Reaction extraction of furfural from pentose solutions in a modified Scheibel column

Furfural, which is one of the most promising platform chemicals derived from biomass, has the potential for the production of biofuels and biochemicals. However, the current industrial furfural production process relies on relatively old and inefficient technology, which has some problems such as low production yields, environmental pollutions, and lack of biomass comprehensive utilization. The main contribution of this paper is the use of a modified Scheibel column to improve the furfural recovery. Integration of pentose dehydration to furfural and the solvent phase extraction of furfural occurred simultaneously in this column. Compared with the prevailing batch biphasic reactor, the use of this modified column intensified the extraction efficiency as well as the furfural recovery. Process parameters including organic feed flow rate, reaction temperature, and stirring speed were evaluated and turned out to be significant. In order to achieve the optimal operating conditions, the CCD design was used to optimize the process parameters, and the maximum furfural yield of 80.5% was obtained.     

糠醛生产工艺的研究进展

糠醛不仅是生产各类精细化学品的平台化合物,而且可以作为能源前体,生产运输燃料.在分析糠醛生产现状基础上,详细介绍了近年来糠醛清洁生产工艺的最新研究成果,并比较各种工艺改进的优缺点.指出两相法生产糠醛并联产纤维乙醇及高附加值化学品等,提高资源综合利用率,减少三废是具有工业化前景、环境友好的糠醛生产技术.     

糠醛生产工艺及制备方法研究进展

糠醛是一种应用广泛的化工原料,其现有生产工艺在产率、能耗及环境污染等方面存在较大问题。本文介绍了现有的主流生产工艺如Quaker Oats工艺,Agrifuran工艺,Petrole-chimie工艺,Escher Wyss工艺及Rosenlew工艺存在的不足,分析了半纤维素生成糠醛的机理及水解动力学研究、糠醛生产设备的更新改造。从溶剂体系、催化剂体系、分离方法、加热方式等多方面探讨发展新的糠醛生产工艺。提出今后的研究重点要放在开发绿色的溶剂及催化剂上,以期对生态环境的危害降至最低。     

Improving Lipid Production of Yarrowia lipolytica by the Aldehyde Dehydrogenase-Mediated Furfural Detoxification

Yarrowia lipolytica, the non-conventional yeast capable of high lipogenesis, is a microbial chassis for producing lipid-based biofuels and chemicals from renewable resources such as lignocellulosic biomass. However, the low tolerance of Y. lipolytica against furfural, a major inhibitory furan aldehyde derived from the pretreatment processes of lignocellulosic biomass, has restricted the efficient conversion of lignocellulosic hydrolysates. In this study, the furfural tolerance of Y. lipolytica has been improved by supporting its endogenous detoxification mechanism. Specifically, the endogenous genes encoding the aldehyde dehydrogenase family proteins were overexpressed in Y. lipolytica to support the conversion of furfural to furoic acid. Among them, YALI0E15400p (FALDH2) has shown the highest conversion rate of furfural to furoic acid and resulted in two-fold increased cell growth and lipid production in the presence of 0.4 g/L of furfural. To our knowledge, this is the first report to identify the native furfural detoxification mechanism and increase furfural resistance through rational engineering in Y. lipolytica. Overall, these results will improve the potential of Y. lipolytica to produce lipids and other value-added chemicals from a carbon-neutral feedstock of lignocellulosic biomass.     

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。     

Biomass-based chemical production using techno-economic and life cycle analysis

Furfural has been selected as one of the top 30 biomass derived platform compounds by the U.S. Department of Energy based on several indicators including the raw material used for production, estimated processing cost, technical complexity, and market potential. In this work, several high value chemicals such as butadiene, surfactants, jet-fuels, and lubricants are produced from furfural. The paper proposes the integrated flowsheet to produce those chemical and techno-economic and life cycle analysis is performed to compare the minimum selling price and environmental impacts of the integrated process. The capital and operating cost for production of lubricants and surfactants is the highest when compared with other products. Production of surfactants performs the best in terms of environmental impacts except in water depletion when compared with other processes while butadiene production performs the worst regarding the environmental effects.     

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。     

Integrated chemo- and biocatalytic processes: a new fashion toward renewable chemicals production from lignocellulosic biomass

Concerns over climate change and environmental pollution resulting from petroleum refining has spurred the exploitation of green replacements for producing chemicals and fuels. Valorization of lignocellulosic biomass into chemicals represents a promising alternative to petroleum refining. Biological and chemical catalysis are two leading routes for lignocellulose variolization, but strategies relying simply on biological or chemical conversion have shown limitations. Integrating biocatalysts with chemocatalysts could leverage the inherent strengths of both while circumventing their respective disadvantages, benefiting product yield and selectivity, and reducing cost and waste generation. This review focuses on the coupled chemocatalytic and biocatalytic synthesis of renewable chemicals from polysaccharides and their derived platform chemicals. In addition, strategies for producing value-added products from lignin via integrated chemical depolymerization and biological conversion are highlighted. The techno-economics of integrating chemocatalysts and biocatalysts in producing chemicals in the context of biorefinery are also discussed. Finally, perspectives on designing integrated chemical and biological catalysis for renewable chemicals production are provided. © 2022 Society of Chemical Industry (SCI).     

Ionic Liquids in Biomass Processing

The ionic liquids have emerged as new solvents and catalysts for processing biomass to value added chemicals and fuels. This review will present the recent developments in applications of ionic liquids in lignocellulosic biomass pretreatments, depolymerization, biodiesel synthesis, dehydration of carbohydrates to renewable feedstock chemicals as well as further transformations of biomass derived feedstocks such as furfural, 5‐hydroxymethylfurfural and levulinic acid to value added chemicals. In addition, the recycling of ionic liquids used in biomass processing is also discussed in the review.     

木质纤维素衍生平台化学品制备液态烷烃的研究进展

液态烷烃C₅₊是汽油、柴油、航空燃油等当前社会的运输燃料的主要成分。本文综述了利用木质纤维素衍生平台化学品制备液体燃料的研究进展,着重总结了生物质衍生平台化学品通过碳链增长得到长链含氧化合物,然后经过加氢脱氧（HDO）得到C₇₊液体烷烃的技术研究进展。木质纤维素衍生平台化学品包括山梨醇、糠醛、5-羟甲基糠醛（HMF）、环戊酮、甲基呋喃、酚类、丙酮、丁醇、乙醇、乙酰丙酸、γ-戊内酯等。其中,糠醛、5-羟甲基糠醛和环戊酮在碱性催化剂作用下能与其他羰基化合物发生羟醛缩合反应实现碳链增长;甲基呋喃、苯类及苯酚类衍生物可以在强酸催化作用下通过烷基化/羟烷基化反应实现碳链增长;丙酮能与乙醇、丁醇发生α-烷基化反应实现碳链增长;乙酰丙酸可以转化为戊酸、丁烯或当归内酯,再分别通过酮基化反应、烯烃齐聚反应和加成反应实现碳链增长。诸多利用生物质衍生物化学品制备长链烷烃的路径中,利用5-羟甲基糠醛和甲基呋喃制备长链烷烃的技术路线存在路径过长、原料不易获取的问题;利用环戊酮和苯酚类物质能够得到高密度长链环烷烃,是一条有竞争力的路线;糠醛和乙酰丙酸易于从生物质中大规模制取,且利用糠醛和乙酰丙酸制备长链烷烃的反应路径短,较易实现工业应用。     

三苯基磷在玉米芯制备糠醛中的应用

研究了三苯基磷在稀硫酸法水解玉米芯制备糠醛中的应用。在三苯基磷用量占玉米芯总量的0.05%～0.5%范围内,考察了三苯基磷的量对糠醛收率的影响。实验结果表明：随着三苯基磷用量的增加,糠醛收率明显提高,当三苯基磷加入量为玉米芯总量的0.25%时,糠醛收率升至86.0%,同传统工艺相比,糠醛收率提高20%～25%。由此可见,通过添加三苯基磷的途径可大幅度提高糠醛收率,在稀硫酸法水解玉米芯制备糠醛工艺中将具有良好的应用前景。     

Heterogen katalysierte Herstellung von Furfural aus Xylose

The results of the dehydration of C₅‐raw material to obtain furfural via heterogeneous catalysis in water are discussed. Furfural has the potential to substitute fossil compounds on a large scale for polymers, solvents, fine chemicals and finally fuels. Industrial catalysts were reviewed and new catalysts were synthesized. The main difference to recent work is the abdication of supercritical fluids, organic solvents, phase modifiers and ionic liquids. With this also the contamination of the product is prevented and higher product qualities are obtained.     

