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.

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.

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.

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.

铝在N,N-二甲基丁胺-氯化铝熔盐中的低温电沉积

开发新型的电解质以及低温电解铝技术是促进铝工业改革创新的重要途径之一。采用N,N-二甲基丁胺、无水氯化铝为原料,混合制备得到了新型低温熔盐。结果证明,该熔盐为氯铝酸型离子液体,可以在其中实现铝的低温电沉积。在此基础上,系统考察了试验温度、电解电位、反应时间对铝的电沉积、表面形貌和化学组成的影响规律,获得了纯度较高的金属铝。有关研究为低温电解铝技术的发展及其在铝精炼和电镀铝中的应用提供了一定的科学依据。

不同米曲霉在高盐稀态酱油中的发酵性能比较

选取3株米曲霉菌株进行高盐稀态酱油发酵,通过形态学分析、成曲酶活力测定、发酵酱油的理化指标、肽分子质量、游离氨基酸含量、有机酸含量及感官评价等指标的比较分析,探讨3株米曲霉在发酵性能方面的差异。研究表明,米曲霉D3具有高产蛋白酶系的菌株特征,5种蛋白酶酶活基本高于米曲霉D1和D2,特别是中性蛋白酶、氨肽酶和羧肽酶。米曲霉D3所酿造的高盐稀态酱油,根据理化指标变化情况分析,符合特级酱油标准。肽分子质量分布结果显示,米曲霉D3菌株能更好的水解蛋白质产生500~3000 Da的小分子肽。在有机酸方面,乳酸和乙酸在米曲霉D3酿造酱油中所含比例具有一定优势,这有利于酱油形成良好的风味。米曲霉D3的感官评价得分最高,消费者的喜爱程度更高。综上,米曲霉D3具有更好的发酵性能,该研究为选育更适合高盐稀态酱油的生产菌株提供数据基础。

新型液态金属电池材料体系及其相关技术的研究与进展

作为一种新型储能技术,液态金属电池以独特的结构赋予了自身低成本、高倍率、长寿命、易于制造和放大等特性,被认为是固定式储能极有前途的解决方案之一。自2006年Sadoway教授提出液态金属电池概念以来,不同的电池材料体系得到广泛的研究。本文在详细介绍液态金属电池工作原理和电池材料选择标准后,按照工作温度分级介绍了高温液态金属电池(>300℃)、中温液态金属电池(100~300℃)以及室温液态金属电池(<40℃)的材料体系。并在此基础上按不同温区系统综述了液态金属电池近年来研究进展,而后讨论了液态电池封装技术的抗腐蚀问题,最后指出了未来液态金属电池可能的发展趋势。

Enhanced electrodeposition and separation of metallic Cr from soluble K2CrO4 on a liquid Zn cathode

Carbon contamination and the formation of low-valence oxides limit the preparation of refractory metals by molten salt electrolysis.In this paper,a liquid Zn cathode is adopted for the electrochemical reduction of soluble K2CrO4 to metallic Cr in CaCl2-KCl molten salt.It is found that CrO4^2-can be directly electrochemically reduced to Cr via a six-electron-transfer step and low-valence Cr oxides is hardly produced.The reduction rate is obviously increased from 16.7 mgCrh^-1cm^-2 on the solid Mo cathode to58.7 mgCrh-1cm-2on liquid Zn cathode.The electrodeposited Cr is distributed in liquid Zn cathode.Carbon contamination is effectively avoided due to the negligible solubility of carbon in the liquid Zn cathode.Furthermore,Cr can be effectively separated and enriched to the bottom of liquid Zn under supergravity field,realizing the efficient acquisition of metallic Cr and recycling of liquid Zn.The method herein provides a promising route for the preparation of refractory metals with high-purity by molten salt electrolysis.

