Kinetic modeling and optimization of biomass pyrolysis for bio-oil production

Thermo-kinetic models for biomass pyrolysis were simulated under both isothermal and non-isothermal conditions to predict the optimum parameters for bio-oil production. A comparative study for wood, sewage sludge, and newspaper print pyrolysis was conducted. The models were numerically solved by using the fourth order Runge–Kutta method in Matlab-7. It was also observed that newspaper print acquired least pyrolysis time to attain optimum bio-oil yield followed by wood and sewage sludge under the identical conditions of temperature and heating rate. Thus, at 10 K/min, the optimum pyrolysis time was 21.0, 23.8, and 42.6 min for newspaper print, wood, and sewage sludge, respectively, whereas the maximum bio-oil yield predicted was 68, 52, and 36%, respectively.     

生物质快速热解制生物油的工艺分析

文章利用Aspen Plus软件建立了一个完整的生物质快速热解制生物油的流程模型,并详细描述模型的建立过程,模型包括原料的预处理、快速热解、焦炭和不冷凝气体的燃烧3个部分。通过对日处理2 000 t玉米秸秆的快速热解制生物油工厂各工段进行模拟,结果表明,整个生产过程各种形式的能耗为468.73×109J/h,能量产出为531.6×109J/h,能量产出大于能量消耗;将能量折算成标准煤用量后可知,生产1 kg生物油的能耗相当于0.758 8 kg标准煤,同时产出的能量相当于0.860 6 kg标准煤;焦炭的燃烧量为总量的86%时,可以满足快速热解过程的能量需求。     

Optimization and characterization studies on bio-oil production from palm shell by pyrolysis using response surface methodology

In this work palm shell waste was pyrolyzed to produces bio-oil. The effects of several parameters on the pyrolysis efficiency were tested to identify the optimal bio-oil production conditions. The tested parameters include temperature, N₂ flow rate, feed-stock particle size, and reaction time. The experiments were conducted using a fix-bed reactor. The efficient response surface methodology (RSM), with a central composite design (CCD), were used for modeling and optimization the process parameters. The results showed that the second-order polynomial equation explains adequately the non-linear nature of the modeled response. An R² value of 0.9337 indicates a sufficient adjustment of the model with the experimental data. The optimal conditions found to be at the temperature of 500 °C, N₂ flow rate of 2 L/min, particle size of 2 mm and reaction time of 60 min and yield of bio-oil was approximately obtained 46.4 wt %. In addition, Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) were used to characterize the gained bio-oil under the optimum condition.     

Hydrogen-rich gas production from a biomass pyrolysis gas by using a plasmatron

Pyrolysis and gasification is an energy conversion technology process that produces industrially useful syngas from various biomasses. However, due to the tars in the product gases generated from the pyrolysis/gasification of biomass, this process damages and causes operation problems with equipment that use product gases such as gas turbines and internal engines.     

A review on current status of hydrogen production from bio-oil

Increase in energy demand and growing environmental awareness has increased interest for alternative renewable energy sources over the last few years. Hydrogen produces only water during combustion, and therefore, it is seen as an alternative fuel for locomotive application. Nonetheless, hydrogen is not an energy source; rather it is an energy carrier. Different techniques are being explored to find an economical way of generating hydrogen from renewable resources. Hydrogen production from water using sunlight is still expensive. Biomass is another alternative to produce hydrogen. Bio-oil derived from biomass using a fast pyrolysis is a potential source for hydrogen production. Although different techniques have been employed to produce hydrogen from bio-oil, significant effort has been put into steam reforming process. This paper reviews major hydrogen production techniques with a great deal of importance given to steam reforming. The important factors that are known to affect hydrogen yield are temperature, steam to carbon ratio, and catalyst type. Literature review of bio-oil steam reforming technique has been done, and a comparison of experimental conditions has been carried out. However, as a major shortcoming, this technique is accompanied by the formation of carbonaceous deposits over the catalyst surface rendering it inactive and requiring frequent regeneration. Coke formation has been cited as the major disadvantage of bio-oil reforming, and it is more pronounced when Ni based catalysts are used.     

