深度共熔溶剂预处理木质纤维素生物质研究进展

木质纤维素生物质转化为生物燃料或化工产品一般需经历预处理、酶解及发酵过程,因其复杂的化学结构,在酶解前通常进行预处理以破坏其致密结构,提高酶与纤维素的可及性。深度共熔溶剂（DES）是一类新型的“绿色”溶剂,具有制备简单、价格低廉、性质可调、可生物降解、可循环使用等优势,可有效去除木质素组分,同时保留大部分纤维素,在生物质预处理方面具有巨大的潜力。本文介绍了DES的构成、分类及理化性质,总结了DES预处理对生物质组分的影响,并对预处理效果的影响因素如底物和DES的类型、溶剂黏度、温度、生物载量、微波及超声波辅助工艺和两阶段处理工艺等方面进行分析,探讨了DES和生物的相容性,最后针对DES存在的问题及缺点,提出了理性设计和大规模利用DES的机遇与挑战,本文可为实现生物质的低成本预处理和高价值利用提供新的思路。     

三元低共熔离子液体中CO2的吸收

由N, N-二甲基乙酰胺、氯化胆碱、乙二醇或丙三醇以不同的摩尔比(1:1:3, 1:1:4)合成了一系列三元低共熔离子液体(n_DMA:n_CC:n_{ethylene glycol}=1:1:3, 1:1:4, n_DMA:n_CC:n_glycerol=1:1:3, 1:1:4)。在293.15～323.15 K温度下, 间隔10℃, 0～600.0 kPa压力范围内, 用等温饱和法测量了CO₂在三元体系中的溶解度。CO₂在体系中的溶解度随压力增大呈线性增大趋势, 随温度升高而减小。计算了亨利常数, 结果表明, CO₂在由N, N-二甲基乙酰胺, 氯化胆碱, 乙二醇以摩尔比1:1:3合成的三元体系, 温度为293.15 K下, 亨利常数最小, 最小值为2.174 MPa·kg·mol^-1。报道了关于CO₂吸收的热动力学性质, 包括焓变、熵变、Gibbs自由能变。其中, 焓变为负值, 说明此吸收为放热过程。     

低共熔溶剂预处理提高甘草渣酶解效果优化

近年来,低共熔溶剂（deep eutectic solvent,DES）以易制备、成本低、易回收等优势,在生物质预处理方面受到广泛关注。本研究以氯化胆碱为氢键受体,乙醇胺为氢键供体,合成DES,研究了不同温度、时间和固液比预处理条件对中药渣组分和酶解效果的影响。结果表明：固液比1∶20、120℃、预处理4h后原料中木质素去除率达到78.42%,纤维素回收率为83.89%。随后对不同条件下所得底物进行酶水解,反应96h后发现,较优条件下所得底物酶解效率为78.57%,较未处理中药渣（30.40%）提高了1.58倍。类分形动力学分析表明,预处理温度对酶解效果影响最大。SEM、XRD和FTIR检测发现,预处理后底物形貌、结晶指数和官能团变化有利于酶解效果的提高。     

低共熔溶剂预处理杨木水解渣拆解木质素

为高效去除木质纤维素中的木质素,获得富含纤维素的底物,实现木质纤维素组分的单一分离与组分全利用,制备合成了6种三元低共熔溶剂(deep eutectic solvent, DES),利用DES预处理已去除半纤维素的杨木水解渣,研究了6种低共熔溶剂对木质素去除和纤维素保留的影响,并优化获得了最佳的预处理工艺参数。结果表明,6种DES中苄基三乙基氯化铵-乙二醇-氯化铁(T-EG-Fe)的预处理效果最优,木质素去除率为80.46%,纤维素保留率为90.81%。优化得到T-EG-Fe预处理杨木水解渣最佳工艺条件为:反应固液比为1∶15,反应温度为130℃,反应时间为5h,在最优条件下预处理得到的固体残渣中纤维素质量分数为92.78%,木质素质量分数为5.33%。T-EG-Fe具有高效拆解木质素的潜力,在木质纤维素预处理过程中具有一定的应用价值。     

Evaluating ternary deep eutectic solvents as novel media for extraction of flavonoids from Ginkgo biloba

Ternary deep eutectic solvents (TDESs) as media are used to extract two flavonoids from Ginkgo biloba. The influence factors of extraction efficiency such as types of TDESs, concentrations of TDESs, solid/liquid ratio, and extraction methods have been investigated. The optimal composition of TDESs is synthesized with choline chloride, oxalic acid, and ethylene glycol (n/n/n, 1/1/3). The extraction of flavonoids is optimized using water-TDESs (50 vol% TDES in water-TDESs) as solvents in heating process (60°C) for 30 min at solid/liquid ratio of 1:10 g/mL. Under this condition, extraction yields of quercetin and myricetin are 1.40 and 1.11 mg/g, respectively.     

