Development of nutrient-embedded biochar pellets as a slow-release

fertilizer for maximizing bioenergy crop production

A Final Report Submitted to
The Southeastern Sun Grant Center
Submitted by
Dr. Nicole Labb
Dr. Amy Johnson
Dr. Pyoungchung Kim
Center for Renewable Carbon
And
Department of Biosystem Engineering and Soil Science
University of Tennessee
Knoxville, TN 37996
Project Period, July 1, 2011 June 30, 2013
November 10, 2013
This project was funded by a grant from the Southeastern Sun Grant Center with funds provided by
the United States Department of Transportation, Research and Innovative Technology
Administration.

ABSTRACT
Biochar pellets produced by blending switchgrass biochar, lignin and fertilizer P and K together
and followed by pelletization were characterized. In addition, their release of nutrients was
investigated for a period of 18 days. Pellets processed at 180 oC with lignin content increasing
from 10 to 30 wt% had higher thermal stability, surface functionality, and durability than pellets
dried at 105 oC. In addition, pellets dried at 180 oC had a slower nutrient release than pellets
dried at 105 oC, with a high release rate within the first 24h followed by a more gradual release
for the next 432h. An increase in lignin content in the biochar pellets also reduced nutrient
release over time. Therefore, both, lignin content and drying temperature of the pellets, control
the release rate of nutrients present in biochar pellets.

Acknowledgment
Support for this research was provided in part by a grant from the Southeastern Sun Grant Center with
funds provided by the U.S. Department of Transportation Research and Innovative Technology
Administration (DTOS59-07-G-00050).

Table of Contents
ABSTRACT ................................................................................................................................................ 2
Acknowledgment ......................................................................................................................................... 2
Executive Summary ................................................................................................................................... 4
Problem ...................................................................................................................................................... 4
Approach and Methodology ........................................................................................................................ 5
Findings ....................................................................................................................................................... 7
Conclusions ............................................................................................................................................... 21
Final (actual) budget ............................................................................................................................... 24
Publication and Presentations ............................................................................................................ 25
Contracts Related to this Project since Project Inception .............................................................. 25

Fig. 1. TGA of biochar and biochar pellets produced with 10, 20, 30% lignin and dried at 105 and 180 oC.
(a) TG (b) DTG of biochar and biochar pellet 10-105 and 10-180. (c) TG (d) DTG of biochar pellet
20-105 and 20-180 (e) TG and (d) DTG of biochar pellet 30-105 and 30-180. ................................ 9
Fig. 2. PCA of FTIR spectra collected from raw biochar and biochar pellets produced at different lignin
content and drying temperature (105 and 180 oC). (a) Scores plot and (b) loadings plot of all
biochar and pellets. (c) Scores plot and (d) loadings plot of biochar pellets 10-105 and 10-180. (e)
Scores plot and (f) loadings plot of biochar pellets 20-105 and 20-180. (g) Scores plot and (h)
loadings plot of biochar pellets 30-105 and 30-180. ....................................................................... 11
Fig. 3. Water uptake of biochar pellets. Lines presented triplicate runs of each sample. (a) 10-105, (b) 10180, (c) 20-105, (d)20-180, (e) 30-105, and (f) 30-180 represent biochar pellets produced with 10,
20 and 30% lignin and dried at 105 and 180 oC respectively. ......................................................... 14
Fig. 4. Nutrient release (K and P) from biochar pellets with lignin content 10, 20 and 30% and dried at
105 and 180 oC. ............................................................................................................................... 17
Fig. 5. Nutrient release (Ca and Mg) from biochar pellets with lignin content 10, 20 and 30% and dried at
105 and 180 oC. ............................................................................................................................... 18
Fig. 6. Nutrient release (K and P) from biochar pellets embedded with K and P fertilizer, lignin content 10,
20 and 30 %, and dried at 105 and 180 oC. ..................................................................................... 19
Fig. 7. Nutrient release (Na and S) from biochar pellets with lignin content 10, 20 and 30% and dried at
105 and 180 oC. ............................................................................................................................... 21
Table 1 Proximate analysis and inorganic elements presented in biochar and biochar pelletsa. .................. 7
Table 2 Mechanical properties of biochar pellets produced with different lignin contents and at different
drying temperature. .................................................................................................................................... 12