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。     

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。     

糠醇生产车间空气环境的监测方法

用装有Tenax-TA吸附剂的采样管采集车间空气中的糠醇及糠醛,并用气相色谱法定性定量检测。在给定的试验条件下,该方法的检测极限分别为糠醇1.06 mg/m~3、糠醛0.17 mg/m~3,平均解吸效率分别为糠醇95.7%、糠醛92.6%,变异系数分别为糠醇3.0%～5.2%、糠醛3.8%～6.1%。Tenax-TA对糠醇和糠醛的穿透容量分别大于16.7、13.5 mg。经现场测试,该法可用于糠醇生产车间的卫生监测。     

Lignocellulosic biomass for the preparation of cellulose‐based hydrogel and its use for optimizing water resources in agriculture

Recently, efforts have been devoted to find ways in utilizing biomass as feedstocks for the production of organic chemicals. This is because of its abundance, renewability and worldwide distribution. Lignocellulosic agricultural waste materials are regarded as abundant, inexpensive, and readily available natural resources for both chemical and paper industries. Hydrogels are polymeric materials that vary in their origin and composition and can absorb large amount of water without dissolving. In our study, cellulose‐based acrylic acid hydrogel was synthesized starting from rice straw as a source for the lignocellulosic material, where cellulose was first isolated after alkaline‐acid pulping treatment followed by bleaching step with sodium hypochlorite resulting of 90.8% holocellulose. The cellulose‐based acrylic acid hydrogel was synthesized applying heterogeneous reaction and shows a swelling ratio more than 3000%. The resulting hydrogel was further characterized with FT‐IR and SEM. On the other hand, comparison between the rice straw‐based hydrogel and the commercially available acrylamide hydrogel was studied for improving maize production in salt affected soil as well as in the growth promoters of maize under water stress. The experimental results demonstrated that the yield parameters were increased with increasing irrigation rates. Both types of hydrogels introduce positive and significant effect compared to the one without adding hydrogels. Also, acrylamide hydrogel was effective for improving almost yield parameters more than applying rice straw‐based hydrogel. Generally, the addition of hydrogel increases the nutrient concentration, uptake, and both of water and nutrients use efficiency. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42652.     

Production of furfural from agricultural wastes by using pressurised water in a batch reactor

Agricultural wastes such as rice husks and sawdust can be used for the manufacture of chemicals including furfural and acetic acid. In the present work the conventional use of superheated steam has been replaced by the use of superheated water in the acidic hydrolysis of rice husk and sawdust. Comparable yields of furfural have been obtained by using superheated water in place of superheated steam in the same temperature and pressure range. This is an attempt to economise the heat requirement and reduce the cost of production of furfural.     

Preliminary Studies on Furfural Production from Lignocellulosics

This study focused on the production of furfural from agricultural and industrial biomass residues by a hydrodistillation process. Corncobs, sugarcane bagasse, and eucalypt wood were treated with sulfuric, hydrochloric, and phosphoric acids as catalysts, with different acid concentrations (1.5 to 5.2 mol.L ^?1). In addition, the eucalypt liquor from the auto-hydrolysis, kraft-dissolving pulp production process was also investigated as a source of furfural, using sulfuric and hydrochloric acids as a catalyst (0.9 and 3.9 mol.L ^?1) . Furfural yields of 30.2, 25.8, and 13.9% were achieved for corncob, sugarcane bagasse, and eucalypt wood, respectively, on the basis of biomass dry weight. The efficiency of conversion from pentose to furfural using eucalypt liquor from the auto-hydrolysis kraft process was 71.5% using HCl 3.9 mol.L ^?1 . Due to the presence of a high amount of pentose, corncob produced the highest amount of furfural, followed by sugarcane bagasse and then eucalypt wood.     

Pervaporation of organic compounds from aqueous mixtures using polydimethylsiloxane‐containing block copolymer membranes

Pervaporation of aqueous mixtures of ethanol, acetone, butanol, isobutanol, and furfural through polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (SDS) triblock copolymer membranes is reported. These mixtures are important for biofuel production from lignocellulosic feedstocks. Feedstock depolymerization results in the formation of furfural which must be removed before fermentation. Ethanol, butanol, isobutanol, and acetone are important fermentation biofuels. The membrane selectivity of SDS is about unity over a wide range of concentrations of aqueous ethanol mixtures, similar to the membrane selectivity of crosslinked polydimethylsiloxane (PDMS). The permeabilities of butanol, isobutanol, and furfural are larger than those of ethanol and acetone. The volatile organic compound permeability through SDS is similar to or higher than that through PDMS across a broad range of temperatures and feed concentrations is found. More selective and permeable membranes are needed to lower the cost of biofuel purification. The SDS membranes developed are but one step toward improved membranes. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2789–2794, 2015