Thermal Pretreatment of Lignocellulosic Biomass

Wei Yan, Tapas C. Acharjee, Charles J. Coronella, and Victor R. Va squez Chemical and Metallurgical Engineering Department, University of Nevada, MS170 Reno, NV 89557; coronella@unr.edu (for correspondence)
Published online 5 August 2009 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ep.10385

Torrefaction is a process to convert diverse lignocellulosic biomass feedstocks into an energy dense homogeneous solid, a pretreatment for subsequent thermochemical conversion. Loblolly pine was treated by wet torrefaction (hot compressed water, 2002608C) and dry torrefaction (nitrogen, 2503008C), with mass yield of solid product ranging between 57 and 89%, and energy densication to 108136% of the original feedstock. The solid product has been characterized, including proximate analysis, ber analysis, ultimate analysis, and equilibrium moisture. In both dry and wet torrefaction, increasing temperature results in decreased mass yield and increased energy densication, and results in a solid with increased carbon content, decreased oxygen content, and decreased volatiles. The biomass is transformed into a fuel similar to a low-rank coal. Generally, the wet torrefaction process produces a solid with greater energy density than dry torrefaction, with the same mass yield. The ber analysis indicates that hemicellulose is quickly removed during wet torrefaction, and the solid product contains substantial quantities of aqueous soluble compounds. The equilibrium moisture content of solids produced by both processes is somewhat decreased from that of the biomass feedstock, indicating a hydrophobic solid suitable for storage and transportation. 2009 American Institute of Chemical
Engineers Environ Prog, 28: 435440, 2009

Keywords: biomass pretreatment, torrefaction, lignocellulosic biomass, thermochemical conversion

INTRODUCTION

Thermochemical conversion is a promising route to convert lignocellulosic biomass to fuel, chemicals, and renewable power [1, 2]. However, both pyrolysis and gasication of raw biomass feedstock have significant, but distinct, technical barriers that must be
2009 American Institute of Chemical Engineers

eliminated for widespread successful commercialization [2, 3]. In both cases, feedstock handling is complex due to the diverse nature of important feedstocks, including commercial timber, agricultural residues as diverse as rice hulls, corn stover and wheat chaff, and energy crops such as switch grass. Seasonal availability and low forest density make feedstock logistics complex and expensive. To solve these problems, there is a need for a process to homogenize the feedstocks, while simultaneously producing a stable, energy-dense, solid fuel. Two distinct thermal pretreatment technologies are investigated in this study: wet torrefaction and dry torrefaction. In the process we call wet torrefaction, also known as hydrothermal pretreatment, biomass is treated in hot compressed water, resulting in three products, including gases, aqueous chemicals, and a solid fuel [46]. The temperature is in the range of 2002608C, and the pressures are up to 700 psi. The solid product contains about 5590% of the mass and 8095% of the fuel value of the original feedstock. The gas product is about 10% by mass of the feedstock, and the aqueous chemicals, primarily sugars, make up the balance [79]. On the other hand, dry torrefaction, sometimes called low-temperature pyrolysis, is a process in which the biomass is heated in an inert gas environment at temperatures ranging from 200 to 3008C [3, 1012]. The dry torrefaction reaction has two products, a solid and a gas. The solid has about 6080% of the mass, and approximately 7090% of the fuel value of the original biomass [1012]. Both torrefaction processes exhibit some common features. The solid product has a higher energy density relative to the starting biomass feedstock in both cases. Both solid products are easily friable and have an aroma similar to wood char. The reaction mechanisms of both torrefaction processes are poorly understood. The objective of this work is to investigate how
October 2009 435

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep

both torrefaction processes affect product distribution and to assess the quality of solid products for thermochemical conversion. Characterization of solid products is performed, which includes proximate analysis, ultimate analysis, higher heating value, ber analysis, and equilibrium moisture content. A comparative study is made to elucidate the capability of both thermal pretreatment technologies to homogenize lignocellulosic biomass and produce the immediate solid fuel for thermochemical conversion.

