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Department of Wood and Paper Science, Chungbuk National University, Cheongju 361-763, South Korea
Department of Forest Genetic Resources, Korea Forest Research Institute, Suwon 441-350, South Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 September 2013
Received in revised form
10 January 2014
Accepted 29 January 2014
Available online xxx
In acid hydrolysis of plant biomass, polysaccharides are converted to monosaccharides, which is basic
raw material for biorenery for fermentation based process. These monosaccharides, however, are not
stable in acidic reaction medium, and are converted to organic acids via furans. Impact of hemicelluloses
and lignin on acid hydrolysis of cellulose was investigated to focus on monosaccharide production with
different degrees of cellulose purity. Two-step concentrated sulphuric acid process was applied to
biomass for monosaccharide conversion. Kinetics of cellulose hydrolysis was analysed using 1H NMR
spectroscopy. Higher reaction temperature in secondary hydrolysis caused severe degradation of the
monosaccharides. In pure and holocellulose, further reaction of glucose in acidic reaction medium
produced formic acid and levulinic acid. However, lignocellulosic biomass generated much less formic
acid and levulinic acid under the same reaction condition. Humin (or pseudo-lignin) was also formed by
the condensation of lignin and furans from monosaccharides in acidic reaction condition. Thus, the
fermentation inhibitors, furans and formic acid, were generated in low quantities by lignocellulosic
biomass than by delignied biomass such as pure cellulose or holocellulose.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Acid hydrolysis
Cellulose
Xylan
Lignin
Formic acid
1
H NMR
1. Introduction
More than 400 thousand years, re has been used as energy
with lignocellulosic biomass as raw material. Lignocellulosic
biomass is formed by glucose, which is converted from carbon dioxide and water at chlorophyll in plant leaf with sunlight energy.
Since civilization, cooking and heating have used wood as solid
fuels until replaced by coal and petroleum-based products. However, global warming and depleting of crude oils lead to more
attraction on renewable energy.
Although renewable energy is an important energy resource in
many countries, less than 15% of primary energy is supplied by
renewable resources [1e3]. Technological progress and global
warming have led to increased application of renewable energies in
modern world. Energy which does not increase the carbon dioxide
in the atmosphere and can be produced by continuously is called as
renewable energy. Geo-thermal, wind, tidal, photovoltalic and
biomass energy is classied as renewable energy category.
Biomass is an important renewable resource that can replace
petroleum-based energy and chemicals [4e6]. Cellulose is the most
abundant organic material and is produced by dehydration and
http://dx.doi.org/10.1016/j.energy.2014.01.104
0360-5442/ 2014 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104
Table 1
Chemical composition of avicell cellulose and goat willow (unit: %).
Avicell cellulose
Goat willow
Acetone
soluble
extractives
Hot-water
soluble
extractives
Lignin
Celluose
Xylan
e
0.8
e
11.4
e
18.3
85.0
51.0
15.0
18.5
Fig 3. Conversion from cellulose to glucose with different second hydrolysis reaction
temperature.
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104
Fig 4. Conversion from cellulose to formic acid with different second hydrolysis reaction temperature.
Fig 5. Different respond to acid hydrolysis with different cellulose raw material (reaction temperature of second hydrolysis with 100 C).
Fig 6. Different respond to acid hydrolysis with different cellulose raw material (reaction temperature of second hydrolysis with 120 C).
Fig 7. Conversion from cellulose to formic acid with different cellulose raw material
(reaction temperature of second hydrolysis with 100 C).
Fig 8. Conversion from cellulose to formic acid with different cellulose raw material
(reaction temperature of second hydrolysis with 120 C).
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104
[13] Rollin JA, Zhu Z, Sathitsuksanoh N, Zhang YHP. Increasing cellulose accessibility is more important than removing lignin: a comparison of cellulose
solvent-based lignocellulose fractionation and soaking in aqueous ammonia.
Biotechnol Bioeng 2011;108(1):22e30.
[14] Shin S-J, Park J-M, Cho DH, Kim YH, Cho N-S. Acid hydrolysis characteristics of
yellow poplar for high concentration of monosaccharides production. J Korean
Wood Sci Technol 2009;37:578e84.
[15] Iranmahboob J, Nadim F, Monemi S. Optimizing acid-hydrolysis: a critical step
for production of ethanol from mixed wood chips. Biomass Bioenergy
2002;22(5):401e4.
[16] Baltz RA, Burcham AF, Sitton OC, Book NL. The recycle of sulphuric acid and
xylose in the prehydrolysis of corn stover. Energy 1982;7(3):259e65.
[17] Sridhar P, Subramaniam G. Recovery of acid from cation exchange
resin regeneration waste by diffusion dialysis. J Membr Sci 1989;45(3):
273e80.
[18] Jeong J, Kim M-S, Kim B-S, Kim S-K, Kim W-B, Lee J-C. Recovery of H2SO4 from
waste acid solution by diffusion dialysis method. J Hazard Mater 2005;124:
203e5.
[19] Alzate CAC, Toro OJS. Energy consumption analysis of integrated owsheets
for production of fuel ethanol from lignocellulosic biomass. Energy
2006;31(13):2447e59.
[20] Felix E, Tilley DR. Integrated energy, environmental and nancial analysis
of ethanol production from cellulosic switchgrass. Energy 2009;34(4):
410e36.
[21] Yuksel F, Yuksel B. The use of ethanolegasoline blend as a fuel in an SI engine.
Renew Energy 2004;29(7):1181e91.
[22] Mack JH, Aceves SM, Dibble RW. Demonstrating direct use of wet ethanol in a
homogeneous charge compression ignition (HCCI) engine. Energy 2009;34(6):
782e7.
[23] Irimescu A. Fuel conversion efciency of a port injection engine fuelled with
gasolineeisobutanol blends. Energy 2011;36:3030e5.
[24] Tran LS, Sirjean B, Glaude P-A, Rournet R, Battin-Leclerc B. Progress in detailed
kinetic modelling of the combustion of oxygenated components of biofuels.
Energy 2012;43:4e18.
[25] Shin S-J, Cho N-S. Conversion factors for carbohydrate analysis by hydrolysis
and 1H-NMR spectroscopy. Cellulose 2008;15:255e60.
[26] Shin S-J. Quantitative analysis of reaction products from glucose and xylose in
acidic aqueous medium by 1H-NMR spectroscopic method. J Kor Wood Sci
Technol 2013;41(4):287e92.
[27] Angyal SJ. The composition of reducing sugars in solution. Adv Carbohydr
Chem Biochem 1984;42:15e68.
[28] Kiemle DJ, Stipanovic A, Mayo KE. Proton NMR methods in the compositional
characterization of polysaccharides. In: Gatenholm Tenenkanen M, editor.
Hemicelluloses: science and technology. Washington, DC: Oxford University
Press; 2002. pp. 122e39.
[29] Girisuta B, Janssen LPBM, Heeres HJ. A kinetic study on the decomposition of
5-hydroxymethylfufural into levulinic acid. Green Chem 2006;8:701e9.
[30] Yang L, Yang N, Pang H, Liao B. Production of levulinic acid from bagasse and
paddy straw by liquefaction in the presence of hydrochloride acid. Clean
2008;36(2):158e63.
[31] Sim J, Shin S-J. Quantitative analysis of 5-HMF produced from fructose. J Korea
TAPPI 2013;45(1):27e34.
[32] Sjostrom E. Wood chemistry. 2nd ed. San Diego: Academic Press; 1993.
[33] Zhao H, Kwak JH, Zhang ZC, Brown HM, Arey BW, Holladay JE. Studying cellulose ber structure by SEM, XRD, NMR and acid hydrolysis. Carbohydr
Polymer 2007;68(2):235e41.
[34] Cho DH, Shin S-J, Kim YH. Effects of acetic and formic acid on ABE production
by Clostridium acetobutylicum and Clostridium beijerinckii. Biotechnol Bioprocess Eng 2012;17:270e5.
[35] Patil SKP, Lund CRF. Formation and growth of humins via aldol addition and
condensation during acid-catalyzed conversion of 5-hydroxymethylfurfural.
Energy Fuels 2011;25:4745e55.
[36] van Zandvoort I, Wang Y, Rasrendra CB, van Eck ERH, Bruijnincx PCA,
Heeres H, et al. Formation, molecular structure, and morphology of humins in
biomass conversion: inuence of feedstock and processing conditions. Chem
Sus Chem 2013;6:1745e58.
Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104