Soil Research Soil Research Society
Soil, land care and environmental research
RESEARCH ARTICLE

Chemical and structural properties of carbonaceous products obtained by pyrolysis and hydrothermal carbonisation of corn stover

A. B. Fuertes A , M. Camps Arbestain B F , M. Sevilla A , J. A. Maciá-Agulló A , S. Fiol C , R. López C , R. J. Smernik D , W. P. Aitkenhead B , F. Arce C and F. Macias E

A Instituto Nacional del Carbón (CSIC), Apartado 73, 33080-Oviedo, Spain.

B New Zealand Biochar Research Centre, Private Bag 11222, Massey University, Palmerston North 4442, New Zealand.

C Departamento de Química Física, Facultad de Química, Universidad de Santiago de Compostela, 15782-Santiago de Compostela, Spain.

D School of Agriculture, Food and Wine, The University of Adelaide, Waite Campus, Urrbrae, SA 5064, Australia.

E Departamento de Edafología y Química Agrícola, Facultad de Biología, Universidad de Santiago de Compostela, 15782-Santiago de Compostela, Spain.

F Corresponding author. Email: M.Camps@massey.ac.nz

Australian Journal of Soil Research 48(7) 618-626 http://dx.doi.org/10.1071/SR10010
Submitted: 5 January 2010  Accepted: 10 May 2010   Published: 28 September 2010

Abstract

The main properties of chars produced from corn stover, either by pyrolysis at 550°C (to produce biochar) or by hydrothermal carbonisation (to produce hydrochar), were studied. Carbonaceous materials were characterised by: SEM imaging, solid-state 13C NMR, FT-IR, Raman spectroscopy, and XPS. The following parameters were determined: elemental composition, cation exchange capacity, acid groups contents, BET, and yield. The hydrochar had a low ash content and low pH (4.7); recovery of C was high (57%), although only about half of the C was aromatic. Atomic O/C and H/C ratios in the hydrochar were higher than in the biochar. The same pattern was observed for the estimated concentration of carboxylic functional groups (0.07 compared with 0.04 mol/kg). The biochar had higher ash content than the hydrochar, and also higher pH (~10) (lime equivalence ~40 kg CaCO3/t). The C recovery (46%) was lower than in the hydrochar, although most of the C recovered was aromatic. Both chars could be used as soil amendments, for very different requirements. Soil responses and the residence times of the chars (especially the hydrochar) must be studied in detail to pursue long-term C sequestration.

Additional keywords: biochar, hydrochar, hydrothermal carbonisation, pyrolysis.


References

Amonette J , Joseph S (2009) Characteristics of biochar. Microchemical properties. In ‘Biochar for environmental management’. (Eds J Lehmann, S Joseph) pp. 33–52. (Earthscan Publications Ltd.: London)

Antal MJ Jr Grønli M 2003 The art, science, and technology of charcoal production. Industrial & Engineering Chemistry Research 42 1619 1640 doi:10.1021/ie0207919

Bergius F , Specht H (1913) ‘Die Anwendung hoher Drucke bei chemischen Vorgängen und eine Nachbildung des Entstehungsprozesses der Steinkhole.’ (Verlag, Wilhelm Knapp: Halle an der Saale, Germany)

Berl E Schmidt A 1932 Über die entstehung der kohlen. II. Die inkohlung von cellulose und lignin in neutralem medium. Justus Liebigs Annalen der Chemie 493 97 123 doi:10.1002/jlac.19324930106

Calvelo-Pereira R , Pardo-Lorenzo R , Aitkenhead W , Macias F , Hedley M , Macia-Agullo JA , Camps-Arbestain M (2010) Influence of pyrolysis temperature on heterotrophic basal soil respiration in biochar/soil mixtures. In ‘NZBRC Biochar Workshop’. Palmerston North, New Zealand, 11–12 February 2010. (Massey University: Palmerston North, New Zealand)

Camps Arbestain M (2010) Biochar research at the NZBRC. The Soil Science Stream. Massey University, Palmerston North, NZ. Available at: www.biochar.co.nz/pdf/NZBRC-2010-v2.pdf

Chapman HD (1965) Cation exchange capacity. In ‘Methods of soil analysis’ (Eds CA Black et al.) (American Society of Agronomy, Inc.: Madison, WI). Agronomy 9, 891–901.