Analytical Methods
Proximate Analysis

MATERIALS AND METHODS

Biomass and Chemicals Loblolly pine (Alabama, USA) was acquired as a typical lignocellulosic biomass for torrefaction. The solutions and lter bags for ber analysis were purchased from ANKOM Technology Inc (Macedon, NY).

Solid samples were analyzed with Perkin Elmer TGA-7 Thermogravimetric Analyzer (Waltham, MA) to determine the contents of moisture, volatile matter, and xed carbon [13]. Thermogravimetric analysis was carried out under a nitrogen purge at a constant rate of 50 mL/min to prevent oxidation of samples. Samples were rst heated up to 1058C at the rate of 108C/min, maintained at 1058C for 10 min, then jump to 9008C at the rate of 508C/min and hold for 60 min. Mass evolved at 1058C is said to be moisture. Mass evolved at temperatures between 105 and 9008C belongs to volatiles. All mass remaining after heating to 9008C consists of xed carbon and ash. Ash content of the pretreated biomass was measured separately using a standard method for ash in biomass [14]. The solid sample was rst dried at 1058C for 24 h and brought to constant weight by igniting at 5758C for 5 h in a mufe furnace.
Ultimate Analysis

Wet Torrefaction Wet torrefaction of loblolly pine was performed in a 100-mL Parr bench-top reactor (Moline, IL) at temperatures ranging from 200 to 2608C. The temperature of the reactor was controlled using PID controller. The reactor pressure was not controlled but indicated by a pressure gauge and ranged from 200 to 700 psi, approximately in accord with the water vapor pressure. For each run, a mixture of loblolly pine and water (water:biomass 5 5:1, w/w) was loaded into the reaction vessel. The biomass sample size was about 2 g. Prior to the reaction, the biomass was stirred manually to ensure complete wetting. Nitrogen was passed through the reactor for 10 min to purge oxygen out of the reactor. The reactor was heated up in 1530 min and maintained at the desired temperature for a desired period of time (5 min). Then, the reactor was cooled to room temperature rapidly by immersion in an ice bath. The gas sample was released. The liquid sample and solid sample were separated and collected for further analysis.

Solid samples were dried in an oven at 1058C for 24 h. Ultimate analysis of both biomass feedstock and pretreated biomass was performed with a FlashEA 1112 (Pittsburgh, PA) elemental analyzer for full determination of C, H, N, S, and O [15].

Higher Heating Value

The higher heating value (HHV) of solid samples was measured in a Parr 1241 adiabatic oxygen bomb calorimeter (Moline, IL) tted with continuous temperature recording [16]. The sample (0.20.5 g) was dried at 1058C in the oven for 24 h prior to analysis.
Fiber Analysis

Dry Torrefaction Dry torrefaction of loblolly pine was carried out in the 100-mL Parr reactor described above, but tted with a glass sample holder to separate the biomass from the hot reactor walls. The pretreatment was performed with a nitrogen ow rate of 10 mL (STP)/min. The glass sample loader with biomass particles (5 g) were placed in the center of reactor. The torrefaction temperature was between 250 and 3008C and was controlled using a PID controller. The temperature program consists of a dynamic heating period following by an isothermal period. After a desired isothermal reaction period (80 min), the sample was cooled to room temperature with continuous nitrogen ow through the reactor. The solid sample was collected for further analysis.
436 October 2009

A modied Van Soest method using the ANKOM A200 Filter Bag Technique (FBT) was used to determine the contents of hemicellulose, cellulose, lignin, and aqueous soluble compounds in solid samples [17, 18]. The solid samples are rst crushed and sieved to the desired particle size (2065 mesh) and were dried at 1058C for 24 h prior to the analysis. The contents of hemicellulose, cellulose, lignin, and solubles were calculated from the difference of neutral detergent ber (NDF), acid detergent ber (ADF), acid detergent liquid (ADL), and ash.
Equilibrium Moisture Content

Previous literature has suggested that torrefaction solid products are relatively hydrophobic [12]. To evaluate that report, the equilibrium moisture content (EMC) was measured at 308C by the static desiccator technique. The solid sample is exposed to an environment with constant humidity and temperature over a long period of time, until the moisture in the solid reaches an equilibrium value. The humidity in the chamber is maintained at a constant value by keeping the air in equilibrium with an aqueous solution that is saturated with a particular salt [19]. Two salt solutions were used, with relative humidities 11.3 and 83.6% for lithium chloride and potassium

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep

Table 1. Thermal pretreatment of loblolly pine.

