Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 2: Gasification systems

Gasification as a thermo-chemical process is defined and limited to combustion and pyrolysis. The gasification of biomass is a thermal treatment, which results in a high production of gaseous products and small quantities of char and ash. The solid phase usually presents a carbon content higher than 76%, which makes it possible to use it directly for industrial purposes. The gaseous products can be burned to generate heat or electricity, or they can potentially be used in the synthesis of liquid transportation fuels, H₂, or chemicals. On the other hand, the liquid phase can be used as fuel in boilers, gas turbines or diesel engines, both for heat or electric power generation. However, the main purpose of biomass gasification is the production of low- or medium heating value gas which can be used as fuel gas in an internal combustion engine for power production. In addition to limiting applications and often compounding environmental problems, these technologies are an inefficient source of usable energy.     

Pyrolysis pretreatment of biomass for entrained-flow gasification

The biomass for entrained-flow gasification needs to be pretreated to significantly increase its heating value and to make it more readily transportable. The pyrolysis pretreatment was conducted in a lab scale fixed-bed reactor; the reactor was heated to elevate the temperature at 5 °C/min before holding at the desired pyrolysis temperature for 1.5 h a fixed time. The effects of pyrolysis temperature on the yield, composition and heating value of the gaseous, liquid and solid products were determined. The pyrolysis removed most oxygenated constituents of rice straw while significantly increased its energy density. Meantime, it changes the physical properties of biomass powders. The results show that the angle of repose, the angle of internal friction of semi-char decrease obviously; the bulk density of semi-char is bigger than that of biomass. This could favor the feeding of biomass. Considering yield and heating value of the solid semi-char product and the feeding problem, the best pyrolysis temperature was 400 °C. The results of this study have confirmed the feasibility of employing pyrolyzed biomass for entrained-flow gasification; they are useful for the additional studies that will be necessary for designing an efficient biomass entrained-flow gasification system.     

Pyrolysis as a technique for separating heavy metals from hyperaccumulators. Part II: Lab-scale pyrolysis of synthetic hyperaccumulator biomass

Synthetic hyperaccumulator biomass (SHB) impregnated with Ni, Zn, Cu, Co or Cr was used to conduct 11 experiments in a lab-scale fluidized bed reactor. Two runs with blank corn stover, with no metal added, were also conducted. The reactor was operated in an entrained mode in a oxygen-free (N₂) environment at 873 K and 1 atm. The apparent gas residence time through the lab-scale reactor was 0.6 s at 873 K.

The material balance for the lab-scale experiments on N₂-free basis varied between 81% and 98%. The presence of a heavy metal in the SHB decreased the char yield and increased the tar yield, compared to the blank. The char and gas yields appeared to depend on the form of the metal salt used to prepare the SHB. However, the metal distribution in the product streams did not seem to be influenced by the chemical form of the metal salt used to prepare the SHB. Greater than 98.5% of the metal in the product stream was concentrated in the char formed by pyrolyzing and gasifying the SHB in the reactor. The metal concentration in the char varied between 0.7 and 15.3% depending on the type of metal in the SHB. However, the metal concentration was increased 4 to 6 times in the char compared to the feed.     

Pyrolysis characteristics of RDF and HPDE blends with biomass

The main objective of this work was to study refuse-derived fuels (RDF) and high-density polyethylene (HDPE) upgrading by pyrolysis of blends of these materials with wood. The study considered three operational conditions: cracking temperature, heating rate, and different wt.% of RDF and HDPE. The results demonstrate that the cracking temperature of 500 °C and the faster heating rates increased the liquid yield for RDF blends. On the other hand, HDPE blends favor gas production at 550 °C and faster heating rates, which enhance the process operativity because polymeric materials generate waxes and are reduced beneath such conditions. Finally, produced gas LHV increases as RDF and HDPE were added. For example, the LHV of the produced gas only with wood at 550 °C and 20 °C/min was 10.34 MJ/m³ and with 25 wt% HDPE was 14.82 MJ/m³.     

