic/basic/metallic sites on the surface. We study the relationship between the nature, synergy,and proximity of active sites and the catalytic performance of the multifunctional catalyst in the tandem reaction, in detail. In the existence of Lewis acid and base sites, the catalysts with medium-strength acidic/basic sites show preferred activity and/or MIBK selectivity. For multifunctional catalysts, the catalytic properties are more than just a collection of active sites, and the Pd/Mg_3Al-MMO catalyst possessing 0.1% Pd loading and ~0.4 acid/base molar ratio exhibits the optimal 42.1% acetone conversion and 37.2% MIBK yield, which is among the best reported so far for this tandem reaction under similar conditions. Moreover, the proximity test indicates that the intimate distance between acidic/basic/metallic sites can greatly shorten the diffusion time of the intermediate species from each active site, leading to an enhancement in the catalytic performance.

Removal of organic solvent from cathodic electrophoretic emulsion paint by vacuum steam stripping

The production of environmental friendly emulsion paint is of great significance. Vacuum steam stripping of methyl isobutyl ketone （MIBK） and methyl ethyl ketone （MEK） from cathodic electrophoretic emulsion was studied. The effects of mass ratio of vapor to feed （V/F）, vacuum degree and feed temperature on removal rate of MIBK and MEK, emulsion size and solid volume fraction of the emulsion were investigated, and the removal of MIBK and MEK from cathodic electrophoretic emulsion by vacuum desorption was also studied. The results show that removal rates of both MIBK and MEK increase with the increase of V/F, vacuum degree and feed temperature. Removal rates of MIBK and MEK are 98.3% and 93.6%, respectively, at the operating condition V/F of 0.7, feed temperature of 27℃ and vacuum degree of 90 kPa. The emulsion size of cathodic electrophoretic emulsion increases slightly with feed temperature when temperature is below 42 ℃, and increases rapidly with feed temperature when temperature is above 42℃. Solid volume fraction increases by 10% as vacuum degree increases from 0 to 90 kPa at V/F of 0.7 and feed temperature of 27 ℃. Compared with vacuum desorption, vacuum steam stripping can get a higher removal rate of MIBK and MEK under the same feed flow, vacuum degree and feed temperature.

Comparative study of degradation of toluene and methyl isobutyl ketone(MIBK)in aqueous solution by pulsed corona discharge plasma

Effectiveness of pulsed power plasma for the degradation of two toxic volatile organic compounds(VOCs),toluene and methyl isobutyl ketone(MIBK),in aqueous solution was evaluated.The plasma degradation of MIBK has been studied for the first time.The influence of initial concentration of target compound,solution pH and scavengers on percentage degradation was evaluated.100%removal of 200 mg/L of toluene and MIBK was achieved both in liquid and gaseous phases after 12 and 16 min of plasma treatment,respectively.The first order rate constant of toluene and MIBK degradation(for 200 mg/L each)was 0.421 and 0.319 min~(-1)respectively when they were treated individually,and these values decreased slightly during degradation of their mixture.MIBK degradation was slower than toluene and it might be due to semi volatile and hydrophilic nature of MIBK.The effect of initial concentration of toluene and MIBK showed different degradation patterns.Highest degradation of both the compounds was obtained in neutral pH and in absence of scavengers.·OH radical was the major reactive species involved in their degradation.Their degradation in real environmental matrices showed that removal reduced significantly in secondary effluent due to scavenging of reactive species by various ions and organic matter.The total number of degradation intermediates identified in case of toluene and MIBK was 11 and 14 respectively and formate was the one recalcitrant byproduct generated.The degradation pathway of toluene and MIBK involving reactions of reactive oxygen and nitrogen species and reductive species is proposed.

THE MASS SPECTRA OF AROMATIC CONJUGATED POLYENIC ACID,METHYL BENZOATE,METHYL PHENYL KETONE,BENZONITRILE AND ANILINE AND THEIR QUANTUM CHEMICAL CALCULATIONS

A quantitative interpretation of mass spectra of complex organic compounds so far is notvery perfect and needs some further investigation. In this paper a mechanism of cleft-rate-determining-steps of aromatic conjugated polyenic acid, methyl benzoate, methyl phenyl ketone,benzonitrile and aniline is proposed, and various quantum parameters of molecular ions ofaromatic conjugated polyenic compounds, together with their framents are calculated bymeans of CNDO/2 method. Through the process of calculation, the peak-height of mass spectracan be quantitatively interpreted, which means that the main factors which influence the cleftforms of simple cleavage of mass spectra of conjugated compounds given by the authorsmight be true to some extent.

Aerobic Oxidation of Methyl Vinyl Ketone in Supercritical Carbon Dioxide

Aerobic oxidation of methyl vinyl ketone to acetal in supercritical carbon dioxide are achieved in high conversion and high selectivity when oxygen pressure reaches to 0.5 MPa. The effects of cocatalysts, additive, pressure and temperature of the reaction are studied in detail.

Rapid alkenylation of quinoxalin-2(1H)-ones enabled by the sequential Mannich-type reaction and solar photocatalysis

Herein,a rapid alkenylation of quinoxalin-2(1H)-ones enabled by a combination of Mannich-type reaction and solar photocatalysis is demonstrated.A wide range of functional groups are compatible,affording the corresponding products in moderate-to-good yields.Control experiments illustrate that the in situ generated^(1)O_(2)plays a central role in this reaction.This green and efficient strategy provides a practical solution for the synthesis of potentially bioactive compounds that containing a 3,4-dihydroquinoxalin-2(1H)-one structure.

Novel Method for Indirect Determination of Iodine in Marine Products by Atomic Fluorescence Spectrometry

A method for the determination of iodine based upon compound H2HgI4, formed between I- and Hg1＋ in nitric acid and extracted in methyl isobutyl ketone（MIBK）, was developed via atomic fluorescence spectrometry（AFS）. After the compound is reduced with potassium borohydrid（KBH4）, the resultant mercury vapor was injected into the instrument and iodine was, therefore, indirectly determined. Experimental parameters such as the conditions of extraction reagents, aqueous phase acidity, elemental mercury diffusion temperature in a vial and other factors were investigated and optimized. Under the optimum experimental conditions, this method shows a detection limit of 0.038μg/L iodine and a linear relationship between 0.04-20 p.g/L. The method was applied to determining the iodine content in marine duck eggs, kelps, laver and Ganoderma lucidum spirulina, showing a relative standard deviation（RSD） of 2.15% and the recoveries in the range of 98.1%-102.5%.