Pretreatment Wet torrefaction Dry torrefaction

Temperature (8C) 200 230 260 250 275 300

Mass yield (%) 88.7 70.6 57.0 83.8 74.2 60.5

HHV (cal/g) 5043.3 5276.8 6342.5 5005.4 5207.2 5627.4

Energy densication ratio 1.08 1.13 1.36 1.07 1.12 1.21

Energy yield (%) 95.8 79.8 77.5 89.7 83.1 73.2

The HHV of dried loblolly pine is 4669.8 cal/g.

Table 2. Ultimate analysis of biomass feedstock and thermal pretreated solid products.

Pretreatment Biomass Wet torrefaction Dry torrefaction

Temperature (8C) 200 230 260 250 275 300

C (%) 50.25 54.72 56.05 72.07 50.73 52.27 54.81

H (%) 5.97 6.03 5.94 4.90 6.21 6.13 5.94

N (%) 0 0.14 0.09 0.16 0.12 0.15 0.14

S (%) 0 0 0 0 0 0 0

O (%) 43.34 39.11 37.92 22.89 42.94 41.45 39.11

chloride, respectively. The solid sample (3 g) was dried at 1058C for 24 h and then immediately transferred into the chamber for 811 days to reach the equilibrium. Equilibrium was determined when the sample mass was constant for three consecutive days.
RESULTS AND DISCUSSION

Wet and dry torrefaction of loblolly pine were performed at various temperatures. All thermal pretreatments and analytical experiments were performed at least twice, and mean values are reported. Mass yield, energy densication ratio, and energy yield are three important measures in this study, which are dened as: Mass yield Mass of dried pretreated solid 3 100% Mass of dried biomass

Energy densification ratio HHV of dried pretreated solid HHV of dried biomass Energy yield mass yield 3 energy densification ratio As summarized in Table 1, the results show that reaction temperature is a signicant variable in both pretreatment processes. In both cases, increasing temperature causes a reduction in both mass and energy yields, while energy densication increases. Over the temperature ranges studied, with similar mass yields,

wet torrefaction yields a higher energy densication, and hence higher energy yield, than dry torrefaction. For example, wet torrefaction at 2608C has a mass yield of 57.0% and an energy yield of 77.5%, while the mass yield of torrefaction at 3008C is 60.5% and the energy yield is 73.2%. Apparently, wet torrefaction is more successful at energy densication. Table 2 shows ultimate analysis of biomass feedstock and thermal pretreated solids. Both torrefaction processes produce a solid fuel with increased carbon content and decreased oxygen content. This is consistent with an increase in energy density of thermal pretreated solids. The change in carbon and oxygen content is signicant, but less dramatic in the case of dry torrefaction. Wet torrefaction can signicantly increase carbon content from 50 up to 72%, and decrease oxygen content from 43 down to 23%. Proximate analysis is commonly used to establish the rank of coals [13] and other solid fuels for suitability of combustion, pyrolysis, and gasication. Table 3 shows the proximate analysis of loblolly pine and torreed loblolly pine. The proximate analysis of raw feedstock is similar to the proximate analysis of biomass wet torreed at low temperatures (200 and 2308C), and it is also similar to that of biomass dry torreed at low temperatures (250 and 2758C). However, when processed at higher temperatures (2608C in the case of wet torrefaction, 3008C in the case of dry torrefaction), the pretreated biomass exhibits decreased volatiles and increased xed carbon content. This result is consistent with trends reported in the literature [20] correlating increased heating value with increasing xed carbon content. The proximate and ultimate analyses suggest that torrefaction converts biomass from a low energy-density feedstock
October 2009 437

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep

Table 3. Proximate analysis of biomass feedstock and thermal pretreated solid products.

Pretreatment Biomass Wet torrefaction Dry torrefaction

Temperature (8C) 200 230 260 250 275 300

Moisture (%) 3.6 1.3 1.3 1.3 0 0 0

Volatiles (%) 83.7 87.1 83.8 73.2 87.7 83.0 82.3

Fixed carbon (%) 12.3 12.4 15.8 26.3 11.8 16.4 17.0

Ash (%) 0.4 0.5 0.4 0.5 0.5 0.6 0.7

Table 4. Fiber analysis of biomass feedstock and thermal pretreated solid products; conversion of individual ber components, relative to initial starting feedstock.

Pretreatment

Temperature (8C)

Hemicellulose (%)

Cellulose (%)

Lignin (%)

Aqueous solubles (%)

Ash (%) 0.4 0.5 0.4 0.5 0.5 0.6 0.7

A. Fiber analysis of biomass feedstock and thermal pretreated solid products Biomass 11.9 54.0 25.0 8.7 Wet torrefaction 200 0.4 47.4 27.8 24.3 230 0 44.1 30.2 25.3 260 0 33.9 33.8 31.8 Dry torrefaction 250 9.2 51.0 34.1 5.2 275 6.5 52.7 36.7 3.5 300 2.3 32.7 62.1 2.2 B. Conversion of individual ber components, relative to initial starting feedstock Wet torrefaction 200 97.0 22.1 1.4 2147.7 230 100.0 42.3 14.7 2105.3 260 100.0 64.2 22.9 2108.3 Dry torrefaction 250 35.2 20.9 214.3 49.9 275 59.5 27.6 28.9 70.1 300 88.3 63.4 250.3 84.7 A negative conversion indicates a ber compound that was apparently produced by torrefaction.

into a high energy-density feedstock, which may have favorable properties for application as a fuel for thermal conversion processes. Fiber analysis is used to show the reactions of the primary components of lignocellulosic biomass, which may help elucidate the reaction mechanism in both pretreatments. Table 4a, as described above the distribution of hemicellulose, cellulose, lignin, aqueous soluble compounds, and ash of the biomass feedstock and pretreated solids. If each ber fraction is considered as a separate component, it is possible to determine the conversion of each component by torrefaction with the aid of the mass yield shown in Table 1. Table 4b, as described above the conversion of each of hemicellulose, cellulose, lignin, and soluble compounds using this approach. A negative conversion indicates that more of that compound is present after torrefaction than was present in the raw biomass. Inspection of Table 4 indicates several noteworthy trends. First, with respect to wet torrefaction, the hemicellulose is nearly completely removed at 2008C, and it is completely reacted at 230 and 2608C. Hemicellulose is clearly quite reactive in hot water. Also
438 October 2009

note that both cellulose and lignin are partially reacted by hot water, and the extent of reaction increases with temperature. Most interesting is the nding that aqueous soluble compounds are apparently produced by the wet torrefaction reaction. This can be explained by considering the products of the degradation of hemicellulose and cellulose, assumed to consist primarily of sugars. The remaining solid product is very porous, and water soluble products are apparently deposited onto the pores of the solid, leaving behind signicant quantities of these compounds. Apparently, the solvents used in the ber analysis are strong enough to remove these compounds. A similar conclusion was reached in a prior study [6]. Next consider the ber analysis of solid product produced by dry torrefaction, also shown in Table 4. Hemicellulose and aqueous soluble compounds are quite reactive, and are reacted at rates increasing with temperature. Cellulose exhibits similar, albeit slower, behavior. Dry torrefaction apparently produces compounds that behave in a manner identical to that of lignin in the NDF/ADF/ADL ber analysis, especially

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep

Table 5. Equilibrium moisture content of biomass feedstock and thermal pretreated solid products.