Cheng CH Lehmann J Engelhard MH 2008 Natural oxidation of black carbon in soils: changes in molecular form and surface charge along a climosequence. Geochimica et Cosmochimica Acta 72 1598 1610 doi:10.1016/j.gca.2008.01.010

Cheng CH Lehmann J Thies JE Burton SD Engelhard MH 2006 Oxidation of black carbon by biotic and abiotic processes. Organic Geochemistry 37 1477 1488 doi:10.1016/j.orggeochem.2006.06.022

Cuesta A Dhamelincourt P Laureyns J Martinez-Alonso A Tascon JMD 1994 Raman microprobe studies on carbon materials. Carbon 32 1523 1532 doi:10.1016/0008-6223(94)90148-1

Downie A , Crosky A , Munroe P (2009) Physical properties of biochar. In ‘Biochar for environmental management. Science and technology’. (Eds J Lehmann, S Joseph) pp. 13–32. (Earthscan: London)

Guo Y Bustin RM 1998 FTIR spectroscopy and reflectance of modern charcoal and fungal decayed woods: Implications for studies of inertite in coals. International Journal of Coal Geology 37 29 53 doi:10.1016/S0166-5162(98)00019-6

Haberhauer G Rafferty B Strebl F Gerzabek MH 1998 Comparison of the composition of forest soil litter derived from three different sites at various decompositional stages using FTIR-spectroscopy. Geoderma 83 331 342 doi:10.1016/S0016-7061(98)00008-1

Hu B Wang K Wu L Yu S-H Antonietti M Titirici MM 2010 Engineering carbon materials from hydrothermal carbonization process of biomass. Advanced Materials 22 813 828 doi:10.1002/adma.200902812

Ibarra JV Munoz E Moliner R 1996 FTIR study of the evolution of coal structure during coalification process. Organic Geochemistry 24 725 735 doi:10.1016/0146-6380(96)00063-0

Karagöz S Bhaskar T Muto A Sakata Y Oshiki T Kishimoto T 2005 Low-temperature catalytic hydrothermal treatment of wood biomass: analysis of liquid products. Chemical Engineering Journal 108 127 137 doi:10.1016/j.cej.2005.01.007

Keiluweit M Nico PS Johnson MG Kleber M 2010 Dynamic molecular structure of plant biomass-derived black carbon (biochar). Environmental Science & Technology 44 1247 1253 doi:10.1021/es9031419

Koch A Krzton A Finqueneisel G Heintz O Weber JV Zimny T 1998 A study of carbonaceous char oxidation in air by semi-quantitative FTIR spectroscopy. Fuel 77 563 569 doi:10.1016/S0016-2361(97)00157-9

Lehmann J 2007 Bio-energy in the black. Frontiers in Ecology and the Environment 5 381 387 doi:10.1890/1540-9295(2007)5[381:BITB]2.0.CO;2

Lehmann J Gaunt J Rondon M 2006 Biochar sequestration in terrestrial ecosystems – a review. Mitigation and Adaptation Strategies for Global Change 11 403 427 doi:10.1007/s11027-005-9006-5

Lehmann J , Joseph S (2009) ‘Biochar for environmental management.’ (Earthscan Publications Ltd: London)

López R Gondar D Iglesias A Fiol S Antelo J Arce F 2008 Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth. European Journal of Soil Science 59 892 899 doi:10.1111/j.1365-2389.2008.01048.x

Matsue N Wada K 1985 A new equilibrium method for cation-exchange capacity measurement. Soil Science Society of America Journal 49 574 578 doi:10.2136/sssaj1985.03615995004900030008x

Petit C Kante K Bandosz TJ 2010 The role of sulphur-containing groups in ammonia retention on activated carbons. Carbon 48 654 667 doi:10.1016/j.carbon.2009.10.007

Petit JR Jouzel J Raynaud D Barkov NI Barnola J-M Basile I Bender M Chappellaz J Davis M Delaygue G Delmotte M Kotlyakov VM Legrand M Lipenkov VY Lorius C Pépin L Ritz C Saltzman E Stievenard M 1999 420 000 years of climate and atmospheric history revealed by the Vostok deep Antartic ice core. Nature 399 429 436 doi:10.1038/20859

Pradhan BK Sandle NK 1998 Effect of different oxidizing agent treatments on the surface properties of activated carbons. Carbon 37 1323 1332 doi:10.1016/S0008-6223(98)00328-5

Ritchie JD Perdue EM 2003 Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter. Geochimica et Cosmochimica Acta 67 85 96 doi:10.1016/S0016-7037(02)01044-X

Seifritz W 1993 Should we store carbon in charcoal? International Journal of Hydrogen Energy 18 405 407 doi:10.1016/0360-3199(93)90219-Z

Sevilla M Fuertes AB 2009 a The production of carbon materials by hydrothermal carbonization of cellulose. Carbon 47 2281 2289 doi:10.1016/j.carbon.2009.04.026

Sevilla M Fuertes AB 2009 b Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides. Chemistry – A European Journal 15 4195 4203 doi:10.1002/chem.200802097

Sheng C 2007 Char structure characterized by Raman spectroscopy and its correlations with combustion reactivity. Fuel 86 2316 2324 doi:10.1016/j.fuel.2007.01.029

Smernik RJ Baldock JA Oades JM 2002 a Impact of remote protonation on 13C CPMAS NMR quantitation of charred and uncharred wood. Solid State Nuclear Magnetic Resonance 22 71 82 doi:10.1006/snmr.2002.0065

Smernik RJ Baldock JA Oades JM Whittaker AK 2002 b Determination of T1rH relaxation rates in charred and uncharred wood and consequences for NMR quantitation. Solid State Nuclear Magnetic Resonance 22 50 70 doi:10.1006/snmr.2002.0064

Smernik RJ Oades JM 2000 a The use of spin counting for determining quantitation in solid state 13C NMR spectra of natural organic matter 1. Model systems and the effects of paramagnetic impurities. Geoderma 96 101 129 doi:10.1016/S0016-7061(00)00006-9

Smernik RJ Oades JM 2000 b The use of spin counting for determining quantitation in solid state 13C NMR spectra of natural organic matter 2. HF-treated soil fractions. Geoderma 96 159 171 doi:10.1016/S0016-7061(00)00007-0

Smith DM Chughtai AR 1995 The surface structure and reactivity of black carbon. Colloids and Surfaces 105 47 77 doi:10.1016/0927-7757(95)03337-1

Titirici M-M Thomas A Antonietti M 2007 Back in the black: hydrothermal carbonization of plant material as an efficient chemical process to treat the CO2 problem? New Journal of Chemistry 31 787 789 doi:10.1039/b616045j

Ueno M Kaeamitsu Y Komiya Y Sun L 2007 Carbonisation and gasification of bagasse for effective utilisation of sugarcane biomass. International Sugar Journal 110 22 26

Van Krevelen DW 1950 Graphical statistical method for the study of structure and reaction processes of coal. Fuel 29 269 284


Van Soest PJ 1967 Development of a comprehensive system of feed analysis and the application to forages. Journal of Animal Science 26 119 128


Van Zwieten L Kimber S Morris S Chan KY Downie A Rust J Joseph S Cowie A 2009 Effects of biochar from slow pyrolysis of papermill waste on agronomic performance and soil fertility. Plant and Soil
doi:10.1007/s11104-009-0050-x

Vimeux F Cuffey KM Jouzel J 2002 New insights into Southern Hemisphere temperature changes from Vostok ice cores using deuterium excess corrections. Earth and Planetary Science Letters 203 829 843 doi:10.1016/S0012-821X(02)00950-0

Watts JF , Wolstenholme J (2003) ‘An introduction to surface analysis by XPS and AES.’ (John Wiley & Sons: Chichester, UK)

Zachos J Pagani M Sloan L Thomas E Billups K 2001 Trends, rhythms, and aberrations in global climate 65 Ma to present. Science 292 686 693 doi:10.1126/science.1059412



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