Efficient and ecological leather processing: replacement of lime and sulphide with dispase assisted by 1-allyl-3-methylimidazolium chloride

Leather is a collagen-based biomass prepared from raw skins or hides by a series of unit operations, in which the unhairing and fiber opening are extremely important operations. However, the conventional Na2S/Ca(OH)2 system used in unhairing and fiber opening has given rise to the pollution to the environment. It is necessary to develop substitute technology for the Na2S/Ca(OH)2. In the present study, 1-allyl-3-methylimidazolium chloride ([AMIm]Cl) was used to cooperate with dispase for cycle unhairing and one-pot beamhouse to recycle waste bovine hides and com-pared with conventional processing. During those processes, the mechanism of [AMIm]Cl-dispase synergistic unhair-ing and collagen fibers opening were studied. Besides, plant hazard, organic matter and [AMIm]Cl of wastewater from [AMIm]Cl-dispase process were respectively investigated and separated to evaluate the environmental and economic benefits of the [AMIm]Cl-dispase process. As a result, enzyme activity after unhairing by [AMIm]Cl-diapase system for using 5 times is higher than that by KCl-dispase system, and needs lower unhairing time, which is because of rapid penetration of [AMIm]Cl-dispase solution in bovine hides. For this reason, the tensile strength and elastic modulus of tanned leather from [AMIm]Cl-dispase process are higher than those from the KCl-diapase and conventional pro-cesses, and its hydrothermal shrinkage temperature is comparable to that of the conventional one. Because of the 58.13% lower wastewater discharge (WD), 66.60% lower total solids (TS), 97.23% lower ammonia nitrogen (NH3-N), non-toxic wastewater and organic matter recovery in wastewater are reached from [AMIm]Cl-dispase process, which is expected to be an alternative to the conventional process to reduce environmental pollution and realize the sustainable development of technology for leather manufacturing.

Scale-up of biomass conversion using 1-ethyl-3-methylimidazolium acetate as the solvent

This scale-up study demonstrated the feasibility of an ionic liquid(IL)pretreatment process at 40 kg scale,using the IL 1-ethyl-3-methylimidazolium acetate([C2C1Im][OAc])as the solvent.The pretreatment was followed by enzymatic hydrolysis through which the process efficiency for biomass conversion to monomeric sugars was determined.The results show that 43 wt%of switchgrass was dissolved in IL after 2 h of pretreatment at 160℃ with 15 wt%solid loading.A 120 h enzymatic hydrolysis of the pretreated switchgrass results in 96%glucan and 98%xylan conversion.[C2C1Im][OAc]pretreatment has been successfully scaled up to 40 kg with improved sugar titers and yields relative to bench scale(6 kg).The mass flow of the overall process was established and the major scale-up challenges of the process were identified.

Synthesis and physico-chemical properties of new green electrolyte 1-butyl-3-methylimidazolium perchlorate

1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as electrochemical window,were investigated and solvent performance was also studied.The results show that this kind of ionic liquid is an excellent electrolyte with low viscosity,high electrical conductivity and wide electrochemical window.In addition,[BMIM]ClO4 is soluble in most conventional solvents and some metal oxides have high solubility in it,which lays the foundation of direct electrolysis of metal oxides in this ionic liquid.

DFT Study on the Structure of Ionic Liquid 1-Ethyl-3-methylimidazolium Hexafluorophosphate

This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.

Interactions of 1-hexyl-3-methylimidazolium Bromide with Acetone

^1H and ^13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide [C6mim]Br at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.

Novel efficient procedure for biodiesel synthesis from waste oils with high acid value using 1-sulfobutyl-3-methylimidazolium hydrosulfate ionic liquid as the catalyst

Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically investigated.The optimum molar ratio of methanol to waste oils,catalyst amount,reaction temperature and reaction time were 8/1,10%(based on the mass of waste oils),140°C and 6 h,respectively,under which the obtained yield of biodiesel reached 94.9%.Also,[BHSO_3MIM][HSO_4] as a catalyst still retained around 97% of its original catalytic activity after successive re-use of 5 batches(6 h per batch),showing the excellent operational stability.Moreover,the acidic IL [BHSO_3MIM][HSO_4] was able to ef ficiently catalyze conversions of waste oils with different amounts of FFAs(free fatty acids) into biodiesel,and showed tremendous application potential.Therefore,an ef ficient and environmentally friendly catalyst is provided for the synthesis of biodiesel from waste oils with high acid value.

