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.

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.

Salt effect on the liquid–liquid equilibrium of the ternary (water + phenol + methyl isobutyl ketone) system: Experimental data and correlation

The effects of NaCl, KCl and Na_2SO_4 on the liquid–liquid equilibrium(LLE) data for the ternary system, water+ phenol + methyl isobutyl ketone, were determined at 0.101 MPa and 333.15 K and 343.15 K.The nonrandom two-liquid(NRTL) model was used to correlate the experimental data and to yield corresponding binary interaction parameters for these salt containing systems.The Hand and Othmer–Tobias equations were used to confirm the dependability of the determined LLE data in this work.Distribution coefficient and selectivity were used to evaluate the extraction performance of methyl isobutyl ketone with the existence of salt.The magnitude of salt effect on the water + phenol + methyl isobutyl ketone(MIBK) system is in the following order: Na_2SO_4>NaCl>KCl.

Catalytic Hydrogenation Performance of Methyl Isobutyl Ketone over Ni/γ-Al_2O_3 Catalysts

Supported nickel-based catalysts were prepared by the incipient wetness impregnation method for the selective hydrogenation of methyl isobutyl ketone to methyl isobutyl carbinol in a fixed-bed reactor. The effects of the nickel source,Ni loading, calcination time, and calcination temperature on the hydrogenation performance were studied. The experimental results showed that the Ni/γ-Al_2O_3 catalyst demonstrated the highest catalytic performance under the preparation conditions by using nickel nitrate as the nickel source with a NiO loading of 20%, followed by calcination at 440°C for 5h. In addition,this catalyst showed the largest specific surface area, best crystal structure, highest active component content, smallest particle size, and uniform distribution of NiO on the surface of the carrier. The nickel-based catalyst prepared using the optimized conditions exhibited a 96.1% conversion of methyl isobutyl ketone, with a methyl isobutyl carbinol selectivity of 99.6%. The described procedure is very effective for the preparation of methyl isobutyl carbinol using methyl isobutyl ketone as the feedstock.

丙酮一步法合成MIBK反应体系热力学研究

对丙酮一步法合成MIBK反应体系进行热力学研究,计算了体系中主、副反应在80~260℃反应焓、反应熵、吉布斯自由能和平衡常数。结果表明:在给定温度范围内,丙酮缩合加氢体系主、副反应均为放热反应,主反应放热量相对较少。随着温度升高,主反应始终自发进行,平衡常数恒大于1;副反应平衡常数逐渐减小,当反应温度>110℃,副反应非自发进行。

不同形貌的Cu/MgO一步气相法催化合成MIBK

使用三种不同形貌的氧化镁纳米材料(纳米片、纳米盘、纳米纤维)分散铜,高分辨透射电子显微镜(HRTEM)分析表明,CuO在三种载体上以高度分散的无定型形式存在。将Cu/MgO催化剂用于丙酮气相缩合和选择性加氢制甲基异丁基酮(MIBK)的反应,结果发现其催化性能与CO_(2)-TPD测量结果以及MgO纳米材料上铜物种的分散性相关。催化剂表面碱性位的总数和密度遵循以下大小顺序:Cu/MgO纳米片>Cu/MgO纳米盘>Cu/MgO纳米纤维。催化丙酮转化时,Cu/MgO纳米片的丙酮转化率和反应速率远高于Cu/MgO纳米盘和纳米纤维,这主要归功于其表面大量的碱性位位点,同时,Cu/MgO纳米片最大的Cu的比表面积提高了其MIBK产率。

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.