Pyrolysis of biomass in a semi-industrial scale reactor: Study of the fuel-nitrogen oxidation during combustion of volatiles

In this work, an experimental study of the NOx-fuel formation, carried out on a semi-industrial scale reactor during combustion of volatiles of the pyrolysis, is performed. Two different biomasses with different nitrogen contents such as a mixture of organic sludge and wood were tested. Results show that the temperature of pyrolysis does not obviously affect the production of NOx-fuel because of the most active precursors (NH₃ and HCN) are already released at low temperatures (400 °C). In the case of sludge mixture, the combustion conditions play the discriminating role in the production of NOx-fuel: the higher the excess air ratio the larger the production of nitrogen oxides from N-fuel.     

A review of recent laboratory research and commercial developments in fast pyrolysis and upgrading

Robust alternative technology choices are required in the paradigm shift from the current crude oil-reliant transport fuel platform to a sustainable, more flexible transport infrastructure. In this vein, fast pyrolysis of biomass and upgrading of the product is deemed to have potential as a technology solution. The objective of this review is to provide an update on recent laboratory research and commercial developments in fast pyrolysis and upgrading techniques. Fast pyrolysis is a relatively mature technology and is on the verge of commercialisation. While upgrading of bio-oils is currently confined to laboratory and pilot scale, an increased understanding of upgrading processes has been achieved in recent times.     

Hydro-upgrading of bio-oils derived from pyrolysis of biomass with different H/Ceff ratios in tetralin over Pt/C and Ru/C

Pyrolysis oils with different effective hydrogen (H/C_eff) ratios are mixed with tetralin at a mass ratio of 1:1 and treated at 400 °C for 2 h under 6 MPa H₂ over Pt/C and Ru/C, respectively, to examine the effect of H/C_eff ratio on the yield and quality of the upgraded oil. Pyrolysis oil with higher H/C_eff ratios results in an upgraded oil with higher yield and H/C_eff ratios. The highest S and O reduction ratios of 96.11% and 56.26% are achieved with added Pt/C at an H/C_eff ratio of 1.39 of the feedstock. In comparison, the highest N reduction ratios of 34.50% is achieved with added Ru/C at an H/C_eff ratio of 1.38 of the feedstock. The N and S poison the catalyst's active sites and reduce the deoxygenation efficiency. Thus, we view that the H/C_eff plays a vital role in improving the properties of the bio-oil.     

Premium quality fuels and chemicals from the fluidised bed pyrolysis of biomass with zeolite catalyst upgrading

Biomass in the form of pine wood was pyrolysed in an externally heated fluidised bed pyrolysis reactor with nitrogen as the fluidising gas. A section of the freeboard of the reactor was packed with zeolite ZSM-5 catalyst. The pyrolysis oils before and after catalysis were collected in a series of condensers and cold traps. In addition, gases were analysed off-line by packed column gas chromatography. The composition of the oils and gases were determined before and after catalysis in relation to process conditions. The oils were analysed by liquid chromatography followed by gas chromatography/mass spectrometry. The results showed that the oils before catalysis were highly oxygenated, after catalysis the oils were markedly reduced in oxygenated species with an increase in aromatic species, producing a premium grade gasoline type fuel. The gases were CO₂, CO, H₂, CH₄, C₂H₄ and C₃H₆ and minor concentrations of other hydrocarbon gases. After catalysis the concentration of CO₂ and CO were increased. Detailed analysis of the upgraded oils showed that there were high concentrations of economically valuable chemicals. However, biologically active polycyclic aromatic species were also present in the catalysed oil, which increased with increasing catalyst temperature.     

