Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1: Pyrolysis systems

Since the energy crises of the 1970s, many countries have become interest in biomass as a fuel source to expand the development of domestic and renewable energy sources and reduce the environmental impacts of energy production. Biomass is used to meet a variety of energy needs, including generating electricity, heating homes, fueling vehicles and providing process heat for industrial facilities. The methods available for energy production from biomass can be divided into two main categories: thermo-chemical and biological conversion routes. There are several thermo-chemical routes for biomass-based energy production, such as direct combustion, liquefaction, pyrolysis, supercritical water extraction, gasification, air–steam gasification and so on. The pyrolysis is thermal degradation of biomass by heat in the absence of oxygen, which results in the production of charcoal (solid), bio-oil (liquid), and fuel gas products. Pyrolysis liquid is referred to in the literature by terms such as pyrolysis oil, bio-oil, bio-crude oil, bio-fuel oil, wood liquid, wood oil, liquid smoke, wood distillates, pyroligneous tar, and pyroligneous acid. Bio-oil can be used as a fuel in boilers, diesel engines or gas turbines for heat and electricity generation.     

Biomass Gasification for Power Generation in Turkey

In this study, different biomass gasification applications and strategies that affect the gasifier which makes electricity in Turkey were investigated. Gasification technologies provide the opportunity to convert renewable biomass materials into clean fuel gases or synthesis gases. These gaseous products can be burned to generate heat or electricity, or they can potentially be used in the synthesis of liquid transportation fuels, hydrogen, or chemicals. Gasification offers a combination of flexibility, efficiency, and environmental acceptability that is essential in meeting future energy requirements. The future of biomass electricity generation lies in biomass integrated gasification/gas turbine technology, which offers high-energy conversion efficiencies.     

Mechanisms of Thermochemical Biomass Conversion Processes. Part 2: Reactions of Gasification

Abstract

Gasification as a thermochemical process is defined and limited to combustion and pyrolysis. The gasification of biomass is a thermal treatment which results in a high proportion of gaseous products and small quantities of char (solid product) and ash. Biomass gasification technologies have historically been based upon partial oxidation or partial combustion principles, resulting in the production of a hot, dirty, low Btu gas that must be directly ducted into boilers or dryers. In addition to limiting applications and often compounding environmental problems, these technologies are an inefficient source of usable energy. The main objective of the present study is to investigate gasification mechanisms of biomass structural constituents. Complete gasification of biomass involves several sequential and parallel reactions. Most of these reactions are endothermic and must be balanced by partial combustion of gas or an external heat source.     

生物质应用于制液体和气体燃料而不是用于发电

我国能源结构从长期看仍将以煤为主,缺油少气。从我国能源结构来讲,生物质利用的最好方式不是发电．因生物质可以生产液体和气体燃料,而风能、太阳能、水能却只能发电。我国秸杆综合利用取得明显成效．在农业和畜牧业的利用领域还可能进一步拓宽,作为燃料利用的量还可能进一步缩减。从我国还在进行的第一次能源大转换来看,我国生物质使用量已大大减少,但还有相当的数量。要减少作为能源使用的生物质传统利用量,把它用于饲料、肥料和工业原料等还有发展前景的用途。在一次能源消费以化石能源为主的时期,中国存在液体燃料和气体燃料短缺的问题,以后进入第三次能源转换时期,新能源和可再生能源替代化石能源之后,液体燃料和气体燃料短缺的问题将会更加突出。因此,生物质应用于生产液体燃料和气体燃料,而不是用于发电。而且生物质发电厂投资高、燃料成本不断上涨,使发电成本高＋生物质发电将长期缺乏竞争力。我国发展生物质液体燃料已具备一定的条件．前几年中石油、中石化和中海油已开始种植可提炼生物液体燃料的能源林。我国非粮生物质液体燃料生产基地正在积极建设之中。我国发展生物质气体燃料也具有一定优势,在沼气、气化和城镇有机废物处理方面都积累了一定的经验。总之生物质生产液体燃料和气体燃料是一种既适应我国当前、又适应未来能源需求的有效措施。     