农林生物质热裂解制取合成气的研究

以树叶为原料，利用热裂解装置进行了试验。并对裂解产物的组成进行了分析。结果表明：树叶热裂解产物为生物油、合成气和炭，其合成气成分主要由CO、CH4、H2和水蒸气组成。     

Distributed production of hydrogen by auto-thermal reforming of fast pyrolysis bio-oil

We demonstrated an auto-thermal reforming process for producing hydrogen from biomass pyrolysis liquids. Using a noble metal catalyst (0.5% Pt/Al₂O₃ from BASF) at a methane-equivalent space velocity of around 2000 h⁻¹, a reformer temperature of 800 °C–850 °C, a steam-to-carbon ratio of 2.8–4.0, and an oxygen-to-carbon ratio of 0.9–1.1, we produced 9–11 g of hydrogen per 100 g of fast pyrolysis bio-oil, which corresponds to 70%–83% of the stoichiometric potential. The elemental composition of bio-oil and the bio-oil carbon-to-gas conversion, which ranged from 70% to 89%, had the most significant impact on the yield of hydrogen. Because of incomplete volatility the remaining 11%–30% of bio-oil carbon formed deposits in the evaporator. Assuming the same process efficiency as that in the laboratory unit, the cost of hydrogen production in a 1500 kg/day plant was estimated at $4.26/kg with the feedstock, fast pyrolysis bio-oil, contributing 56.3% of the production cost.     

Economic tradeoff between biochar and bio-oil production via pyrolysis

This paper examines some of the economic tradeoffs in the joint production of biochar and bio-oil from cellulosic biomass. The pyrolysis process can be performed at different final temperatures, and with different heating rates. While most carbonization technologies operating at low heating rates (large biomass particles) result in higher yields of charcoal, fast pyrolysis (which processes small biomass particles) is the preferred technology to produce bio-oils. Varying operational and design parameters can change the relative quantity and quality of biochar and bio-oil produced for a given feedstock. These changes in quantity and quality of both products affect the potential revenue from their production and sale. We estimate quadratic production functions for biochar and bio-oil. The results are then used to calculate a product transformation curve that characterizes the yields of bio-oil and biochar that can be produced for a given amount of feedstock, movement along the curve corresponds to changes in temperatures, and it can be used to infer optimal pyrolysis temperature settings for a given ratio of biochar and bio-oil prices.     

Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review

The past decades have seen increasing interest in developing pyrolysis pathways to produce biofuels and bio-based chemicals from lignocellulosic biomass. Pyrolysis is a key stage in other thermochemical conversion processes, such as combustion and gasification. Understanding the reaction mechanisms of biomass pyrolysis will facilitate the process optimization and reactor design of commercial-scale biorefineries. However, the multiscale complexity of the biomass structures and reactions involved in pyrolysis make it challenging to elucidate the mechanism. This article provides a broad review of the state-of-art biomass pyrolysis research. Considering the complexity of the biomass structure, the pyrolysis characteristics of its three major individual components (cellulose, hemicellulose and lignin) are discussed in detail. Recently developed experimental technologies, such as Py-GC–MS/FID, TG-MS/TG-FTIR, in situ spectroscopy, 2D-PCIS, isotopic labeling method, in situ EPR and PIMS have been employed for biomass pyrolysis research, including online monitoring of the evolution of key intermediate products and the qualitative and quantitative measurement of the pyrolysis products. Based on experimental results, many macroscopic kinetic modeling methods with comprehensive mechanism schemes, such as the distributed activation energy model (DAEM), isoconversional method, detailed lumped kinetic model, kinetic Monte Carlo model, have been developed to simulate the mass loss behavior during biomass pyrolysis and to predict the resulting product distribution. Combined with molecular simulations of the elemental reaction routes, an in-depth understanding of the biomass pyrolysis mechanism may be obtained. Aiming to further improve the quality of pyrolysis products, the effects of various catalytic methods and feedstock pretreatment technologies on the pyrolysis behavior are also reviewed. At last, a brief conclusion for the challenge and perspectives of biomass pyrolysis is provided.     

Investigation on hydrogen production by catalytic steam reforming of maize stalk fast pyrolysis bio-oil

Hydrogen production via catalytic steam reforming of maize stalk fast pyrolysis bio-oil over the nickel/alumina supported catalysts promoted with cerium was studied using a laboratory scale fixed bed coupled with Fourier transform infrared spectroscopy/thermal conductivity detection analysis (FTIR/TCD). The effects of nickel loading, reaction temperature, water to carbon molar ratio (WCMR) and bio-oil weight hourly space velocity (W_bHSV) on hydrogen production were investigated. The highest hydrogen yield of 71.4% was obtained over the 14.9%Ni-2.0%Ce/A1₂O₃ catalyst under the reforming conditions of temperature = 900 °C, WCMR = 6 and W_bHSV = 12 h⁻¹. Increasing reaction temperature from 600 to 900 °C resulted in the significant increase of hydrogen yield. The hydrogen yield was significantly enhanced by increasing the WCMR from 1 to 3, whereas it increased slightly by further increasing WCMR. The hydrogen yield decreased with the increase of W_bHSV. Meanwhile, the coke deposition percentage changed little with increasing W_bHSV up to 12 h⁻¹ and then it increased by 4.5% with the further increase of W_bHSV from 12 to 24 h⁻¹.     