采用HTLcs前驱体制备的丙酮一步法制MIBK催化剂

采用共沉淀法制备Cu Mg A1三元类水滑石,进而煅烧得到CuO MgO Al2O3催化剂用于丙酮加氢一步合成甲基异丁基酮(MIBK)反应。研究了催化剂活性组分配比及反应条件对转化率和选择性的影响,经筛选得到催化剂体系的最佳组成为:n(Cu)∶n(Mg)∶n(Al)=4∶16∶10,适宜的反应条件为:温度240℃,n(H2)∶n(丙酮)=2.5,液空速为4.8mL/h·g,在该条件下丙酮转化率达73.88%,MIBK选择性达55.23%。

丙酮和氢气合成MIBK的工艺研究

在小型装置上,采用M-3催化剂,对丙酮加氢合成MIBK的工艺条件进行了研究。考察了反应温度、压力、空速对反应的影响,确定了适合于该反应的最佳条件。并对M-3催化剂进行了7 200 h寿命试验。结果表明,寿命试验全程丙酮平均转化率为30.68%,MIBK选择性为94.71%。M-3催化剂具有耐温性能好、温度使用范围宽、催化活性高、使用寿命长的优点。

3-庚酮+乙酸乙酯、3-庚酮+乙酸丁酯、3-庚酮+TBP、MIBK+TBP二元体系的过量摩尔体积和黏度

常压下测定了3-庚酮+乙酸乙酯、3-庚酮+乙酸丁酯、3-庚酮+磷酸三丁酯(TBP)、4-甲基-2-戊酮(MI-BK)+磷酸三丁酯4个二元体系在293.15～318.15K下的密度和黏度值,计算了二元体系的过量摩尔体积VE和过量黏度Δη,并用Redlich-Kister方程对VE和Δη进行了关联。混合溶剂的黏度数据采用Orrick-Erbar(O-E)基团贡献法进行了关联和预测,增加了O-E方法中的(—O)3—PO基团贡献值。结果表明,O-E方法可根据现有的纯溶剂的黏度数据预测得到混合溶剂的黏度,平均误差小于15%。

磷酸三丁酯、4-甲基-2戊酮对铝锂溶液中锂的萃取行为

以磷酸三丁酯(TBP)作为主要萃取剂,4-甲基2-戊酮(MIBK)作为协助萃取剂,三氯化铁(FeCl3)作为共萃剂,以铝锂溶液体系作为试验对象,全面系统的研究了萃取剂的各组成成分、水相溶液的pH值、铁锂原子比、萃取相比、萃取时间以及静置时间对铝锂溶液中锂的萃取效果的影响。通过正交试验确定了萃取反应的最佳反应参数:萃取相比为5∶2,铁锂原子比为2∶1,pH值为1.5,TBP体积分数为70%,MIBK体积分数为15%,萃取时间为10 min。在此条件下,锂的单级萃取率可达82%,锂铝单级分离因数可达51。对萃取分离过程的反应机理进行了研究,深入探索了铁锂共萃取效应,确定了反应产生的萃合物形态为LiFeCl4·2TBP·MIBK,并探究了萃合物形成过程中的键合方式。该萃取方法经济高效,适用于铝锂溶液中锂的分离。

甲基异丁基酮行业发展现状及趋势

介绍了甲基异丁基酮行业发展现状;重点分析了甲基异丁基酮生产技术、全球主要企业及产能、国内下游消费、价格变化和原料供给等情况;据此,提出了甲基异丁基酮行业未来高质量发展的5点建议。

铜锆类水滑石催化合成MIBK的研究

甲基异丁基酮(MIBK)是性能优异的高级溶剂,主要的合成方法是丙酮一步法。水滑石因其独特的结构与性能,被作为催化剂材料广泛应用。二氧化锆作为催化剂助剂,具有良好的性能。本文采用铜锆类水滑石为前体制成催化剂进行丙酮合成MIBK的反应,研究了反应条件如反应温度、氢酮比及空速对产物的影响,结果表明在反应温度为200℃,氢酮比1,空速1h-1时,丙酮的平均转化率为78.04%,MIBK的选择性可达51.75%,MIBK的收率为46.95%。