Executive Summary
For the last five years, the application of as-produced biochar for amending soil quality and
increasing crop production has been documented in the literature (Lehmann et al., 2011).
Although biochar is incorporated into soil as an amendment, organic or inorganic fertilizer is still
required to maximize crop production. However, conventional fertilizers are inefficient, in
particular, in soils with low cation exchange capacity and in humid climate conditions. Low
nutrient retention capacity in soil causes low crop production and contaminates the ground water
leading to financial loss for farmers. Therefore, it is essential to design slow-release fertilizers
with low solubility that can supply nutrients to soil and plants over long period of time. Biochar
embedded with fertilizer is one potential way to slowly release nutrients to soil throughout plant
growing season and to provide most of the nutrients to bioenergy crops without leaching losses.
In addition, nutrients already contained in the biochar, such as P and K, are recycled into soil.
These benefits will increase energy crop yields and reduce costs for fertilizer. Therefore,
utilization of biochar pellets embedded with fertilizer could enhance soil productivity and quality
in terms of bioenergy crop production and carbon sequestration. In this work, we developed a
soil fertilizer product biochar pellets embedded with fertilizer which could maximize
bioenergy crop production and reduce CO2 emissions in soil and therefore be an environmentally
benign slow-release fertilizer.

Problem
Biochar is a carbon-rich product that is produced from biomass through thermochemical
process, pyrolysis and gasification, under limited or absent oxygen (Lehmann et al., 2011).
Biochar contains recalcitrant carbonaceous structures and minerals depending on biomass types
and operation parameters of process. Biochar produced from lignocellulosic feedstock has high
carbon content, whereas biochar generated from nutrient-rich feedstock such as poultry litter has
characteristics similar to a fertilizer (Cantrell et al., 2012). Biochar pH ranges from 5 to 13, ash
content from 1.4% to 73%, carbon content from 66.5 to 91.6%, and surface areas range from 1 to
400 m2 g-1. Cation exchange capacity (CEC) of biochar ranges from 10 to 69 cmol kg-1 (Kim et
al., 2013). When applied to soil, biochar provides plant nutrients, increases CEC and water
holding capacity, and improves the soil as a microbial habitat (Lehmann et al., 2011).
When lignocellulosic biomass-derived biochar produced by fast pyrolysis is incorporated
into soil application, organic or inorganic fertilizers are still needed to improve crop yield. Many
studies that have investigated value-added biochars as a soil amendment suggested the blending
of lignocellulosic biochars with nutrient-rich manures, compost or poultry litter before soil
application (Hua et al., 2009; Ro et al., 2010). The incorporation of biochar with sludge
composite into land application was found to significantly reduce nitrogen loss (Hua et al., 2009).
However, storage, transportation and soil application of biochar are challenging because biochar
is brittle, and has wide particle size distribution and low density. Blue Leaf Inc. reported a loss as
high as 30% by wind-blown during handing, transport to the field and soil application of biochar.
In particular, 25% of the biochar applied was lost during spreading to the field (Husk & Major,
2008). 20 - 53% of biochar incorporated into soil was also lost by surface runoff during intense
rain events (Major et al., 2010).
4

Therefore, it is essential to design value-added biochar materials that can supply nutrients
to soil over long period of time with minimum loss of biochars and nutrients. Pelletization of
biochar is one potential way to reduce transportation and handling costs and significantly
decrease loss of biochar during soil application (Reza et al., 2012). Biochar pellet has been used
as an alternative to biomass pellet mostly for heating material (Abdullah & Wu, 2009). For soil
application, lignocellulosic and poultry litter feedstocks were blended, pelletized and slowly
pyrolyzed to produce biochar pellets (Cantrell & Martin II, 2012). However, there is little
information available on biochar pellets that can control nutrient release rate from the pellets as a
slow release fertilizer. Slow release fertilizer is required to gradually release nutrients to soil
throughout the growing season and to provide most of the nutrients to plant without leaching
losses (Fernndez-Escobar et al., 2004), which can, furthermore, reduce loss in farmer profit and
minimize potential damage to the environment (Mortain et al., 2004). Therefore, the objective of
this study was to develop biochar pellets embedded with plant fertilizer as an environmentally
benign slow-release fertilizer. Biochar generated in the process of bio-oil production by fast
pyrolysis was blended with commercial fertilizer and different ratio of lignin, and subsequently
pelletized. The produced biochar pellets were mechanically and chemically characterized and
their capacity to release nutrients was assessed.

