Fast Pyrolysis Development - Venderbosch Et Al. 2010

Review
Fast pyrolysis technology development

RH Venderbosch, BTG Biomass Technology Group BV, Enschede, the Netherlands W Prins, Faculty of Bioscience Engineering, University of Ghent, Belgium and BTG Biomass Technology Group BV, Enschede, the Netherlands Received October 21, 2009; revised version received November 30, 2009; accepted December 14, 2009 Published online in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.205; Biofuels, Bioprod. Bioref. 4:178-208 (2010) Abstract: While the intention of slow pyrolysis is to produce mainly charcoal, fast pyrolysis is meant to convert biomass to a maximum quantity of liquids (bio-oil). Both processes have in common that the biomass feedstock is densied to reduce storage space and transport costs. A comfortable, more stable and cleaner intermediate energy carrier is obtained, which is much more uniform and well dened. In this review, the principles of fast pyrolysis are discussed, and the main technologies reviewed (demo scale: uid bed, rotating cone and vacuum pyrolysis; pilot plant: ablative and twin screw pyrolysis). Possible product applications are discussed in relation to the bio-oil properties. General mass and energy balance are provided as well, together with some remarks on the economics. Challenges for the coming years are (1) improvement of the reliability of pyrolysis reactors and processes; (2) the demonstration of the oils utilization in boilers, engines and turbines; and (3) the development of technologies for the production of chemicals and biofuels from pyrolysis oils. One important conclusion in relation to biofuel production is that the type of oxygen functionalities (viz. as an alcohol, ketone, aldehyde, ether, or ester) in the oil should be controlled, rather then merely focusing on a reduction of just the oxygen content itself. 2010 Society of Chemical Industry and John Wiley & Sons, Ltd Keywords: pyrolysis, technology, review, bio-oil, biomass
Introduction
nvironmental concerns and possible future shortages have boosted research into alternatives for fossil-derived products. Biomass is abundantly available worldwide and considered to be renewable. Despite its complexity, the use of biomass is rapidly expanding. Agriculture, petrochemical industries, and individual entrepreneurs, meanwhile, have developed a significant production of socalled first-generation biofuels from vegetable oils (biodiesel), sugar and starch (bioethanol). The scale of production of
these first-generation fuels (<100 MWth) appears to be significantly lower than that of unit operations in traditional petroleum refineries (several GWth s). Obviously the production of first-generation biofuels is in competition with the food/feed industry. This is a non-ethical situation with a limited CO2 reduction potential that is acceptable only to get started while developing the techniques for secondgeneration biofuels derived from lignocellulosic biomass (residues like wood thinning, bagasse, rice husks, straw, etc.). Second-generation biofuels can be made by (1) hydrolysis and fermentation of cellulosic materials to ethanol; (2) gasification
Correspondence to: RH Venderbosch, BTG Biomass Technology Group B.V., Josink Esweg 34, 7545 PN Enschede, The Netherlands. E-mail: venderbosch@btgworld.com
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2010 Society of Chemical Industry and John Wiley & Sons, Ltd
Review: Fast pyrolysis technology development
RH Venderbosch, W Prins
of lignocelluloses to syngas and further conversion to methanol or gasoline/diesel, for example; and (3) liquefaction of lignocelluloses with further upgrading, either by gasification (see 2), or by hydro-de-oxygenation (CO2 and H2O removal). Large-scale implementation of biomass technologies is hindered by a number of adverse biomass properties causing difficulties or excessive costs in its processing. Such problems are in the highly distributed occurrence of biomass and its low annual yields (usually less than 10 ton per hectare (dry and ash-free), as well as in the wide variety in biomass structure and energy density (compare, for example, wood logs with rice husks). To overcome these disadvantages of biomass, one could include a pre-treatment process as a first step. In the overall conversion chain, fast pyrolysis, being such a pre-treatment process, creates a uniform, liquid intermediate that is virtually ash-free and has a significantly increased energy density. It can be produced at a scale matching the size of cost-efficient biomass collection, stored until transport to the nearest harbor, and finally shipped together with the production of many other pyrolysis plants to a central site (e.g., a refinery or a power station) for further conversion to heat, electricity, chemicals, or fuels at any desirable time. The handling and processing of liquids has many advantages in comparison with processing solid or gaseous feed streams. Interest in the production of pyrolysis liquids from biomass has grown rapidly in recent years, due to the potential possibilities of: de-coupling liquid fuel production (scale, time, and location) from its utilization; separating minerals on the site of liquid fuel production (to be recycled to the soil as a nutrient); producing a renewable fuel for boilers, engines, and turbines, power stations and gasifiers; secondary conversion to motor-fuels, additives or special chemicals (biomass refinery); and primary separation of the sugar and lignin fractions in biomass with subsequently further upgrading (biomass refinery).
eries (e.g., conversion of lignin residues to bio-oil (and biochar), fermentation of the fast pyrolysis sugar fraction, etc.). Many reviews on pyrolysis can be found in the literature14 and in three handbooks edited by Bridgwater, 57 while the PyNe website and PyNe (now ThermalNet) newsletters show the state-of-the-art. The reviews should be read with some care, as the data presented do not always reflect the actual case due to a lack of precise information on actual feedstock, processing conditions, variations in feeds used, and a lack of detail on the (usually proprietary) technologies. Pyrolysis processes are carried out in the absence of oxygen, at atmospheric pressure and temperatures ranging from 300 to 600C. Charcoal is the main product of the traditional slow pyrolysis process, in which the biomass (usually wood) is heated slowly to temperatures between 300 and 400C. To the contrary, fast pyrolysis processes are characterized by a high rate of particle heating to temperatures around 500C, and a rapid cooling of the produced vapors to condense the liquids. This yields a maximum quantity of dark-brown mobile liquid with a heating value roughly equal to that of wood, which is approximately half the heating value of fossil fuel oil. The earliest recorded use of this technique was in Egypt, where the product was used for sealing boats.8 In more recent times, a number of chemicals were derived from the liquids as well (e.g., methanol, acetic acids, etc., and liquid smoke). While the function of slow pyrolysis is to produce mainly charcoal and gas, fast pyrolysis is meant to convert biomass into a maximum quantity of liquids. They are both meant to pre-treat the biomass to facilitate transport, storage, and utilization. Principles Thermal decomposition of biomass results in the production of char and non-condensable gas (the main slow pyrolysis products) and condensable vapors (the liquid product aimed at in fast pyrolysis). It is realized by rapid heat transfer to the surface of the particle and subsequent heat penetration into the particle by conduction. For fast pyrolysis conditions, meant to maximize the liquid yield, the temperature development inside the particle, and the corresponding intrinsic reaction kinetics dominate the conversion rates and product distributions. Principally, biomass is decomposed to a mixture of defragmented lignin and (hemi)cellulose, and
An interesting aspect here is that pyrolysis could connect (conventional) agricultural business to (petro)chemical processes. Besides, fast pyrolysis can be integrated with biological processes in many ways, to form dedicated biorefin-
2010 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 4:178208 (2010); DOI: 10.1002/bbb
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fractions derived from extractives (if present). The intention of fast pyrolysis is to prevent the primary decomposition products (1) to be cracked thermally or catalytically (over char formed already) to small non-condensable gas molecules on the one hand; or (2) to be recombined/polymerized to char (precursors) on the other. Such conditions would then lead to a maximum yield of condensable vapors and include the rapid heating of small biomass feed particles. Besides, it is also essential to create a short residence time for the primary products, both inside the decomposing particle and in the equipment before the condenser. For chemicals or fuel application, an additional target would be to control the chemical composition of the condensables; for instance, by applying catalysts. First reactor developers adopted the concept of flash pyrolysis in which small particles (<1 mm) were used to achieve high oil yields. Later research showed that the oil yield is much less dependent on biomass particle size and vapor residence times than originally assumed.9,10 The composition of the oil, however, is sensitive for these parameters. High external heat transfer to the biomass particles can be realized by mixing the cold biomass feed stream intensively with an excess of pre-heated, expectedly inert, heat carrier (e.g., hot sand). A number of reactor designs have been explored that may be capable of achieving high heat transfer rates, such as fluidized beds and mechanical mixing devices. For an efficient heat transfer through the biomass particle, though, a relatively small heat penetration depth is required, which limits the size of biomass particles to, typically, 5 mm. Size here reflects a distance of two times the actual (heat) penetration depth of the particle. For such particles, the decomposition rate is controlled by a combination of intra-particle heat conduction and the decomposition kinetics. Oil yield values observed in continuously operated laboratory reactors and pilot plants, for wood as a feedstock material, are usually in the range of 60 to 70 wt.% (dry-feed basis). Although generally reported in reviews, oil yields over 70% are exceptional and only for well-defined feedstocks as cellulose. Energetic yields are a bit lower, approx. 55 to 65%. It is obvious that the energy left in the byproducts should be used as well; for example, for drying the feedstock and/or steam-electricity production. If the objective is to derive chemicals from the pyrolysis liquid, it is essential to operate the process at the proper conditions (temperature, residence time, feedstock type, and feedstock
pre-treatment) in order to maximize the yield of the specific component aimed at. When fuels are required, less stringent criteria must be met; the conversion of as much biomass energy as possible to the liquid product is then decisive. Until recently, most R&D work has been focused on maximizing the overall oil yield, without paying sufficient attention to the product composition and quality. Next to water, the major components of biomass are: cellulose (mostly glucans), with a composition roughly according to (C6H10O5)n, and n = 500 to 4000; hemicellulose (mostly xylans), with an average composition according to (C5H8O4)n, and n = 50 to 200; and lignin, consisting of highly branched, substituted, mononuclear aromatic polymers, often bound to adjacent cellulose and hemicellulose fibers to form a lignocellulosic complex.
Cellulose, hemicellulose, and lignin all have a different thermal decomposition behavior, and each individually depends also on heating rates and the presence of contaminants.11 A typical temperature dependence of the decomposition through thermo-gravimetric analysis (TGA) for reed, carried out by the University of Groningen is given in Figure I. The total mass loss rate is plotted versus the temperature in Figure IA, while the TGA data are interpreted in terms of cellulose (almost 30%), hemicellulose (25%), and lignin (20%) in lB. The differential plot for these fractions is given on the left hand side against the original biomass data. Hemicellulose is the first component to decompose, starting at about 220C and completed around 400C. Cellulose appears to be stable up to approx. 310C, where after almost all cellulose is converted to non-condensable gas and condensable organic vapors at 320420C. Though lignin may begin to decompose already at 160C, it appears to be a slow, steady process extending up to 800900C. At fast pyrolysis temperatures of around 500C, the conversion of lignin is probably limited to 40%. In general, for fast pyrolysis, a solid residues remains (char, not shown in Fig. 1), which is then mainly derived from lignin and some hemicellulose fractions, respectively 40 and 20 wt-% of the original sample.12 A conclusion from such TGA data can be that the oil is derived mainly from cellulose, and only partially from hemicellulose (depending on the heating rate up to approx. 80% conversion to oil and gas) and lignin (roughly 50% conversion to oil and gas). The explanation is that in the
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0.04 Mass Loss Rate (wt.%/C) Mass Loss Rate (wt.%/C)
0.04
cellulose
0.03
0.03
0.02
0.02
hemicellulose
0.01
0.01
water
lignin
0 0 100 200 300 400 500 Temperature (C)
0 0 100 200 300 400 500 Temperature (C)
Figure 1. Thermogravimetric analysis curve for Reed (A) and the differential plot interpreted in terms of hemicellulose, cellulose and lignin (B). TGA curves are prepared by the University of Groningen.
biomass structure, lignin and hemicellulose are linked through covalent bonds (ester and ether) and cannot be released that easily upon pyrolysis; cellulose and hemicellulose are linked by much weaker hydrogen bonds.13 Indirect evidence for this hypothesis is given by the composition of the pyrolysis-derived char, which has an elemental composition close to that of lignin. The pyrolysis of biomass can be either endothermic or exothermic, depending on the temperature of the reactions and the type of feed. For (hemi)cellulosic materials, the pyrolysis is endothermic at temperatures below about 450C, and exothermic at higher temperatures. As argued already, vapors formed inside the pores of a decomposing biomass particle are subject to further cracking, leading to the formation of additional gas and/or (stabilized) tars. The sugar-like fractions especially can be readily re-polymerized, increasing the overall char yield (mostly ex-bed of the pyrolysis process). This may be the purpose of slow pyrolysis but should be avoided in fast pyrolysis. For the small particles used in fast pyrolysis, secondary cracking inside the particles is relatively unimportant due to a lack of residence time. When the vapor products enter the surrounding gas phase, however, they will further decompose if they are not condensed quickly enough. Although other mechanisms have been proposed as well, Fig. 2 shows a possible reaction pathway for biomass pyrolysis. Schemes like these, including three lumped product classes, were originally proposed by Shafi zadeh et al.14,15 and start with a reaction that is first order in the decomposing component. Unfortunately, there is great variety in the results of reaction rate measurements, even for a single biomass type, such as wood. Published rate and selectivity
expressions maybe useful in describing trends, but they can hardly be used for reliable quantitative predictions.10,1618 It should be realized here that biomass is a natural material, with widely varying structural and compositional properties. Despite all such uncertainties in the required input data, many scientists still propose single particle models based on fundamental chemical and physical phenomena taking place inside the particles. Kinetic data are proposed for the pyrolysis of wood, but a small variation in ash content seriously affects these reaction rates, and probably the pyrolysis pathways themselves. Already stated in 1991, it should not be expected that any simple one-step kinetic scheme can account for all the facts concerning the pyrolytic behavior of [just] carbohydrates.19 Although the predictive power is limited, and insufficient for scaling-up purposes, modeling is still useful to create a better understanding.18
Gas (g) (CO,CO2,CH4) bio-oil (l)
Char (s) + gas (CO2) + bio-oil (l)
Wood (s) Char (s)
Wood vapors (g)
Gas (g) (CO,CO2,CH4) Re-polymerisation
Primary phase Secondary phase decomposition cracking + condensation reactions 450 550C <1 s 400 500C >1 s
atmospheric weeks / months
Figure 2: Representation of the reaction paths for wood pyrolysis.
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Effect of ash A photograph of bio-oil is given in Figure 3. The maximum possible oil yield thus depends on various parameters, and this includes feedstock properties, water content, temperature and vapor residence time. The maximum possible oil yield thus depends on various parameters, and this includes feedstock properties, water content, temperature, and vapor residence time. In addition, ash in the biomass can have a dominant effect on the oil yield and composition.20,21 The trend line in Fig. 4 is based on published data points. In general, the yields of char and gas increase significantly for higher ash contents in the biomass, viz. at the expense of oil yields. Sodium and potassium will have a large impact, but sulfur- and phosphorus-containing ammonium salts can also dramatically affect oil yields and promote char formation.22 Although there is evidence that ash (including metals) can have a catalytic effect on the thermal degradation of biomass during pyrolysis, data like in Fig. 4 should be interpreted
with care as they are derived for different types of biomass as well. Figure 4 may suggest otherwise, but not all ash-like materials are detrimental for the oil yield; silicon and metals other than the alkalis appear quite inactive in the pyrolysis process. It has been suggested that alkali metals have the potential to lower the optimal pyrolysis temperature as well. Consequently, for biomass types with high ash content, which is generally the case for the technological interesting low-valued residues, the oil-yield can drop to values, sometimes below 50 wt.%. Though extremely relevant for both the oil yield and oil quality, limited research has been carried out to understand the effects of ash on the pyrolysis reactions. Oil properties Representative values for wood-derived pyrolysis oil properties are collected from various resources and listed in Table 1. It is a liquid, typically dark red-brown to almost black, a color that depends on the chemical composition and the presence of micro-carbon (Fig. 3). The density of the liquid is
Table 1. The range of elemental composition and properties for wood-derived pyrolysis oil.13 Physical property
Water content (wt.%) pH Density (kg/m ) Elemental analysis (wt.% moisture free) C H N S O Ash 5565 57 0.10.4 0.000.05 Balance 0.010.30 Yields (wt.%) Organic liquid Water Char Gas HHV (MJ/kg) 1619 6075 1015 1015 1020
3
Pyrolysis conditions
1530 2.83.8 105001250 Temperature (K) Gas residence time (s) Particle size (m) Moisture (wt.%) Cellulose (wt.%) Ash (wt.%) 750825 0.52 2002000 212 4555 0.53
Viscosity (315 K, cP) ASTM vacuum Distillation (wt.%) 430 K 466 K 492 K Distillate
251000
~10 ~20 ~40 ~50 Solubility (wt.%) Hexane Toluene Acetone Acetic acid ~1 1520 >95 >95
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about 1200 kg/m3, which is significantly higher than that of fuel oil. It has a distinctive acid, smoky smell, and can irritate the eyes. The viscosity of the oil varies from 25 up to 1000 cP, depending on the water content and the amount of light components in the oil. It is important to note that oil properties depend on feedstock and operating conditions, but may change during storage, a process indicated as ageing, which (by lack of definition) is usually noticed by an increased viscosity in time and a possible phase separation of the oil in a watery phase and a viscous organic phase. Due to the presence of large amounts of oxygenated components, the oil has a polar nature and does not mix readily with hydrocarbons. In general, it contains less nitrogen than petroleum products, and almost no metal and sulfur components. However, some of the nitrogen is transferred to the oil product as well: feed materials with a high nitrogen contents yield oil with higher pH-values and larger amounts of nitrogen in the oil. Degradation products from the biomass constituents include organic acids (like formic and acetic acid), giving the oil its low pH of about 2 to almost 4. The oil attacks carbon steel,
and storage of the oils should be in acid-proof materials like stainless steel or poly-olefins. Water is an integral part of the single-phase chemical solution. The (hydrophilic) bio-oils have water contents of typically 1535 wt.%, and water cannot be removed by conventional methods like distillation. This high water content is a serious drawback if considering the heating values: the higher heating value (HHV) is below 19 MJ/kg (compared to 4244 MJ/kg for conventional fuel oils). Above a certain water-content level, viz. in the range of 30 to 45 wt.%, phase separation may occur. Depending on the type of feedstock and process conditions the ratio of oil over aqueous phase varies from 50:50 to 30:70, and the presence of these two phases can complicate the oils application. In many cases, sufficient drying of the biomass feedstock material prior to pyrolysis prevents phase separation. Applying different condensation temperatures will yield oils with different water contents (affecting the oil yield as well), and there is quite some room for optimization.23 Usually the choice of the feedstock and process (characteristics) will determine the oil quality and possible phases. Beneficial effects of the water content have also been reported, viz. in case of combustion. It causes a decrease in viscosity of the oil (facilitating transport, pumping, and atomization); it improves stability; it lowers the combustion
80 70
Oil and char yield (wt.%)
oil
60 50 40 30
char Trendline oil (Chariamonti et al. 2007)
20
gas
10 0 0 1 2 3 4 5 6 7 8 Ash content (wt.%)