Semi-quantitative and multivariate analysis of the thermal degradation of carbon-oxygen double bonds in biomass

The aim of this paper was to investigate biomass pyrolysis using diffuse reflectance infrared Fourier transform (DRIFT) studies. The pyrolysis tests were conducted in a nitrogen atmosphere from room temperature (RT) to 600 °C. Infrared techniques provide fast, low-cost and non-destructive analysis. A combination of qualitative and quantitative analysis was applied. Pyrolysis was conducted in an environmental chamber which enabled in-situ spectral measurement. The mass of samples used in DRIFT tests was 3.0 ± 0.1 mg. A semi-quantitative analysis of the oxidation stage was performed for each biomass sample. For a variety of biomass samples, pyrolysis in the temperature range of 250–350° lead to an increase in carbon-carbon double bonds which were formed from cellulose decomposition. The research results showed that the wavenumber assigned to the CO band in carboxylic acids and esters (1742 cm^?1) depends on the temperature and varies with different biomass samples. Also, the intensity of the CO band for ketones and aldehydes (1665 cm^?1) varies with the type of biomass and the pyrolysis temperature. Principal component analysis (PCA) gave information about the similarity of reactions occurring during the pyrolysis of various biomass samples. Efficient conversion of biomass resources to energy requires accurate and detailed knowledge of chemical behaviour during degradation.     

Pyrolysis of North-American grass species: Effect of feedstock composition and taxonomy on pyrolysis products

In the Midwest of the U.S., several members of the Poaceae family can be grown as bioenergy crops. Besides Miscanthus and switchgrass, which have been extensively studied, native Midwestern grasses such as big bluestem, coastal panicgrass, deertongue, indiangrass, sandreed and sideoats grama can be grown in monoculture or polyculture plantations. In addition to climate, soil fertility and water availability, the selection of bioenergy crops depends on the choice of conversion technology. One such technology, fast pyrolysis, is a thermochemical approach for converting biomass into a liquid product known as bio-oil, a hydrocarbon fuel intermediate. In this research, the eight aforementioned grass varieties were characterized by fiber and metal analyses as well as calorimetry and thermal gravimetry. Conversion by analytical pyrolysis showed that although variability exists, all eight grasses produced a similar spectrum of chemical compounds. Principal component analysis of pyrolysis-GC/MS data detected statistically significant differences amongst the grass varieties on the basis of six key chemical markers: glycolaldehyde, acetic acid, acetol, methyl glyoxal, 4-vinylphenol and levoglucosan. Though taxonomic classification was not found to affect product composition, correlation analysis verified that biomass composition and thermal properties might be responsible for the differences in pyrolysis products.     

Characterization of the physicochemical and structural evolution of biomass particles during combined pyrolysis and CO2 gasification

The combination of pyrolysis and CO₂ gasification was studied to synergistically improve the syngas yield and biochar quality. The subsequent 60-min CO₂ gasification at 800 °C after pyrolysis increased the syngas yield from 23.4% to 40.7% while decreasing the yields of biochar and bio-oil from 27.3% to 17.1% and from 49.3% to 42.2%, respectively. The BET area of the biochar obtained by the subsequent 60-min CO₂ gasification at 800 °C was 384.5 m²/g, compared to 6.8 m²/g for the biochar obtained by the 60-min pyrolysis at 800 °C, and 1.4 m²/g for the raw biomass. The biochar obtained above 500 °C was virtually amorphous.     

Effect of cellulose and lignin content on pyrolysis and combustion characteristics for several types of biomass

Fundamental pyrolysis and combustion behaviors for several types of biomass are tested by a thermo-gravimetric analyzer. The main compositions of cellulose and lignin contents for several types of biomass are analyzed chemically. Based on the main composition results obtained, the experimental results for the actual biomass samples are compared with those for the simulated biomass, which is made of the mixture of the cellulose with lignin chemical. The morphological changes before and after the reactions are also observed by a scanning electron microscope. The main compositions in the biomass consisted of cellulose and lignin. The cellulose content was more than lignin for the biomass samples selected in this study. The reaction for the actual biomass samples proceeded with the two stages. The first and second stage corresponded to devolatilization and char combustion during combustion, respectively. The first stage showed rapid mass decrease caused by cellulose decomposition. At the second stage, lignin decomposed for pyrolysis and its char burned for combustion. For the biomass with higher cellulose content, the pyrolysis rate became faster. While, the biomass with higher lignin content gave slower pyrolysis rate. The cellulose and lignin content in the biomasses was one of the important parameters to evaluate the pyrolysis characteristics. The combustion characteristics for the actual biomass depends on the char morphology produced.     