MIBC脱氢制备MIBK宏观动力学研究

采用共沉淀法制备的铜系CuO/ZnO/Al_2O_3脱氢催化剂,在常压下进行了甲基异丁基甲醇的气相脱氢制备甲基异丁基酮的反应实验.研究了单管反应器中反应温度和MIBC进料液时空速对脱氢反应的影响,并建立了宏观动力学方程。结果表明在温度为483~513K,液时空速为1.0~2.0h^(-1)的条件下,甲基异丁基甲醇脱氢单程转化率最高达到91.11%,甲基异丁基酮的选择性大于99.0%.将实验结果用最小二乘法拟合得到该反应的宏观动力学方程为-r=k(p(1.975/MIBC))-(1/k)P(1.980/MIBC),其中k=9.542×10~7exp(-E/RT),E为58.08kJ·mol^(-1)。动力学方程的关联线性度和方差分析计算表明,所建立的宏观动力学方程较好地描述了甲基异丁基甲醇的气相脱氢反应。

MIBK加氢制MIBC热力学研究

计算了MIBK加氢制MIBC气相及液相反应的标准摩尔生成焓及反应温度范围内的平衡常数。计算结果表明,反应平衡常数随反应温度的升高而减小,较低的反应温度有利于反应的进行。此外,研究了反应温度、压力及氢酮比对反应平衡转化率的影响,确定出MIBK加氢制MIBC适宜的反应条件为:反应温度≯240℃,反应压力≮3.5MPa,氢酮比≮2。为该技术的工艺条件设计提供了理论依据。

合成MIBK的多元金属催化剂的制备及评价

采用浸渍法制备了适用于丙酮一步法合成甲基异丁基酮的双功能多金属催化剂。采用间歇高压反应釜在温度为160℃,压力为1.8MPa时,进行了液相丙酮1步法实验评价催化剂。考察了催化剂的载体、催化剂焙烧条件、不同金属活性组成及其含量对催化剂性能的影响。结果表明,以HZSM-5分子筛作为载体,负载Pd、Cu、Zn、Ni以载体质量为基准的质量分数分别为0.2%、0.5%、0.1%、0.8%时所制得的多金属催化剂,其丙酮的转化率为42.7%,MIBK的选择性为95.6%。多金属催化剂与单金属催化剂相比,丙酮的转化率与产品的选择性都大大提高。

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.

Study on the Removal of MIBK from Aqueous Solution by Vacuum Membrane Distillation

Methyl isobutyl ketone(MIBK) is widely used as extraction agent in hydrometallurgy. As it has a definite solubility in water, so when using MIBK as extraction agent, there will be MIBK in stripping solutions inevitably, which not only pollutes working conditions, but also affects the quality of ultimate product. In order to remove MIBK from aqueous solutions, the means of flat vacuum membrane distillation(VMD) is studied in the paper. The area of the membrane used in the study is 0.02 m 2, the initial volume of feed is 2 L, each experiment was conducted over a time period of 60 120 min. The influences of the factors such as temperature(34.8 55.0 ℃); pressure in the permeate side(10.67 14.67 kPa) and feed flow rate(27.8 69.4 mL/s) were experimentally studied. Increasing the temperature or reducing the pressure in the permeate side results in a faster removal of MIBK; however there is a decrease in removal factor β , increasing the feed flow rate results in a faster removal of MIBK and an increase of removal factor β , especially in the range of lower flow rate. The study indicates that the aim of MIBK removal and recycle from dilute aqueous solutions can be achieved by VMD.

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.

MIBK萃取高浓煤化工含酚废水的应用研究进展

甲基异丁基甲酮(MIBK)是高浓煤化工含酚废水处理中萃取脱酚优选萃取剂。总结了与溶剂萃取脱酚紧密相连的甲基异丁基甲酮-酚/有机酸-水液液相平衡研究现状。也对围绕甲基异丁基甲酮萃取脱酚为核心的酚氨回收流程变革过程进行回顾,同时对酚氨回收设计及MIBK相关的萃取运行及研究提出思路,为极大稳定后续生化处理的操作提供方便。