Figure 4. Relationship between oil yield and ash content in the biomass. The solid lines represent trend lines taken from literature,20 while the broken line is a trend line based upon more than 20 data Figure 3. Fast pyrolysis oil. point for wood.21
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temperature and, as a consequence, it may cause a reduction of the NOx emission. Generally speaking, the (organic) oil yield achieved in fast pyrolysis should be as high as possible. Besides, the oil should have a much higher (volumetric) energy content than the original biomass, and must be more stable towards biological degradation. Composition and stability Pyrolysis oils are produced by the rapid quenching of fragmented biomass, these fragments being derived from the biomass constituents, cellulose, hemicellulose, and lignin. The largest fragments that are conveyed to the condenser in the vapor phase have a molecular mass that is far too high for being a gas component at temperatures around 500C. They may be present in the vapor phase as aerosols, or are produced upon freezing the vapors. This liquid product collected in the condenser includes the complete spectrum of oxygenated compounds, with molecular weights ranging from 18 to over 10 000 g/mol, the higher values probably caused by repolymerization of the biomass fragments. Whereas some researchers think the oil is a (micro-)emulsion of these compounds, there is also reason to believe the oil is a mixture of soluble components, likely with water as the solvent and polar sugar constituents behaving as bridging agents in the dissolution of hydrophilic lignin material.24 GC-analysis (including 2D-GC, GC-MS etc) appears, to a certain extent, valuable in the interpretation of the oil quality. However, the usefulness of GC data is limited due to the (unknown) destructive effect of the technique on the oil
composition. GC injection includes vaporization of the feed, which is known to be difficult for pyrolysis oils and causing some coking in the injection part of the system. Moreover, chemical reactions occurring in the GC column cannot be excluded either, and it is questionable whether the components actually detected are really present in the feed oil. Other techniques of which the potentials for pyrolysis-oil analysis are being investigated are Gel Permeation Chromatography (GPC) and High Performance Liquid Chromatography (HPLC), but both methods need to be handled with great care. Fortunately, development of new techniques to footprint the oils is ongoing. As the oil can not be distilled without severe repolymerization and thus chemical degradation, a solvent fractionation technique, illustrated in Fig. 5, is developed to analyze the oil in an alternative way, and reveal the presence of certain fractions present in the oil:25 water solubles (acids, alcohols, diethylethers); ether solubles (aldehydes, ketones, lignin monomers, etc.); ether insolubles ((anhydo)sugars, hydroxyl acids); n-hexane solubles (fatty acids, extractives, etc.); DCM solubles (low molecular lignin fragment, extractives); and DCM insolubles (degraded lignins, high molecular lignin fragments, including solids)
The ether insolubles in particular (the sugar components, a syrup-like fraction) appear to have high oxygen contents (up to 50%) if compared to, for example, the DCM solubles and insolubles (25 to 30% oxygen). Ongoing research is aimed at
Water (by KF titration) Solids (by MeOH-DCM extraction)
BIO-OIL water extraction
N-HEXANE SOLUBLES
Extractives
WATER-SOLUBLES ether extraction
WATER INSOLUBLES DCM extraction DCM SOLUBLES DCM INSOLUBLES

