Catherine Brewer, Rachel Unger, Robert Brown Center for Sustainable Environmental Technologies Iowa State University

August 11, 2009

Biochar Engineering Incubation Study Overview Meet the Chars General Characterization Results Solid-State 13C NMR Future Work

Characterization: What kind of char did we make?

Soil Testing: How well does our char work?

Production: How do we make good biochar?

Formulation: What is good biochar?

Two Part Study:

Char characterization 8 week soil incubation

Collaboration between CSET and Agronomy 17 chars made under known conditions Results to be used to select chars for microplot field study

Study ID # 1

Reactor Fluidized Bed Pyrolyzer

Reaction Conditions Fast Pyrolysis

Reaction Temperature (C) 500

2
3 4 5 6

Free-fall Pyrolyzer
Free-fall Pyrolyzer Free-fall Pyrolyzer Fluidized Bed Gasifier

Incomplete Fast Pyrolysis

Incomplete Fast Pyrolysis Incomplete Fast Pyrolysis Air-Blown Gasification

600
550 500 732 500

Fixed Bed Pyrolyzer Slow Pyrolysis for 30 min

Study ID # 7 8 9

Reactor

Reaction Conditions

Reaction Temperature (C) 450 550 500

Fluidized Bed Pyrolyzer Fast Pyrolysis Fluidized Bed Pyrolyzer Fast Pyrolysis Fluidized Bed Pyrolyzer Fast Pyrolysis 60%/40% O2/Steam Gasification 50%/50% O2/Steam Gasification 40%/60% O2/Steam Gasification Slow Pyrolysis for 2 hours

10
11 12 13

Fluidized Bed Gasifier

Fluidized Bed Gasifier Fluidized Bed Gasifier Fixed Bed Pyrolyzer

824
775 796 500

Study ID #

Feedstock Wood Waste (Chippewa Valley Ethanol Company/Frontline Bioenergy) Mixed Hardwood (Struemph Charcoal Company, Belle, MO) Oak Flour Eastern Hemlock (Advanced BioRefinery Inc., Ottowa, Ontario)

Reactor Commercial Fluidized Bed Gasifier Commercial Charcoal Kiln Fluidized Bed Pyrolyzer Commercial Auger Pyrolyzer

Reaction Conditions Gasification ~800C Slow Pyrolysis ~400-500C Fast Pyrolysis 500C Fast Pyrolysis 550C

14

15 16 17

100 90 80 Ash Content (wt%) 70 60 50 Corn Stover Fast Pyrolysis Corn Stover Gasification Corn Stover Slow Pyrolysis Switchgrass Fast Pyrolysis

40
30 20 10 0 400 500 600 700 Reaction Temperature (C) 800

Switchgrass Gasification
Switchgrass Slow Pyrolysis Hardwoods

60 BET Surface Area (m/g) 50 Corn Stover Fast Pyrolysis 40 30 20 10 0 400 500 600 700 Reaction Temperature (C) 800 Corn Stover Gasification Corn Stover Slow Pyrolysis Switchgrass Fast Pyrolysis

Switchgrass Gasification
Switchgrass Slow Pyrolysis Hardwoods

The Techniques:
Qualitative 1H-13C Cross Polarization Magic Angle

Spinning (CP/MAS) with TOtal Supression of Spinning Sidebands (TOSS) Quantitative 13C Direct Polarization (DP/MAS) DP/MAS with Dipolar Dephasing, a.k.a. Gated Decoupling (GADE) DP/MAS with Recoupled Dipolar Dephasing, a.k.a. Gated Recoupling (GARE)

Solid-State 13C NMR

Switchgrass Feedstock, Fast and Slow Pyrolysis Chars by CP/TOSS at 7 kHz MAS frequency. OCH: includes both alcohol and ether moieties

Solid-State 13C NMR

Corn Stover Fast Pyrolysis Chars by CP/TOSS at 7 kHz MAS frequency. OCH: includes both alcohol and ether moieties

Solid-State 13C NMR

Corn Stover Slow Pyrolysis Char (right) and Fast Pyrolysis Char (Below) by DP and DP/GADE at 14kHz MAS frequency. Shows protonated (-) and non-protonated (-) fractions. Note more O-containing groups in fast pyrolysis char; more aromatic H in slow pyrolysis char.

The Final Product: estimates of aromatic ring cluster size from

Integration of spectral

regions to estimate number of edge carbons Calculation of aromatic H-C bond distances from DP/GARE dephasing times
Brewer, C.E.; Schmidt-Rohr, K.; Satrio, J.A.; Brown R.C. Environmental Progress & Sustainable Energy 2009, In Press.

 1.

2. 3.

DP/MAS/GARE Process Obtain dephasing time curves of known proton-carbon bond distances Collect DP/MAS/GARE spectra of sampes Compare dephasing time curves to known samples to estimate bond distances

1 0.9 0.8 Intensity (S/S0) 0.7 0.6 0.5 0.4

C-C-H C-C-C-H Char A Char B

0.3
0.2 0.1 0 0 0.5 1 1.5 Dephasing Time (ms) 2

Production and characterization of standard chars for use in inter-departmental projects NMR characterization of switchgrass and corn stover slow pyrolysis chars produced over a wider range of temperatures (200800C) and reaction times Char-alone cation exchange capacity measurement methodology

National Science Foundation Graduate Research Fellowship (NSF GRF) CSET colleagues (char samples, CHNS and HHV analysis) Klaus Schmidt-Rohr and Yan-Yan Hu (NMR) Pierce Fleming (CEC) John McClelland and Roger Jones (FTIR-PAS)

CEC Extractable Colors from Corn Stover Fast Pyrolysis Chars Separation Issues