低共熔溶剂用于萃取分离的研究进展

作为一种新型的绿色溶剂,低共熔溶剂（DES）拥有与离子液体媲美的优良特性,如挥发性小、可设计性等,且具有成本低廉和制备简单的优势,使得DES正逐步替代传统有机溶剂,在萃取分离应用方面得到广泛的关注。本文综述了近年来国内外有关DES在萃取分离方面的研究报道,阐述了DES直接用于液液萃取、在线生成DES的缔合萃取和通过DES分解完成萃取的应用,并分析比较了各过程的特点和存在的问题;介绍了DES在不同萃取体系中的稳定性和DES的回收方法;总结了DES萃取分离体系的理论发展和萃取机理的研究进展;展望了DES用于萃取分离的工业化前景,指出了目前面临的DES理论、萃取机理、循环稳定性等方面的挑战,分析了进一步的研究趋势。     

咪唑类三元低共熔溶剂捕集低压SO2的实验研究

近几年来,以氢键受体（HBA）和氢键供体（HBD）组成的低共熔溶剂（DESs）以其类似于离子液体的性质被认为是一种有潜力的SO₂吸附剂。为制备用于低压SO₂吸收的容量大、价格合理、循环性能好的低共熔溶剂,选用咪唑(Im)作为功能化组分,以价格低廉的甘油(Gly)、PEG200和乙二醇(EG)作为第二HBD,与作为HBA的氯化胆碱(CC)构建CC-GIy-Im、CC-PEG200-Im、CC-EG-Im三元功能化低共熔溶剂,并用于低压SO₂的捕集实验研究。着重考察了第二HBD种类、咪唑含量、温度等因素对DESs吸收SO₂的性能影响。结果表明：在所选的第二HBD中,PEG200的性能最佳,其构建的低共熔溶剂密度、黏度适中,热稳定性好,吸收性好;CC-PEG200-Im（1∶2∶7）在40℃下,对1% SO₂的吸收量达到0.236 g SO₂/g DES;经5次吸收-解吸循环后,低共熔溶剂吸收性能仍然稳定;¹H NMR谱图分析结果表明,CC-PEG200-Im对SO₂的吸收机理为化学吸收。     

Extraction of ferulic acid from oil palm pressed fiber by a choline chloride based deep eutectic solvent

Results on the extraction of ferulic acid from palm pressed fiber using deep eutectic solvent (DES) of choline chloride-acetic acid (ChCl-AA) and choline chloride-citric acid (ChCl-CA) are reported. Acetic acid was found to be a better hydrogen bond donor to choline chloride than citric acid for the extraction of ferulic acid. Influence of water content in both DES was investigated whereby ChCl-AA and ChCl-CA experienced a drop in viscosity from 9.678 to 1.429 and 22.658 ± 1.655 mm²/s, respectively as the water content in the DES increased from 0 to 50 wt%. The drop in viscosity contributed to higher extraction efficiency in which 41,155 ± 940 mg/kg ferulic acid was obtained after 6 h reflux when ChCl-AA with 30 wt% water was used for the extraction compared to 30,940 ± 621 mg/kg when neat ChCl-AA was used. Further increase in water content in the DES however, did not lead to higher extraction efficiency. Although viscosity of the DES could be improved with the addition of water, there is a threshold where the DES could tolerate the presence of water without changing its solvent behavior. Surface response model revealed that interaction between heating duration and water content in DES, as well as second order effect of both heating duration and water content in DES played important roles in the extraction of ferulic acid from oil palm pressed fiber. The optimum condition for extraction of ferulic acid from palm pressed fiber was heating for 6 h with DES containing 30 wt% water.     

