Fabrication of Regenerated Cellulose Fibers with Good Strength and Biocompatibility from Green Spinning Process of Ionic Liquid

In this study, 1-ethyl-3-methylimidazolium diethyl phosphate, having the advantages of regulating the performance of cellulose dissolution and degradation, simplicity in synthesis, is chosen as solvent to dissolve wood pulp cellulose for regenerated cellulose fibers (RCFs) manufacture using dry-jet wet spinning equipment. The effect of draw ratios on RCFs’ mechanical properties in three bathes, including coagulation bath, stretch bath, and washing bath is investigated and a series of RCFs with high strength are obtained. The morphology, crystallinity, thermal stability, and dyeing behavior of the prepared RCFs are analyzed and discussed. More importantly, the biocompatibility of the RCFs, which is first performed, demonstrated that the toxicity of RCFs is as low as the viscose fibers. These RCFs could be easily dyed by natural turmeric and antibacterial fibers are obtained finally. In conclusion, this work provides tools for achievement of RCFs with good strength and environmental friendliness by changing the draw ratios, and also further develops a new green process for fabricating RCFs based on ionic liquids.     

Green solvents for green technologies

In many industrial processes, large quantities of volatile and flammable organic solvents are used in various reaction systems and separation steps defining a major part of the environmental and economic performance of a process. Accordingly, a growing area of research in the development of green technologies is devoted to designing new, environment‐friendly and tunable solvents the use of which would meet both technological and economic demands. Among proposed solvents, room temperature ionic liquids, supercritical and subcritical fluids and solvents from natural and renewable sources stand out as the most promising approaches for current solvent innovation. A brief overview of up‐to‐date knowledge regarding these solvents is presented herein, with special emphasis on their properties, applications and further perspectives as truly green industrial solvents. © 2015 Society of Chemical Industry     

Ionic Liquids—A Review of Their Toxicity to Living Organisms

Ionic liquids (ILs) were initially hailed as a green alternative to traditional solvents because of their almost non-existent vapor pressure as ecological replacement of most common volatile solvents in industrial processes for their damaging effects on the environment. It is common knowledge that they are not as green as desired, and more thought must be put into the biological consequences of their industrial use. Still, compared to the amount of research studying their physicochemical properties and potential applications in different areas, there is a scarcity of scientific papers regarding how these substances interact with different organisms. The intent of this review was to compile the information published in this area since 2015 to allow the reader to better understand how, for example, bacteria, plants, fish, etc., react to the presence of this family of liquids. In general, lipophilicity is one of the main drivers of toxicity and thus the type of cation. The anion tends to play a minor (but not negligible) role, but more research is needed since, owing to the very nature of ILs, except for the most common ones (imidazolium and ammonium-based), many of them are subject to only one or two articles.     

过氧化氢及其基本有机化学品绿色合成技术

烃类氧化与氮化反应是生产基础有机化学品和高附加值产品的主要反应,在满足和丰富人类物质需求方面贡献巨大,传统的工业氧化与氮化工艺导致严重的环境问题,亟需绿色化转型。作为公认的绿色氧化剂,过氧化氢在烃类氧化和氮化的绿色生产工艺中应用广泛。文章简要介绍了国内外过氧化氢生产现状,重点介绍了中国石化石油化工科学研究院浆态床过氧化氢生产技术,以己内酰胺、环氧丙烷和环氧氯丙烷为例,介绍了过氧化氢在绿色烃类氧化和氮化反应中的应用,汇报了石油化工科学研究院近年来在绿色化工方面的主要研究进展及工业实践结果。多个成套绿色化工技术的成功开发突破了国外对我国的技术封锁,为多个化工生产基地提供全流程绿色生产技术,有力保障了我国化工行业的绿色化转型。     

