Producing biochars with enhanced surface activity through alkaline pretreatment of feedstocks
K. Hina A , P. Bishop A , M. Camps Arbestain A E , R. Calvelo-Pereira B , J. A. Maciá-Agulló C , J. Hindmarsh D , J. A. Hanly A , F. Macías B and M. J. Hedley AA Institute of Natural Resources, Private Bag 11222, Massey University, Palmerston North 4442, New Zealand.
B Departamento de Edafología y Química Agrícola, Facultad de Biología, Universidad de Santiago de Compostela, 15782-Santiago, Spain.
C Instituto Nacional del Carbón (CSIC), Apartado 73, 33080-Oviedo, Spain.
D Institute of Food, Nutrition and Human Health, Massey University, Palmerston North 4442, New Zealand.
E Corresponding author. Email: m.camps@massey.ac.nz
Australian Journal of Soil Research 48(7) 606-617 https://doi.org/10.1071/SR10015
Submitted: 5 January 2010 Accepted: 14 May 2010 Published: 28 September 2010
Abstract
Surface-activated biochars not only represent a useful carbon sink, but can also act as useful filtering materials to extract plant nutrients (e.g. NH4+) from wastes (e.g. animal or municipal waste streams) and added thereafter to soils. Biochars produced by low-temperature pyrolysis of fibrous debarking waste from pine (PI) and eucalyptus (EU) were pre-treated with either diluted (L) or undiluted (S) alkaline tannery waste (L-PI, S-PI, L-EU, S-EU). Biochars produced from untreated feedstock were used as controls. Samples were characterised by FT-IR, solid-state CP MAS 13C NMR, XPS, SEM microphotographs, and BET specific surface area. Elemental composition, carbon recovery, yield, surface charge, and NH4+ sorption/desorption properties were also studied.
Carbon recovery was lower in biochars prepared from L-EU and S-EU (43 and 42%, respectively) than in control EU (45%) but these biochars showed greater changes in their chemical characteristics than those made from L-PI and S-PI, which showed minimal decrease in recovered carbon. The specific surface area of the biochars decreased with treatments, although acidic surface groups increased. In subsequent sorption experiments, treated biochars retained more NH4+ from a 40 mg N/L waste stream (e.g. 61% retention in control EU and 83% in S-EU). Desorption was low, especially in treated biochars relative to untreated biochars (0.1–2% v. 14–27%). The results suggest that surface activated biochars can be obtained with negligible impairment to the carbon recovered.
Additional keywords: acidic surface groups, ammonium retention, biochar, tannery waste.
Acknowledgements
The authors acknowledge the Manawatu Microscopy and Imaging Centre (MMIC) and Doug Hopcroft for assistance in preparing the samples and operating the SEM images, and Edwin Mercer from Carter Holt Harvey NZ Ltd for supplying the feedstocks. Authors are also grateful to Gonzalo Almendros, Sarah Fiol, Bob Stewart, Mike Bretherton, Anne West, and Ian Furkert for timely guidance and comments. J.A.M.-A. acknowledges the assistance of the Spanish Ministry of Science and Education for its award of a Juan de la Cierva contract. M.C.A. is very grateful for financial support from the Ministery of Agriculture and Forestry of New Zealand. The authors thank the anonymous reviewers for their valuable suggestions and comments on the manuscript.
Ahmedna M,
Marsall WE, Rao RM
(2000) Production of granular activated carbon from select agricultural by-products and evaluation of their physical, chemical and adsorption properties. Bioresource Technology 71, 113–123.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Arriagada R,
Garcia R,
Molina-Sabio M, Rodriguez-Reinoso F
(1997) Effect of steam activation on the porosity and chemical nature of activated carbons from Eucalyptus globulus and peach stones. Microporous Materials 8, 123–130.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Baldock JA, Smernick RJ
(2002) Chemical composition and bioavailability of thermally altered Pinus resinosa (red pine) wood. Organic Geochemistry 33, 1093–1109.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Bandosz TJ, Petit C
(2009) On the reactive adsorption of ammonia on activated carbons modified by impregnation with inorganic compounds. Journal of Colloid and Interface Science 338, 329–345.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
Bridgwater AV
(2003) Renewable fuels and chemicals by thermal processing of biomass. Chemical Engineering Journal 91, 87–102.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Bundy LG, Bremner JM
(1972) A simple titrimetric method for determination of inorganic carbon in soils. Soil Science Society of America Journal 36(2), 273–275.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Chen X,
Jeyaseelan S, Graham N
(2002) Physical and chemical properties study of the activated carbon made from sewage sludge. Waste Management 22, 755–760.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
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.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
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.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Chiang HL,
Tsai JH,
Tsai CL, Hsu YC
(2000) Adsorption characteristics of alkaline activated carbon exemplified by water vapour, H2S and CH3SH gas. Separation Science and Technology 35, 903–918.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Duggan O, Allen SJ
(1997) Study of the physical and chemical characteristics of a range of chemically treated, lignite based carbons. Water Science and Technology 35, 21–27.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Emmerich FG, Luengo CA
(1996) Babassu charcoal: A sulfurless renewable thermo-reducing feedstock for steelmaking. Biomass and Bioenergy 10, 41–44.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Faix O,
Jakab E,
Till F, Szekely T
(1988) Study on low mass thermal degradation products of milledwood lignins by thermogravimetry-mass-spectrometry. Wood Science and Technology 22, 323–334.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Guo Y, Bustin RM
(1998) FTIR spectroscopy and reflectance of modern charcoal and fungal decayed woods: Implications for studies of Inertinite in coals. International Journal of Coal Geology 37, 29–53.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
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.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Ibarra JV,
Munoz E, Moliner R
(1996) FTIR study of the evolution of coal structure during coalification process. Organic Geochemistry 24, 725–735.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Krull ES,
Swanston CW,
Skjemstad JO, McGowan JA
(2006) Importance of charcoal in determining the age and chemistry of organic carbon in surface soils. Journal of Geophysical Research 111(G4), G04001.
| Crossref |
Lee W, Reucroft P
(1999) Vapor adsorption on coal- and wood-based chemically activated carbons (III) NH3 and H2S adsorption in the low relative pressure range. Carbon 37, 21–26.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Lehmann J
(2007) Biol.-energy in the black. Frontiers in Ecology and the Environment 5, 381–387.
| Crossref | GoogleScholarGoogle Scholar |
Lewis NG, Yamamoto E
(1990) Lignin: occurrence, biogenesis and biodegradation. Annual Review of Plant Biology 41, 455–496.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Lillo-Ródenas MA,
Marco-Lozar JP,
Cazorla-Amoros D, Linares-Solano A
(2007) Activated carbons prepared by pyrolysis of mixtures of carbon precursor/alkaline hydroxide. Journal of Analytical and Applied Pyrolysis 80, 166–174.
| Crossref | GoogleScholarGoogle Scholar |
Linares-Solano A,
Lozano-Castello D,
Lillo-Rodenas MA, Cazorla-Amoros D
(2008) Carbon activation by alkaline hydroxides: preparation and reactions, porosity and performance. Chemistry and Physics of Carbon 30, 1–62.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Liu C,
Shao Y, Jia DM
(2008) Chemically modified starch reinforced natural rubber composites. Polymer 49, 2176–2181.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
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.
| Crossref | GoogleScholarGoogle Scholar |
Lozano-Castelló D,
Maciá-Agulló JA,
Cazorla-Amorós D,
Linares-Solano A,
Müller M,
Burghammer M, Riekel C
(2006) Isotropic and anisotropic microporosity development upon chemical activation of carbon fibers, revealed by microbeam small-angle X-ray scattering. Carbon 44, 1121–1129.
| Crossref | GoogleScholarGoogle Scholar |
Maciá-Agulló JA,
Moore BC,
Cazorla-Amorós D, Linares-Solano A
(2007) Influence of carbon fibres crystallinities on their chemical activation by KOH and NaOH. Microporous and Mesoporous Materials 101, 397–405.
| Crossref | GoogleScholarGoogle Scholar |
Montane D,
Torné-Fernández V, Fierro V
(2005) Activated carbons from lignin: kinetic modeling of the pyrolysis of Kraft lignin activated with phosphoric acid. Chemical Engineering Journal 106, 1–12.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Petit C,
Kante K, Bandosz TJ
(2010) The role of sulphur-containing groups in ammonia retention on activated carbons. Carbon 48, 654–667.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Pradhan BK, Sandle NK
(1999) Effect of different oxidizing agent treatments on the surface properties of activated carbons. Carbon 37, 1323–1332.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Preston CM,
Trofymow JA,
Niw J, Fyfe CA
(1998)
13CPMAS-NMR spectroscopy and chemical analysis of coarse woody debris in coastal forests of Vancouver Island. Forest Ecology and Management 111, 51–68.
| Crossref | GoogleScholarGoogle Scholar |
Raymundo-Piñero E,
Azaïs P,
Cacciaguerra T,
Cazorla-Amorós D,
Linares-Solano A, Béguin F
(2005) KOH and NaOH activation mechanisms of multiwalled carbon nanotubes with different structural organisation. Carbon 43, 786–795.
| Crossref | GoogleScholarGoogle Scholar |
Raymundo-Piñero E,
Cazorla-Amorós D,
Linares-Solano A,
Find J,
Wild U, Schlögl R
(2002) Structural characterization of N-containing activated carbon fibers prepared from a low softening point petroleum pitch and a melamine resin. Carbon 40, 597–608.
| Crossref | GoogleScholarGoogle Scholar |
Rodriguez-Reinoso F, Molina-Sabio M
(1992) Activated carbons from lignocellulosic materials by chemical and/or physical activation: an overview. Carbon 30, 111–118.
Sharma RK,
Wooten JB,
Baliga VL,
Lin X,
Chan WG, Hajaligol MR
(2004) Characterization of chars from pyrolysis of lignin. Fuel 83, 1469–1482.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Smith DM, Chughtai AR
(1995) The surface structure and reactivity of black carbon. Colloids and Surfaces 105, 47–77.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Tatzber M,
Stemmer M,
Spiegel H,
Katzlberger C,
Haberhauer G, Gerzabek MH
(2007) An alternative method to measure carbonate in soils by FT-IR spectroscopy. Environmental Chemistry Letters 5, 9–12.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Tiessen H,
Roberts T, Stewart J
(1983) Carbonate analysis in soils and minerals by acid digestion and two-endpoint titration. Communications in Soil Science and Plant Analysis 14(2), 161–166.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Tsutsumi Y,
Kondo R,
Sakai K, Imamura H
(1995) The difference of reactivity between syringyl lignin and guaiacyl lignin in alkaline systems. Holzforschung 49, 423–428.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Van Soest PJ
(1967) Development of a comprehensive system of feed analysis and the application to forages. Journal of Animal Science 26, 119–128.
Vassileva P,
Tzvetkova P, Nickolov R
(2009) Removal of ammonium ions from aqueous solutions with coal-based activated carbons modified by oxidation. Fuel 88, 387–390.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
Wang SK,
Wang K,
Liu Q,
Gu Y,
Luo Z,
Cen K, Fransson T
(2009) Comparison of the pyrolysis behavior of lignins from different tree species. Biotechnology Advances 27, 562–567.
| Crossref | GoogleScholarGoogle Scholar |
CAS |
PubMed |
|
