利用可再生农林生物质资源的炼油厂——推动化学工业迈入“碳水化合物”新时代

本文首先介绍了国外以玉米、废弃生物质为原料发展生物炼油厂的设想;然后根据我国国情和已有技术基础,设想了以甜高梁、木薯为原料生产乙醇车用汽油和化工产品的生物炼油厂,以及以菜籽油、棉籽油为原料生产生物柴油和化工产品的生物炼油厂;最后探讨了遇到的问题和采取的对策。     

细胞工厂与生物炼制

生物炼制是以可再生生物质资源为原料,生产能源与化工产品的新兴工业模式。是转变经济增长模式,保障社会经济可持续发展的重大战略需求。微生物细胞工厂是生物炼制技术至关重要的核心。世界各国纷纷设立重大研究计划支持细胞工厂的研究,以期获得生物炼制技术的领先地位。本文简要概括了细胞工厂和生物炼制这一新兴工业模式,回顾了生物炼制细胞工厂的重大计划和进展,讨论了目前亟待解决的关键问题和研究对策。     

生物炼制工业过程及产品

生物炼制是人类面对日益枯竭的化石资源和其所产生的严重环境污染的必然选择。本文从生物炼制和石油炼制的比较出发简要介绍了生物炼制的概念、基本分类和理论框架,并重点分析了生物炼制过程工程的相关技术和进展,主要包括生物质原料的预处理、过程相关的酶水解技术以及发酵菌种改良等。本文还概括了生物炼制相关的碳水化合物、脂肪类以及其他类产品的相关产品群,分析了一些重要生物基产品的生产过程、研发趋势以及所面临的机遇和挑战。     

细胞工厂与生物炼制

生物炼制是以可再生生物质资源为原料,生产能源与化工产品的新兴工业模式.是转变经济增长模式,保障社会经济可持续发展的重大战略需求.微生物细胞工厂是生物炼制技术至关重要的核心.世界各国纷纷设立重大研究计划支持细胞工厂的研究,以期获得生物炼制技术的领先地位.本文简要概括了细胞工厂和生物炼制这一新兴工业模式,回顾了生物炼制细胞工厂的重大计划和进展,讨论了目前亟待解决的关键问题和研究对策.     

生物炼制工业过程及产品

生物炼制是人类面对日益枯竭的化石资源和其所产生的严重环境污染的必然选择.本文从生物炼制和石油炼制的比较出发简要介绍了生物炼制的概念、基本分类和理论框架,并重点分析了生物炼制过程工程的相关技术和进展,主要包括生物质原料的预处理、过程相关的酶水解技术以及发酵菌种改良等.本文还概括了生物炼制相关的碳水化合物、脂肪类以及其他类产品的相关产品群,分析了一些重要生物基产品的生产过程、研发趋势以及所面临的机遇和挑战.     

High oleic safflower biolubricant through double transesterification with methanol and pentaerythritol: Production,characterization, and antioxidant addition

Double transesterification from vegetable oils could play an important role in biodiesel and biolubricant production, with the possible implementation of biorefineries to replace refineries based on petroleum. The oxidative stability of the original sample will influence the quality of the intermediate and final products, recommending highly stable raw materials or the use of antioxidants to keep quality parameters during storage. The aim of this work was to obtain a stable biolubricant, assessing its production through a double transesterification with methanol and pentaerythritol from high-oleic safflower oil and adding antioxidants, paying attention to quality parameters. Consequently, a biorefinery that produced high-quality products was proposed. In conclusion, high biodiesel and biolubricant yields were obtained (>97 and >94%, respectively) with the following chemical conditions for the latter: FAME/alcohol ratio, 1:0.33; pressure, 260 mmHg; catalyst concentration, 1.0%; temperature, 160 °C. The oxidative stability of biodiesel complied with the standard (10.78 h) due to its high methyl oleate content (exceeding 80%), whereas this parameter was shorter for the biolubricant (2.86 h), possibly due to its molecular structure. Consequently, antioxidant addition was needed, and tert-Butylhydroquinone at low concentration (500 ppm) kept viscosity and acid number of high-oleic safflower biolubricant during oxidation conditions (up to 8 h). However, tannic acid did not keep these properties in biolubricant. In conclusion, by using the right antioxidant, all the products of the proposed biorefinery were stable during oxidizing conditions, making this biorefinery more competitive.     

Challenges and Future Perspectives of Promising Biotechnologies for Lignocellulosic Biorefinery

Lignocellulose is a kind of renewable bioresource containing abundant polysaccharides, which can be used for biochemicals and biofuels production. However, the complex structure hinders the final efficiency of lignocellulosic biorefinery. This review comprehensively summarizes the hydrolases and typical microorganisms for lignocellulosic degradation. Moreover, the commonly used bioprocesses for lignocellulosic biorefinery are also discussed, including separated hydrolysis and fermentation, simultaneous saccharification and fermentation and consolidated bioprocessing. Among these methods, construction of microbial co-culturing systems via consolidated bioprocessing is regarded as a potential strategy to efficiently produce biochemicals and biofuels, providing theoretical direction for constructing efficient and stable biorefinery process system in the future.     

Process Modeling of Comprehensive Integrated Forest Biorefinery—An Integrated Approach

The key to expanding the energy supply, increasing energy security, and reducing the dependency on foreign oil is to develop advanced technologies to efficiently transform our renewable bioresources into domestically produced bioenergy and bioproducts. Conventional biorefineries, i.e., forest products industry’s pulp and paper mills with long history of sustainable utilization of lignocellulose (wood), offer a suitable platform for being expanded into future integrated forest biorefineries. Due to the pre-existing infrastructure in current forest products operations, this could present a very cost-effective approach to future biorefineries. In order to better understand the overall process, technical, economic, and environmental impacts, a detailed process modeling of the whole integrated forest biorefinery is presented here. This approach uses a combination of Aspen Plus®, WinGEMS®, and Microsoft Excel® to simulate the entire biorefinery in detail with sophisticated communication interface between the three simulations. Preliminary results for a simple case study of an integrated biorefinery show the feasibility of this approach. Further investigations, including additional details, more process options, and complete integration, are currently underway.     

Cost reduction approaches for fermentable sugar production from sugarcane bagasse and its impact on techno-economics and the environment

Cellulose - In an enzymatically driven lignocellulosic biorefinery, pretreatment and hydrolysis modules are the two most significant cost contributors for obtaining high gravity sugar solutions....     

A Techno-economic Analysis of Polyhydroxyalkanoate and Hydrogen Production from Syngas Fermentation of Gasified Biomass

A techno-economic analysis was conducted to investigate the feasibility of a gasification-based hybrid biorefinery producing both hydrogen gas and polyhydroxyalkanoates (PHA), biodegradable polymer materials that can be an attractive substitute for conventional petrochemical plastics. The biorefinery considered used switchgrass as a feedstock and converted that raw material through thermochemical methods into syngas, a gaseous mixture composed mainly of hydrogen and carbon monoxide. The syngas was then fermented using Rhodospirillum rubrum, a purple non-sulfur bacterium, to produce PHA and to enrich hydrogen in the syngas. Total daily production of the biorefinery was assumed to be 12 Mg of PHA and 50 Mg of hydrogen gas. Grassroots capital for the biorefinery was estimated to be 55 million, with annual operating costs at55 million, with annual operating costs at 6.7 million. With a market value of 2.00/kg assumed for the hydrogen, the cost of producing PHA was determined to be2.00/kg assumed for the hydrogen, the cost of producing PHA was determined to be 1.65/kg.     

Continuous Succinic Acid Fermentation by Actinobacillus Succinogenes: Assessment of Growth and Succinic Acid Production Kinetics

Applied Biochemistry and Biotechnology - Succinic acid is one of the most interesting platform chemicals that can be produced in a biorefinery approach. The paper reports the characterization of...     

Biorefining: the role of endoglucanases in refining of cellulose fibers

Cellulose - With an annual production of more than 400 million tons, paper is the main product of the largest biorefinery process industrially implemented. Enzymes have been used for pulp refining...     

Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass?

Certain ionic liquids have been shown to dissolve cellulose, other biopolymers, and even raw biomass under relatively mild conditions. This particular ability of some ionic liquids, accompanied by a series of concurrent advantages, enables the development of improved processing strategies for the manufacturing of a plethora of biopolymer-based advanced materials. The more recent discoveries of dissolution of lignocellulosic materials (e.g., wood) in ionic liquids, with at least partial separation of the major constituent biopolymers, suggest further paths towards the achievement of a truly sustainable chemical and energy economy based on the concept of a biorefinery which provides chemicals, materials, and energy. Nonetheless, questions remain about the use of ionic liquids and the advisability of introducing any new process which utilizes bulk synthetic chemicals which have to be made, disposed of, and prevented from entering the environment. In this article, we discuss our own journey from the discovery of the dissolution of cellulose in ionic liquids to the cusp of an enabling technology for a true biorefinery and consider some of the key questions which remain.     

Biogas Potential of the Side Streams Obtained in a Novel Phenolic Extraction System from Olive Mill Solid Waste

The olive oil production is an important industrial sector in many Mediterranean areas, but it is currently struggled by the necessity of a proper valorisation of the olive mill solid waste or alperujo. The alperujo is the main by-product generated during the two-phase olive oil extraction, accounting for up to 80% of the initial olive mass. The alperujo is a source of valuable compounds, such as the pomace olive oil or highly interesting phenolic compounds. In the present research, a novel biorefinery approach has been used for phenolic compounds recovery. However, the extraction of these valuables compounds generates different exhausted phases with high organic matter content that are required to be managed. This study consists of the evaluation of the anaerobic biodegradability of the different fractions obtained in a novel biorefinery approach for the integral valorisation of alperujo. The results show that the different phases obtained during the biorefinery of the alperujo can be effectively subjected to anaerobic digestion and no inhibition processes were detected. The highest methane yield coefficients were obtained for the phases obtained after a two-months storages, i.e., suspended solids and liquid phase free of suspended solids, which generated 366 ± 7 mL CH₄/g VS and 358 ± 6 mL CH₄/g VS, respectively. The phenol extraction process reduced the methane yield coefficient around 25% due to the retention of biodegradable compounds during the extraction process. Regardless of this drop, the anaerobic digestion is a suitable technology for the stabilization of the different generated residual phases, whereas the high market price of the extracted phenols can largely compensate the slight decrease in the methane generation.     

Bioraffinerien

The development of biorefineries plays an important role for the solution of future global challenges such as the supply for an increasing world population, the finite nature of fossil resources or environmental and climate protection. Biorefineries guarantee high efficiency and sustainability in material and energetic use of biomass by integrating different processes. However, in order for biorefineries to become commercially feasible, significant further research is required. This concerns the integration of different measures for coherent technological concepts, the upscaling from a laboratory scale to an industrial scale, raw material supply, the optimization of methods and products of the primary‐ and secondary refinery including the principles of sustainability. The German Roadmap Biorefineries determines systematically the current status of the various biorefinery concepts, analyses them regarding economical and ecological aspects and contains concrete recommendations for research and development. The Roadmap gives a comprehensive overview of a range of technologies and the ways how they can be realized. The Roadmap's aim is to develop and to operate biorefinery concepts until 2030 that are highly efficient, in line with the future requirements and ecologically advan‐tageous.     

Strategies for the Removal of Polysaccharides from Biorefinery Lignins: Process Optimization and Techno Economic Evaluation

The utilization of biorefinery lignins as a renewable resource for the production of bio-based chemicals and materials remain a challenge because of the high polysaccharide content of this variety of lignins. This study provides two simple methods; (i) the alkaline hydrolysis-acid precipitation method and (ii) the acid hydrolysis method for the removal of polysaccharides from polymeric biorefinery lignin samples. Both purification strategies are optimized for two different hardwood hydrolysis lignins, HL1 and HL2, containing 15.1% and 10.1% of polysaccharides, respectively. The treated lignins are characterized by polysaccharide content, molecular weight, hydroxyl content, and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR). Preliminary techno-economic calculations are also carried out for both purification processes to assess the economic potential of these technologies. The results indicate that both protocols could be used for the purification of HL1 and HL2 hydrolysis lignins because of the minimal polysaccharide content obtained in the treated lignins. Nevertheless, from an industrial and economic perspective the acid hydrolysis technology using low acid concentrations and high temperatures is favored over the alkaline hydrolysis-acid precipitation strategy.     