聚(己二酸丁二醇酯-对苯二甲酸丁二醇酯)生产技术现状及其研究进展

阐述了目前国内外聚(己二酸丁二醇酯-对苯二甲酸丁二醇酯)（PBAT）工业生产技术特点和产业化现状,通过对比指出了PBAT与传统塑料在性能、成本等方面尚存差距。系统介绍了现阶段国内外研究人员通过熔体混合、溶剂浇铸和原位聚合三种不同方法,制备可降解材料（聚乳酸、聚乙烯醇、聚碳酸亚丙酯和聚丁二酸丁二醇酯）、纳米材料（纤维素纳米晶体、改性纤维素纳米晶体、海泡石和蒙脱土）以及天然高分子材料（淀粉、乙酰化绿竹纤维和工业木质素）改性PBAT复合材料的研究进展,并对PBAT复合材料的降解原理和降解性能进行了讨论。最后对PBAT未来的研究进行了展望,指出PBAT生产技术的未来研究方向应该向综合性能高、低成本和绿色方向发展。     

Melt electrospinning today: An opportune time for an emerging polymer process

Over the last decade, melt electrospinning has emerged as an alternative polymer processing technology to alleviate concerns associated with solvents in traditional electrospinning. This has resulted in the fabrication of ultrafine fibers from an increasing range of synthetic polymers and composite systems, to materials including ceramics, driving new applications in technical areas such as textiles, filtration, environment and energy as well as biomedicine. In this article, we review the significant advancements in theoretical modeling of the underlying physical principles, coupled with experimental validation using a variety of technical devices and designs that allows well-controlled fiber formation using optimized material and operating parameters. Innovative device designs are indicating avenues towards higher throughput of randomly collected melt electrospun fibers for the production of commodity nonwoven substrates, similar to solution electrospinning and many other industrial fiber-forming processes. However, we identify a recent shift in perception towards melt electrospinning in the literature, where the adaptation of additive manufacturing approaches to device designs enables precise fiber placement with filament resolutions not yet demonstrated by more established melt-extrusion based direct writing technologies. New, highly ordered arrangements of ultrafine fibers with distinctive surface topology, encapsulating and sensing properties are opening new fields of application in areas such as drug delivery, biosensors and regenerative medicine as high performance materials. The development of these materials is reviewed with an emphasis on an area of current research, where melt electrospun scaffolds are contributing to promising treatment strategies to regenerate or replace human tissue and for the new field of in vitro disease models as well as humanized mice models.     

新型溶剂法制备再生纤维素纤维研究进展

再生纤维素纤维以可再生、可生物降解的天然纤维素为原料,它的研究和开发对充分利用纤维素资源和促进纤维行业的可持续发展具有重要意义.离子液体和碱溶液溶剂体系对纤维素具有独特的溶解性能,为再生纤维素纤维的制备提供了新方法.这种新型的再生纤维素纤维具有制备过程简单、对环境无污染、纤维力学性能优异或生产成本低等优点,发展前景十分广阔.综述了离子液体法和碱溶液法再生纤维素纤维的最新研究进展,包括溶剂种类及其溶解能力、纤维素原料的性质与选择、纤维的制备方法和力学性能等,同时归纳和对比了各因素对新型再生纤维素纤维力学性能的影响.最后展望了两种新型再生纤维素纤维存在的挑战、未来发展趋势和工业化前景.     

Hydrogen peroxide and applications in green hydrocarbon nitridation and oxidation

Basic organic chemicals and high value-added products are mainly produced by hydrocarbon nitridation and oxidation.However,several drawbacks limit the application of the traditional oxidation and nitrida-tion technologies in the future,such as complex processes,poor intrinsic safety,low atom utilization,and serious environmental pollution.The green nitridation and oxidation technologies are urgently needed.Hydrogen peroxide,a well-known green oxidant,is widely used in green hydrocarbon oxidation and nitridation.But its industrial production in China adopts fixed-bed technology,which is fall behind slurry-bed technology adopted by advanced foreign chemical companies,limiting the development of hydrogen peroxide industry and green hydrocarbon nitridation or oxidation industry.This article reviews the industrial production technologies of hydrogen peroxide and basic organic chemicals such as capro-lactam,aniline,propene oxide,epichlorohydrin,phenol,and benzenediol,especially introduces the green production technologies of basic organic chemicals related with H2O2.The article also emphasis on the efforts of Chinese researchers in developing its own slurry-bed technology of hydrogen peroxide produc-tion,and corresponding green hydrocarbon nitridation or oxidation technologies with hydrogen perox-ide.Compared with traditional nitridation or oxidation technologies,green production technologies of caprolactam,propene oxide,epichlorohydrin,and benzenediol with hydrogen peroxide promote the nitrogen atom utilization from 60％ to near 100％ and the carbon atom utilization from 80％ to near 100％.The waste emissions and environmental investments are reduced dramatically.Technological blockade against the green chemical industry of China are partially broken down,and technological upgrade in the chemical industry of China is guaranteed.     

Back to the future: Fatty acids,the green genie to design smart soft materials

Fatty acids are widely used in industries for various applications as soaps or in their crystalline form. Fatty acid soaps are used as surface-active agent to stabilize foams and emulsions, for detergency, and surface wetting. Fatty acid molecules in organic solvents are used as low-molecular-mass organic gelators. Currently, there is a renewed interest in using fatty acids in industrial applications instead of petrochemical surfactants since fatty acid soaps are green surfactants. Fatty acids exhibit also many advantages, including the design of responsive soft-materials. Fatty acid soaps are natural pH and thermoresponsive surfactants, which can lead to responsive foams and emulsions. In their crystalline form, fatty acid crystals in both aqueous and non-aqueous solvents stabilize liquid foams. These crystals are also efficient in the production of liquid marbles. Fatty acids are solvosurfactants with the ability to form microemulsions and capillary suspensions. In this review, we illustrate how fatty acid molecules can be used in the manufacture of multiresponsive soft-materials ranging from aqueous and non-aqueous foams, emulsions, nanoemulsions, microemulsions, liquid marbles and capillary suspensions.     

Crops: a green approach toward self-assembled soft materials

To date, a wide range of industrial materials such as solvents, fuels, synthetic fibers, and chemical products are being manufactured from petroleum resources. However, rapid depletion of fossil and petroleum resources is encouraging current and future chemists to orient their research toward designing safer chemicals, products, and processes from renewable feedstock with an increased awareness of environmental and industrial impact. Advances in genetics, biotechnology, process chemistry, and engineering are leading to a new manufacturing concept for converting renewable biomass to valuable fuels and products, generally known as the biorefinery concept. The swift integration of crop-based materials synthesis and biorefinery manufacturing technologies offers the potential for new advances in sustainable energy alternatives and biomaterials that will lead to a new manufacturing paradigm. This Account presents a novel and emerging concept of generating various forms of soft materials from crops (an alternate feedstock). In future research, developing biobased soft materials will be a fascinating yet demanding practice, which will have direct impact on industrial applications as an economically viable alternative. Here we discuss some remarkable examples of glycolipids generated from industrial byproducts such as cashew nut shell liquid, which upon self-assembly produced soft nanoarchitectures including lipid nanotubes, twisted/helical nanofibers, low-molecular-weight gels, and liquid crystals. Synthetic methods applied to a "chiral pool" of carbohydrates using the selectivity of enzyme catalysis yield amphiphilic products derived from biobased feedstock including amygdalin, trehalose, and vitamin C. This has been achieved with a lipase-mediated regioselective synthetic procedure to obtain such amphiphiles in quantitative yields. Amygdalin amphiphiles showed unique gelation behavior in a broad range of solvents such as nonpolar hexanes to polar aqueous solutions. Importantly, an enzyme triggered drug-delivery model for hydrophobic drugs was demonstrated by using these supramolecularly assembled hydrogels. Following a similar biocatalytic approach, vitamin C amphiphiles were synthesized with different hydrocarbon chain lengths, and their ability to self-assemble into molecular gels and liquid crystals has been studied in detail. Such biobased soft materials were successfully used to develop novel organic-inorganic hybrid materials by in situ synthesis of metal nanoparticles. The self-assembled soft materials were characterized by several spectroscopic techniques, UV-visible, infrared, and fluorescence spectrophotometers, as well as microscopic methods including polarized optical, confocal, scanning, and transmission electron microscopes, and thermal analysis. The molecular packing of the hierarchically assembled bilayer membranes was fully elucidated by X-ray analysis. We envision that the results summarized in this Account will encourage interdisciplinary collaboration between scientists in the fields of organic synthesis, soft materials research, and green chemistry to develop functional materials from underutilized crop-based renewable feedstock, with innovation driven both by material needs and environmentally benign design principles.     

Nanofiltrationsmembranen für Trennprobleme in organischen Lösungen

Nanofiltration Membranes for Separation Problems in Organic Solutions . Nanofiltration based on rejection and flux features intermediate between those ultrafiltration and reverse osmosis is one of the technically and scientifically interesting membrane processes with a great future. Moreover, most commercial available nanofiltration membranes are only suitable for separation processes in aqueous solutions. A small number of composite membranes with a highly cross-linked selective layer show a technically interesting resistance towards organic solvents, such as ketones, esters, ethers or alcohols. The present article describes such nanofiltration membranes used for separation of low molecular weight chemical compounds from polar or nonpolar solvents, but also for the removal of organic compound from aqueous solutions. Methods of manufacturing and modifying such solvent stable composite membranes are shown, as are the conditioning of membranes and examples of industrial application.     

微反应器耦合离子液体强化萃取过程的研究进展

离子液体作为一种绿色溶剂在强化萃取过程中获得了广泛的应用，但是高昂的生产成本以及以高黏度为特征的流体力学性质阻碍了其工业化应用。微化工技术为基于离子液体的连续化萃取提供了一种高效的过程强化平台。近年来，微化工技术与离子液体技术的耦合强化在萃取分离领域越来越受到关注。本文主要综述了微流动萃取技术的基本现状、离子液体参与的萃取过程特征、微反应器内涉及离子液体的互不相溶液-液两相流型、传质及其强化机制，重点介绍了微反应器在基于离子液体萃取金属、有机物等过程中的应用、微流动萃取过程放大的研究进展，并对涉及离子液体的多级萃取、功能化离子液体的萃取应用及其相应的微流动萃取放大等研究方向进行了展望。     

水介质中2-巯基嘧啶脱巯基的绿色合成工艺研究

采用中性水介质代替传统的有机溶剂,以活性Raney-Ni考察了2-巯基嘧啶脱巯基的绿色合成工艺,对含有氨基和羟基的2-巯基嘧啶的脱巯基反应条件进行优化,研究了取代基效应、反应溶剂、反应温度对Raney-Ni直接脱硫的产率影响,同时对Raney Ni及水的回收利用进行了考察,并以此制备了4-氨基-6-羟基嘧啶、4-氨基嘧啶、5,6-二氨基-4-羟基嘧啶和4-羟基嘧啶,其脱硫收率分别为98%、74%、87%及89%。该工艺反应条件为加热回流搅拌,反应时间1-4 h,可避免有机溶剂的使用,具有生产安全等优点     

A controllability analysis of a pilot‐scale CO2 capture plant using ionic liquids

Nowadays there is a world concern on the impact and effect of large CO₂ atmospheric concentrations on human health. Fossil‐fuel combustion processes in power plants are among the major contributors to this issue. Hence, it becomes important to develop new clean and sustainable processes aimed to reduce the amount of CO₂ released to atmosphere by combustion processes in power plants. One of the best feasible manners to achieve this purposes lies in the use of a closed‐loop control system able to keep the amount of green‐house gases under specification even in the presence of unexpected scenarios. Of course, CO₂ capture has been extensively researched in the past. However, in this regard the industrial practice has consisted in using Amines leading to sustainability and safety issues. Hence, it makes sense to seek for new and potentially environmental friendly process design to address CO₂ reduction from power plants but applying a new type of sustainable stripping solvents. In this work we address the sustainable CO₂ reduction issue from a process control point of view applying a previous design proposed by our research team based on the deployment of Ionic Liquids (IL) as potential green solvents and developing an efficient and decentralized multiloop control system. We demonstrate that the closed‐loop system is able to maintain the CO₂ concentration levels under specification by testing in presence of several demanding scenarios. Overall, from an economic, sustainable and control point of view it looks feasible to replace the traditional amines‐based CO₂ capture process by other alternatives based on the application of IL as potential green solvents. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3298–3309, 2016     