Biomass upgrading by torrefaction for the production of biofuels: A review

An overview of the research on biomass upgrading by torrefaction for the production of biofuels is presented. Torrefaction is a thermal conversion method of biomass in the low temperature range of 200–300 °C. Biomass is pre-treated to produce a high quality solid biofuel that can be used for combustion and gasification. In this review the characteristics of torrefaction are described and a short history of torrefaction is given. Torrefaction is based on the removal of oxygen from biomass which aims to produce a fuel with increased energy density by decomposing the reactive hemicellulose fraction. Different reaction conditions (temperature, inert gas, reaction time) and biomass resources lead to various solid, liquid and gaseous products. A short overview of the different mass and energy balances is presented. Finally, the technology options and the most promising torrefaction applications and their economic potential are described.     

Coal dust gasification in the filtration combustion mode with syngas production

A new method for the gasification of fine solid fuel was proposed and worked out, by partial oxidation in a flow of gaseous oxidant with filtration of the suspended fuel through an inert porous matrix. In this case, the solid fuel gasification was carrying out similar to the filtration combustion of gases. The gasification of fine solid coal allows one to produce a combustible gas rich in H₂ and CO was studied. A possibility of pulverized coal gasification in a fixed bed reactor with production of gaseous products containing up to 13% by volume of hydrogen and carbon monoxide was shown experimentally.     

An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasification, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day⁻¹ of OME₃, OME₄, and OME₅ (which are suitable as diesel additives) can be produced from 277.3 tonnes day⁻¹ of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno-economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.     

Numerical simulation of hydrogen production by gasification of large biomass particles in high temperature fluidized bed reactor

Biomass as a renewable fuel compared to fossil fuels usually contains high moisture content and volatile release. Hydrogen production by large particle biomass gasification is a promising technology for utilizing high moisture content biomass particle in the high temperature fluidized bed reactor. In the present work, simulation of large particles biomass gasification investigated at high temperature by using the discrete phase model (DPM). Combustible gases with homogeneous gas phase reactions, drying process with a heterogeneous reaction, primary and secondary pyrolysis with independent parallel-reaction by using two-competing-rate model to control a high and low temperature were used. During the thermochemical process of biomass, gaseous products containing of H₂, H₂O, CH₄, CO and CO₂ was obtained. The effects of concentration, mole and mass fraction and hydrodynamics effects on gaseous production during gasification were studied. The results showed that hydrodynamic effect of hot bed is different from cold bed. Concentration and molar fraction of CO and H₂ production by continually and stably state and small amount of CO₂, H₂O, and CH₄ was obtained. The hydrodynamic of bed plays the significant role on the rate of gaseous products.     

Co-gasification of biomass and coal for methanol synthesis

In recent years, a growing interest has been observed in the application of methanol as an alternative liquid fuel, which can be used directly for powering Otto engines or fuel cells achieving high thermodynamic efficiencies and relatively low environmental impacts. Biomass and coal can be considered as a potential fuel for gasification and further syn-gas production and methanol synthesis. In the near future, the economy of methanol production through coal and biomass gasifications can be achieved by their linking with modern gas-steam power systems. The essence of linking is the full utilisation of the capacity of coal/biomass gasification installations. The up-to-date experience of coal and biomass gasification, including gas processing towards syn-gas and methanol production, is described and discussed. A conceptual flow diagram of pressurized and oxygen feeded co-gasification of biomass and coal integrated with combined cycle and parallel methanol production is evaluated. The effect of methanol production rate on the economy of power production is assessed.     

Design of an integrated process for simultaneous chemical looping hydrogen production and electricity generation with CO2 capture

This study was aimed at proposing a novel integrated process for co-production of hydrogen and electricity through integrating biomass gasification, chemical looping combustion, and electrical power generation cycle with CO₂ capture. Syngas obtained from biomass gasification was used as fuel for chemical looping combustion process. Calcium oxide metal oxide was used as oxygen carrier in the chemical looping system. The effluent stream of the chemical looping system was then transferred through a bottoming power generation cycle with carbon capture capability. The products achieved through the proposed process were highly-pure hydrogen and electricity generated by chemical looping and power generation cycle, respectively. Moreover, LNG cold energy was used as heat sink to improve the electrical power generation efficiency of the process. Sensitivity analysis was also carried out to scrutinize the effects of influential parameters, i.e., carbonator temperature, steam/biomass ratio, gasification temperature, gas turbine inlet stream temperature, and liquefied natural gas (LNG) flow rate on the plant performance. Overall, the optimum heat integration was achieved among the sub-systems of the plant while a high energy efficiency and zero CO₂ emission were also accomplished. The findings of the present study could assist future investigations in analyzing the performance of integrated processes and in investigating optimal operating conditions of such systems.     