Waste biomass to liquids: Low temperature conversion of sugarcane bagasse to bio-oil. The effect of combined hydrolysis treatments

This article describes the influence of different sugarcane bagasse hydrolysis pretreatments on modifications to biomass feedstock and the characteristics of the resultant pyrolysis products. Sugarcane bagasse was pretreated with acid, alkaline or sequential acid/alkaline solutions and pretreated samples were then subjected to a low temperature conversion (LTC) process under He or O₂/He atmospheres at 350-450 °C. Both pretreated samples and sugarcane bagasse in natura were analyzed by determination of their chemical composition and by thermogravimetric, FTIR and SEM analyses. The gases yielded during LTC were monitored on-line by quadrupole mass spectrometry, and the liquid fractions obtained were characterized by FTIR and ¹H and ¹³C NMR. Irrespective of the sugarcane bagasse pretreatment applied, the main bio-oil component obtained was levoglucosan. However, the LTC yield of bio-oil depended on the hydrolysis treatment of the biomass and decreased in the presence of O₂. The acid hydrolysis pretreatment increased the LTC bio-oil yield notably.     

Fundamentals, kinetics and endothermicity of the biomass pyrolysis reaction

The paper reviews the pyrolysis of biomass constituents and possible secondary reactions. Biomass pyrolysis yields mostly liquid and solid fuel, easy to store and transport.Relevant working conditions for experiments and large-scale operation are: (i) biomass particles < 200 μm, (ii) a particle heating rate of at least about 80 K min⁻¹ and (iii) a reactor environment where the internal resistance to heat penetration is smaller than the external resistance to heat transfer (Biot-number, Bi < 1).The circumstances of TGA and DSC experiments meet these requirements and fully determine the reaction kinetics and endothermicity of the pyrolysis reaction. The reaction rate constant and the heat of reaction are essential parameters in the design of a pyrolysis reactor. For most of the biomass species tested, the first order reaction rate constant is large and >0.5 s⁻¹. The heat of reaction ranges from 207 to 434 kJ kg⁻¹. All results tie in with literature data, although the reader is cautioned in using literature data since experiments were not always performed under relevant testing conditions.     

A study on torrefaction of various biomass materials and its impact on lignocellulosic structure simulated by a thermogravimetry

Torrefaction processes of four kinds of biomass materials, including bamboo, willow, coconut shell and wood (Ficus benjamina L.), were investigated using the thermogravimetric analysis (TGA). Particular emphasis is placed on the impact of torrefaction on hemicellulose, cellulose and lignin contained in the biomass. Two different torrefaction processes, consisting of a light torrefaction process at 240 °C and a severe torrefaction process at 275 °C, were considered. From the torrefaction processes, the biomass could be divided into two groups; one was the relatively active biomass such as bamboo and willow, and the other was the relatively inactive biomass composed of coconut shell and wood. When the light torrefaction was performed, the results indicated that the hemicellulose contained in the biomass was destroyed in a significant way, whereas cellulose and lignin were affected only slightly. Once the severe torrefaction was carried out, it further had a noticeable effect on cellulose, especially in the bamboo and willow. The light torrefaction and severe torrefaction were followed by a chemically frozen zone, regardless of what the biomass was. From the viewpoint of torrefaction application, the investigated biomass torrefied in less than 1 h with light torrefaction is an appropriate operation for producing fuels with higher energy density.     

Converting Eucalyptus biomass into ethanol: Financial and sensitivity analysis in a co-current dilute acid process. Part II

The technical and financial performance of high yield Eucalyptus biomass in a co-current dilute acid pretreatment followed by enzymatic hydrolysis process was simulated using WinGEMS^® and Excel^®. Average ethanol yield per dry Mg of Eucalyptus biomass was approximately 347.6 L of ethanol (with average carbohydrate content in the biomass around 66.1%) at a cost of $0.49 L⁻¹ of ethanol, cash cost of ∼ $0.46 L⁻¹ and CAPEX of $1.03 L⁻¹ of ethanol. The main cost drivers are: biomass, enzyme, tax, fuel (gasoline), depreciation and labor. Profitability of the process is very sensitive to biomass cost, carbohydrate content (%) in biomass and enzyme cost. Biomass delivered cost was simulated and financially evaluated in Part I; here in Part II the conversion of this raw material into cellulosic ethanol using the dilute acid process is evaluated.     

Recent progress in thermochemical techniques to produce hydrogen gas from biomass: A state of the art review

The present work comprehensively covers the literature that describes the thermochemical techniques of hydrogen production from biomass. This survey highlights the current approaches, relevant methods, technologies and resources adopted for high yield hydrogen production. Prominent thermochemical methods i.e. pyrolysis, gasification, supercritical water gasification, hydrothermal upgrading followed by steam gasification, bio-oil reforming, and pyrolysis inline reforming have been discussed thoroughly in view of the current research trend and latest emerging technologies. Influences of important factors and parameters on hydrogen yield, such as biomass type, temperature, steam to biomass ratio, retention time, biomass particle size, heating rate, etc. have also been extensively studied. Catalyst is a vital integrant that has received enough attention due to its encouraging influence on hydrogen production. Literature confirms that hydrogen obtained from biomass has high-energy efficiency and potential to reduce greenhouse gases hence, it deserves versatile applications in the coming future. The study also reveals that hydrogen production through steam reforming, pyrolysis, and in-line reforming deliver a considerable amount of hydrogen from biomass with higher process efficiency. It has been identified that higher temperature, suitable steam to biomass ratio and catalyst type favor useful hydrogen yield. Nevertheless, hydrogen is not readily available in the sufficient amount and production cost is still high. Tar generation during thermochemical processing of biomass is also a concern and requires consistent efforts to minimize it.     

Economic analysis of energy production from coal/biomass upgrading; Part 1: Hydrogen production

Hydrogen production by steam-gasification is an interesting method compared to other common methods which has a wide range of applications including Proton Exchange Membrane (PEM) fuel cells and gas engines. The current research was aimed to provide a detailed economic study on gasification of biomass and coal for syngas and hydrogen production using the Aspen Plus software. The effect of plant size on hydrogen selling price was evaluated from biomass, coal, and biomass-coal gasification. With the plant size increasing from 200 tonnes/day to 400 tonnes/day, the hydrogen selling price decreased sharply from 11.5 to 9.1 $/m³ for biomass, from 10.4 to 8.2 $/m³ for coal, and from 10.1 to 7.7 $/m³ which means that the particle size has a key role in the process, and operation in larger plants is more affordable.     

Thermal energy storage in building integrated thermal systems: A review. Part 1. active storage systems

Energy consumed by heating, ventilation and air conditioning systems (HVAC) in buildings represents an important part of the global energy consumed in Europe. Thermal energy storage is considered as a promising technology to improve the energy efficiency of these systems, and if incorporated in the building envelope the energy demand can be reduced. Many studies are on applications of thermal energy storage in buildings, but few consider their integration in the building. The inclusion of thermal storage in a functional and constructive way could promote these systems in the commercial and residential building sector, as well as providing user-friendly tools to architects and engineers to help implementation at the design stage. The aim of this paper is to review and identify thermal storage building integrated systems and to classify them depending on the location of the thermal storage system.