Approach and Methodology

1. Production of biochar
Air-dried switchgrass (Panicum virgatum L.) was obtained from a local producer in
eastern Tennessee. The switchgrass containing 7 - 8% moisture was milled to less than 4 mm
particle sizes and then pyrolyzed at 525 oC with a residence time of 40s and feeding rate of 10kg
h-1 in the presence of N2 using a continuous auger pyrolysis process. A detailed description of the
process is provided elsewhere (Kim et al., 2011).
2. Pelletization of nutrient-embedded biochar
The biochar produced by the auger pyrolysis process was blended with different
percentages of lignin (10, 20 and 30 wt%) as a binder using a mixer (Black lynx mixer, Monarch
In.). Lignin (Indulin AT, kraft pine lignin) was obtained from MeadWestvast Inc. Indulin AT
lignin was a purified kraft lignin, where sodium and hemicellulose were removed by an acid
hydrolysis process (Beis et al., 2010). During mixing biochar and lignin, liquid fertilizer (12: 4: 8
= N: P2O5 : K2O, Scotts Miracle-Gro) was added to water at 1.0 wt% of total biochar and lignin
mixture and then the water mixture (40 - 50 wt% of total biochar and lignin) was sprayed into the
mixture of biochar and lignin. The moisturized biochar mixtures were pelletized using a pellet
mill (model PP220, Pellet Pros) that consisted of a die with cylindrical press channels (6mm
diameter) and rollers that force the biochar to be squeezed through the channels. Pressures in the
die can reach up to 172 MPa and the pelletized biochars came out of the mill with a temperature
around 65 - 85 oC (Manufacturers information). Pellets with dimensions of 6 - 10 mm in length
and 5.9 6.0 mm in diameter were produced. The pelletized biochars were then heated at 105 or
180 oC for 24 h to dry. The heated biochars were cooled down and then stored in glass bottles.
The biochar pellets produced with different lignin wt% and drying temperature are referred as
10-105, 10-180, 20-105, 20-180, 30-105 and 30-180, where the first number refers to % of lignin
and the second the temperature used to dry the pellets