Numerical study on rotordynamic coefficients of the seal of molten salt pump

Molten salt pump is applied to pump high-temperature molten salt as the primary coolant of a molten salt reactor.The pump,generally a vertical rotor system,suffers from radial force generated by the liquid seal component,and the rotordynamic characteristics of the pump are affected considerably.In this paper,the rotordynamic coefficients of the tooth-on-stator liquid seal in molten salt pump are studied.The flow in the seal region is simulated using computational fluid dynamics technique.Parameters of the inlet loss and the pre-swirl at the inlet region of the seal are calculated.The coefficients of resistance and the wall parameters are obtained from the simulation results by data fitting method.The rotordynamic coefficients are analyzed based on the bulk-flow model of liquid seal.The rotordynamic characteristics,with and without the liquid seal,of the objective molten salt pump are inspected.The first critical speed of the rotor is found to increase.Harmonic analysis shows that the pump,being sensitive to unbalance force though,can operate safely under its design specifications.

A Green Microwave-Assisted Synthesis of New Pyridazinium-Based Ionic Liquids as an Environmentally Friendly Alternative

A green microwave-assisted procedure for the preparation of a series of fifteen new N-alkylpyridazinium ionic liquids with different functionality in the alkyl chain is described. For the first time, target ionic liquids were prepared using standard methodology and under microwave irradiation in short duration of time with quantitative yields. In most cases, the microwave-assisted reaction is an environmentally friendly alternative to traditional methods.

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。

Synthesis of multi-hydroxyl and sulfonyl dual-functionalized room temperature ionic liquids

Starting from the hydroxylamine (dimethyl amino ethanol, triethanolamine) and 1,3-propane sultone, a series of hydroxyl and sulfonyl dual-functionalized zwitterionic salts and corresponding acidic room temperature ionic liquids have been synthesized. The hydroxyl groups of the synthesized substances were confirmed by the 1H NMR measurement. These zwitterionic salts and ionic liquids may be used for synthesizing other functionalized ionic liquids or ionic liquid-polymer (polyelectrolyte).

The New Understanding of Potash Development Scale and the Comprehensive Utilization of Resources in Chaerhan Salt lake

This paper briefly introduces resources characteristics and development advantages for Charhan salt lake;and elaborated the technology progress to increase potassium mining scale systematically,the impact of the

The Effect of Ionic Liquids on the CaCO_3 Crystal Growth

In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.

四元体系(NaB_(5)O_(8)+KB_(5)O_(8)+RbB_(5)O_(8)+H_(2)O)288.15 K固液相平衡与相图研究

我国东台吉乃尔盐湖卤水中锂钾硼含量显著,水盐体系相平衡与相图为盐湖矿物的分离提取提供了理论基础。本文对四元体系(NaB_(5)O_(8)+KB_(5)O_(8)+RbB_(5)O_(8)+H_(2)O)在288.15 K时的相平衡与相图采用等温溶解平衡法研究,实验得出溶解度以及平衡液相的密度和折光率这两个主要物化性质,分析且鉴定出存在的盐湖矿物种类。研究发现:288.15 K时,该体系稳定相图中的共饱点(NaB_(5)O_(8)·5H_(2)O+KB_(5)O_(8)·4H_(2)O+RbB_(5)O_(8)·4H_(2)O)的液相组成为w(NaB_(5)O_(8))=9.02%、w(KB_(5)O_(8))=0.47%、w(RbB_(5)O_(8))=0.21%,且3种盐类矿物(NaB_(5)O_(8)·5H_(2)O、KB_(5)O_(8)·4H_(2)O、RbB_(5)O_(8)·4H_(2)O)的体系没有固溶体或复盐生成。三个矿物中RbB_(5)O_(8)·4H_(2)O的结晶区面积最大,溶解度最小。液相的折光率和密度均随Z(NaB_(5)O_(8))的增加呈规律性变化,密度和折光率均采用经验公式进行相对误差计算,所得计算值与实验值吻合较好。

Novel Catalytic Hydrodechlorination of CCl_2F_2 over Supported PdCl_2-(n-C_4H_9)_4N^+Cl^- Molten salts

A novel supported liquid phase film catalyst: Supported PdCl2-(n-C4H9),N+Cl- molten salts was found to be an effective catalyst with good stability for selective hydrodechlorination of CCl2F2 (CFC-12) to its alternatives CH2F2 and CHClF2. Addition of CoCl2, GaCl3 and CuCl2 to PdCl2-(n-C4H9),N+Cl- modifies the catalytic performance of supported molten salts.

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。