生物基糠醛催化转化制备戊二醇的研究进展

生物基糠醛制备戊二醇的工艺相比于传统的石油基路线,具有原料来源广泛、生产过程绿色无污染等优点。本文总结了国内外以生物基糠醛为原料制备戊二醇的研究现状,并对应用于糠醛催化加氢制备戊二醇的铑、铱、铂、铜基催化剂分别进行了归纳整理,同时详细论述了两种糠醛氢解路线,即糠醛加氢分别以糠醇和四氢糠醇为中间体而氢解生成戊二醇的过程。在此基础上,提出了解决目前糠醛氢解制备戊二醇过程中存在的反应物浓度低、活性差、反应压力高等问题的建议。对未来从经济、环保等多角度出发设计并完善生物基戊二醇的生产工艺以及拓展高效利用生物基糠醛制备下游精细化工产品的方法做出了展望。为开发在温和条件下高效、稳定的催化生物基糠醛氢解的催化剂体系提供了参考。     

Extraction of Furfural with Carbon Dioxide

Abstract

A new approach to separate furfural from aqueous waste has been investigated. Recovery of furfural and acetic acid from aqueous effluents of a paper mill has successfully been applied on an industrial scale since 1981.

The process is based on the extraction of furfural and acetic acid by the solvent trooctylphosphineoxide (TOPO). Common extraction of both substances may cause the formation of resin residues. Improvement was expected by selective extraction of furfural with chlorinated hydrocarbons, but ecological reasons stopped further development of this project.

The current investigation is centered in the evaluation of extraction of furfural by supercritical carbon dioxide. The influence of temperature and pressure on the extraction properties has been worked out. The investigation has considered the multi-component system furfural-acetic acid-water-carbon dioxide. Solubility of furfural in liquid and supercritical carbon dioxide has been measured, and equilibrium data for the ternary system furfural-water-CO₂ as well as for the quaternary system furfuralacetic acid-water-CO₂ have been determined. A high-pressure extraction column has been used for evaluation of mass transfer rates.     

双柱循环色谱分离过程的最优化

提出一种双柱循环色谱分离过程最优化方法。以分离产率作为目标函数 ,以回收率作为约束条件 ,应用参数灵敏度分析法比较各参数对分离产率影响的大小 ,选择灵敏度大的操作参数作为可优化参数 ,采用改进单纯形法对双柱循环色谱分离蔗糖还原糖过程进行了最优化计算。参数灵敏度分析结果表明 ,吸附剂填充高度和进料负荷具有较高的灵敏度 ,是影响分离产率的主要因素 ,被选为可优化参数。与平面搜索法比较 ,使用文中提出的优化方法不仅能获得与使用平面搜索法一致的结果 ,而且计算简便、收敛速度较快 ,文中提出的最优化方法双柱循环色谱分离过程进行最优化是可行的和有效的     

Experimental,equilibrium modelling,and column design for the reactive separation of biomass-derived 2-furoic acid

Electrochemical conversion of biomass to value-added chemicals has gained impetus in recent years. Herein, we present a methodology for recovering biomass-derived 2-furoic acid from the dilute aqueous stream by reactive extraction. The reactive extraction was performed using a chemical extractant, trioctylamine (TOA), with diluents (octanol, chloroform, and diethyl ether). Equilibrium parameters influencing the recovery of 2-furoic acid were evaluated. Using TOA in various diluents, the 2-furoic acid was recovered with 85%–99% efficiency. A 1:1 complex of the 2-furoic acid—TOA was formed in the organic phase, and the experimental equilibrium complexation constant was compared with that obtained from the relative basicity and Langmuir models. The equilibrium parameters were used for column design to estimate the solvent to feed ratio (S/F) and the number of theoretical stages (NTS). The NTS required is 12 to attain 99% recovery of 2-furoic acid in counter-current extraction. The present study sheds light on the reactive extraction process adopted for process intensification with electrochemical conversion, paving the way for the commercialization of valuable products obtained from biomass.     

异丙醇-环己烷萃取精馏过程模拟与优化

利用化工流程模拟软件Aspen Plus对异丙醇-环己烷共沸物系的双塔连续萃取精馏过程进行了模拟计算与优化。首先根据溶剂相似相溶原理,先初选出糠醛和硝基苯作为备选溶剂,再通过汽液平衡试验及ChemCAD模拟筛选,确定糠醛为最适宜溶剂,选择NRTL模型作为物性方法,使用RadFrac模块进行模拟计算,并利用灵敏度分析模块对各工艺参数进行优化。结果表明,最适宜工艺方案为：萃取精馏塔理论塔板数为30,原料在第26块板进料,溶剂在第12块板进料,物质的量回流比为1.8,溶剂质量比为3∶1;溶剂回收塔理论板数为15,进料位置在第10块板,物质的量回流比为1.0。分离效果可达到环己烷质量分数为99.74%,异丙醇质量分数为99.61%。模拟和优化结果为分离过程的优化操作和设计提供了依据。     

生物质转化制糠醛及其应用

在一步法糠醛生产技术的基础上重点对两步法糠醛生产技术,糠醛生产流程及糠醛的应用进行了综述。由于两步法糠醛生产技术结合两段水解工艺,在生产糠醛的同时可获得燃料乙醇,得率可以达到70%以上,同时提高了原料的利用率。所以两步法必将成为糠醛生产的重要研究方向。     

糠醛的水解制备和应用研究进展

糠醛是由可再生的生物质为原料转化得到的高价值化工产品，具有广阔的应用前景。本文综述了近年来生物质催化水解制备糠醛的研究进展，同时总结了糠醛衍生产品的制备和应用。在对半纤维素水解产糖反应和木糖脱水反应进行机理分析的基础上，从反应原料、溶剂体系、催化剂和分离方法等方面归纳总结了生物质催化水解制备糠醛的最新研究进展，并提出当前生物质制备糠醛方法中存在的问题和应对方案。在此基础上，分析了糠醛经氢化、胺化、氧化、缩醛化、聚合等反应获得高价值衍生产品的研究进展。提出要实现糠醛绿色高效的生产和应用，应着力设计低成本、低能耗、低污染且高效率的催化反应体系，同时推进重要糠醛衍生产品的综合高效利用。     

Dispersed air flotation and foam fractionation for the recovery of microalgae in the production of biodiesel

Microalgae biomass has great potential for being used as feedstock for the sustainable production of biodiesel, as it is able to produce 7–31 times more oil than the top terrestrial crop. It is a green alternative to the currently utilized energy sources as it can reduce CO, CO₂ and hydrocarbon emissions. However, downstream processing costs for the dilute biomass are a major challenge. Foam flotation has been recently investigated for the recovery of microalgae cells from dilute liquid suspensions. A number of variables on the effectiveness of foam flotation for microalgae have been investigated, which include surfactant type and concentration, cell concentration, pH, hydrophobicity, time, growth stage, flow rate, ionic strength, alkalinity, temperature, bubble size, and column size. It appears to be a promising method for the recovery of algae for biofuel production, as a result of the high removal recoveries, good enrichment ratios, ability to process large volumes of biomass, and its ease of operation. However, literature on this subject is scarce, and there are research gaps that should be investigated including characterization of microalgae cells and impact on foam separation and the effect of surfactant as a treatment prior to lipid extraction.     

糠醛的生物炼制技术研究进展

生物炼制是新时代应对能源危机和环境污染的极佳策略,基于生物炼制可以将低值的生物质资源转化为各类高附加值产品。糠醛是一种来自生物质资源的高附加值平台化合物,在能源、医药、化工等领域具有重要应用。糠醛的工业生产已经近一个世纪,工业生产技术已经比较成熟,但是目前工业生产过程中还存在不少问题。为解决糠醛工业生产中存在的问题,研究者对制备糠醛的新技术和新工艺进行了研究与探索。本文首先介绍了糠醛的性质及应用,分析了糠醛的工业生产技术现状和所面临的问题,如利用无机酸作催化剂时会腐蚀设备,催化剂不易回收,存在污染水源等问题。然后详细叙述了水解法和热解法制备糠醛的技术研究现状以及微波加热辅助新工艺的特点,最后展望了糠醛制备技术的未来发展方向。     

汽爆法生产糠醛新工艺

研究了用汽爆法取代糠醛生产工艺中的酸解步骤,得出了新工艺的最佳工艺参数。取玉米秸秆20 g在1.4 MPa压力、维压时间4 min下汽爆,所得物料用60 mL热水（80 ℃）水提2 h,水提液中木糖含量可达9.96 g/L,木糖浸出率为2.79%。取350 mL水提液,加入甲苯30 mL、5%稀硫酸10 mL,于165 ℃反应精馏3 h,糠醛得率可达84%,糠醛总的质量收率为2.2%。结果表明,本工艺产生的三废量大幅减少。     

糠醛废水中的醋酸回收工艺

使用自制络合萃取剂,采用脉冲填料塔通过络合萃取回收糠醛废水中的醋酸,萃取效率可达到97％～99％。测定了该物系的液液平衡数据,试验考察了影响萃取效率的因素。以醋酸的精制可利用减压精馏蒸出和共沸精馏脱水来实现。萃取液中醋酸蒸出率接近100％,脱水效果良好,得到合格的工业级醋酸。     

基于相图分析的润滑油糠醛精制工艺改进

针对原料油中饱和分与芳香分分离精度低导致糠醛精制工艺抽余油收率低、抽出油质量差的问题,提出基于热力学相图分析的糠醛精制工艺的改进策略。基于虚拟组分法简化润滑油组分为饱和分、芳香分和极性分,采用NRTL模型预测不同温度下的相平衡数据,分析抽提过程液液相平衡关系及操作条件对萃取过程的影响规律,发现温度是影响平衡组成和传质效率的关键因素。基于相图对萃取过程的分析,通过设计多级抽出液回收系统,多温度梯级分离抽出液,解决抽提塔在较低温度下难以操作的问题。结合实际糠醛精制装置进行模拟计算,结果表明设置多级抽出液回收系统,抽提过程溶剂比及冷热公用工程量适当增加,抽余油收率较原工艺提高10%以上,抽出油质量极大改善,显著提升糠醛精制工艺的分离效率。     

生物质快速热解制糠醛的实验研究及理论探讨综述

糠醛是生物质快速热解的重要产物之一,通过对生物质进行定向热解可实现糠醛的选择性制备,从而获得一种新型的糠醛制备方法,实现生物质的高值化利用。概述了国内外对纤维素和半纤维素热解形成糠醛机理的实验研究和密度泛函理论分析,总结了生物质选择性热解制备糠醛的工艺技术,指出了今后的研究需要,明确糠醛的热解形成机理以及优化糠醛选择性制备的技术。     

木质纤维素制备5-羟甲基糠醛的催化过程强化

5-羟甲基糠醛(HMF)是一种链接可再生生物质资源与燃料化合物及化学中间体的重要新型平台化合物。文中对高温(180—200℃)条件下,金属氯化物为催化剂,离子液体[BMIM]Cl为溶剂,木质纤维素(相思木木屑)为原料快速制备HMF和糠醛的反应过程进行了研究。通过对反应温度、原料用量、盐酸(HCl)添加量、催化剂种类及用量等因素进行考察,优化了反应条件。研究结果表明:与文献报道的低温下纤维素降解反应相比,高温条件可使木质纤维素为原料制备HMF的反应过程得到强化。在所考察的金属氯化物催化剂中,CrCl3.6H2O的催化效果最优,其中以CrCl3.6H2O为催化剂,200℃下反应4 min时产物HMF及糠醛的收率分别可达55.0%和22.9%。该高温反应过程反应快速、产物收率高,无需木质纤维素原料的预处理操作,为工业上简单快速制备HMF提供了一种可行方法。     

高温液态水条件下木糖直接转化制备糠醛的工艺

使用自制的高温高压反应釜,在高温液态水（HTW）的条件下对木糖直接转化制备糠醛的过程进行了研究。考察了HTW作为反应介质对木糖转化率和糠醛产率的影响,并与文献中所采用催化剂的催化效果进行了对比,探索了不同的溶剂对反应产物中糠醛的萃取效果。研究结果表明：HTW作为反应介质对木糖直接转化制备糠醛具有优良的反应性能,可以替代液体酸和固体酸作用于木糖制糠醛,在优化的工艺条件下,当木糖初始浓度为10%（g/g）、反应温度为200 ℃、反应时间为3 h时,糠醛的产率高达78%。此外,乙酸丁酯作为萃取剂对于糠醛的萃取具有良好的萃取效率。所得结果为工业化生产糠醛奠定了实验基础和理论依据。     

Intermolecular Diels-Alder Cycloadditions of Furfural-Based Chemicals from Renewable Resources: A Focus on the Regio- and Diastereoselectivity in the Reaction with Alkenes

A recent strong trend toward green and sustainable chemistry has promoted the intensive use of renewable carbon sources for the production of polymers, biofuels, chemicals, monomers and other valuable products. The Diels-Alder reaction is of great importance in the chemistry of renewable resources and provides an atom-economic pathway for fine chemical synthesis and for the production of materials. The biobased furans furfural and 5-(hydroxymethyl)furfural, which can be easily obtained from the carbohydrate part of plant biomass, were recognized as “platform chemicals” that will help to replace the existing oil-based refining to biorefining. Diels-Alder cycloaddition of furanic dienes with various dienophiles represents the ideal example of a “green” process characterized by a 100% atom economy and a reasonable E-factor. In this review, we first summarize the literature data on the regio- and diastereoselectivity of intermolecular Diels-Alder reactions of furfural derivatives with alkenes with the aim of establishing the current progress in the efficient production of practically important low-molecular-weight products. The information provided here will be useful and relevant to scientists in many fields, including medical and pharmaceutical research, polymer development and materials science.     

减四线油生产环保橡胶油的工艺研究

本论文研究了以减四线油为原料,通过糠醛精制工艺及加氢精制工艺生产环保橡胶油,探讨了工艺条件对产品性质的影响,并对两种工艺的优缺点进行了比较。研究结果表明,通过糠醛抽提工艺及加氢精制工艺均可得到CA值12%左右的环保橡胶油,但加氢精制工艺的收率高达97%以上,比糠醛抽提工艺的收率高10%以上。     

A REVIEW OF THE INDUSTRIAL AND RECENT POTENTIAL APPLICATIONS OF TRIOCTYLPHOSPHINE OXIDE

ABSTRACT

The industrial applications of trioctylphosphine oxide, more commonly known as TOPO, make use of its complexing powers with metals and with hydrogen donor organic compounds. Commercial uses as a solvent extraction reagent are in the recovery of uranium from wet process phosphoric acid and in the recovery of byproduct acetic acid and furfural generated during sulphite wood pulping. Recently investigated potential uses include the separation of niobium from tantalum and the extraction of organic compounds, such as citric acid, from fermentation broths. Each process is discussed briefly.     

溶剂连续循环萃取法提取烟叶中茄尼醇

在传统的间歇萃取溶剂提纯法的基础上加以改进,提出了溶剂连续循环液液萃取法提取烟叶中茄尼醇的流程与装置,并进行了实验研究,确定了优化的工艺参数:以混合烃类A为萃取溶剂,溶剂与原料烟叶质量比为18∶1,萃取时间为5—6 h,加热温度控制在高于溶剂沸点10℃左右。实验结果表明,采用这种方法,产品提取率比原有方法提高8.3%,溶剂回收率提高2.3%,产品质量稳定,实验周期、溶剂用量明显减少,可以有效降低提取生物质中茄尼醇的生产成本。     

从雨生红球藻藻泥中选择性提取虾青素

以雨生红球藻湿藻泥为原料,研究了不同有机溶剂对胞内油脂和虾青素选择性提取分离的影响,通过酸解破壁提高虾青素和油脂的提取效率。结果表明,连续乙醇提取可对胞内色素和油脂有效分级提取,先提取出极性组分(叶绿素和极性脂),再提取中性组分(类胡萝卜素和中性脂)。中等极性溶剂或溶剂体系对类胡萝卜素的选择性和提取率较好;乙醇/乙酸乙酯混合溶剂提取类胡萝卜素的总得率(干重)达25.31 mg/g,提取率为69.35%。对雨生红球藻湿细胞进行酸解破壁处理有助于提高虾青素和油脂的提取率。在最优酸解破壁条件(盐酸浓度1 mol/L,温度60℃,时间60 min)下,含水80%的雨生红球藻藻泥的油脂总得率(干重)达418 mg/g,总脂提取率达97%。