HMM lignin (high molecular lignins, solids)
LMM lignin (low molecular lignins, extractives)
ETHER SOLUBLES
Ether solubles: (Aldehydes, ketons, lignin monomers)
ETHER INSOLUBLES
Sugars (anhydrosugars, anhydro-oligomers, Hydroxyacids (C<10))
Figure 5. Fractionation scheme for chemical characterization.25
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revealing the various components in each fraction, and their effects on storage, stability, upgrading, etc. The results from solvent fractionation and GC-MS can be combined.25 The main part of GC-eluted compounds is in the ether-soluble fraction of the fractionation scheme, with the DCM (in-)solubles not being detected in a GC. Table 2 shows the combined results of solvent extraction, GC/MSD and CHN analyses for reference pine liquid. Although this method may not be the future standard for bio-oil analysis, it could be an important technique relevant to understanding how the oxygen is actually bound to the carbon (alcohol, keton, or as an ether/ester). An important property of pyrolysis oil is its changing characteristics over time. Such an instability can be observed by a viscosity increase during storage, some formation of carbon dioxide, an increased water content, and eventually by phase separation. Definitions to address this unstable character are lacking. The detailed mechanism of this ageing, the causes of it, and the consequences for further use are still unclear, and will depend highly on the various oxygen functionalities in the oil (and therefore
feedstock type, operating conditions, initial quality, storage temperatures, etc.). At room temperature, the ageing of bio-oil occurs over periods of months or years, depending on the type of feedstock, and its initial quality. At elevated temperatures, however, the polymerization reactions are enhanced significantly, and it is therefore recommended to avoid (long) storage at temperatures above 50C. Recent work indicates that recombination/polymerization of oil fragments, accompanied by separation and evaporation of small molecules (including CO and CO2), could be an important cause.25 Although the reasons for instability may be unclear, the major chemical change in wood-derived oil is due to an increase in the DCM insoluble fraction and a significant decrease in the ether insoluble constituents (sugars). The increase in the average molecular weight in time, the viscosity (of the organic fraction) and pour point, and/or changes in the molecular structure cause phase separation. The instability of the oil and the varying quality of oils produced worldwide could be hurdles to further development of oil applications. Much depends on the eventual
Table 2. Chemical composition of reference pine oil and its fractions.25 Reference Pine Oil
Water
Acids Formic acid Acetic acid Propionic acid Glycolic acid Alcohols
wet
wt-%
wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-%
dry
0
5,6 1,5 3,4 0,2 0,6
C
40,0
H
6,7
N
0
23,9
4,3
53,3
2,23
2,9
0,3 2,6
60,0
13,3
26,7
Ethylene glycol Isopropanol

Aldehydes and ketones Nonaromatic Aldehydes Aromatic Aldehydes Nonaromatic Ketones Furans Pyrans Sugars Anhydro--D-arabino-furanose, 1,5 Anhydro--D-glucopyranose(Levoglucosan) Dianhydro-a-D-glucopyranose, 1,4:3,6 LMM lignin Catechols Lignin derived Phenols Guaiacols (Methoxy phenols) HMM lignin Extractives
15,41
20,3 9,72 0,009 5,36 3,37 1,10 45,3 0,27 4,01 0,17 17,7 0,06 0,09 3,82
59,9
6,5
0,1
33,5
34,44
44,1
6,6
0,1
49,2
13,44
68
6,7
0,1
25,2
1,950 4,35
2,6 5,7
63,5 75,4
5,9 9,0
0,3 0,2
30,3
15,4
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end application: although technologies are being demonstrated already at a significant scale (up to a 100 ton biomass throughput per day), standards and specifications are still underdeveloped. Some progress has been made however in recent years.26 Various physical and chemical methods for the characterization and analysis of pyrolysis liquids in relation to their future applications have now been identified. This applies to properties such as the viscosity, water content, pH, density, elemental composition, LHV, ash content, char content, surface tension, solubility in different solvents, ageing characteristics, and pour and flash points. Catalytic pyrolysis It has been recognized already in the early days of fast pyrolysis R&D that application of catalysis could be of major importance in controlling the oil quality and its chemical composition.27,28 Without any catalyst involvement, the biooil derived from fast pyrolysis is a mixture of hundreds of different, highly oxygenated chemical compounds. Catalysis could be applied for a number of reasons, and at a number of different positions in the process. Lower pyrolysis temperatures, a higher chemical and physical stability, high yields of target components, and an improved miscibility with refinery streams, are all goals strived for. Bio-oils can be upgraded by either applying catalysts in the production process (catalytic pyrolysis), or by post-treatment of the bio-oil over a catalyst bed. This post-treatment may be the thermal cracking of re-evaporated bio-oil in a hot fluidized bed of Fluidized Catalytic Cracking (FCC) catalyst particles (bio-oil FCC), or the catalytic hydrodeoxygenation at elevated temperatures and hydrogen pressures (hydrotreatment). When, in catalytic pyrolysis, the catalyst particles are mixed into the reactor together with the inert heat carrier (often sand), there is an immediate contact between the catalyst and pyrolysis products. Besides, in pyrolysis processes with a separate char combustor, the catalyst can be regenerated continuously (coke burn off ). Requirements are then that the particle properties of the catalyst should match those of the inert heat carrier while its activity should be maximal at the optimal fast pyrolysis temperature. More flexibility regarding the design of the catalyst and the conditions of the catalytic treatment is created when a separate reactor is installed in the pyrolysis vapor stream to the
condenser. The latter procedure is mostly applied in research projects. Results of laboratory investigations are, until now, quite poor regarding the understanding of what is actually taking place. Mostly, the approach is to carry out catalytic pyrolysis experiments for selected types of biomass and analyze the liquids obtained for their contents of alkanes alkenes and aromatics. Yield numbers remain often unclear, but obviously the yield of the desired liquid is far below the theoretically maximum possible value. Significant amounts of coke, water, and carbon oxides are produced.29,30 Fast pyrolysis technologies The aim of the slow pyrolysis process is to produce mainly charcoal, whereas the fast pyrolysis process should convert the biomass into a maximum quantity of liquid. As mentioned in the introduction, both processes have in common that the energy in the biomass feedstock is concentrated in a smaller volume by which transport costs and storage space can be reduced. Also beneficial is that a more uniform, stable, and cleaner-burning product is obtained, that could serve as an intermediate energy carrier and feedstock for subsequent processing. In an industrial process, the byproducts char or gas (both 10 to 20 wt.%) would be used primarily as a fuel for the generation of the required process heat (including feedstock drying). But the byproducts left could also be applied otherwise. Active carbon, carbon black, or a pelletized fuel could be produced from the char. The char is also proposed as a soil improver (biochar).31 For specific purposes, such as entrained flow gasification (syngas production), recombination to a char-oil slurry is sometimes considered. The gaseous byproduct, essentially a mixture of CO and CO2, could also be used for electricity production in an engine, if cleaned properly. Apart from possible flue gas emissions resulting from the char combustion, there are no waste streams. The ash in the original biomass will be largely concentrated in the char product and is separated when the char is combusted in the process for drying and heating the biomass feed stream. It allows recycling of the minerals as a natural fertilizer to the site where the biomass was grown originally. The essential characteristics of a fast pyrolysis reactor for maximal oil production are the very rapid heating of the biomass, an operating temperature around 500C, and a rapid quenching of the produced vapors. Crucial in the pyrolysis
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reactor is the ability to have high heat transfer rates to (and preferably also inside) the solid particles. On an average basis, it can be estimated that 1.5 MJ/kg is required, mainly for heating the biomass (which is 2/3 of that of water evaporation). Moreover, the time and temperature profi les of the vapors produced affect the composition of the oil as well. In small laboratory reactors, where very rapid transfer rates are achieved, and vapor residence times of only a few tenths of a second can be realized, oil yield can be maximized. For heat transfer limited systems, and longer residence times of the pyrolysis vapors at higher temperatures, occurring especially in real-scale installations, the consequences of secondary cracking can become quite significant. In practice, high external medium-to-solid heat transfer rates are required (say >500 W/m2K); intraparticle biomass heat transfer limitation should be avoided (requiring particles <5 mm to limit the heat penetration depth); and vapor phase residence times should be kept below a few seconds in order to maintain the oil yield. In case a pyrolysis plant is meant to produce a liquid fuel for combustion or gasification, the process could be designed in a way that maximizes the energy conversion to the liquid product. When the bio-oil product is meant to derive biofuels or chemicals from it, however, factors other than just the vapor residence time should also be considered. The composition of the oil can be steered by process conditions, equipment dimensions, and the application of catalysis. The latter is an ongoing research item at various laboratories. Although laboratory studies regarding the thermal decomposition of various organic substances have been carried out for a much longer period, the technology development of flash and fast pyrolysis started only some 20 years ago when the advantages of liquefying biomass in such a simple way were gradually recognized. During the 1980s and the early 1990s, research was focused on the development of special reactors, such as the vortex reactor, rotating blades reactor, rotating cone reactor, cyclone reactor, transported bed reactor, vacuum reactor, and the fluid bed reactor. Since the late 1990s, the process realization emerged, resulting in the construction of pilot plants in Spain (Union Fenosa), Italy (Enel), UK (Wellman), Canada (Pyrovac, Dynamotive), Finland (Fortum) and the Netherlands (BTG). In the USA and Canada, Ensyns entrained flow bed process is applied at a scale of around 1 ton/hr for commercial production of
a food flavor called liquid smoke. Dynamotive and BTG designed and operated demonstration installations of 2 to 4 tons biomass throughput per hour for utilization of bio-oil in energy production primarily. Meanwhile, many pilotplant projects stopped, sooner or later after the initial testing. At the time of writing, the plants of Union Fenosa, Enel, Wellman, Fortum, and Pyrovacs large-scale installation in Jonquiere, Canada, are no longer in operation. This may be caused by a lack of confidence in economic prospects and markets at the time, or by legislative limitations. On reflection, the state-of-the-art in the development of pyrolysis seems comparable with the situation in 1936 in the petrochemical industry, when the Houdry (FCC) process was first demonstrated on a scale of 2000 barrels per day. Today, fast pyrolysis is attracting increased interest. Fields of science other than engineering (e.g., agriculture, organic chemistry, catalysis, separation technology) are getting involved, together accelerating the developments in bio-oil applications. Oil companies and food/feed industries are building biofuel departments and looking for existing knowledge matching their strategies and targets regarding renewable resources. Also, new developers of fast pyrolysis technology are showing their intentions with the construction of pilot plants based on proprietary technology. A selection of historical developments aiming at demonstrationscale pyrolysis technologies will be discussed later, with an emphasis on the rotating cone technology of BTG. Entrained down-ow Early attempts of fast pyrolysis have been carried out in entrained flow reactors, where biomass particles (1 to 5 mm) were fed to a hot, down-flow reactor. The reaction was supposedly complete within a residence time <1 s, if the reactor tube was held at temperatures in between 700 and 800C. Unlike many other fast pyrolysis reactors later on, no extra hot solid material was used to transport and heat the biomass particles. An early process was developed at Georgia Tech Research Institute (USA) and a first unit transferred to Egemin (Belgium) for further development and scale up in a project funded partly by the European Commission. The plant was dismantled in 1993. It appeared that the feedstock was incompletely pyrolyzed in the reactor, particularly when larger particles were used (6 mm). Insufficient heat transfer
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to the solid biomass particles during their short travel in the reactor was the likely cause.32 This resulted in total liquids yields of less than 40 wt.% on dry feed basis. Ablative reactor Ablative pyrolysis was then considered as a possible alternative to entrained flow reactors. The principle of ablative pyrolysis is given in Fig. 6. The surface, heated by hot flue gas, is rotating, and biomass is pressed onto the hot surface (approx. 600C). The flue gas is produced by combustion of pyrolysis gases and/or produced char. In the 1990s, BBC (Canada) demonstrated an ablative flash pyrolysis technique for the disposal of tires at a 1025 kg/hr capacity.33 The process was licensed to Castle Capital (a holding company of several companies involved in the fabrication of
pressure vessels, military vehicle modification etc.) for the erection of a 50 t/d plant in Halifax, Nova Scotia, using solid wastes. It is unknown to the authors what happened to these plans. Much of the pioneering work on ablative pyrolysis was carried out by NREL (Golden, CO, USA, formerly known as SERI).34 In their approach, the forces to press the biomass to a hot surface are centrifugal forces in a so-called vortex reactor. The biomass, though, appeared to be insufficiently converted, requiring the solids to be redirected back to the entrance. In 1989, NREL entered a consortium with Interchem Industries Inc. (USA) to develop and exploit NRELs ablative pyrolysis for the production of phenol adhesives and alternative fuels. However, the construction of a demonstration plant was never completed. NREL is no longer contractually involved with this firm, and abandoned the vortex design concept in 1997.
oil
(a)
biomass Oil hot disc char air oil gas excess gas
(b)
gas char fluid bed biomass air recyclegas excess
sand loop
air gas
biomass
sand oil
Biomass sand
char / sand loop char combustion air recycle gas gas air oil sand biomass char combustion char/sand loop oil
char
air
biomass
molten salt
vacuumvessel char
gas air
Figure 6A. Ablative, CFB and vacuum technologies.
Figure 6B. Fluid bed, screw (auger) and rotating cone technologies.
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In the 1990s, Aston University (Birmingham, UK), built and tested a prototype rotating blade reactor for ablative pyrolysis on a small scale of 3 kg/hr.35 Oil samples were produced in yields of up to 80 wt.%. Work in a cyclone reactor continued at CNRS (France) in this century, yielding up to 74% bio-oil.36 At present, the German company Pytec is the only company developing ablative pyrolysis technology, with a pilot plant of 250 kg/hr in operation near Hamburg and plans for demonstration of a 2 t/hr unit in Mecklenburg-Vorpommern.3739 In general the following limitations for this ablative technology can be expected: Limited heat transfer rates to the hot surface due to the indirect heating principle. This is caused by both a relatively small temperature difference between hot flue gas (likely around 800oC) and the pyrolysis reactor (around 500oC), and a low heat transfer coefficient. Experiments in which electricity is used as a heat source (quite usual in R&D work) can be misleading in designing a large scale process. Restrictions in feedstock morphology (particle shape, structure and density), the particle size and its free-flowing characteristics, because the material needs to be pressed against a hot surface.
sand-to-biomass heat transfer is excellent (over 500 W/m2K), the heat transfer from the heating coils to the fluid bed will be low, due to the resistance inside the coils (gas-to-coil wall heat transfer estimated 100200 W/m2K), and the limiting driving force of around 300C as a maximum (800 down to 600C in coils versus 500550C in the fluid bed). In an optimistic case, at least 10 to 20 m2 surface area is required per ton/hr of biomass fed. The University of Waterloo in Canada reported early work in the beginning of the 1980s on fluid bed pyrolysis. In 1990, a 200 kg/hr demonstration plant was built by Union Fenosa, a utility company in Spain for the generation, transmission, and distribution of electricity. (This plant has since been dismantled).41 Another 200 kg/hr fluid bed system was developed and constructed by Enco Enterprises Inc., on a standard trailer in the late 1980s and early 1990s, with the intention of converting peat moss into liquid fuel. After extensive testing, however, it became clear that scale-up opportunities were limited. The project was abandoned and a heated auger system (screw conveyor) was adopted (more details later in this review).42 The Canadian company, Dynamotive Corporation, however, further commercialized the fluid bed technology of the University of Waterloo. Design and development of the first commercial plant at West Lorne started in 2002. A process scheme has been presented elsewhere.43,44 The plant started operations in early February 2005 with a design capacity of 100 tons per day of waste sawdust. At the beginning of 2008, the plant was not in full production and did not reach the designed bio-oil production capacity, presumably due to design and construction problems. The company did not wait for the West Lorne plant and started to build a second plant in Guelph in 2006 with a design capacity of 200 tons per day. Operational performances for both plants cannot be found in the open literature. The oil of the West Lorne facility was meant originally for combustion in Orendas GT 2500 gas turbine to produce electricity. Figure 7 shows a photograph of the West-Lorne plant. The Orenda turbine is an industrial Mashproekt-designed engine, with nine axial, and one radial stage compressor. Due to variations in the oil quality (perhaps off-spec) and a limited supply of the oil, the turbine has hardly been used. Scale-up of fluid bed pyrolysis seems thus limited in case the heat is indirectly transferred through submersed coils
Finally, although strictly speaking not an ablative type of reactor, TNO operated a 30 kg/hr pilot plant at the University of Twente in the Netherlands. Their PyRosreactor integrates pyrolysis and high-temperature gas cleaning in one unit, and consists of a cyclone with a rotating particle separator. The biomass is fed to the cyclone by an inert transport gas, with a solid acting as a heat carrier.40 So far no yield data have been presented in the open literature. Fluid bed A simple method for the rapid heating of biomass particles is to mix them with the moving sand particles of a high-temperature fluid bed. High heat transfer rates can be achieved, as the bed usually contains small sand particles, generally about 250 m. The heat required is generated by combustion of the pyrolysis gases, and/or char, and is eventually transferred to the fluid bed by heating coils. While the
189
Figure 7. The Dynamotives West Lorne plant: wood feed hopper on left, char product hopper on right.
or alike, as in the case of Dynamotive, but the application of a twin fluid bed with solids exchange (and separation of biomass pyrolysis and char-gas combustion) could solve this problem (see Table 3 for mass and energy balances of a twin fluid bed process). An example of such a system is a fluid bed designed and constructed by Wellman Process Engineering in an EU project coordinated by Aston University in Birmingham, UK. Here the fluid bed was surrounded by the char combustor, with heat transfer through the separating wall and by exchange of solids. The construction of the pilot plant was indeed completed in early 1999, but due to permit problems it could never be started. The installation has not been used since then. Biomass Engineering Ltd is now erecting a similar (250 kg/hr) installation. Improvements include the collection system for the pyrolysis liquids, hot gas fi ltration, the handling and combustion of the char (to provide process energy internally), and so on. Vapo Oil and Fortum Oil together undertook another initiative from 2001 onwards and developed a new-patented principle for fluid bed pyrolysis.45 Pictures of the plant are presented in Fig. 8. The project was abandoned, presumably for economic reasons. Although fluid bed operation seems a pretty well understood technology for pyrolysis,1 experimental experiences in fluid bed pyrolysis still indicate a number of serious
Figure 8. ForesteraTM pilot: reactor and product storage area.
technical problems to overcome. Referring to Fig. 6, the following remarks can be made: Cyclones are applied to separate the vapors and solids, and thus avoid large quantities of char and bed material ending up in the bio-oil. Char fines in the oil cause increased instability, problems in pumping and, more importantly, difficulties in the end-use applications (turbines, engines, boilers). Perhaps because of the difficulties in char separation, as the char is pyrophobic and easily catches fire, Dynamotive now deliberately leaves the char in the oil, naming it Intermediate Bio-oil (BioOil Plus).46
190
1
70x70x70 mm 30% moisture
<10 mm <10 % moisture
2 4
6
Water
7 8
Table 3. Mass and energy balances for 2000 kg/hr (daf) fluid bed pyrolysis. Input
Stream no. Organics Water O2 N2 CO2 Pyrolysis gas Char Ash Sand Total Temp. (K) Pressure (bar) Chem. heat (MW) Heat (MW) 2,920 291 1 10.4 2,220 291 1 10.4 3,000 291 1 1,000 326 1.2 2.1 304 1 0.42 804 1 1.3 7.41 20 20 66,600 1,200 317 1 6.6 257 804 1 2.1 0.05 0.33 3,860 400 1 1,000 200 155 245 12 8 1 2,000 900
Reactor feed
2 2,000 200
Air
3
Inert carrier gas

