Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this study,one-pot,green and safe synthesis of DCF from 2,5-diformylfuran(DFF)and hydroxylamine ionic liquid salts was proposed.Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source.Ionic liquid exhibited three-fold function of cosolvent,catalysis and phase separation.The conversion of DFF and yield of DCF reached 100%under the following optimum reaction conditions:temperature of 120℃ for 70 min,volume ratio of paraxylene:[HSO_(3)-b-Py]
HSO4 of 2:1,and molar ratio of DFF:(NH_(2)OH)_(2)
[HSO_(3)-b-Py]
HSO4 of 1:1.5.The reaction mechanism for the synthesis of DCF was proposed,and the kinetic model was established.The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime(DFFD)was 1.06 and 0.16,and the reaction activation energy was 64.07 kJ·mol^(-1) and 59.37 kJ·mol^(-1) respectively.After the reaction,the ionic liquid was easy to separate,recover and recycle.

Salt Effect on the Liquid-Liquid Equilibrium of （Water ＋ Propionic Acid ＋ Cyclohexanol） System at T=（298.2,303.2,and 308.2） K

Effects of salt and temperature on the liquid phase equilibrium of the(water + propionic acid + cyclohexanol) system were investigated.The liquid-liquid equilibrium data in the presence of KCl for various salt ionic strength of 0.5,1.0,1.5,2.0,and 2.5 mol·dm3 and in absence of the salt at T=(298.2,303.2,and 308.2)K were determined.The experimental results were correlated based on the Othmer-Tobias equation and Pitzer ion-interaction model.Thermodynamic properties such as distribution coefficients and activity coefficients of propionic acid in water + cyclohexanol were determined.In addition,the separation factor,S,of the chosen solvent was obtained for the investigated system.

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.

Separation of methyl linolenate and its analogues by functional mixture of imidazolium based ionic liquid-organic solvent-cuprous salt

Methyl linolenate was separated from its analogues by a new extraction system constructed by solvent,imidazolium based ionic liquids and cuprous salt. Firstly, the effect of ionic liquid on the dissolution of CuCl in acetonitrile, N,N-dimethylformamide(DMF), methanol and water was evaluated by visual observation.[C4Mim][Cl]can improve the dissolution of CuCl in acetonitrile. Then, for the new system as acetonitrile-ILs-CuCl, extraction equilibrium, distribution ratio and selectivity of methyl linolenate and its analogues were determined by gas chromatography analysis and the mass balance. The extraction time, IL structures and CuCl concentrations were investigated. Distribution ratio decreased slightly, but selectivity increased significantly with the addition of CuCl,[C4Mim][Cl] or [C4Vim][NTF2] into acetonitrile.[C4Vim][NTF2] had higher selectivity than [C4Mim][Cl].But the selectivity of the system combining CuCl with [C4Vim][NTF2] was much lower than with [C4 Mim][Cl].For the CuCl-[C4Mim][Cl]-acetonitrile, the extraction efficiency was better than CuCl-acetonitrile, increasing Cu^+ concentration effectively improved the separation selectivity when ratio of CuCl/[C4Mim][Cl] was less than 1. Compared with previous aqueous AgNO3 extractions, the method of using CuCl is a much cheaper and practical way to enrich unsaturated fatty acid.

Correlation and Prediction of Salt Effect on Vapor Liquid Equilibrium for the System of 2-Propanol/Water

Binary vapor liquid equilibrium (VLE) data were measured for the systems of 2-propanol/ ethanediol and ethanediol/potassium acetate (KAc). VLE data for the system of propanol/ethanediol was tested using thermodynamic consistency test. The average values of Δy1 and Δ P were 0.0776 and 0.1542 kPa, respectively. The above two sets of VLE data were correlated with the NRTL model. Ternary VLE data for the system of 2-propanol/water/KAc was used to obtain the more suitable parameters of NRTL model for binary systems of 2-propanol/KAc and water/KAc (called TDCM). For multicomponent systems, ternary and quaternary, the VLE values predicted by the NRTL model agreed well with the litera-ture data. Influence of KAc, ethanediol, and the mixture of KAc and ethanediol on volatility between 2-propanol and water was investigated respectively. The results showed that the above-mentioned materials and mixture had different influence on volatility between 2-propanol and water. The method for correla-tion and prediction of salt-containing VLE is simple and effective for the said system.

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.

Salt-Containing Extractive Distillation of 1-Propanol/Water System 1.Prediction of Salt Effect on Vapor Liquid Equilibrium

This paper has studied the vapor-liquid equilibrium (VLE) for the salt-containing extractive distillation of the 1-propanol/water system. Binary VLE data were measured for the systems of 1-propanol (1)/KAc (4), ethanediol (3)/KAc (4), and 1-propanol (1)/ethanediol (3), with the VLE data correlated with the NRTL model in order to obtain the model parameters of these binary systems. The binary VLE data cited in technical literature were correlated to obtain the model parameters for other binary systems. VLE data of ternary and quaternary systems predicted by the NRTL model agreed well with the literature data. The influence of KAc, ethanediol, and the KAc/ethanediol mixture on volatility between 1-propanol and water was investigated respectively. Test results showed that the above-mentioned materials (KAc, ethanediol) and their mixture (KAc and ethanediol) have different influence on the volatility. When x3=0.5, and x4=0.05, the azeotropic point can be eliminated. The NRTL model method of salt-containing VLE is simple and effective for the prediction of the system's VLE data.

Lithium Ion Extraction from the High Ration Mg/Li Salt Lake Brine with Ionic Liquid in Triisobutyl Phosphate and Kerosene

1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fields,especially in

Tuning hybrid liquid/solid electrolytes by lowering Li salt concentration for lithium batteries

Hybrid liquid/solid electrolytes（HLSEs） consisting of conventional organic liquid electrolyte（LE）, polyacrylonitrile（PAN）, and ceramic lithium ion conductor Li（1.5）Al（0.5）Ge（1.5）（PO4）3（LAGP） are proposed and investigated. The HLSE has a high ionic conductivity of over 2.25 × 10^（-3） S/cm at 25？C, and an extended electrochemical window of up to 4.8 V versus Li/Li＋. The Li｜HLSE｜Li symmetric cells and Li｜HLSE｜Li FePO4 cells exhibit small interfacial area specific resistances（ASRs） comparable to that of LE while much smaller than that of ceramic LAGP electrolyte, and excellent performance at room temperature. Bis（trifluoromethane sulfonimide） salt in HLSE significantly affects the properties and electrochemical behaviors. Side reactions can be effectively suppressed by lowering the concentration of Li salt. It is a feasible strategy for pursuing the high energy density batteries with higher safety.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

超级13Cr不锈钢在油田模拟液中的应力腐蚀研究

为延长超深井超级13Cr不锈钢油管的生命周期,降低生产过程中复杂钻完井工作液及地层产出流体导致的应力腐蚀,开展了应力腐蚀产生机理分析,并提出了应对策略;基于聚合成膜缓蚀机理研发了缓蚀剂;在模拟工况和标准工况下,评价了超级13Cr不锈钢在酸液及加/未加缓蚀剂的返排液中的应力腐蚀情况。结果表明,加入缓蚀剂的酸液达到缓蚀要求;在返排液中,超级13Cr不锈钢的宏观腐蚀速率较大;在酸液及返排液中,超级13Cr不锈钢发生应力腐蚀,且在返排液中应力腐蚀较严重;在实验温度为140℃、压力为10 MPa的条件下,超级13Cr不锈钢在返排液中7 d后的应力腐蚀裂纹宽度为3~5μm,而加入体积分数为1%的缓蚀剂后测试72 h,超级13Cr不锈钢试片未产生应力腐蚀,说明该缓蚀剂可抑制超级13Cr不锈钢在高温环境中的应力腐蚀开裂。研究结果对超深井钻完井安全施工及安全生产具有借鉴意义。

熔盐电解质体系及在制备铝合金中的研究进展

铝合金具有抗腐蚀、易于加工、强度高、密度小等优点,在各行各业中都有着大量的应用。采用熔盐电解法制备铝合金具有生产工艺简单、效率高、生产成本低、生产周期短等特点,近些年来得到广泛关注,其中熔盐体系的选择成为主要的研究热点。本文以温度划分熔盐体系为高温熔盐和离子液体,综述了这2种熔盐体系的优点、分类以及一些反应机理,并从这2类熔盐体系出发,分别介绍了一些铝合金的制备工艺以及相关的技术创新。最后,分别阐述了高温熔盐和离子液体所存在的优缺点,并对其未来发展趋势进行了展望。

盐析辅助液液萃取-超高效液相色谱-串联质谱法快速测定糕点中14种生物碱

目的建立一种应用盐析辅助液液萃取前处理技术结合超高效液相色谱-串联质谱法快速测定糕点中14种常见有毒生物碱的分析方法。方法样品加水超声处理后,在碱性条件下(pH=11),用乙腈提取,加入氯化钠盐析分层。取乙腈相氮吹至干后用40%甲醇水溶液复溶,使用0.1%甲酸-5 mmol/L甲酸铵的水溶液和乙腈为流动相,在C18色谱柱(100 mm×2.1 mm,2.5μm)上通过梯度洗脱实现目标物分离,在串联质谱正离子多反应监测模式下进行检测,溶剂标准曲线外标法定量。结果14种生物碱在0.5~100.0 ng/mL的范围内具有良好的线性关系,相关系数均≥0.999,检出限和定量限范围分别为0.1~2.2μg/kg和0.3~7.1μg/kg。在8.00、50.00和200.00μg/kg的加标浓度下,14种生物碱的平均回收率为76.3%~105.7%,相对标准偏差为1.2%~9.8%(n=6)。结论本方法简单、快速、准确,能满足糕点中14种生物碱的快速筛查和定量分析,可用于疑似生物碱中毒的应急事件处理。

焦化厂脱硫废液回收工艺的研究

传统脱硫废液的处理方法如分布结晶法、阴离子树脂交换法等均具有回收利用率低的缺点,且不能实现硫氰酸钠及硫代硫酸钠的高纯度回收。基于此,根据脱硫废液副盐中硫氰酸钠易溶于醇而其他主要成分不溶于醇的性质,提出了脱硫废液醇处理方法,分离回收副盐中的硫氰酸钠和硫代硫酸钠,解决焦化企业脱硫废液难处理的问题。

煤气脱硫中脱硫液的处理

为进一步探究煤气脱硫环节中脱硫液的有效处理方法,以某焦化企业的煤气脱硫液提盐工艺为研究对象,针对其当前存在的问题,对脱硫液提盐工艺做全方位优化,并通过实验确定了较优的工艺参数。实际应用结果表明,该工艺在产品质量、成本等指标上均具有一定优势,具有一定的实际应用价值。

蒸盐调理剂对煤化工高盐废水蒸发尾液减量的研究分析

为实现煤化工废水的减量和资源回收利用,需对处理后废水进行膜浓缩和蒸发处理,以达到高盐废水的减量或零排放,但煤化工高盐废水因高COD、高硬度等原因,在蒸发过程中无法实现完全蒸发,一般会产生一定量的残留尾液无法继续蒸发浓缩,需作为危废委外处置。本研究采用自配的蒸盐调理剂,对蒸发尾液加药调理和过滤,可以提高蒸发尾液的蒸发效率,实现高盐废水蒸发尾液的继续减量。

胺液在线净化对降低焦化液化气硫含量的影响

焦化脱硫溶剂再生装置胺液中热稳态盐超标使脱硫效果变差、通过装置运行情况分析发现,胺液质量提升,可以有效避免液化气在脱硫过程中发生副反应形成硫醚及二硫化物,降低胺液发泡性能,从而可以长期稳定提高液化气的脱硫效果,大幅降低焦化液化气的总硫含量。

柴达木盆地大柴旦盐湖硼矿特征及成因研究

柴达木盆地是我国最大的盐湖产业基地,大柴旦盐湖为盆地内重要的固液相硼矿床,其卤水中富含硼、锂、钾、镁、钠、溴、碘等。通过勘查大柴旦地质背景和卤水储层地质特征,分析大柴旦湖水(地表卤水)、潜卤水、承压卤水水文地质特征、水化学特征,结果表明大柴旦地区硼、锂来源于地球深部,断裂构造为导卤构造,钾、钠、镁等盐类来源于周缘花岗岩,新构造运动形成大柴旦断陷盆地接受沉积,干旱的气候条件下沉积盐类地层,随着地下水补给增加,岩盐层溶解,形成高矿化度卤水,相应的硼、钾、锂等溶解于卤水之中,形成卤水(液体硼矿)。

考虑水盐相变的盐渍土基质吸力的温度效应

基质吸力是引起土体中水分迁移的驱动力,对探究土体中水盐迁移动态具有重要的意义。为研究由温度变化诱发的盐渍土孔隙溶液相变对土体基质吸力的影响,用pF meter测试了不同NaCl和Na_(2)SO_(4)比例的盐渍土在不同温度条件下的基质吸力。试验结果表明:在水盐相变发生前,盐渍土基质吸力随温度的降低呈线性增加;而当降温过程中有水盐相变发生时,土体基质吸力随温度的变化趋势会发生明显突变。NaCl和Na_(2)SO_(4)对土体水盐相变规律影响不同,使得含不同比例NaCl和Na_(2)SO_(4)的复合盐渍土基质吸力呈现较大的区别。2%NaCl+4%Na_(2)SO_(4)的盐渍土在19和-9℃附近发生盐结晶相变和二次相变,而4%NaCl+2%Na_(2)SO_(4)的盐渍土两次相变分别发生在11和-16℃附近。水盐相变导致土体液态含水率明显降低,进而引起复合盐渍土基质吸力在两个相变阶段均有明显增加。NaCl抑制土体中液态水发生冰水相变,Na_(2)SO_(4)容易在正温结晶,故Na_(2)SO_(4)主要影响土体正温时的盐结晶规律,NaCl则主要影响土体在负温条件下的冰晶产生规律;二者比例不同造成土体盐结晶温度和二次相变温度有明显差异,使得复合盐渍土的水盐相变规律更加复杂,其基质吸力随温度的变化更加难以预测。此外,该研究进一步探究了冰、盐结晶量对基质吸力变化的贡献,为深入理解盐渍土的相变过程和基质吸力之间的关系提供了有效参考。

废盐无害化处理工艺研究

为了解决制备精四氯化锆过程中产出废盐的处理难题,根据废盐微观形貌分析结果,将废盐加水溶解,利用强酸性体系使废盐中的金属离子溶出进入溶液,通过采用不同搅拌方式、浸出时间、压滤方式以及浸出试剂等实验,研究金属元素的分配及迁移规律。通过实验室条件摸索试验、放大试验以及条件优化试验,使处理后废盐中锆平均收率大于80%,不同阶段废盐锆收率基本稳定,处理每吨废盐用水量在10 t以下,中和渣及水溶渣pH值达到国家《危险废物鉴别标准腐蚀性鉴别》(GB 5085.1-2007)标准要求。