Pretreatment Biomass Wet torrefaction Dry torrefaction

Temperature (8C) 200 230 260 250 275 300

EMC (%), RH 5 11.3% 3.5 1.8 0.9 0.4 2.3 2.2 2.3

EMC (%), RH 5 83.6% 15.6 12.8 8.2 5.3 10.4 8.7 8.7

RH, relative humidity. All EMC measurements were done at 308C.

at 3008C. This was unexpected, but might be explained in consideration of the chemistry of the torrefaction reaction. Previous work [21] described low temperature pyrolysis of cellulose as a scission reaction with signicant aromatization and cross-linking, producing a solid which has characteristics similar to that of lignin. At 250 and 2758C, generation of lignin-like compounds was quite limited, but at 3008C, signicant lignin was generated; this is seen as consistent with the aromatization reactions described above. Equilibrium moisture content (EMC) can be used as an indicator of hydrophobicity of a solid. For lignocellulosic biomass, moisture can be absorbed into the cell walls and hydrogen-bonded to the hydroxyl groups of the cell wall components [22]. Breakdown of these hydroxyl groups with thermal pretreatments results in lower EMC and the solid is said to become more hydrophobic. A solid with reduced EMC can be stored stably over time, with low risk of biological deterioration. Also, transportation of stored hydrophobic solids is less expensive, because there will less moisture to transport along with the biomass. Table 5 clearly shows that pretreated solids become more hydrophobic in comparison with biomass feedstock. The EMC of pretreated biomass decreases with increasing pretreatment temperature, and wet torrefaction produces a solid more hydrophobic than that produced by dry torrefaction. At RH 5 84%, EMC of torreed biomass decreases from 16% for raw biomass to 5% (wet process) and to 9% (dry process).
CONCLUSION

biomass has been transformed into a fuel with properties resembling low rank coal. The reduced EMC indicates that the pretreated solid is more hydrophobic and can be easily stored to accommodate seasonal availability. Although both thermal pretreatments show some common features, the reaction mechanism is quite different as reected by the ber analysis. In wet torrefaction, hemicellulose is very reactive even at 2008C, while both cellulose and lignin can be dissolved partially at higher temperatures. Both cellulose and hemicellulose are somewhat reactive in dry torrefaction, producing a solid that resists dissolution, similar to lignin. The solid product produced by dry torrefaction is not at all soluble by ber analysis measurements. This study reports analysis on initial scoping experiments; there is no attempt to optimize the conditions of torrefaction. In particular, the optimal reaction time and temperature have not been identied, nor have reaction kinetics. Pretreated biomass presumably will be pelletized for feeding to a thermochemical conversion process, and there is no attempt here to describe the solid characteristics for required handling (friability, morphology, etc.). To establish techo-economic feasibility, mass and energy balance of both torrefaction processes and the subsequent thermal conversion process (e.g. gasication or fast pyrolysis) must be investigated as well. We anticipate further reports from our lab and from other labs on these issues.

ACKNOWLEDGMENTS

Wet and dry torrefaction are promising methods to convert diverse lignocellulosic biomass feedstocks to a homogeneous solid fuel for subsequent thermochemical conversion. In both thermal pretreatments, reaction temperature signicantly affects the product distribution and energy densication, and character of solid product. The energy density of pretreated loblolly pine can be increased by 736%, depending on the pretreatment conditions. Torreed biomass has increased xed carbon (proximate analysis) and atomic carbon (ultimate analysis), indicating that the

We gratefully acknowledge nancial support from the US Department of Energy (Award Number: DEFG36-01GO11082). The authors acknowledge meaningful conversations with project partners, including Larry Felix of the Gas Technology Institute (GTI), Kent Hoekman of the Desert Research Institute (DRI), and Craig Einfeldt of Changing World Technologies (CWT). The authors gratefully acknowledge assistance of Jeremey Riggle of DRI for his help in conducting the ultimate analyses, and assistance of Jason Hastings at UNR who conducted most of the torrefaction experiments.
October 2009 439