4
Pyrolysis vapours
5
Heat carrier
6
Bio-oil
7 1200 400
Surplus char
8
Flue gas
9
740 250 2,400 470
600 2,400
Inert gas used for fluidization of the reactor bed logically is the non-condensable part of the pyrolysis gas. This gas needs to be reheated and compressed, which requires careful cleaning to avoid blockage of heat exchangers, blowers, etc. For comparison, gas cleaning appears to be one of the main hurdles in conventional gasification. A similar problem can be noted for CFB operation.
Circulating uid bed (CFB) The first CFB process was developed at the University of Western Ontario in the late 1970s and early 1980s.
Biomass could be converted to bio-oil at yields of over 70 wt.%. The principle is shown in Fig. 6: Biomass is screwed into a (riser or fast fluidization) reactor, where extensive contacting between inert particles (sand) and biomass takes place. Together with the char, sand is entrained out of the reactor, and sent to a combustor chamber where the char is combusted. The main advantage of the CFB system compared to fluid bed and ablative is the direct heat supply to the biomass by recirculation of sand, reheated by combustion of pyrolysis char.
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In the beginning of the 1990s, Ensyn Technologies Inc., in Ottawa, Canada developed industrial applications for their so-called Rapid Thermal Processing (RTP), in which woody biomass is converted to pyrolysis liquids as a source of valuable chemicals and fuel.4749 Commercialization was enabled through the granting of an exclusive license to Red Arrow Food Products Company Ltd of Wisconsin for certain product applications in the food industry, mainly wood flavors. Ensyn and Red Arrow have been producing large quantities of bio-oil for the production of specialty products since 1990. A fairly large circulating fluid bed pilot plant of 625 kg/hr throughput capacity has been built in Bastardo, Italy. The plant is stated running on demand, which is in practice never or hardly ever.50 A 100 kg/hr, a 40 kg/hr and a 10 kg/ hr R&D unit were available at Ensyns site in Ottawa, while a 20 kg/hr PDU-unit is built for research purposes at VTT in Finland. By 2007, eight RTP plants are in commercial operation, ranging from 1 to 100 t/day. Details of the operation (or operational performance) are unknown. Recently, Ensyn went into a Joint Venture (JV) with UOP, under the name Envergent Technologies LCC to commercialize the pyrolysis technology for fuel substitution and electricity generation.51 Another JV was announced by Finnish companies Metso and UPM to develop bio-oil production combined with (preferably existing) CFB biomass combustion units. The technology is based on the integration of conventional biomass-based fluidized bed boilers with a (non-disclosed) pyrolysis reactor (in cooperation with VTT). The pyrolysis unit utilizes the circulating hot sand from the boiler as a heat source. Test production will begin at Metsos test unit in Tampere (Finland) in June 2009.52 Just as for fluid bed technology, CFB technology is said to be well understood,42 but actual operation in pyrolysis appears problematic with substantial erosion problems, and complications due to operational parameters, such as the use of seals between various vessels (dip legs). This is a problem solved in the chemical industry (see FCC Fluid Catalytic Cracking processes). Nevertheless, and similar to fluid bed technology, the large amounts of gas needed for fluidization of the reactor should be the non-condensable part of the pyrolysis gas. This gas must be reheated and compressed, which requires careful cleaning to avoid blockage of heat exchangers, blowers, etc. As already mentioned, gas cleaning appears to be one of the
main hurdles in conventional gasification. Finally, for realizing the rather low solids hold-up in riser systems at solid fluxes of 100 to 200 kg/m2s, the gas flow rate in the riser is high, in the order of 1000 m3/hr (ton/hr biomass). Vacuum moving bed The biomass vacuum pyrolysis process was developed by Roy at Pyrovac Institute Inc., between 1988 and 2002, after having carried out R&D work at the Universit de Sherbrooke (19811985) and Universit Laval (19851988), both in Canada. The process includes a combination of slow and fast pyrolysis conditions. Course solids are heated relatively slowly to temperatures higher than those of slow pyrolysis, while the gas is removed from the hot temperature zone relatively quickly by applying a reduced pressure of less than 20 kPa in the process. An attempt to commercialize the process was carried out by Pyrovac International by the end of the 1990s. In this concept, biomass material was conveyed over a long horizontal grate, which was heated indirectly by a mixture of molten salts composed of potassium nitrate, sodium nitrite, and sodium nitrate.53 The salt itself was heated by a gas burner fed with the non-condensable gases produced by the pyrolysis process. Limitations in external heat transfer were avoided as much as possible by applying a patented internal agitation raking mechanism, but obviously internal heat transfer limitations could not be avoided. A 3.0 t/hr demonstration plant for bark residues was erected in the City of Saguenay Quebec, Canada, and taken into operation between 1999 and 2002 (Fig. 9). Crumb rubber was also successfully tested in 2002. The system proved to be functional except for a limitation encountered at one of the two condensing packed towers, which somehow impaired the organic vapor condensing performance. That condensing tower was on its way to be modified when the joint partner of Pyrovac Group, UNA B.V. (now NUON B.V.) was acquired by Reliant Energy Inc., in Houston. Because the pyrolysis project did not fit into the core business, Reliant Energy withdrew from the JV and Pyrovac was subsequently brought to an end in June 2002. The process equipment and the building were purchased by a third party from the bankruptcy in 2003 and the assets were kept in good shape till today. A group of investors led by US-based NewEarth Renewable Energy is now planning to restart the plant in
192
Inc., and Advanced BioRefinery Inc. started working with heated augers systems using a hot, high-density heat carrier (e.g., metal beads, see Fig. 6).56 ABRI-Tech is a JV between Advanced BioRefinery Inc., and Forespect Inc., the latter being a forest products company located in Namure, Quebec, Canada. The system has evolved to the point where the company builds, for sale, a 1 t/d unit and a 50 t/d unit. The first commercial 50 t/d system is presently (October 2009) being commissioned in Iowa and will produce bio-oil and bio-char from agricultural residues (Fig. 10).57 Forschungszentrum Karlsruhe (FZK) developed a fast pyrolysis reactor to convert straw to pyrolysis oil and char to serve as a high-energy slurry feedstock for entrained flow gasification (the Bioliq Process).58 The reactor design is adopted from the Lurgi-Ruhrgas twin-screw mixer reactor that was developed decades ago for oil shale, tar sand, and refinery vacuum residues (LR coking). Chopped biomass is mixed with hot sand in the double-screw reactor and decomposed to vapors and char. The hot sand loop is maintained pneumatically or mechanically. Just like in BTGs rotating cone technology, heat transfer to the biomass particles takes place by intimate contact with a heat carrier, with no need for an inert carrier gas. At the time of
Figure 9. The Pyrovac installation in Jonquire, Canada ( Christian Roy).48
2010 for industrial production of torrefied wood, wood charcoal, and bio-oils. 5455 Auger systems After concluding that design limitations precluded the scale up of their fluid bed, ABRI-Tech the former Encon Enterprise
Figure 10. ABRI-Techs Auger pyrolysis system of 50 t/d plant. The left side of the picture is the dryer/pulverizer. The reactor and condenser are the two modules on the right side of the photo. ( Peter Fransham).
193
writing (October 2009), the construction of a 500 kg biomass per hour pilot plant was completed but no test runs were reported yet. The pilot plant uses sand as a heating medium, whereas the R&D work was carried out while testing different heat carriers including metal beads. BTGs technology: Rotating cone reactor Fast pyrolysis has been a continuous research item in the Netherlands at Twente University for a few decades. Researchers started with the principle that intense mixing of biomass and hot inert particles is the most effective way to transfer heat to the biomass, but that fluid bed mixing requires too much ineffective inert carrier gas. A highintensity reactor for the pyrolysis of biomass was developed where no inert gases were required, while simplifying the reactor parts and peripheral equipment as oil condenser, gas cleaning, etc. The original idea in 1989 to rely on a merely ablative principle without inert sand was later modified to a sand-transported-bed rotating cone reactor (RCR).16 The concept is depicted in Fig. 6. Instead of mixing the biomass in a hot sand fluidized bed driven by inert gas, the pyrolysis reactions take place upon mechanical mixing of biomass and sand. Similar to the CFB operation, the sand and char are further transported to a separate fluid bed where the combustion of char takes place. The RCR enables a high solids throughput and short vapor residence times. R&D work was continued by BTG Biomass Technology Group.59,60 Figure 11 shows the first prototype built by BTG and Royal Schelde in Vlissingen as part of a test unit for Shenyang Agricultural University. It was shipped to China in 1994. Biomass particles are fed near the bottom of the rotating cone together with an excess flow of heat-carrier material like sand, and then transported upwards along the cone wall in a spiral trajectory by the centrifugal forces (up to 600 rpm). An electrical oven in which the sand and char are trapped surrounds the RCR. The produced vapors pass through a cyclone before entering the condenser, in which the vapors are quenched by re-circulated oil. Subsequently, the University of Twente constructed a novel reactor system (throughput capacity of up to 20 kg/hr).61 In contrast with Wagenaars original reactor, where sand is fed at the top, this rotating cone had a number of holes near the bottom, through which the sand was sucked into the cone. To
compensate for heat losses and provide both the energy for heating the biomass particles and consequently the overall endothermic pyrolysis reactions, the char produced during pyrolysis was burnt in a fluid bed around the rotating cone (combustion chamber). Experiments with sand and catalysts demonstrated that autothermal operation can indeed be achieved with this system, but unfortunately, the operational flexibility of this advanced concept appeared to be poor, and therefore the concept was not considered for further scale-up. BTG scaled up Wagenaars RCR technology, first to about 50 kg/hr in 1997. The cone reactor was integrated in a circulating sand system composed of a riser, a fluid bed char combustor, the RCR reactor, and a down comer. Char is burnt in the combustor to generate the heat required for the pyrolysis process, viz. by (re-)heating the inert sand that is re-circulated to the reactor. Oil is the only product of this lab facility, and gases were flared. In 2001, the system was further scaled up to 250 kg/hr. Through the past ten years, about 100 tons of bio-oil has been produced from over 50 different materials. Oil is partially sent out to universities, institutes, and industrial companies for application research. In addition
Figure 11. Photo of the rotating cone reactor.
194
to this pilot plan installation, a smaller (5 kg/hr) test unit has been erected in BTGs laboratories, for quick screening of potential feedstock materials in a continuously operated system. Initially, researchers reported that the RCR principle would be limited to particles < 1 mm in diameter. Over the years, however, the method of mixing in the cone and the pyrolysis system were improved considerably. The overall efficiency of the process has increased, the acceptable particle diameter demonstrated to be up to 10 mm, and product quality and consistency for different feedstocks have improved considerably. In 2001, a first detailed design for a 1 t/hr diaper sludge pyrolysis unit was prepared under a license for the company Bio-Oil Nederland (BON). BON is now a wholly owned subsidiary of Bio-Oil Holding N.V. (BOH), with no relation to BTG anymore. The company ambitiously plans to start up the first of four, 5 t/hr installations in 2010, intentionally on SRF, in Delfzijl (the Netherlands). No information is publicly available on the technology at the moment, but it is likely deviating from the original BTG design. In 2004, BTG sold the worlds fi rst commercial unit of 50 t/d on so-called Empty Fruit Bunch (EFB) in Malaysia. EFB is a leftover from palm oil mills. In the Malaysian plant, EFB is taken directly from a nearby palm mill, pressed, shredded, dried, and converted to bio-oil. From
bucket elevator EFB 1st shredder press
reception to oil delivery takes about 1 h, time that is consumed almost entirely by the pre-treating process. Genting Bio-Oil Sdn Bhd (GBO) commissioned its bio-oil pilot plant in Ayer Itam, Johor (Malaysia) in 2006. While undergoing some engineering upgrades, full commercial operations have been targeted for 2009.62 The overall (simplified) scheme is given in Fig. 12, which includes the complete chain from EFB reception, storage, pre-treatment (pressing, shredding, and drying), storage (approx. 4 ton) and conversion.63 The heat required for the drying of the EFB (up to 70 wt.% moisture upon reception) is taken from the pyrolysis unit, and a steam production system is fully integrated in the production unit. Pictures of the EFB and the pyrolysis plant are given in Fig. 13. From mid-2005, the plant was running on a daily basis, showing the potentials but also the shortcomings. The main achievements over the last years are listed below: Over a thousand tons of bio-oil have been produced from more than 5000 tons of wet (up to 70% moisture) EFB. Oil was co-fired, replacing conventional diesel in a system located 300 km from the site. Drying of de-watered EFB from around 50 wt.% moisture content down to 5 wt.% is possible using the excess heat from the pyrolysis process.
Flue gas Flue gas combustor feeding reactor ash flare air air Oil oil cooling storage condensor water
wet air 2e shredder
drier
air
boiler
air
Figure 12. Process scheme of the Malaysian plant for fast pyrolysis of empty fruit bunches (EFB), including the complete chain from EFB reception, storage, pre-treatment and conversion.
195
Figure 13. EFB Material and the pyrolysis plant in Malaysia. ((use separate powerpoint le))
Oil quality can be controlled by tuning operation conditions. Any excess energy recovered from the process after drying of the (very) wet EFB, is potentially available to generate electricity for on site use. The maximum capacity of the plant achieved is about 1.7 t/hr (design capacity was 2 t/hr). No problems were observed in the actual reactor system. Technical problems related to erosion due to high-velocity sand in riser parts, cyclones, etc., could be overcome.
Some shortcomings of the system at that time should be mentioned as well: Fluid bed combustion of the char from EFB created a high risk of blockages, but this appeared to be due specifically to the nature of the EFB ash (a.o. low melting point).
Considerable pre-treatment of EFB is necessary and wear and tear in pre-treatment equipment is significant (for instance in presses and shredders). By average, the bio-oil yield on basis of good quality dried EFB is 50 to 60 wt.%; the oil yield is lower than for wood (typically 70 wt.%), while the water content is higher. The supply rate of wet EFB from the palm mill and the quality varies considerably, viz. from 22.5 t/hr during daylight, and 11.5 t/hr at night with moisture contents up to 70%. Large amounts of EFB cannot be stored easily. Efficient heat integration, together with an improved reliability of the total system, will be the challenge for the coming years.
Considering the status of the pyrolysis process at the beginning of the plant design in 2004, the progress made in Malaysia is significant. From an initial set of experiments in
196
2003 (8 hours and maximum 100 kg/hr feeding), the system has been scaled up to a 24 hours/day running factory, where a direct link has been established between the palm mill and the pyrolysis plant. In addition, the process is applied here for a difficult type of biomass feedstock as, next to being fluff y and wet, the ash of the mineral-rich feed has a very low melting point (below 650oC). In 2007, BTG established BTG-Bioliquids with the objective to commercialize the technology.64 On its website, BTG-Bioliquids announces the construction by Empyro BV of a 5 t/hr wood based pyrolysis installation on a site in Hengelo (the Netherlands). The project is supported by the 7th framework program of the European Commission. Bio-oil fuel applications A key advantage of producing liquids from biomass is that its production can be de-coupled in time, scale, and place from the final application. The current status of primary, secondary, and tertiary processing of pyrolysis liquids is further presented in Table 4. Due to its high oxygen content and the presence of a significant portion of water, the heating value of bio-oil is much lower than for fossil fuel. Nevertheless, flame combustion tests showed that fast pyrolysis oils can replace heavy and light fuel oils in industrial boiler applications. In its combustion characteristics, the oil is more similar to light fuel oil, although significant differences in ignition, viscosity, energy content, stability, pH, and emission levels are observed. Problems identified
in flame combustion of bio-oil are related to these deviating characteristics, but can be overcome in practice. Meanwhile, bio-oil has been used commercially to co-fire a coal utility boiler for power generation at Manitowoc Public Utilities in Wisconsin (USA). It has also been approved as a fuel for utility boilers in Swedish district heating applications. After an extensive boiler test program in Sweden in 1996 and 1997, a commercial project was said to commence in 1998, but results were never reported. A successful co-firing test with 15 tons of bio-oil was conducted in 2002 in a 350 MWe natural-gas fired power station in the Netherlands.65 Some data are presented in Fig. 14 and Table 5. A four-hour co-firing session was carried out at a bio-oil throughput of 1.6 m3 per hour, or an equivalent of 8 MWth. While co-firing bio-oil in the boiler, the power output setting of the plant remained constant at about 250 MWe, and in the test, the plant control reduced the natural gas flow to the boiler to compensate for the injection of thermal heat of the bio-oil, indeed corresponding to 8 MWLHV (Fig. 14). Low ash deposition rates were also reported recently for a 100 kW combustion test rig during the combustion of bio-oil.66 Oil from the Malaysian plant was routinely used to replace expensive diesel for start-up of a fluid bed combustor near Kuala Lumpur International Airport. No results have been reported in open literature. Since 2006, BTG has been actively involved in research on the combustion of the oil in a standard 250 kW hot water generation unit, to replace
Table 4. The status of primary, secondary and tertiary processing of pyrolysis products. Primary product
Liquid
Secondary processing
Transport Combustion2 Engine/turbine1 Stabilization2 Upgrading2 Extraction1,5 Conversion3 Conversion2 Combustion Engine/turbine3 Fuel cell1 transport combustion5 slurrying2 active carbon
Secondary product
Fuel Heat/steam Electricity Stabilized oil Hydrocarbons Chemicals Chemicals Gas Heat/steam Electricity Electricity Fuel Heat/power Liquid fuel
Tertiary processing
Combustion Steam turbine5 Engine/turbine1 Rening2 Rening1,5 Rening1,2 Fuel cell1 Steam turbine
Final product
Heat/steam/electricity Electricity Electricity Diesel/gasoline Chemicals Chemicals Electricity Slectricity
Gas
(Bio)char
Combustion Combustion3
Heat/steam/electricity Heat/power
Indices: 1 = conceptual, 2 = laboratory, 3 = pilot, 4 = demonstration and 5 = commercial (Bridgwater, 1997). Indicated in bold are the most promising options on a short time scale.
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Gas turbine
Boiler
Steam cycle
Stack NOx Stack losses 33 MWth
NG 2 90 MWe 3
Flue gas
6 River cooling 274 MWth
1 Air
HC62
HC61 NG 5 Bio-oil
161 MWe
Figure 14. Mass and energy balances of Harculo power station.
Table 5. Power settings of Harculo station and the M&E balance as indicated in Fig. 13. Input Natural gas [MWth]
Gas turbine HC62 Steam turbine HC61 Total plant HC60 293.5 264.8 558.3
Output Heat [MWth]

0 133.8 0
Efciency Heat [MWth]

203.9 @ 520C 237.2 @ 30C 307.2 @ 30C 30.5 40.5 45.0
Power [MWe]
89.6 161.5 251.0
* natural gas LHV: 35.57 MJ/Nm3; 0.808 kg/Nm3
Stream I.D.
T [C] P [bar] Flow [kg/s] LHV [MWth] Heat [MWth]
1 Air
16 1.00 358 0 0
2 Natural gas
16 8.45 6.67 293.45 0
3 Flue gas
520 1.06 365 0 203.88
4 Flue gas
520 1.02 123 0 70.05
5 Natural gas
16 1.2 6.02 264.80 0
6 Flue gas
97 1.00 371 0 32.65
diesel and/or natural gas. For this purpose, sufficient quantities of palm-derived oil from Malaysia were transported to the Netherlands, and a dedicated oil lance was developed. Results derived from a Dutch cooperation between BTG, Stork-Thermeq, and ECN will be reported in due course. A subsequent project is concerned with testing in a larger, commercial boiler set-up, owned by Stork Thermeq. Generally, the production of electricity is more interesting than the production of heat because of the higher added value of electricity, and its ease of distribution and marketing. Diesel engines are relatively insensitive to the contaminants
present in pyrolysis oils, especially in the case of large- and medium-scale engines, and bio-oil may be used. Tests have been performed by diesel (re)manufacturers like Ormrod Diesels and Wrtsil Diesel, in collaboration with research institutes such as Aston University, VTT, MIT, and the University of Rostock.6769 A review of diesel engines was prepared in 2001 by one of the present authors,70 while another, very useful review on use of such liquids in engines and gas turbines was prepared by the University of Florence and VTT in 2007.21 In general, diesel engine development and testing suffers from insufficient quantities of available bio-oil and a lack
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of interest from engine (parts) manufacturers. Nevertheless, the results obtained indicate that engine deterioration can be a serious problem. Traditional diesel engines are designed to operate on acid free fuels, however, and all engine components are manufactured in such a way and with such (steel) materials as to comply with these fossil fuels. For fast pyrolysis oils, severe wear and erosion was observed in the injection needles, due to the fuels acidity and the presence of abrasive particles. Nozzles lasted longer when filtered oil was used, but it is clear that standard nozzle materials are inadequate. A high bio-oil viscosity and stability loss with rising temperatures are other major problems, already referred to. Damages to nozzles and injection systems, and buildup of carbon deposits in the combustion chamber and the exhaust valves are reported. Engines with larger cylinder bores (i.e., medium- and low-speed engines) are expected to be the most suitable because of less stringent construction tolerances. For smaller bore engines, reduction of the oil viscosity could be needed. Injection modification and/or a high turbulence combustion chamber are required. Because the bio-oil has poor ignition properties (cetane index below 10), it should be enriched by the addition of cetane improvers, and the application of a dual fuel system is most appropriate.71 Self-cleaning injectors are possibly required. At the end of the 1990s, Wrtsila stopped the development work, mainly due to lack of quality and quantity of pyrolysis oils at that time. In spite of all these problems, it has also been reported that modifications to both the bio-oil and the engine can make pyrolysis oils quite acceptable for diesels. One option to reduce the need for adaptations is the use of emulsions of bio-oil in diesel.72 This would not only offer prospects for stand-alone electricity production units, but potentially for the application of fast pyrolysis oils in the transportation sector (ships, trucks, tractors, or busses) in the future. A substantial RTD effort with involvement of manufacturers is required to realize this application. German researchers reported a successful 12-hour run on bio-oil in a modified Mercedes diesel engine, but exact details are not provided.73 Recently, a joint project started between European and Russian partners to further develop a pyrolysis oil diesel engine/turbine.74 Experience with bio-oil combustion in gas turbines is also limited. R&D projects known were carried out by Orenda Division of Magellan Aerospace Corporation (Canada),
ENEL Thermal Research Center (Italy), and Rostock University (Germany). Orenda is actively searching for opportunities to run their Orenda GT2500 on pyrolysis oils. The GT2500 uses diesel oil and /or kerosene, and unlike aero-derived turbines, an external silo-type combustor is adopted. This chamber provides a ready access to the main components. Several modifications are reported necessary:75 A complete low-pressure bio-oil supply system, including preheating and fi ltering of the bio-oil. An improved bio-oil nozzle design to allow larger fuel flows and dual fuel operation. Redesign of the hot section, including section vanes and blades. Stainless steel part and modification of polymeric components.
Despite their involvement in Dynamotives plant in West Lorne, the non-availability of sufficient quality bio-oil still remains the main reason why limited test runs are carried out by Orenda. A 75 kWe nominal gas turbine was tested in dual fuel mode by Rostock University in 2001, showing deposits in the combustion chamber and turbine blades, and higher emissions of CO and hydrocarbons. Bio-oil may have another suitable end-application, viz. its use as a fuel for gasification. It should be noted here that in refineries, gasification (next to combustion) is merely an end-of-pipe technique, using (cheap) feedstocks that cannot be used elsewhere in the process. Regarding co-gasification of biomass residues, to produce syngas for further processing (e.g., methanol, Fischer-Tropsch), pyrolysis could play an important role as a pre-treatment technique, facilitating the cheaper transport and handling of biomass feedstocks from origin to the site of gasification, over distances that biomass can never be shipped economically. Use of the oil in entrained flow gasification is the main application Forschungszentrum Karlsruhe (FZK) is aiming at.76 Residue gasifiers can indeed be fed on bio-oil,77 and issues of concern are mainly the pH (feed train) and alkaline ash content. R&D on (small-scale) entrained flow gasification of pyrolysis oils have only been reported by BTG.78 Pilot experiments were performed by BTG in UETs (now Chorens) entrained flow gasifier in Freiberg (Germany) at about 500 kWth with pure oxygen (results are not yet published).
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Pyrolysis oils could be used (pure or modified) as a feedstock for the production of transport fuel, which, with the growing demand for biofuels, is of strong interest worldwide. The simplest use of bio-oil may be in the diesel engine, but, as stated before, the oil as such is not suitable for (even) a stationary diesel engine. Upgrading of the oil to products more appropriate for further use is being considered by many organizations and institutes. Bio-oils can be upgraded atmospherically using conventional FCC catalyst in the pyrolysis process itself or, at elevated pressures, by hydrotreating. FCC-like upgrading dates back to the 1990s, assuming that, similar to ZSM-5 processing, oxygen will be rejected from the oils structure as CO2 .27,79-81 They showed a limited yield of hydrocarbon products of about 20 wt.% (or 40% energetically), mainly due to charring coking of the feed. Hydrotreating of bio-oils was reviewed in 2007.82 The early work originates from the late 1980s, using the slow pyrolysis oils derived from carbonization or hydrothermal liquefaction processes.83 It was shown that for deoxygenation, temperatures in the order of 300 to 400oC, and residence times > 1 hour are required. Until 2000, the real goal remained unclear. The overall objective was to produce transportation fuels (diesel and gasoline like components), and the target seemed to be the reduction of the oxygen content in the oil. Since the use, for instance, of MTBE, butanol and ethanol in
transportation fuels, the common believe of petrorefi neries shifted from absolutely no oxygen in the pool of transportation fuels, toward allowing adding small amounts of oxygen in the appropriate functionality (viz. alcohol or/and ethers). Since 2000, the intention of upgrading bio-oil shifted from using it directly as a transportation fuel (or blending component) after upgrading, toward co-refi ning upgraded bio-oil together with crude oil (derivatives). Hydrotreated bio-oils can be well co-refined, with rather high efficiencies, in FCC processes.84 The University of Groningen carried out pioneering work on the hydrotreatment of such oils revealing a clear resemblance with hydroprocessing of sugars.85 After an almost 10-year period of reduced activities in this hydroprocessing area, the concept has recently attracted considerable interest again in the USA.86 Co-refining in standard refineries is the main subject matter of a large European project BioCoup, showing that upgraded pyrolysis oils are suitable for such co-refining (Fig. 15). First papers were presented recently.87,88 Complex chemical process engineering factors such as water evaporation, dry-out phenomena, mass transfer, reaction kinetics, and occurrence of parallel and consecutive reactions, are considered and quite some progress has been made. Successful co-refining of upgraded oils has been demonstrated at lab scale,89 and papers will be published in due course.
OVERALL BIOREFINERY CONCEPT incorporating fractionation with liquefaction
Hydrocarbon-rich bio-liquid Primary fractionation Lignin-rich bio-liquid and liquefaction Co-processing in conventional petroleum refinery De-oxygenation (blending) Conversion Oxygenated products Conventional fuels and chemicals
Biomass residues
Derivatives of hemicelluloses and celluloses Process residues Energy production
Figure 15. Biocoups concept of co-rening bio-oil in existing reneries.
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Other approaches to arrive at transport fuels include alcohol treatment (analogous to vegetable oil esterification), reducing the oils acidity and, after phase separation, water content. These studies, initiated by the University of Groningen are still exploratory in nature.90 Another interesting application may be fermentation. Anhydrosugars that are produced by pyrolysis of biomass can be converted by hydrolysis to fermentable solutions as well.91,92 Feasibility studies show that this route to produce ethanol from lignocellulose may be an attractive alternative to acid and enzymatic hydrolysis. A further acid hydrolysis step of the levoglucosan to free sugars is necessary, and this should take place at elevated temperatures of around 100oC. Fermentation of pyrolyzates and their hydrolyzates is under investigation, and there is much uncertainty about the best process conditions and the detoxification steps required. Attempts to sustain yeast growth in grass-derived bio-oil hydrolyzates were unsuccessful, but success was achieved in fermenting a hydrolyzate from a wood-derived bio-oil and this supports the concept of pyrolysis with ethanol as a major product. More research is required to improve the fermentability of wood-derived bio-oil hydrolyzate and to establish whether its fermentability is due to the chemistry of wood vs grass pyrolysis feedstock, the pyrolysis process conditions existent in the commercial- vs lab-scale reactor system, or a combination of these two variables.93 Chemicals in bio-oil Hundreds of compounds have been recognized in (GC) analysis as fragments of the basic compounds of biomass, viz. the lignin (amongst others: phenols, eugenols, and guaiacols), and the cellulose or hemicellulose (sugars, acetaldehyde, and formic acids). Although GC analysis may not be the most appropriate analysis tool for bio-oil (as discussed earlier), large fractions of acetic acid, acetol, and hydroxyacetaldehyde are identified (Table 2). Until now, approximately 40 to 50% of the oils identity (excluding the water) has been revealed, but the large, less severely cracked or de-/re-polymerized molecules (derived from the cellulose and the lignin) in the oils can still not be identified. Figure 5 shows that all types of (oxygen) functionalities are present: acids, sugars, alcohols, ketones, aldehydes, phenols and their derivatives, furans and other mixed oxygenates. Also (poly)phenols are present, sometimes
in rather high concentrations. These phenolic fractions then include phenol, eugenol, guaiacols and their derivatives, and the so-called pyrolytic lignin (poly-phenols) representing the water insoluble components. It is likely that this pyrolytic lignin which contain the fragments of the original lignin, also contains polymerized carbohydrate (fractions). Components in the oil interesting to consider for future chemicals production are the carbohydrate fragments. These are sugar derivatives such as all types of anhydrosugars and oligosaccharides, formaldehyde, furfural alcohols, hydroxyacetaldehyde and so on. Due to the principle of GC analysis, in which only the distillable components in the oil can be identified and quantified, levoglucosan is usually referred to as an important type of sugar to be isolated (Fig. 5). However, much more sugars, approx. 30 wt.% of the oil, must be present. Aspects to be considered here are that the original feedstock, the process conditions, and condensing parameters are of major importance for the type of chemicals in the oil. To complicate this further, pre-treatment of wood may result in an increase of one particular component at the expense of the other. As mentioned earlier, ash is known to influence the reactions in the pyrolysis process, and may contribute to higher yields of certain products. Last but not least, the analysis of bio-oil can also be complicated. As an example of the observed variation in composition of wood-derived pyrolysis oil, a study published in 1997 indicated that not a single compound of over 100 has been identified by all 10 laboratories where pyrolysis oils could be analyzed at that time.94 It should also be repeated that GC analysis does not reveal the identity or quantity of components that do not evaporate in the injection system. Part of the discrepancy in the analysis results of the various laboratories is also caused by the continuous improvements in methodology during the last few years, (increased use of GC-MS, HPLC, etc.) and the factual identification of the various components. The applications for bio-oil are now further detailed, starting from application of the unfractionated oil, and applications in which fractions or isolated compounds are relevant. Unfractionated bio-oil Resins for MDF or OSB: Work to examine the potential use of the pyrolysis oil as a raw material in wood panel
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manufacture is ongoing. The use of bio-oil has been investigated over the years for the replacement of formaldehyde phenols in resins for particleboards. Due to the high cross-linking capability of the lignin-derived compounds in the bio-oil, a polymer with an improved strength can be obtained when mixed with conventional urea-formaldehyde resins. Research in this area published at the end of 2000, concludes that bio-oils can be used in the manufacture of resins in phenol substitution rates up to 50%.95 A review of the production of renewable phenol resins based on pyrolysis products published recently, concludes that none of the phenol production and fractionation techniques available allows a complete substitution of the resin.81 Partial substitution seems more likely though. Fertilizers and soil conditioners: Reaction of bio-oil with ammonia, urea, or other amino compounds produces stable amides, amines, etc. They are non-toxic to plants and can be used as slow release organic fertilizers. Additional benefits are that the lignin degradation products and their reaction products are good for soil conditioning, control of soil acidity, amelioration of the effects of excess Al and Fe, increasing availability of phosphate, and crop stimulation. Furthermore, they are excellent agents for nutrient metals such as Mo, Fe, B, Zn, Mn, and Cu. Other functional groups in the bio-oil-derived fertilizers are nutrients such as Ca, K and P.96,97 DynaMotive co-operated with two fertilizer manufacturers on the commercialization of bio-oil-derived products, but so far no specific commercial product outlets have been demonstrated. Pure bio-oil can be mixed with lime to form BioLime, a trademark of Dynamotive Technologies Corporation in Canada. Injection of this mixture into flue-gas tunnels should result in complete removal of sulfur oxides, but also in a significant reduction of nitrogen oxides. The research on this has stopped, and no references have been found in literature hereafter. Fractions derived from bio-oil In wood-derived pyrolysis oil, specific oxygenated compounds are present in quite substantial amounts. The recovery of such pure compounds from the complex bio-oil may be technically feasible but probably economically unattractive because of the high costs for the recovery of the
chemical and its low concentration in the oil. The relevant chemical components are now presented. Wood flavors: The only commercial application of woodderived bio-oil known to date is that of wood flavor or liquid smoke. A number of companies produce these liquids by adding water to the bio-oil. A red-colored product is then obtained, that can be sprayed over meat before further cooking. The taste, color, and smell of the meat are thus created artificially. A range of food-flavoring products, based on pyrolysis oils, has been patented and commercialized by Red Arrow Products Company (USA)98 and the former Chemviron, ProFagus (Germany). Phenolic compounds: A significant part of the oil is the phenolic fraction, consisting of small amounts of phenol, eugenol, cresols, and xylenols, and larger quantities of alkylated (poly-) phenols (the so-called water insoluble pyrolytic lignin). Recoveries of phenolic compounds up to 50 wt.% have been reported, but only for specific feedstocks. The amount of the smaller, more expensive, phenolic components in bio-oil is usually limited, probably because the original lignin in the biomass is only partly cracked. Moreover, it is likely contaminated by re-polymerized lignin and sugar fragments (from the hemicellulose) as well. Phenolics have also been proposed for use as an alternative wood preservative to replace creosotes.99 Sugars: Levoglucosan, together with levoglucosenone and HAA, are the few sugars derivatives and detectable in GC equipment. It seems that this in itself is the main reason that the first two components especially received a lot of attention: other sugars which are present cannot be traced back in the oil using GC. An extensive overview on levoglucosan is given elsewhere.7 The existing market for levoglucosan is very small (and the product high-priced), but it may well be an intermediate product suitable for further fermentation, as indicated earlier. Most pyrolysis technologies could be adapted for levoglucosan production by pre-hydrolysis of the feedstock and/or demineralization.100 Levoglucosenone is said to be applicable in the synthesis of antibiotics/pheromones, rare sugars, butenolide, immuno-suppresive agents, whisky lactones, and so on, and can be present in amounts up to 24 wt.%. Progress in the last few years to valorize bio-oil on the basis of these two interesting products is limited, though. On the contrary, hydroxy-acetaldehyde is
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a commercial product. It can be present in relatively large amounts in the bio-oil (up to almost 20 wt.%), and is used in browning food (cheese, meat, sausages, and poultry or fish). A possible application is the use as a precursor for glyoxal OHC-CHO, which is an important chemical produced by oxidation of ethylene glycol.101 Acids: Components that can also be derived from bio-oil are mainly the carboxylic acids, from which salts such as calcium acetate and calcium formate can be produced.102,103 In the aqueous fraction of the bio-oil, these acids are present in amounts up to 10 wt.%. They have potential applications such as road or runway de-icing, sulfur dioxide removal during fossil fuel combustion, or as a catalyst during coal combustion. Furfural-derivatives: Furfural and furfurylalcohol can be produced from carbohydrates (glucose, maltose, cellobiose, amylose and cellulose) in amounts up to 30 wt.%.104 Economics A key factor in the development to commercial implementation is the economic viability of fast pyrolysis processes. Currently the main interest in Europe is electricity generation from biomass. CO2 mitigation, socio-economic benefits from re-deployment of surplus agricultural land, and energy independence are driving forces. These have led to significant fiscal incentives. Apart from such incentives, inflation, (in)direct effects of oil prices, local costs and labor strongly affect the economics of pyrolysis plants. Therefore, it does not make sense to discuss economics in much detail. General data, collected by BTG and confirmed in other studies, show that the range of capital costs for the pyrolysis plant alone is in between 200 and 500/kWth input biomass, depending on the technology, scale, degree of heat integration, location, etc. The main parts of the BTG pyrolysis plant are the reactor, riser, combustor, and condenser. The costs of pre-treatment, feeding, buildings, and infrastructure are not included, but may add up to another 50 to 100%, depending on the initial feedstock properties (size, water content, dimensions, free-flowing behavior, bulk density, and so on). Costs related to the heat integration system (heat recovery, steam generation, drying, etc.) are usually not addressed in the studies of economics. One of the main challenges of BTGs process concept is the efficient generation and further use of the excess heat generated in the system. The Malaysian plant showed that (1)
the heat required for drying the wet feedstock is delivered by the process itself; and (2) electricity can be generated from the excess heat available, even after use for drying. An important aspect to consider in plant economics is the observation that the cost for the actual pyrolysis reactor is just a fraction of the overall plant costs. At the same time, a proper reactor choice in particular offers the possibility to reduce costs upfront (i.e., in feeding and pre-treatment) or in peripheral equipment. The rotating cone reactor in the Malaysian plant, for instance, costs about 2 to 3% of the complete plant, but reduces the overall costs of the total plant significantly because the absence of inert gases limits the costs of secondary equipment. Studies over the years indicated that pyrolysis oils can be produced at costs in a range of 4 to 14/GJ (corresponding 65 to 225/t), with feedstock costing between 0 and 100/t (0 to 6/GJ).105,106 Such figures match quite well with the data of the Malaysian plant. But again, it should be noted that they strongly depend on process technology, the scale of operation, feedstock, year of construction, and so on. Generally speaking, it can be stated that the costs of pyrolysis processes should be rather low, because the operating conditions are less extreme than for combustion or gasification (lower temperatures and atmospheric pressure). Biomass pre-treatment, heat integration and the required operation reliability, however, can be factors seriously increasing the overall investment costs. Concluding remarks Pyrolysis definitely remains an interesting pre-treatment technique enabling (intercontinental) transport of large volumes of biomass. The proof of principle (reactor concept), and proof of concept (plant set-up) have been demonstrated, amongst other by BTG (Malaysia), DynaMotive (Canada) and Ensyn (USA and Canada). Fast pyrolysis is still an immature technology, of which many aspects are unknown. Although a number of installations were erected, they all suffer from a lack of operational hours and no process has really been demonstrated. Interested industries like heat and electricity producers, oil companies and food/feed companies, are waiting for full-scale demonstration including continuous operation (>7000 hours per year) preferably of multiple plants on a scale of 5 to 10 tons biomass feedstock
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per hour. Here, the problem is that the opportunities for commercial bio-oil production are limited due to lack of economic applications. The oil should, for the time being, be used to substitute fossil fuels in heat and power production, by combustion in conventional boilers or co-combustion in power stations. The focus for the next few years is to produce oil, and to apply simple and cheap applications. Once the process and peripherals have been proven, larger amounts of oil will become available for the development and commercial-scale demonstration of other bio-oil applications, such as turbines, diesel engines and/or further upgrading to biofuels. Obviously the construction and operation of demonstration installations needs to be supported by government bodies and risk-taking investors, viz. in a sustainable way. Past failures in biomass demonstration projects were often caused by a serious lack of financing after the first period of plant design and erection. Challenges within the coming years are related to improving: the operational reliability of demonstration scale pyrolysis processes; the feedstock flexibility (accepting all kinds of biomass residues, instead of only wood); the heat transfer to the pyrolysis reactor and from the char combustor; and the process heat integration and its control.
are undesirable, and to understand how to steer the pyrolysis process itself in this respect, for instance, by catalysis. With respect to bio-oil upgrading, an important conclusion is that reduction and control of the oxygen functionalities should be the ultimate goal instead of the reduction in oxygen content itself. Actual demonstration that pyrolysis oils can be used as a feedstock in refi neries, as aimed at in the European BioCoup project, will certainly boost the further development of fast pyrolysis. For BTGs system in particular, the progress made in Malaysia from the beginning of the plant design in 2004 to date is quite satisfactory. From an initial set of experiments in 2003 (8 hours and maximum 100 kg/hr feeding), the system has been scaled up to a 24 hours/day running factory, where a direct link has been established between the palm mill and the pyrolysis plant. In addition, the process is applied to a very difficult biomass feedstock material, which is fluff y (not free flowing) and wet, and has a high ash content (with a very low melting point). Problems resolved are largely related to boundary conditions (feeding, pre-treatment, ash-related problems and heat recovery) instead of to the actual pyrolysis process itself. All the experiences and knowledge acquired by BTG over the past 20 years of RTD will be condensed in the design of a new wood based demo-pant of 125 t/d, to be erected by Empyro BV in 2010/2011 at a site in Hengelo, the Netherlands. A BTG daughter company called BTG-Bioliquids takes care of the future commercialization of BTGs fast pyrolysis technology. Acknowledgements The authors would like to thank Erik Heeres and Agnes Ardiyanti from the University of Groningen for carrying out the TGA experiments reported in Fig. 1, and Dietrich Meier for allowing us to use his presentation of pyrolysis technologies as input for Fig. 6. References
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In the meantime, R&D should be directed to improvement of the quality (and stability) of the oil in relation to the end-application envisaged. Although nice, uniform bio-oil samples have always been available during the last 20 years, only limited fundamental know-how has been generated on the exact composition of the bio-oil. Much attention was paid to (destructive!) GC analysis techniques, while nowadays it is gradually being recognized and understood that the components quantified are not necessarily (in that concentration) present in the original oils. In addition, the authors believe that the compounds or fractions in the oil, causing its specific characteristics (pH, ageing, viscosity, phase separation, and so on) have not been fully identified nor are the reactions taking place understood. One particular issue is the exact role of the various oxygen functionalities in the oil. It is important to establish which functionalities are desired and which ones
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Robbie Venderbosch After his PhD at the Twente University in 1998, Robbie Venderbosch joined BTG Biomass Technology Group BV. He has more than ten years (practical) experience in thermochemical processes for biomass and its further use. Robbie Venderbosch has expertise and responsibilities in the field of engineering and implementation of fluidized bed system coupled with chemical reaction, biomass energy processes (ranging from concept to detailed design), construction and operation of laboratory, pilot and demonstration scale set-ups and process instrumentation, and process control (both software and hardware). He was responsible for the delivery of BTGs commercial pyrolysis plant to a client in Malaysia.
Wolter Prins Wolter Prins received his Masters in Chemical Engineering from the University of Groningen and his doctoral degree from the University of Twente in Enschede, the Netherlands. In 1984, he was appointed Assistant Professor in the Department of Chemical Technology at the University of Twente. Since 1992, he has combined his work at the University with a position as head of R&D in BTG Biomass Technology Group BV in Enschede. In 2008, he was appointed as Professor for Bioresources Processing in the Bioscience Engineering faculty of the University of Ghent. Wolter Prins published around a hundred papers in the area of novel gas-solid reactors, heat and mass transfer in fluidized beds, and thermochemical conversion of biomass. He participated in the European Network for Pyrolysis (Pyne) for many years, and was invited by NEDO and the Chinese Academy of Sciences to present his work in Japan and China respectively.
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Review

Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

0.04 Mass Loss Rate (wt.%/C) Mass Loss Rate (wt.%/C)

0 0 100 200 300 400 500 Temperature (C)

0 0 100 200 300 400 500 Temperature (C)

Gas (g) (CO,CO2,CH4) bio-oil (l)

Char (s) + gas (CO2) + bio-oil (l)

Wood (s) Char (s)

Wood vapors (g)

Gas (g) (CO,CO2,CH4) Re-polymerisation

atmospheric weeks / months

Figure 2: Representation of the reaction paths for wood pyrolysis.

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

10 0 0 1 2 3 4 5 6 7 8 Ash content (wt.%)

Review: Fast pyrolysis technology development

BIO-OIL water extraction

WATER-SOLUBLES ether extraction

WATER INSOLUBLES DCM extraction DCM SOLUBLES DCM INSOLUBLES

LMM lignin (low molecular lignins, extractives)

Figure 5. Fractionation scheme for chemical characterization.25

Review: Fast pyrolysis technology development

Ethylene glycol Isopropanol

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Figure 6A. Ablative, CFB and vacuum technologies.

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Figure 8. ForesteraTM pilot: reactor and product storage area.

Review: Fast pyrolysis technology development

<10 mm <10 % moisture

Inert carrier gas

740 250 2,400 470

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Figure 9. The Pyrovac installation in Jonquire, Canada ( Christian Roy).48

Review: Fast pyrolysis technology development

Figure 11. Photo of the rotating cone reactor.

Review: Fast pyrolysis technology development

wet air 2e shredder

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Stack NOx Stack losses 33 MWth

6 River cooling 274 MWth

Figure 14. Mass and energy balances of Harculo power station.

Output Heat [MWth]

Efciency Heat [MWth]

* natural gas LHV: 35.57 MJ/Nm3; 0.808 kg/Nm3

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

OVERALL BIOREFINERY CONCEPT incorporating fractionation with liquefaction

Derivatives of hemicelluloses and celluloses Process residues Energy production

Figure 15. Biocoups concept of co-rening bio-oil in existing reneries.

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development

Review: Fast pyrolysis technology development