Bifunctional imidazole-PTSA deep eutectic solvent for synthesizing long-chain ester IBIBE in reactive extraction

The traditional production of long-chain organic esters like isobutyl isobutyrate (BIBE) suffers from severe problems due to the homogenous catalyst in process and complex system thermodynamics. In this work, an innovative bifunctional deep eutectic solvent (DES) is introduced, playing as both reaction catalyst and extraction solvent, to intensify the esterification process. The DES was formed by imidazole (Im) and p-toluenesulfonic acid (PTSA), which was for the first time found acid–base tunable, represented by weak basic DES [3Im:PTSA] and strong acidic DES [Im:2PTSA]. The formation mechanisms of [3Im:PTSA] and [Im:2PTSA] were illustrated by Fourier-transform infrared spectroscopy (FTIR) and COnductor-like Screening MOdel for Real Solvent (COSMO-RS) combined with the Im-PTSA phase diagram. The dual functions of the acidic [Im:2PTSA] in reactive extraction were evaluated by σ-potential analysis and esterification experiments. The high conversion, easy product separation, and good solvent reusability confirm the excellent catalytic and solvent effect of [Im:2PTSA]. © 2018 American Institute of Chemical Engineers AIChE J, 65: 675–683, 2019     

桑葚果渣花色苷的低共熔溶剂提取与分离

以桑葚果渣为原料,在低共熔溶剂(DESs)中,经DESs提取与大孔树脂分离两步,回收了果渣中花色苷.测试了不同类型DESs与提取方法对花色苷提取率的影响,通过不同型号大孔树脂作为吸附载体对花色苷进行回收以脱除DESs.采用HPLC、HPLC-MS对花色苷进行定量与定性分析.结果表明,DESs中草酸-氯化胆碱〔n(草酸)...     

苯酚型低共熔溶剂中硫酸钛作为催化剂高效氧化脱硫

低共熔溶剂广泛应用于氧化脱硫过程,开发新型的低共熔溶剂并进一步提升脱硫效果具有重要的意义。 以氯化胆碱为氢键受体,苯酚为氢键供体合成了ChCl/2Ph型低共熔溶剂。通过FT-IR和¹H NMR证实了苯酚和氯化胆碱之间存在氢键作用。以苯酚型低共熔溶剂为萃取剂,双氧水为氧化剂,硫酸钛为催化剂氧化脱除模拟油中的二苯并噻吩。考察了反应温度、V(ChCl/2Ph)/V(Oil)、n(H₂O₂)/n(S)、催化剂用量以及硫化物类型对脱硫率影响。实验表明最佳反应条件如下：模拟油量为5 ml,V(ChCl/2Ph)/V(Oil)=2∶10, n(H₂O₂)/n(S)=6,催化剂用量为0.01 g,反应温度为40℃,反应时间180 min。在此条件下脱硫率可以达到98.2%。求得体系的表观活化能为41.9 kJ/mol。含有催化剂的低共熔溶剂相可以重复使用5次且活性没有明显降低。机理研究表明形成钛的过氧化物和Br?nsted酸性是具有较高脱硫活性的关键。     

Kinetics of polyvinyl butyral (PVB) synthesis reaction catalyzed by deep eutectic solvent

In this work, the kinetics of the polyvinyl butyral (PVB) synthesis reaction catalyzed by the deep eutectic solvents (DESs) at the low-temperature stage was studied to control the particle size of PVB resin and optimize its synthesis process. The effects of stirring speed, the concentration of polyvinyl alcohol (PVA), catalyst dosage, and temperature on the synthesis reaction of PVB were investigated. The data obtained from kinetic experiments at 283.15–298.15 K were fitted with the shrinking core models, and the results showed that the model controlled by internal diffusion fitted well with the experimental data. The internal diffusion coefficient, D_A, of n-butanal in the product layer was further calculated by the obtained model parameters, and it was applied to predict the synthesis reaction of PVB at different concentrations of n-butanal. The results indicated that the shrinking core model controlled by internal diffusion is suitable to describe the kinetics of the PVB synthesis reaction. DES played a dual role in catalysis and dispersion in the synthesis of PVB, and it was a green catalyst with good potential for PVB industrial applications.     