考虑环境影响的产业规划决策

在工业规划决策中,引入环境价值与环境容量的概念对环境影响因素进行量化的评估,纳入经济效益优化,以达到经济、环境效益的综合最优。提出了以绿色效益F、绿色效益率E来量化产业发展的经济和环境效益的总体优劣,建立了以绿色效益F为目标函数的产业规划决策数学模型。以某磷化工产业为背景,进行了案例计算分析。     

Die Entwicklung von Iösungsmittelselektiven Membranen und ihre Anwendung in der Gastrennung und Pervaporation

Development of solvent-selective membranes and their use in gas separation and pervaporation. Pervaporation and gas separation are two membrane processes whose industrial and economic importance has increased considerably in recent years because they are particularly suitable for selective removal of organic solvents from aqueous and gaseous mixtures. The problem of solvent removal is encountered, inter alia, in the purification of certain industrial gaseous and liquid effluents. However, the removal of solvents is also significant in petrochemistry and biotechnology and both pervaporation and gas separation can again be efficiently used here. On the basis of the equations relating to mass transfer in homogeneous polymers, criteria for the choice of polymers for high-selectivity membrane production are discussed. The development of suitable membranes and membrane modules is described. Two industrially and economically relevant examples, viz. recovery of organic solvents from gaseous effluent and the continuous removal of ethanol from bioreactors, illustrate the scope and limitations of the procedures.     

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。     

Polyelectrolyte and carbon nanotube multilayers made from ionic liquid solutions

The inevitable contact of substrates with water during the traditional practice of layer-by-layer assembly (LBL) creates problems for multiple potential applications of LBL films in electronics. To resolve this issue, we demonstrate here the possibility of a LBL process using ionic liquids (ILs), which potentially eliminates corrosion and hydration processes related to aqueous media and opens additional possibilities in structural control of LBL films. ILs are also considered to be one of the best "green" processing solvents, and hence, are advantageous in respect to traditional organic solvents. Poly(ethyleneimine) (PEI) and poly(sodium styrenesulfonate) (PSS) were dispersed in a hydrophilic IL and successfully deposited in the LBL fashion. To produce electroactive thin films with significance to electronics, a similar process was realized for PSS-modified single-walled carbon nanotubes (SWNT-PSS) and poly(vinyl alcohol) (PVA). Characterization of the coating using standard spectroscopy and microscopy techniques typical of the multilayer field indicated that there are both similarities and differences in the structure and properties of LBL films build from ILs and aqueous solutions. The films exhibited electrical conductivity of 10(2) S m(-1) with transparency as high as 98% for visible light, which is comparable to similar parameters for many carbon nanotube and graphene films prepared by both aqueous LBL and other methods.     

Challenges in the development of new green solvents for polymer dissolution

As chemical legislation grows more strict and the UK moves towards a bioeconomy, acceptable solvents for industrial dissolution of polymers are growing scarce. An estimated 78% of solvent use in the EU is in sectors such as paints and coatings, printing inks and adhesives, in which polymer dissolution is a critical function. Academic research in safe, sustainable solvents is growing, but largely in the field of reaction solvents, leaving solvents for polymers underdeveloped by comparison. This challenge can be addressed through the adoption of computational tools, improved communication between industry and academia and increased research funding. Recent progress in green solvent development provides a number of models that can be adapted to the problem of polymer dissolution research. © 2020 Society of Chemical Industry     

熔融纺丝工艺制备碳纤维原丝

聚丙烯腈基碳纤维的制备主要采用溶液纺丝方法,生产过程需要溶剂回收,工艺流程长,因此制造成本高。笔者主要介绍了聚丙烯腈基碳纤维的制备工艺概况,特别介绍了熔融纺丝路线制备聚丙烯腈原丝的方法。利用共聚改性、增塑改性、纺丝后处理等方法,可以制备聚丙烯腈基碳纤维,并提出了由熔融纺丝制备聚丙烯腈基碳纤维的可行路线。