Power generation using fast pyrolysis liquids from biomass

Power production from biomass derived pyrolysis liquids has been under development for the past few years. If technically successful, it would make decentralized bio-energy production possible. Several technologies and system components have been developed by academia, R&D organizations, and industrial companies in many countries. Much experience has been gained and many useful results published. The present work aims at reviewing the most significant experience in power generation from biomass liquids produced by fast pyrolysis processes. Power plant technologies addressed are diesel engines, gas turbines, and natural gas/steam power plants. Main results are reviewed and R&D needs identified for each technology. The analysis shows that even for the most promising solutions long-term demonstration has not yet been achieved. Pyrolysis liquid use in gas turbine plants and in co-firing mode in large power stations are technically most advanced. Recent work with diesel engines also appears quite promising.     

A review of catalytic hydrogen production processes from biomass

Hydrogen is believed to be critical for the energy and environmental sustainability. Hydrogen is a clean energy carrier which can be used for transportation and stationary power generation. However, hydrogen is not readily available in sufficient quantities and the production cost is still high for transportation purpose. The technical challenges to achieve a stable hydrogen economy include improving process efficiencies, lowering the cost of production and harnessing renewable sources for hydrogen production. Lignocellulosic biomass is one of the most abundant forms of renewable resource available. Currently there are not many commercial technologies able to produce hydrogen from biomass. This review focuses on the available technologies and recent developments in biomass conversion to hydrogen. Hydrogen production from biomass is discussed as a two stage process – in the first stage raw biomass is converted to hydrogen substrate in either gas, liquid or solid phase. In the second stage these substrates are catalytically converted to hydrogen.     

Characterization of bio-oil obtained from fruit pulp pyrolysis

Apricot pulps was pyrolyzed in a fixed-bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 5 °C/min. Final temperature range studied was between 300 and 700 °C and the highest liquid product yield was obtained at 550 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. For the optimum conditions, pyrolysis of peach pulp was furthermore studied. Liquid products obtained under the most suitable conditions were characterized by FTIR and ¹H-NMR. In addition, gas chromatography/mass spectrophotometer was achieved on all pyrolysis oils. Characterization showed that bio-oil could be a potential source for synthetic fuels and chemical feedstock.     

Hydrogen production from biomass combining pyrolysis and the secondary decomposition

An efficient method of hydrogen production from biomass was studied in this paper. The pyrolysis of biomass was combined with the secondary decomposition of gaseous intermediate for hydrogen-rich gas production, with the avoidance of N₂ and CO₂ dilution to the energy density of gaseous effluents. In order to acquire the optimum conditions for hydrogen generation, effects of operating parameters on this two-step decomposition of biomass were analyzed through simulation of thermodynamic equilibrium and experiments using Ni/cordierite catalyst. The results indicate that the operating parameters, including pyrolysis temperature 923 K, 18 min of residence time, the secondary decomposition temperature 1123 K and molar steam to carbon ratio 2, satisfy all the criteria for high hydrogen content and energy efficiency. Hydrogen content of above 60% and hydrogen yield of around 65 g/kg biomass were achieved with optimized conditions. The hydrogen-rich gas is preferred for potential utilization in downstream fuel cells for the implementation of distributed energy supply, and is also practical for pure hydrogen production.     

生物质热解制炭与制气一体化研究

在自行设计的管式炉上进行生物质热解制炭与制气一体化研究,对生物质种类和热解终温两个因素进行了实验和分析,得到了生物质热解过程中气体析出的规律和固体炭的产率。当以制炭和制气一体化为目的,在4种生物质原料中选用麦秆,热解终温选择500℃时,可以得到较大的固体炭产率和气体析出浓度。     