Effects of Solid Acid Supports on the Bifunctional Catalysis of Levulinic Acid to γ‐Valerolactone: Catalytic Activity and Stability

Heterogeneous transformation of levulinic acid (LA) to γ‐valerolactone (GVL) is regarded as a critical process of the lignocellulose‐based biorefinery system. Substantial progress on the catalytic conversion of LA to GVL has been continuously achieved recently. However, the traditional research paradigm typically emphasizes the metal‐catalyzed hydrogenation step, but lacks profound insights into the potential impacts of catalyst supports. Herein, an overview of the bifunctional catalytic system classified by representative solid acid supports for LA conversion to GVL is presented, and effects of critical factors on metal‐ and acid‐ catalyzed processes are discussed. Particularly, impacts of key issues on catalytic stability are thoroughly summarized and analyzed. Challenges and suggestions are also proposed from the perspective of increases in both catalytic activity and stability. This review potentially contributes to the rational design of high‐efficiency catalysts used in the biomass valorization for renewable energy production.     

TS-1/H2O2碱溶液中低温氧化愈创木酚制备马来酸（英）

可再生生物质资源的开发与利用能够缓解化石燃料产生的温室气体对环境的负面影响.在生物质燃料制备过程中联产高附加值化学品能大幅提高生物质炼制的经济性.愈创木酚是常见的木质纤维素快速热解产物.本文研究了低温液相氧化愈创木酚制备马来酸,并重点考察了催化剂添加量、pH值、反应时间和反应温度等反应条件的影响.研究发现,在钛硅沸石-过氧化氢碱溶液氧化反应体系中（80℃,pH=13.3）,20₃0mol%的愈创木酚可以选择性转化为马来酸.同时初步探讨了愈创木酚氧化开环转化为马来酸的反应机理.     

Recent Trends in Green and Sustainable Chemistry & Waste Valorisation: Rethinking Plastics in a circular economy

The review presents the recent trends in green and sustainable chemistry, as well as waste valorization and their applicability to understand and realize the concept of a circular economy. It also provides a comprehensive global perspective of the linear plastics economy and makes the case for its transformation into a circular plastics economy. Furthermore, bioconversion in a food waste biorefinery to produce fructose as an example of a high value-added product is given as a case study to demonstrate the feasibility of a circular economy.     

Effects of Liquid Hot Water Pretreatment on Enzymatic Hydrolysis and Physicochemical Changes of Corncobs

Liquid hot water (LHW) pretreatment is an efficient chemical-free strategy for enhancing enzymatic digestibility of lignocellulosic biomass for conversion to fuels and chemicals in biorefinery. In this study, effects of LHW on removals of hemicelluloses and lignin from corncobs were studied under varying reaction conditions. LHW pretreatment at 160 °C for 10 min promoted the highest levels of hemicellulose solubilization into the liquid phase, resulting into the maximized pentose yield of 58.8% in the liquid and more than 60% removal of lignin from the solid, with 73.1% glucose recovery from enzymatic hydrolysis of the pretreated biomass using 10 FPU/g Celluclast?. This led to the maximal glucose and pentose recoveries of 81.9 and 71.2%, respectively, when combining sugars from the liquid phase from LHW and hydrolysis of the solid. Scanning electron microscopy revealed disruption of the intact biomass structure allowing increasing enzyme’s accessibility to the cellulose microfibers which showed higher crystallinity index compared to the native biomass as shown by x-ray diffraction with a marked increase in surface area as revealed by BET measurement. The work provides an insight into effects of LHW on modification of physicochemical properties of corncobs and an efficient approach for its processing in biorefinery industry.