A comprehensive review of direct carbon fuel cell technology

Fuel cells are under development for a range of applications for transport, stationary and portable power appliances. Fuel cell technology has advanced to the stage where commercial field trials for both transport and stationary applications are in progress. The electric efficiency typically varies between 40 and 60% for gaseous or liquid fuels. About 30–40% of the energy of the fuel is available as heat, the quality of which varies based on the operating temperature of the fuel cell. The utilisation of this heat component to further boost system efficiency is dictated by the application and end-use requirements. Fuel cells utilise either a gaseous or liquid fuel with most using hydrogen or synthetic gas produced by a variety of different means (reforming of natural gas or liquefied petroleum gas, reforming of liquid fuels such as diesel and kerosene, coal or biomass gasification, or hydrogen produced via water splitting/electrolysis). Direct Carbon Fuel Cells (DCFC) utilise solid carbon as the fuel and have historically attracted less investment than other types of gas or liquid fed fuel cells. However, volatility in gas and oil commodity prices and the increasing concern about the environmental impact of burning heavy fossil fuels for power generation has led to DCFCs gaining more attention within the global research community. A DCFC converts the chemical energy in solid carbon directly into electricity through its direct electrochemical oxidation. The fuel utilisation can be almost 100% as the fuel feed and product gases are distinct phases and thus can be easily separated. This is not the case with other fuel cell types for which the fuel utilisation within the cell is typically limited to below 85%. The theoretical efficiency is also high, around 100%. The combination of these two factors, lead to the projected electric efficiency of DCFC approaching 80% - approximately twice the efficiency of current generation coal fired power plants, thus leading to a 50% reduction in greenhouse gas emissions. The amount of CO₂ for storage/sequestration is also halved. Moreover, the exit gas is an almost pure CO₂ stream, requiring little or no gas separation before compression for sequestration. Therefore, the energy and cost penalties to capture the CO₂ will also be significantly less than for other technologies. Furthermore, a variety of abundant fuels such as coal, coke, tar, biomass and organic waste can be used. Despite these advantages, the technology is at an early stage of development requiring solutions to many complex challenges related to materials degradation, fuel delivery, reaction kinetics, stack fabrication and system design, before it can be considered for commercialisation. This paper, following a brief introduction to other fuel cells, reviews in detail the current status of the direct carbon fuel cell technology, recent progress, technical challenges and discusses the future of the technology.     

An overview of solar decarbonization processes,reacting oxide materials,and thermochemical reactors for hydrogen and syngas production

Solar decarbonization processes are related to the different thermochemical conversion pathways of hydrocarbon feedstocks for solar fuels production using concentrated solar energy as the external source of high-temperature process heat. The main investigated routes aim to convert gaseous and solid feedstocks (methane, coal, biomass …) into hydrogen and syngas via solar cracking/pyrolysis, reforming/gasification, and two-step chemical looping processes using metal oxides as oxygen carriers, further associated with thermochemical H₂O/CO₂ splitting cycles. They can also be combined with metallurgical processes for production of energy-intensive metals via solar carbothermal reduction of metal oxides. Syngas can be further converted to liquid fuels while the produced metals can be used as energy storage media or commodities. Overall, such solar-driven processes allow for improvements of conversion yields, elimination of fossil fuel or partial feedstock combustion as heat source and associated CO₂ emissions, and storage of intermittent solar energy in storable and dispatchable chemical fuels, thereby outperforming the conventional processes. The different solar thermochemical pathways for hydrogen and syngas production from gaseous and solid carbonaceous feedstocks are presented, along with their possible combination with chemical looping or metallurgical processes. The considered routes encompass the cracking/pyrolysis (producing solid carbon and hydrogen) and the reforming/gasification (producing syngas). They are further extended to chemical looping processes involving redox materials as well as metallurgical processes when metal production is targeted. This review provides a broad overview of the solar decarbonization pathways based on solid or gaseous hydrocarbons for their conversion into clean hydrogen, syngas or metals. The involved metal oxides and oxygen carrier materials as well as the solar reactors developed to operate each decarbonization route are further described.     

The use of biomass syngas in IC engines and CCGT plants: A comparative analysis

This paper studies the use of biomass syngas, obtained from pyrolysis or gasification, in traditional energy-production systems, specifically internal combustion (IC) engines and combined cycle gas turbine (CCGT) plants. The biomass conversion stage has been simulated by means of a gas–solid thermodynamic model. The IC and CCGT plant configurations were optimised to maximise heat and power production. Several types of biomass feedstock were studied to assess their potential for energy production and their effect on the environment. This system was also compared with the coupling between biomass gasification and fuel cells.     

Conversion of waste tires to liquid products via sodium carbonate catalytic pyrolysis

This study deals with the pyrolysis of waste tires supplied from the transport industry. The base material of tire is latex, which is derived from natural rubber trees. Nowadays rubber (Hevea brasiliensis) is a fast-growing tropical tree crop, which is being cultivated for latex and ultimately for tire production. Waste tires can be recycled for energy and valuable materials in many ways; however tire burning is the most common practice for heat generation. In recent years, the catalytic conversion of waste tires through pyrolysis into liquid, solid, and gas products was investigated. Liquids product was produced from the catalytic pyrolysis of waste tire at high temperature (up to 600°C) using sodium carbonate (Na₂CO₃) as a catalyst. Thermo-physical characteristics of the produced liquid samples showed that up to 85% of the produced oil can be used in internal combustion engines. Gasoline and diesel fuel contents in the liquid products are 45% and 40%, respectively. The gas chromatographic (GC) analysis of the volatile fraction of pyrolysis products showed styrene (28.1%) and butadiene (10.7%) as dominant compounds. The gaseous phase includes C₁–C₄ hydrocarbons (4.8%) and the liquid phase includes C₅–C₈ hydrocarbons (6.5%) of the total products.     

Meeting emission standards with high-sulfur coals

The economics of strategies for meeting sulfur oxides (SO_x) emission standards from furnaces fueled with high-sulfur coals has been assessed based on published data. The strategy of SO_x control depends on how the coal is utilized. For large power plants, flue-gas desulfurization (FGD) is preferable to conversion of coal to clean fuel. In comparison with coal conversion, the total capital and operating costs for FGD are almost an order of magnitude lower, thermal efficiencies are higher, and utility requirements are lower. Even with possible breakthroughs in coal-conversion technologies, it appears that FGD will remain the economically preferred route to desulfurization. FGD has been in commercial operation since 1968, and the reliability of the process has reached an acceptable level. For industrial furnaces, direct combustion is preferred to gasification because gasification is inherently expensive. Fluidized-bed combustion is the only viable option for clean direct combustion of coal in small industrial furnaces. Fluidized-bed combustion has reached commercial status and is economically competitive in many parts of the world. For furnaces requiring gaseous or liquid fuels, gasification to medium-Btu gas is preferred. For domestic and commercial uses, coal can be gasified to clean, low-Btu gas. This is an old process and might be amenable to cost reduction through application of new technologies. The only other economically viable approach involves the production of clean solid fuel by compounding coal with additives such as limestone and manganese nodules.     

Valorisation of vegetable market wastes to gas fuel via catalytic hydrothermal processing

Residues of leek, cabbage and cauliflower from the market places as representatives of lignocellulosic biomass were processed via hydrothermal gasification to produce energy fuel. The experiments were carried out in a batch reactor at temperatures 300, 400, 500 and 600 °C and corresponding pressures varying in the range of 7.5–43 MPa. Natural mineral additives trona, dolomite and borax were used as homogenous catalysts to determine their effects on the gasification. More than 70 wt% of carbon in vegetable residue samples were detected in the gas phase after the hydrothermal gasification process at 600 °C. The addition of trona mineral further promoted the gasification reactions and as a result, less than 5 wt% carbon remained in the solid residue at the same temperature, degrading the biomass samples into gas and liquid products. The fuel gas with the highest calorific value was recorded to be 25.6 MJ/Nm³, from the hydrothermal gasification of cabbage at 600 °C, when dolomite was used as the homogeneous catalyst. The liquid products obtained in the aqueous phase were detected as organic acids, aldehydes, ketones, furfurals and phenols. The gas products were consisted of hydrogen, carbon dioxide, methane, and as minors; carbon monoxide and low molecular weight hydrocarbons (ethane, propane, etc.). Above 500 °C, all biomass samples yielded 50–55 vol% of CH₄ and H₂ while the CO₂ composition was around 40 vol% as the gas product.     

An innovative biomass gasification process and its coupling with microturbine and fuel cell systems

The use of biomass, wood in particular, is one of the oldest forms of producing energy for heating or cooking. Nowadays, new technologies concerning the utilisation of biomass or waste residues are in demand and the trend to use them in decentralised applications for combined heat and power (CHP) production provides an attractive challenge to develop them. At the TU München an innovative allothermal gasification technology, the Biomass Heatpipe Reformer (BioHPR) has been developed. The aim of this project was to integrate the technology of liquid metal heatpipes in the gasification process in order to produce a hydrogen rich product gas from biomass or residues. The gasification product can be further used in microturbine or SOFC systems. The present paper presents the aforementioned gasification technology, its coupling with innovative CHP systems (with microturbine or fuel cells) and investigates, through the simulation of these systems, the optimum conditions of the integrated systems in order to reach the highest possible efficiencies.     

Clean combustion of solid fuels

A chemical-looping process is proposed for the clean combustion of solid fuels for electric power or heat generation. The process is based on coal gasification with CO₂ to produce CO. The CO then reduces CaSO₄, which is used as an oxygen carrier, in a separate reactor to give CaS and CO₂. A portion of the CO₂ is recycled for the gasification stage and the rest can be sent for sequestration. The CaS is sent to another reactor for oxidation with air and to generate heat or power. The overall thermal effect is the same as direct combustion, but separation of CO₂ and other pollutants, such as sulphur, is achieved. In comparison with conventional chemical-looping combustion of natural gas, much less water is present in the CO₂ product, and hence the loss of heat energy and corrosion of the fuel–reactor system can be reduced.     

生物质流化床气化技术应用研究现状

按所得产品不同,可将生物质气化技术分为制氢、发电和合成液体燃料3大类。文章介绍了生物质流化床水蒸气气化制氢、催化气化制氢和超临界水气化制氢的工艺特点;分析了生物质流化床气化发电的技术、经济可行性;简述了生物质流化床气化合成液体燃料的研究现状;指出气化产出气化学当量比调变、焦油去除问题和合成气净化是生物质流化床气化技术应用的主要瓶颈,认为定向气化是今后研究的主要方向。     

Photochemical hydrocarbon fuel regeneration: Hydrogen-rich fuel from CO2

This paper presents the concept of photochemical hydrocarbon fuel regeneration by CO₂ transformation to hydrogen-rich fuel. The first stage of this system is CO₂ capture and algae (Chlorella vulgaris) growing. The second stage is the gasification of algae biomass to produce hydrogen-rich gas and its combustion. To compile the heat and mass balance, the thermodynamic analysis was performed under various operating parameters: temperature 400–800 °C, pressure 1–10 bar 1 kg of biomass was gasified with 1.2 kg of water. The heat of combustion of hydrogen-rich gas after gasification is up to 43% higher than the heat of combustion of initial biomass. The fuel regeneration degree is up to 0.9 when 30% of CO₂ is captured by water and proceded by algae. Moreover, the analyzed photochemical fuel regeneration system allows heat recuperation. The heat regeneration degree is calculated and the maximum value is about 0.9 is reached at 600 °C.