Life cycle assessment of electricity generation using fast pyrolysis bio-oil

Biomass is expected to become an important energy source in U.S. electricity generation under state-lead renewable portfolio standards. This paper investigated the greenhouse gas (GHG) emissions for energy generated from forest resources through pyrolysis-based processing. The GHG emissions of producing pyrolysis bio-oil (pyrolysis oil) from different forest resources were first investigated; logging residues collected from natural regeneration mixed hardwood stands, hybrid poplar cultivated and harvested from abandoned agricultural lands, short rotation forestry (SRF) willow plantations and waste wood available at the site of the pyrolysis plant. Effects of biomass transportation were investigated through a range of distances to a central pyrolysis facility through road transport by semi-truck. Pyrolysis oil is assumed to be converted to electrical power through co-combustion in conventional fossil fuels power plants, gas turbine combined cycle (GTCC) and diesel generators. Life cycle GHG emissions were compared with power generated using fossil fuels and power generated using biomass direct combustion in a conventional Rankine power plant. Life cycle GHG savings of 77%–99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion, depending on the biomass feedstock and combustion technologies used. Several scenario analyses were conducted to determine effects of pyrolysis oil transportation distance, N-fertilizer inputs to energy crop plantations, and assumed electricity mixes for pyrolysis oil production.     

A review on operating parameters for optimum liquid oil yield in biomass pyrolysis

Pyrolysis is one of the potential routes to harness energy and useful chemicals from biomass. The major objective of biomass pyrolysis is to produce liquid fuel, which is easier to transport, store and can be an alternative to energy source. The yield and composition of pyrolysis oil depend upon biomass feedstock and operating parameters. It is often necessary to explore about the effect of variables on response yield and instinct about their optimization. This study reviews operating variables from existing literature on biomass pyrolysis. The major operating variables include final pyrolysis temperature, inert gas sweeping, residence times, rate of biomass heating, mineral matter, size of biomass particle and moisture contents of biomass. The scope of this paper is to review the influence of operating parameters on production of pyrolysis oil.     

Biohydrogen production from Imperata cylindrica bio-oil using non-stoichiometric and thermodynamic model

This paper presents a non-stoichiometric and thermodynamic model for steam reforming of Imperata cylindrica bio-oil for biohydrogen production. Thermodynamic analyses of major bio-oil components such as formic acid, propanoic acid, oleic acid, hexadecanoic acid and octanol produced from fast pyrolysis of I. cylindrica was examined. Sensitivity analyses of the operating conditions; temperature (100–1000 °C), pressure (1–10 atm) and steam to fuel ratio (1–10) were determined. The results showed an increase in biohydrogen yield with increasing temperature although the effect of pressure was negligible. Furthermore, increase in steam to fuel ratio favoured biohydrogen production. Maximum yield of 60 ± 10% at 500–810 °C temperature range and steam to fuel ratio 5–9 was obtained for formic acid, propanoic acid and octanol. The heavier components hexadecanoic and oleic acid maximum hydrogen yield are 40% (740 °C and S/F = 9) and 43% (810 °C and S/F = 8) respectively. However, the effect of pressure on biohydrogen yield at the selected reforming temperatures was negligible. Overall, the results of the study demonstrate that the non-stoichiometry and thermodynamic model can successfully predict biohydrogen yield as well as the composition of gas mixtures from the gasification and steam reforming of bio-oil from biomass resources. This will serve as a useful guide for further experimental works and process development.     

Two-step steam pyrolysis of biomass for hydrogen production

In this study, different char based catalysts were evaluated in order to increase hydrogen production from the steam pyrolysis of olive pomace in two stage fixed bed reactor system. Biomass char, nickel loaded biomass char, coal char and nickel or iron loaded coal chars were used as catalyst. Acid washed biomass char was also tested to investigate the effect of inorganics in char on catalytic activity for hydrogen production. Catalysts were characterized by using Brunauer–Emmet–Teller (BET) method, X-ray diffraction (XRD) analyzer, X-ray fluorescence (XRF) and thermogravimetric analyzer (TGA). The results showed that the steam in absence of catalyst had no influence on hydrogen production. Increase in catalytic bed temperature (from 500 °C to 700 °C) enhanced hydrogen production in presence of Ni-impregnated and non-impregnated biomass char. Inherent inorganic content of char had great effect on hydrogen production. Ni based biomass char exhibited the highest catalytic activity in terms of hydrogen production. Besides, Ni and Fe based coal char had catalytic activity on H₂ production. On the other hand, the results showed that biomass char was not thermally stable under steam pyrolysis conditions. Weight loss of catalyst during steam pyrolysis could be attributed to steam gasification of biomass char itself. In contrast, properties of coal char based catalysts after steam pyrolysis process remained nearly unchanged, leading to better thermal stability than biomass char.     

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 °C with N₂ as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N₂, particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 °C) and 2 L/min of N₂ flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques.