Biochar Characterization in Complex Soil Mixtures Paper No:

- High Resolution Nitrogen Pore Distribution Analysis (HRPDA)

Larry Murrell1,Yun-feng Chang2, and Greg Thiele3
1. Independent Consultant, 2. Sigma Innova LLC, 3. Micromeritics Analytical Services

Introduction Analytical Technique Cabot ‘Unique’ Carbon Black BP 2000 mixed with Mississippi Loess

• Experimental technique used for catalysts and sorbents • Volumetric dosing N2 adsorption at liquid nitrogen • Cabot Black Pearl 2000 developed for fuel cells
temperature gives accurate ‘map’, or ‘blue print’, of both BET Surface Total Pore t-plot Micro-
size and amount of voids in materials < 3000 Å BET Surface Total Pore t-plot Micro- Sample Area Volume pore Area
• Results for ‘state-of-art’ Cabot carbon black diameter (cc/g) (m2/g)
Sample Area Volume pore Area (m2/g)
(m2/g) (cc/g) (m2/g) Loess 20 0.02 7
• When combined with Hg porosimetry detailed structure
• Results for Cabot carbon black mixed with soil of porous materials produced from 500 micrometer Black Pearl 1500 3.0 1123
diameter to about 5 Å or 0.5 nm 1 wt. % Black 40 0.07 28
2000 Pearl 2000/Loess
• Results for commercial charcoal subjected to
• Two techniques are complimentary and provide 3 wt. % Black 70 0.13 50
freeze-thaw cycles • Black Pearl 2000 represents an apparently unique carbon black
complete detail of void structure in porous materials development with combination of high surface area and high pore volume
Pearl 2000/Loess
with wide pore distribution between 10 and 100 nm diameter
• Total analysis time per sample: 16 hours • Calculated BET surface areas of 35 and 65 m2/g and total pore volume
• Future application potential for biochar samples of 0.05 and 0.11 cc/g for two samples agree with experimental results

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BP 2000 mixed with Mississippi Loess “Blue-Print” of BP 2000 in Loess Soil Commercial Charcoal Results Charcoal Sample: Fresh and After Aging
Volume Frequency vs. Diameter
BET Surface Area Increase Caused by BP 2000 Total Pore Volume of Mixture Differential Pore Volume vs. Pore Width
BET Surface Total Pore Fresh Charcoal Treated Charcoal
120 0.25 1% Black Pearl / Loess Soil 3% Black Pearl / Loess Soil 5% Black Pearl / Loess Soil
y = 0.0386x + 0.0231
R2 = 0.9922 Sample Area (m2/g) Volume (cc/g) 3
BET Surface Area (m /g)

Total Pore Volume (m /g)

100 y = 19.692x - 1.3559 0.20

0.2
2

R2 = 0.9877

Volume Frequency Percent

80
0.15
Differential Pore Volume (cm³/g)

2
60 0.15

0.1 Charcoal 2.9 0.006

40

0.05 0.10 1
20

0 0
Charcoal with
0 1 2 3 4 5 6
Concentration of BP 2000 in Mississippi Loess (wt%)
0 1 2 3 4 5 6 0.05
8-cycles 5.5 0.009
Concentration of BP 2000 in Mississippi Loess (wt%) 0

‘freeze-thaw-cycles’ 0.5 1 5 10
Particle Diameter (µm)
50 100 500 1,000

0.00
• surface area variation tracks well with • Pore volume variation tracks 10 50 100
Pore Width (Angstroms)
500 1,000
• Hg porosimetry shows eight cycles of freeze-thaw-freeze treatment
amount of Black Pearl 2000 in mixture well with amount of Black Pearl
2000 in mixture
• N2 porosimetry provides information < 3000 Å diameter shifts particle distribution to smaller particle
• Complex and detailed pattern of void spaces related to “bunch-of-grapes” • Hg porosimetry provides information on particles < 360 • Smaller particle size will lead to higher BET surface area
structure about 800 nm size made from strings of primary particles micrometer diameter and explains 2 cc/g water uptake • We are probably missing the fresh charcoal interstitial volume because
it is too large to be seen (>360 micrometers)

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Charcoal Sample: Fresh and After Aging BP 2000 Transformed by Freeze-Thaw Cycles Conclusions Future Direction

Charcoal as received
Log Differential Intrusion vs Pore size
Charcoal after 8 freeze thaw cycles
Black Pearl 2000 as received
Differential Pore Volume vs. Pore Width
Black Pearl 2000 after freeze-thaw • Micromeritics analysis proves mixture of carbon black with soil
• Prove applicability to biochar samples aged in soils
can be analyzed by HRPDA • Find partners with Micromeritics to apply HRPDA
Log Differential Intrusion (mL/g)

0.4 3
technique to historic biochar beds in Amazon Basin
Differential Pore Volume (cm³/g)

• Commercial charcoal has low surface area and low pore - Soil samples
2 volume and is shown to be unstable to ‘freeze-thaw-freeze’
0.2
cycles - Ceramic green ware in these soils
1 • Use technique to aid development of structure-
0.0
• Hg porosimetry (combined) with HRPDA give complete ‘blue function relationships for understanding biochar crop
10 5 1 0.5
Pore size Diameter (µm)
0.1 0.05 0.01
0
print’ of micro-, meso-, and macropores yield improvements
5 10 50 100 500 1,000 5,000
Pore Width (Angstroms )

• As received charcoal (red) and following eight freeze-thaw cycles (blue) • Biochar analysis possible for moderate surface area samples
• Application of techniques to synthetic soils
• Large 3-7 micron size particle are being fractured into smaller size particles • As received BP 2000 (red) and following eight freeze-thaw cycles (green)
following freeze-thaw cycles - note especially the decrease in the pores at the largest size

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