深共融溶剂催化制备二酯类化合物

二酯类化合物广泛应用于有机中间体、药物、增塑剂、香料等领域,开发其绿色、高效的合成新方法具有重要意义。论文报道了深共融溶剂（DESs）催化二羧酸类化合物与醇的酯化反应合成二酯类化合物,收率最高可达95%,并且DESs循环使用8次后收率仍保持88%以上。运用1H NMR和13C NMR对产物进行了结构表征。该方法具有操作简单、产率高、易分离和催化剂可循环使用等优点。     

Development of dispersive liquid-liquid microextraction based on deep eutectic solvent using as complexing agent and extraction solvent: application for extraction of heavy metals

ABSTRACT

A green and efficient dispersive liquid-liquid microextraction method based on a new deep eutectic solvent has been developed for the preconcentration and extraction of cobalt and nickel ions. The deep eutectic solvent is formed by mixing choline chloride (hydrogen bond acceptor) and 4-aminophenol (hydrogen bond donor). Then, it is used as a chelating agent as well as extraction solvent. Under the optimum experimental conditions, the linear ranges for Ni(II) and Co(II) were 0.80–50 and 0.50–50 µgL^?1, respectively, by flame atomic absorption spectrometry. The obtained detection limits were 0.30 and 0.22 µg L^?1 for Ni(II) and Co(II), respectively.     

基于尿素/氯化胆碱低共熔溶剂体系纳米流体制备及其热物性研究

随着电子工业的快速发展,传统换热工质由于其较低的热导率已无法满足越来越高的换热需求。另一方面,传统的换热工质受限其相对较窄的液程范围而无法使用于复杂的温况或特殊的工作条件。低共熔溶剂（DESs）具有与离子液体相似的低饱和蒸气压、高沸点及强稳定性等优势,在传热领域具有巨大的潜力。制备了以尿素/氯化胆碱低共熔溶剂体系为基液,石墨烯、Al₂O₃、TiO₂三种纳米粒子填充的纳米流体,研究了黏度、热导率等热物性与纳米粒子和基液组成之间的关系,并系统地研究了纳米粒子结构对其稳定性的影响。实验结果表明,纳米粒子的填充会在一定程度上增加基液的黏度,其中石墨烯填充的纳米流体的黏度增加最大。此外,石墨烯能显著提高DESs的导热性能,其中6%（质量）石墨烯纳米流体热导率相比基液可增加29.0%。     

新型银基低共熔溶剂制备及其在1-己烯/正己烷分离中的应用

相同碳数的正构烯烃与正构烷烃因其结构相似,使其相对挥发度较小、分离难度较大。低共熔溶剂（DES）作为一种可设计的绿色分离介质被广泛应用于该类混合物的分离中,此外过渡金属与烯烃双键之间的化学络合作用是促进正构烯烃/烷烃分离的一个重要方法。鉴于此,开发了新型银基低共熔溶剂（Ag-DES）,并将其应用于1-己烯/正己烷的分离,系统探究了原料中烯烃浓度、银离子与烯烃摩尔比、分离温度等对1-己烯分离性能的影响,结果显示Ag-DES具有良好的1-己烯/正己烷分离选择性,选择性在3.5~18之间,并具有出色的循环稳定性。进一步通过FT-Raman表征和量化计算揭示了Ag-DES与烯烃之间的化学络合作用和较强氢键作用是实现其与烷烃分离的本质原因,表明应用Ag-DES的反应萃取分离强化方法可实现从F-T合成油中绿色高效分离C₆α-烯烃。     

甲酸/盐酸胍DES温和高效分离毛竹木质素

以毛竹为原料,采用甲酸/盐酸胍酸性低共熔溶剂（DES）温和高效分离木质素,并对其结构、热稳定性和抗氧化性进行了表征。结果表明,甲酸/盐酸胍（摩尔比为4:1）DES实现了温和短时条件下（100 ℃,2 h）高效分离木质素（得率为59.31%）,当进一步升温至120 ℃时,得率可达73.98%,其原因是该酸性体系中氢质子使木质素中大量的β-O-4、β-β、β-5连接键断裂,促使木质素大分子解聚成小分子而溶出。分离的木质素纯度高于96.6%,分子量低（Mw=1040~2040 g/mol）,多分散系数小于1.5,结构均一,热稳定性好。同时,该木质素抗氧化活性强（IC50=0.016~0.045 mg/ml）,优于商业抗氧化剂丁基羟基茴香醚（IC50=0.056 mg/ml）。