Removal of Trace Olefins from Aromatics by Catalytic Alkylation Using 1-Alkyl-3-methylimidazolium Bromochloroaluminate Catalyst

Removal of trace olefins from aromatic liquids had been investigated in the presence of various ionic liquids like 1-ethyl-3-methylimidazoliurn bromochloroaluminate （EMIMBr-AlCl3）, 1-butyl-3-methylimidazolium bromochloroaluminate （BMIMBr-AlCl3）, l-hexyl-3-methylimidazolium bromochloroaluminate （HMIMBr-AlCl3）, and 1-octyl-3-methylimidazolium bromochloroaluminate （OMIMBr-A1C13）. It was found that the longer the alkyl chain of ionic liquid cations was, the higher the olefins conversion would be. OMIMBr-AlCl3 （with 0.67 molar fraction of AlCl3） had an obvious performance on olefins removal. The influences of various reaction parameters such as the dosage of catalyst, the reaction temperature, and the reaction time on the reaction catalyzed by OMIMBr-AlCl3 were investigated. Under optimum reaction conditions, a higher than 99% conversion of olefins was achieved. The preliminary results revealed that the process could save time, consume less energy, separate products easier, and cause less pollution to the environment.

Oil recovery tests with ionic liquids: A review and evaluation of 1-decyl-3-methylimidazolium triflate

The main advantages of the use of ionic liquids in enhanced oil recovery are their tunability and stability in harsh environmental conditions. In this work, a comprehensive review of ionic liquids proposed to improve current chemical oil recovery methods has been presented, focusing on core flooding experiments. With an almost infinite number of possible ionic liquids, the amount of experiments carried out up to now has been very limited. However, results are promising, with additional recovery after secondary flooding of up to 32% of the original oil in place. Most formulations with ionic liquids have been proposed for sandstone reservoirs, the number of studies with carbonate cores being very scarce. The possibilities of a new room temperature surface active ionic liquid, 1-decyl-3-methylimidazolium triflate,for this application were analyzed. It was shown that it is able to drastically reduce the water/oil interfacial tension. An optimized formulation was proposed for carbonate reservoirs. After secondary flooding with brine, an additional recovery of 10.5% of original oil in place was achieved at room conditions. A combination of the proposed method followed by a polymer flooding step with polyacrylamide led to a lesser but still significant recovery, reducing the costs associated to the ionic liquid.

Isobaric Vapor–Liquid Equilibrium for tert-Butyl Alcohol + Water + Propane-1,3-Diol + 1-Ethyl-3-Methylimidazolium Chloride at 101.3 kPa

In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.

Synthesis and Characterization of Poly [2,2-( m-phenylene) -5,5-bibenzimidazole] in 1-butyl-3-methylimidazolium Chloride

Poly[ 2, 2-（m.phenylene） -5, 5-bibenzimidazole] （mPBI） were synthesized by mixing 3, 3＇, 4, 4＇-tetraaminobiphenyl and isophthallc acid in 1 -butyl-3 -methyUmidazolinm chloride （ E BMIM] CI）. Intrinsic viscosity of mPBI polymers was 0.67 dL/g which was measured in 96% sulfuric acid. The polymer was characterized by Fourier transform infrared spectroscopy （FTIR）, nuclear magnetic resonance （ 1H-NMR ）, and thermogravimetric analysis （TGA）. The effects of polymerization conditions on the intrinsic viscosity of mPBI were investigated. It showed that the molecular weight of polymer mainly depended on pre-reaction time and reaction temperature. Comparison of structure and properties of mPBI synthesized in ionic liquids（ILs） and polyphosphoric acid was also reported. It indicates that the ionic liquids are a kind of good solvents in synthesis process of m_PBI and ionic liquids mainly affect molecular weight of mPBL

Impact of Ionic Liquid 1-Ethyl-3-Methylimidazolium Acetate Mediated Extraction on Lignin Features

This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM[OAc]) and comparing it with that of organosolv and milled wood methods. Ionic liquid mediated lignin (ILL) using EMIM[OAc]), ethanol organosolv lignin (EOL) and milled wood lignin (MWL) were isolated from Typha capensis (TC) and subjected to several analytical characterizations. Experimental data shows that ILL exhibited a relatively lower degree of condensation, lower aromatic C-C structures and a higher aliphatic OH with values of 0.42/Ar, 1.94/Ar and 1.33/Ar moieties compared with EOL values of 0.92/Ar, 2.22/Ar and 0.51/Ar moieties respectively. The ILL was depolymerized under mild conditions giving relatively higher β-aryl ether linkages content, higher molecular mass, and exhibited closer structures and reactivity to native lignin than EOL. These insights on TC lignin depolymerization in EMIM[OAc]) acetate may contribute to better value-addition of lignocellulosic biomass.

反相气相色谱法表征1-烯丙基-3-甲基氯代咪唑离子液体的表面性质

采用反相气相色谱(IGC)技术研究了不同温度下1-烯丙基-3-甲基氯代咪唑([AMIM]Cl)的表面性质。以正己烷、正庚烷、正辛烷和正壬烷作为非极性探针分子测定[AMIM]Cl在343.15、353.15、363.15和373.15 K温度下的表面色散自由能;以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、四氢呋喃作为极性探针分子测定离子液体Lewis酸碱性质,并测定了吸附自由能和吸附自由焓变等热动力学参数。实验结果表明,[AMIM]Cl的酸解离平衡常数Ka为0.34,碱解离平衡常数Kb为1.68,其表面呈Lewis两性偏碱性特点。在343.15、353.15、363.15和373.15 K温度下,[AMIM]Cl的表面色散自由能分别为52.26、50.82、46.08和42.05 mJ/m2。这一结果对研究离子液体的表面性质及应用有指导作用。

Ab Initio Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium and AlCl_3

The Hartree-Fock method has been employed to investigate the electronic structures of EMIM＋（1- ethyl-3-methylimidazolium＋）, AlCl4^-, and EMIM＋-AlCl4^-. Full optimization and frequency analyses of EMIM＋, AlCl4^-, ten initial EMIM＋-AlCl4^- geometries have been carried out using the Gaussian-94 soft-package at 6- 31＋G（d,p） basis set level for hydrogen, carbon, nitrogen, chlorine, and aluminum atoms. The electronic structures of the lowest energy of EMIM＋-AlCl4^-pairs, single EMIM^＋, and AlCl4^- have been comparatively studied. The calculated results showed that the optimized EMIM^＋-AlCl4^-pair conformer of lowest energy was AlCl4^-outside the five-ring plane between methyl group and ethyl group with a H6--C122 distance of 2.7 A. The frequency analyses suggested that all stationary points were minimum points because of no imaginary frequency appearing, and the assigned frequencies were in agreement with experimental report. The interaction energy between EMIM^＋ and AlCl4^-was 776.2 kJ/mol.

DFT Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (Ⅰ)

The density functional theory （DFT） has been employed to investigate the electronic structures ofEMIM^＋（1-ethyl-3-methylimidazolium＋）, CuCl2^-, Cu2Cl3^- and EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^＋, CuCl2^-, Cu2Cl3^-, eight initial EMIM^＋-CuCl2^-, and six initial EMIM^＋-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I＋G （d, p） basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^- pairs, single EMIM^＋, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^＋-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^＋-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^＋ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^＋. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^＋, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^＋-CuCl2^-, and EMIM^＋-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.

厚朴提取物HK-1在5个种属肝微粒体中的代谢

目的研究厚朴抗炎有效成分(E)-5-allyl-3'-(prop-1-enyl)biphenyl-2,4'-diol(HK-1)在人、大鼠、比格犬、猴和小鼠的肝微粒体中的代谢稳定性,确定HK-1在大鼠肝微粒体中代谢表型。方法将HK-1在5个种属肝微粒体中孵育,采用UPLC-MS/MS检测方法,通过测定HK-1的剩余浓度,考察它们的代谢稳定性并外推其体内代谢清除率。化学抑制剂法鉴定在大鼠肝微粒体中HK-1的代谢表型。结果 HK-1在人、大鼠、比格犬、猴和小鼠5个种属肝微粒体中半衰期(t_(1/2))分别为9.04、7.36、2.17、4.94、18.09 min;肝微粒体中固有清除率CL_(int)分别为153.40、188.20、639.02、280.60、76.60 m L/(min·mg蛋白);体内固有清除率CL'_(int)分别为151.87、338.76、949.21、416.69、301.61 m L/(min·kg)。在大鼠肝微粒体中HK-1主要被细胞色素CYP2E1、CYP2C、CYP1A2催化代谢。结论HK-1在肝微粒体中由多种酶代谢且代谢很快,其中人肝微粒体和大鼠肝微粒体中半衰期和固有清除率相似,可将大鼠肝微粒体预估人肝微粒体不良反应的风险。

Preparation of WO3/C Composite and Its Application in Oxidative Desulfurization of Fuel

The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.

Selective Synthesis of 2,6-Dimethylnaphthalene by Transalkylation in the Presence of Acid Ionic Liquids [C_nmim]Cl-AlCl_3

A highly selective synthesis of 2,6-dimethylnaphthanlene（2,6-DMN） by transalkylation between 2-methylnaphthanlene（2-MN） and 1,2,4,5-tetramethylbenzene（TeMB） was performed with 1-alkyl-3-methylimidazo- lium aluminum chloride（[Cnmim]Cl-AlCl3） ionic liquids（ILs） as catalysts. The influences of the alkyl group as the organic cation, the acidic strength of [C4mim]Cl-AlCl3 ILs as well as the reaction conditions on the catalytic performance were investigated. [C4mim]Cl-AlCl3 ILs[x（AlCl3）=71%] exhibited high activity and selectivity toward 2,6-DMN. The selectivity to 2,6-DMN and the 2,6-DMN/2,7-DMN ratio reached up to 68.2% and 3.7：1, respectively. The UV-Vis spectrum of TeMB treated by different ILs shows that the protonated degree of TeMB dependeds on the acidity strength of ILs, which has a significant impact on the reaction results. The high protonated degree of TeMB is advantageous to enhancing the conversion of transalkylation and the large stereo-hindrance effect of TeMB is favorable to improving the selecivity to 2,6-DMN.

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.

Phase Behavior of Liquid Crystals Formed in [C12mim]CI/H2O and [C12mim] Cl/Alcohols Systems

Phase behaviors of different binary systems involving 1-dodecyl-3-methylimidazolium chlo- ride （[C12mim]Cl） and H20, [C12mim]Cl and different alcohols （1-butanol, 1-pentanol, 1- hexanol and 1-octanol） are investigated at 25 ℃. Hexagonal liquid crystal phase （H1） is identified in [C12mim]Cl/H2O system, and lamellar liquid-crystalline （Lα） phase is found in [C12mim]Cl/alcohols systems by using polarized optical microscopy and small-angle X-ray scattering techniques. The formation of such phases is considered as a synergetic result of the solvatophobic force and the hydrogen-bonded network comprising an imidazoliuin ring, chloride ion and water （or alcohols）, which can be confirmed by Fourier transform infrared spectra. It is noticeable that in [C12mim]Cl/1-octanol system, the lattice spacings of lamellar phase increase with increasing C12mimCl concentration, which is opposite to the results of [C12mim]Cl/H2O system. This may result mainly from stronger static repulsion among hydrophilic headgroups of imidazolium salts arranged in the bilayers of lamellar structures. Further measurements by differential scanning calorimetry indicate that the lamellar phase is stable within a wide temperature range above room temperature. However, the lattice spacings decrease with the increase of temperature, which may. be due to the softening of the hydrocarbon chain of [C12mim]Cl molecules. In different alcohols systems, it is found that the lamellar lyotropic liquid crystal structure is easier to be formed when the carbon chain length becomes longer.

Dispersive liquid–liquid microextraction of silver nanoparticles in water using ionic liquid1-octyl-3-methylimidazolium hexafluorophosphate

Using the ionic liquid（IL）1-octyl-3-methylimidazolium hexafluorophosphate as the extractant and methanol as the dispersion solvent,a dispersive liquid–liquid microextraction method was developed to extract silver nanoparticles（AgN Ps）from environmental water samples.Parameters that influenced the extraction efficiency such as IL concentration,pH and extraction time were optimized.Under the optimized conditions,the highest extraction efficiency for AgN Ps was above 90% with an enrichment factor of 〉90.The extracted AgN Ps in the IL phase were identified by transmission electron microscopy and ultraviolet–visible spectroscopy,and quantified by inductively coupled plasma mass spectrometry after microwave digestion,with a detection limit of 0.01 μg/L.The spiked recovery of AgN Ps was 84.4% with a relative standard deviation（RSD）of 3.8%（n = 6）at a spiked level of 5 μg/L,and 89.7% with a RSD of 2.2%（n = 6）at a spiked level of 300 μg/L,respectively.Commonly existed environmental ions had a very limited influence on the extraction efficiency.The developed method was successfully applied to the analysis of Ag NPs in river water,lake water,and the influent and effluent of a wastewater treatment plant,with recoveries in the range of 71.0%–90.9% at spiking levels of 0.11–4.7 μg/L.