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep

LITERATURE CITED

1. Tester, J.W. (2005). Sustainable energy, Cambridge, Massachusetts: MIT Press. 2. U.S. Department of Energy. (2008). Biomass multiyear program, Ofce of the Biomass Program, Energy Efciency and Renewable Energy. 3. Prins, M.J., Ptasinski, K.J., & Janssen, J.J.G.F. (2006). More efcient biomass gasication via torrefaction, Energy, 31, 34583470. 4. Ando, H., Sakadi, T., Kokusho, T., Shibata, M., Uemura, Y., & Hatate, Y. (2000). Decomposition behavior of plant biomass in hot-compressed water, Industrial and Engineering Chemistry Research, 39, 36883693. 5. Sasaki, M., Adschiri, T., & Arai, K. (2003). Fractionation of sugarcane bagasse by hydrothermal treatment, Bioresource Technology, 86, 301304. 6. Yan, W., Coronella, C.J., & Vasquez, V.R. Wet torrefaction of lignocellulosic biomass, Biomass Bioenergy, Submitted for publication. 7. Sun, Y. & Cheng, J. (1992). Hydrolysis of lignocellulosic material from ethanol production, Bioresource Technology, 39, 107115. 8. Bobleter, O. (1994). Hydrothermal degradation of polymers derived from plants, Progress in Polymer Science, 19, 797841. 9. Pertersen, M., Larsen, J., & Thomsen, H.M. (2009). Optimization of hydrothermal pretreatment of wheat straw for production of bioethanol at low water consumption without addition of chemicals, Biomass Bioenergy, 33, 834840. 10. Prins, J.M., Ptasinski, J.K., & Janssen, J.J.G.F. (2006). Torrefaction of wood. I. Weight loss kinetics, Journal of Analytical and Applied Pyrolysis, 77, 2834. 11. Prins, J.M., Ptasinski, J.K., & Janssen J.J.G.F. (2006). Torrefaction of wood. II. Analysis of products, Journal of Analytical and Applied Pyrolysis, 77, 3540.

12. Bergman, P.C.A., Boersma, A.R., Zwart, R.W.R., & Kiel, J.H.A. (2005). Torrefaction for biomass coring in existing coal-red power stations (Biocoal), Energy Research Centre of the Netherlands, ECN-C-05-013. 13. Donahue, J.C. & Rais, A.E. (2009). Proximate analysis of coal, Journal of Chemical Education, 86, 222224. 14. Ehrman, T. (1994). Standard method for ash in biomass, NREL Laboratory Analytical Procedure LAP-005. 15. ASTM D3176-89.(2002). Standard practice for ultimate analysis of coal and coke, West Conshohocken, PA: ASTM International. 16. Operating instructions for the 1241 oxygen bomb calorimeter, Parr Instruments, No. 203M, pp. 1 13. 17. Goering, H.K. & Van Soest, P.J. (1970). Forage ber analysis, USDA Agriculture Handbook, 379, 19. 18. ANKOM. (1995). Acid detergent and neutral detergent ber using ANKOMs ber analyzer F200, Fairport, NY: Ankom Technology Corporation. 19. Mehta, S. & Sing, A. (2006). Adsorption isotherms for red chili, European Food Research Technology, 223, 849852. 20. Ayhan, D. (2003). Relationships between heating value and lignin, xed carbon and volatile material contents of shells from biomass products, Energy Source, 25, 62935. 21. Agrawal, K.R. (1988). Kinetics of reactions involved in pyrolysis of cellulose. I. The three reaction model, Canadian Journal of Chemical Engineering, 66, 403412. 22. Andersson, M. & Tillman, A.M. (1989). Acetylation of jute: effects on strength, rot resistance and hydrophobicity, Journal of Applied Polymer Science, 37, 34373447.

440 October 2009

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep