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Biofuels and Biomass
Particle Size- and Crystallinity-Controlled Phosphorus Release from Biochars Xiumei Jian, Minori Uchimiya, and Alexander Orlov Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00680 • Publication Date (Web): 13 May 2019 Downloaded from http://pubs.acs.org on May 18, 2019
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Energy & Fuels
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Particle Size- and Crystallinity-Controlled
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Phosphorus Release from Biochars
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Xiumei Jian, a,b Minori Uchimiya,*,a,c and Alexander Orlov*,a
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aDepartment
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bCollege
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cUSDA-ARS
of Material Science and Engineering, State University of New York, 100 Nicolls Road, Stony Brook, New York 11794, USA of Materials and Energy, South China Agricultural University, Guangzhou, Guangdong 510640, China Southern Regional Research Center, 1100 Robert E. Lee Boulevard, New Orleans, Louisiana 70124, USA
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*Corresponding
author
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[email protected] 12
*Corresponding
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Abstract
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Controlled-release sterile organic phosphorus fertilizers could be co-produced (as biochars) with
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biofuels using the existing thermochemical conversion platforms. However, the availability of
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nutrient elements in biochar changes in amended soils, as a result of sizing (fragmentation) and
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other biogeochemical processes. This study investigated particle size- (25,400>all other
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temperatures for the asymmetric (2935 cm-1) and symmetric (2862 cm-1) C-H stretching
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of aliphatic CHx. In conclusion, Figure 2c indicates the decomposition of polysaccharide
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C-H (including chitin) at 200-400 °C, and the formation of polyaromatic ring structures
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near 500 °C, in agreement with the literature.29,30
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Figure 3 explores the wavenumber range (1300-1800 cm-1) attributable to carboxyl
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C=O (1700-1740 cm-1), C=C (1600 cm-1), amide I (1600-1700 cm-1), CO32- (1422 cm-1),
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and phenolic O-H bending (1375 cm-1).31,36 This wavenumber range is often used to
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highlight “fingerprint region” of biochars attributable to the ionizable oxygen-donor
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ligands.29,30,37 Characteristic peaks of C=O stretching at 1680-1740 cm-1 are expected
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to shift by conjugation (e.g., phenyl, alkene, and α, β–unsaturated carbonyls) towards
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lower frequency as the pyrolysis reaction progresses.17
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withdrawing groups will shift peaks toward higher frequency.31
The formation of electron-
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Synchronous map in Figure 3a shows two primary auto-peaks attributable to
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carbonate C-O (1430 cm-1) and amide I (1670 cm-1). Those bands correspond to the
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primary components of shrimp shell: 30-40% (dry weight) protein and minerals
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(primarily calcium carbonate),38 and 20% chitin.39
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carboxyl C=O is visible at 1793 cm-1 in Figure 3a. Based on the cross-peaks of the
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synchronous map, carbonate (1430 cm-1) is positively correlated with carboxyl (1793
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cm-1), and negatively correlated with amide I (1670 cm-1); amide I and carboxyl are
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negatively correlated (Figure 3a). These trends (same directionality of carbonate and
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carboxyl, and opposite directionality of those from amide I) are observable in Figure 3c
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for each pyrolysis temperature. Amide I (1668 cm-1) in chitin is consumed above 200-
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300 °C,40 while carboxyl C=O (1795 cm-1) and carbonate C-O (1427 cm-1) had maximum
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peak heights at 500-600 °C.
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trend with increasing pyrolysis temperature: (1) consumption of chitin and protein
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amides in the feedstock, (2) formation (600 °C) of
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carbonate and carboxyl.
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functionality of biochar is expected to maximize near 500 °C in both bulk and water-
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soluble phases.42
Minor auto-peak attributable to
Collectively, these observations indicate the following
Carbonate is thermally stable below 800 °C.41
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Carboxyl
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Figure 4 presents analogous plots for the wavenumber range (850-1200 cm-1) known
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to be influenced by various overlapping P-O and C-O peaks.31 In the synchronous map
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(Figure 4a), three auto-peaks with the following decreasing intensity were observed (in cm-1):
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870>1040>1000. Because the 1040 cm-1 band showed opposite directionality (in response to
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increasing pyrolysis temperature) to both 870 and 1000 cm-1 bands, 1040 cm-1 was assigned to P-
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O, while 870 and 1000 cm-1 were assigned to C-O. FTIR spectra of hydroxyapatite and other
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phosphorus mineral standards contain a characteristic peak at 1030-1130 cm-1.43 As shown in
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Figure 4c, P-O functionality (1043 cm-1) reached maximum at 800 °C and decreased at lower
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pyrolysis temperature, in agreement with higher total P content as a function of pyrolysis
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temperature (Table S1, Supporting Information). Oppositely, polysaccharide C-O (primarily
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attributable to chitin; 868 and 1012 cm-1 bands in Figure 4c) in the feedstock decomposed above
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400 °C. Overall, the peak height comparison (c) in Figures 1-4 illustrated more detailed
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temperature dependency (in 100 °C increments) than 2DCOS capturing the overall
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directional trends as a function of pyrolysis temperature.
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Timecourses of phosphate dissolution. Figure 5 compares total phosphorus (T-P) and
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orthophosphate (O-P) release kinetics for