3. Characterization of biochar pellets

Raw biochar and the corresponding biochar pellets produced using different lignin ratios
(10, 20 and 30 wt%) and drying temperatures (105 and 180 oC) were mechanically and
chemically characterized. Proximate analysis, including moisture content, volatile matter and ash
content, was measured by following ASTM D1762-84. Ultimate analysis, including carbon,
hydrogen and nitrogen, was measured by CHN analyzer (PerkinElmer). Inorganic elements in
biochars were analyzed by inductively coupled plasma-optical emission spectroscopy with an
optima 7300 DV spectrometer (ICP-OES, PerkinElmer) after microwave digestion (Kim et al.,
2011). Surface functionality was measured by Fourier Transform Infrared (FTIR) spectroscopy
with an attenuated total reflectance mode (PerkinElmer Spectrum One spectrometer). FTIR
spectra were analyzed using principal component analysis (PCA) to classify the samples by their
spectral features (Kim et al., 2011). Thermal decomposition of biochar pellets under air
atmosphere was analyzed using a thermogravimetric analyzer (Pyris 1 TGA, PerkinElmer) (Kim
et al., 2011).
Density of biochar pellets was calculated by measuring diameter, length and mass of 10
cylindrical biochar pellets. Compressive mechanical strength of the biochar pellets was obtained
by compression testing and determined as the force at break (Instron). Compression tests were
performed using a disc shaped metal probe that was attached to a 100 kN load cell. The test was
run at a compression rate of 1.0 mm min-1 and stopped after the pellet fell apart. The average
force at break and standard deviation were calculated based on 10 replications per test.
Durability of biochar pellets was tested by abrasion index using the MICUM test (Reza et al.,
2012). The rotating drum featured an inner diameter of 100 mm and a depth of 95 mm with three
baffles of 2550. Sixty pellets were loaded into a rotating drum and rotated with 50 rotations per
minute. After rotation, the pellets were screened using a 2 mm sieve. Particles that fall through
screen were weighed. Water adsorption behavior of biochar pellets was measured by the
capillary rise method (Zhang et al., 2011). Cylindrical pellet (3 - 4g) hung to the microbalance
(Dynamic contact analyzer, DCA-32, Thermo Cahn Ins.) was immersed into distilled water and
held below the water surface (1.0 mm) for a total of 8h run. The amount of adsorbed water as a
function of time was recorded every 3 sec. This test was performed at room temperature and in
triplicates.
4. Nutrient release from biochar pellets
Nutrient release from biochar pellets was assessed by batch extraction experiment using a
vacuum extractor (Sampletek) equipped with 24 cylinders. The vacuum extraction was
performed by drawing the extractant into receiving syringes through mechanical force controlled
by a programmable micro-processor. Filter pulp (1g) was put into the bottom of the cylinder (60
mL) and thereafter biochar pellets (approximately 5g) were added (60 mL). Successive batch
extraction was performed with removal and replacement of water (50 mL) for desired time until
432h (18 days). The collected water was filtered using 0.45 mm filter and stored in a refrigerator
until analysis by ICP-OES.

Findings
1. Characterization of biochar pellets
1.1. Chemical composition
The chemical characteristics of the biochar pellets are presented in Table 1. Switchgrass
biochar contained 5.6% of ash, 40.6% of volatile matter and high amounts of inorganic
compounds such as K (3622 mg kg-1), Ca (4055 mg kg-1), Mg (2504 mg kg-1) and other
compounds. Lignin, used in this study as a binder, contained 2.4 wt% of ash and high amount of
Na (6397 mg kg-1) and S (10381 mg kg-1), which derived from the Kraft process, although
Indulin AT lignin was purified by acid hydrolysis. As lignin was blended with biochar with
increasing ratio from 10 to 30 wt%, volatile matter increased from 42.2 to 46% in biochar pellets
dried at 105 oC and from 41.6 to 44.7% in biochar pellets dried at 180 oC. With increasing lignin
ratios, the amount of major inorganic compounds K, Ca, Mg and P in biochar pellets decreased,
whereas the amount of Na, and S increased. The pellets embedded with fertilizer contained 8366
8500 mg kg-1 of K and 2050 2324 mg kg-1 of P.
Table 1 Proximate analysis and inorganic elements presented in biochar and biochar pelletsa.
Proximate analysis (%)

Inorganic elements (mg/kg)

Sample

Water Volatile Ash Fixed

K
Ca
content Matter content carbon
1.4
40.6
5.6 52.4 3622 4055
Biochar
(0.3) (1.9) (0.9) (1.6) (118) (105)
605 137
Lignin
2.4
(14) (9)
10%
0.9
42.2
5.6 52.1 4368 4308
lignin (0.6) (2.1) (0.3) (2.4) (153) (36)
Biochar
20%
0.3
43.2
5.0 51.8 3266 3996
Pellet
lignin (0.3) (0.9) (0.2) (1.0) (74) (220)
30%
1.1
46.0
4.8 49.2 2852 3432
lignin (0.1) (2.1) (0.3) (1.8) (97) (210)
10%
0.9
42.2
5.6 52.1 8366 4308
lignin (0.6) (2.1) (0.3) (2.4) (195) (36)
Biochar
Pellet with 20%
0.3
43.2
5.0 51.8 8500 3996
fertilizer lignin (0.3) (0.9) (0.2) (1.0) (222) (220)
30%
1.1
46.0
4.8 49.2 8428 3432
lignin (0.1) (2.1) (0.3) (1.8) (15) (210)
a
All samples were average values calculated from N = 3 replicate
deviation values in parentheses

Mg

Na

2504 87
815
(10) (1) (28)
164 6397 14
(2) (193) (1)
2713 1202 836
(32) (17) (15)
2457 1950 801
(71) (106) (47)
2179 2816 722
(74) (94) (24)
2713 1202 2324
(32) (17) (176)
2457 1950 2250
(71) (106) (96)
2179 2816 2050
(74) (94) (53)
measurements, with

S
498
(29)
10381
(209)
1630
(23)
2595
(134)
3745
(115)
1630
(23)
2595
(134)
3745
(115)
standard

1.2. Thermal properties

Thermogravimetric (TG) and derivative TG (DTG) combustion curves (Fig. 1) under air
condition were analyzed for thermal decomposition of biochar pellets. Raw biochar and biochar
pellets produced with 10 wt% lignin and dried at 105 and 180 oC possessed similar TG and DTG
thermograms (Fig. 1a and 1b). The DTG curves in Fig. 1b showed that the maximum mass loss
rate (DTG peak) occurred at 327 - 330 oC and was associated with thermal decomposition of
cellulose, hemicellulose and lignin that volatilized and followed by producing the corresponding
biochars. The DTG peaks at 412 445 oC were assigned to thermal degradation of the biochars
derived from cellulose, hemicellulose and lignin (Kim et al., 2011). As lignin content increased
from 10 to 20 and 30 wt% in biochar, a shift toward higher combustion temperature (Fig. 1c)
was observed in the pellets dried at 180 oC (Fig. 1d). The peaks at 327-330 oC did not shift in
biochar pellets dried at 105 oC. However, the DTG peaks at 450-480 oC were broader at higher
temperature in biochar pellets dried at 180 oC with increasing lignin content to 30 wt%. The
observed shift of DTG shoulder peak was attributed to condensed and cross-linked lignin that
was produced at high temperature (180 oC).

60
40
Biochar
Pellet 10-105
Pellet 10-180

20

200

400
600
o
Temp ( C)

Mass loss (wt%)

DTG (dm%/dt)
Pellet 20-105
Pellet 20-180

800

DTG (d)

-0.04
-0.06
-0.08
-0.10
-0.12
-0.16

400
600
o
Temp ( C)

800

200

40
Pellet 30-105
Pellet 30-180
400
600
o
Temp ( C)

800

DTG (f)

-0.02

DTG (dm%/dt)

60

400
600
o
Temp ( C)

0.00

80

200

400
600
o
Temp ( C)

-0.14

TG (e)

-0.12

-0.02

40

20

-0.10

0.00

60

100

-0.08

200

80

200

-0.06

-0.16

800

TG (c)

-0.04

-0.14

100

20

DTG (b)

-0.02

80

Mass loss (wt%)

0.00

TG (a)
DTG (dm%/dt)

Mass loss (wt%)

100

-0.04
-0.06
-0.08
-0.10
-0.12
-0.14
-0.16

800

200

400
600
o
Temp ( C)

800

Fig. 1. TGA of biochar and biochar pellets produced with 10, 20, 30% lignin and dried at 105
and 180 oC. (a) TG (b) DTG of biochar and biochar pellet 10-105 and 10-180. (c) TG (d) DTG of
biochar pellet 20-105 and 20-180 (e) TG and (d) DTG of biochar pellet 30-105 and 30-180.

1.3. Surface functionality

The surface functionality of biochar pellets was assessed by FTIR-ATR (in the 4,000 600 cm-1 range). As expected, the addition of lignin as a binder (from 0 to 30 wt%) led to a
significant increase in the peak intensity at 1266 cm-1 (C-O stretching in lignin) and at 1511 cm-1
(C=C stretching vibration of lignin). In order to clearly delineate the differences in the FTIR
spectra collected on the biochar pellets with different binder ratios and drying temperatures,
principal component analysis (PCA) was performed on the 1,800 600 cm-1 region (Fig. 2). The
scores plot (Fig. 2a) of the PCA for biochar and the corresponding pellets containing 10 to 30 wt%
of lignin and drying temperature at 105 and 180 oC showed a noticeable separation with
increasing amount of lignin by the first principal component (PC1, accounting for 64% of the
total spectral variance). As expected from the PC1 loadings (Fig. 2b), the variables responsible
for this separation were bands related to lignin (C-H bonds in guaiacyl ring (1140 cm-1), C-O
stretching (1200 and 1266 cm-1) and C=C stretching (1511cm-1)).
PCA was also conducted on biochar pellets containing the same amount of lignin but
processed at two temperatures (Fig. 2c, 2e and 2f). A separation between the two sample sets
demonstrated that temperature significantly impacted the chemistry of the pellets. The
corresponding loadings plots (Fig. 2d, 2f and 2h) showed that biochar pellets dried at 180 oC
contained higher amount of aromatic rings (1430 1630 cm-1) and C-O-C stretching (1385 cm-1),
which evidenced the formation of ether groups through condensation. These results indicate that
lignin dried at higher temperature (180 oC) than its glass transition temperature (150 - 160 oC)
softens and flows, resulting in bonding biochar particles and followed by aromatic condensation
and cross-linking (Stelte et al., 2012).

10

0.15

(a)
10-105

PC2 (18%)

20-180

-3

-2

-1
0
PC1 (64%)

0.05
0.00

-0.10
0.10

10-105
Loadings

10-180

-1.5

(e)

-0.05
0.05

20-105

0.0

20-180

-0.5

0.00
0.05
-0.05

-1.0

-0.10
0.10
1800

-1.5
-1.5
1.5

-1.0
1.0

-0.5
0.5

0.5 -1.0
1.0 -1.5
1.5 -2.0
2.0
0.0 -0.5
PC1 (59%)

0.15

(g)

1.0
0.5

30-180

0.0

30-105

(h)

600

PC1 (40%)

0.05
0.00
-0.05

-0.5
-1.0
-1.5

1600 1400 1200 1000 800

-1
Wavenumber (cm )

0.10

Loadings

PC2 (21%)

0.00

1800 1600 1400 1200 1000 800

600
-1
Wavenumber (cm )
-0.10
0.10
(f)
PC1 (59%)

0.5 -1.0
1.0 -1.5
1.5 2.0
0.0 -0.5
-2.0
PC1 (55%)

Loadings

PC2 (22%)

-0.5
0.5

0.5

1.5

PC1 (55%)

-0.10
0.10
-1.5 -1.0
1.5
1.0

1.0

600

0.05
-0.05

-1.0

1.5

(d)

800

-0.05
0.05

0.0
-0.5

PC1 (64%)

-0.10
1800 1600 1400 1200 1000
-1
Wavenumber (cm )

(c)

0.5

(b)

-0.05

Raw
biochar

-2

PC2 (28%)

30-180

20-105

-1

1.0

30-105

10-180

1.5

0.10

Loadings

-1.0

-0.5
0.0
0.5
PC1 (40%)

1.0

1.5

-0.10
1800 1600 1400 1200 1000
-1
Wavenumber (cm )

800

600

Fig. 2. PCA of FTIR spectra collected from raw biochar and biochar pellets produced at different
lignin content and drying temperature (105 and 180 oC). (a) Scores plot and (b) loadings plot of
all biochar and pellets. (c) Scores plot and (d) loadings plot of biochar pellets 10-105 and 10-180.
(e) Scores plot and (f) loadings plot of biochar pellets 20-105 and 20-180. (g) Scores plot and (h)
loadings plot of biochar pellets 30-105 and 30-180.
11

1.4. Mechanical properties

Density calculated by measuring weight and dimension of the pellets showed that biochar
pellets dried at 105 oC with different lignin content of 10, 20 and 30% had similar density,
ranging from 861 to 878 kg/m3, whereas biochar pellets dried at 180 oC had a lower density from
875 to 776 kg/m3 with increasing lignin ratios. This was attributed to the removal of volatile
matters present in lignin (Table 1) without any change in the shape of the pellet during drying
(180 oC). Maximum compressive strength, measured by applying the maximum load that a
biochar pellet can sustain without any crack or breakage, decreased from 3.54 to 2.33 MPa for
pellets dried at 105 oC. The same pattern was observed for biochar pellets dried at 180 oC (4.68
to 2.51 MPa). These results indicate that biochar pellets containing higher lignin amount became
harder and more brittle due to the excessive glass transition temperature of lignin during drying
temperature (180 oC) (Reza et al., 2012). When compared to torrefied biochar pellet produced
using hydraulic press (7.5 Megaton, estimated 2,000 MPa) with a controlled temperature (140 oC)
(Reza et al., 2012), our biochar pellets produced using a pellet mill (172 MPa) under temperature
of 65 - 85 oC had approximately 21 - 85 times lower compressive strength. Biochar pellets
produced with increasing lignin content from 10 to 30 % showed a decrease in abrasion index
from 15.3 to 5.6 % when dried at 105 oC and from 14.1 to 3.9 % when dried at 180 oC.
Decreasing abrasion index with increasing lignin content indicates the increase of durability of
biochar pellets.
Table 2 Mechanical properties of biochar pellets produced with different lignin contents and at
different drying temperature.
Sample
Drying
temp.
105 oC
Biochar
pellet
180 oC
a
b

Density
(kg/m3)

Abrasion
index
(wt %)

Durability
(%)

Maximum
compressive
strength (MPa)

10%

878(45)

15.3 (0.6)

84.7

3.54 (1.38)

20%

861(57)

11.8 (0.0)

88.2

2.48(0.84)

30%

863(36)

5.6 (0.1)

94.4

2.33 (0.76)

10%

875(22)

14. 1 (0.5)

85.9

4.68 (0.99)

20%

812(48)

11.1 (1.5)

88.9

3.26 (0.89)

30%

776(35)

3.9 (1.5)

96.1

2.51 (0.35)

Added
binder

Density was calculated by measuring diameter, length and mass of 10 cylindrical biochar pellets.
Durability was calculated by difference (durability % =100 abrasion index %).

12

1.5. Water uptake of biochar pellets

Capillary rise (wicking), a process by which liquid penetrates spontaneously into porous
material by capillary force (Siebold et al., 1997), was applied to measure water uptake of biochar
pellets (Fig. 3). The water uptake curves of biochar pellets produced with 10, 20 and 30% lignin
and dried at 105 oC (Fig. 3a, 3c and 3e) showed two stages of water uptake; a sharp increase in
the first 10 - 20 min followed by a gradual increase overtime. During the first stage of the rapid
water uptake, biochar pellets with 10% lignin and dried at 105 oC, adsorbed up to 35 - 41 wt% of
water, while pellets with 20 % lignin adsorbed 51 53 wt% and pellets with 30% lignin
adsorbed 64 69 wt% of water. This difference in adsorption could be attributed to the presence
of hydrophilic surface functionalities (C=O, O-H and C-O-C) in the biochar pellets and lignin
(Fig. 2). Biochar pellets dried at 180 oC had a water uptake of 57 63 wt% within the first 23
min followed by a gradual uptake overtime, a trend similar to that of biochar pellets dried at 105
o
C. However, biochar pellets dried at 180 oC demonstrated a higher water adsorption capacity
(accumulated 72 76 wt%) than biochar pellets dried at 105 oC (accumulated 52 56 wt%) after
8h, which may be attributed to increasing functional groups by lignin condensation at 180 oC
(Fig. 2). Biochar pellets produced with higher amount of lignin (20 and 30 %) and dried at 180
o
C possessed a different water uptake behavior than the other biochar pellets. Within the first 15
min, a sharp water uptake (19 22 wt%) was observed, however compared to biochar pellets
dried at 105 oC, the amount adsorbed is lower. In the second stage of water uptake, a sharper
water uptake was observed for the pellets with 20 % lignin at 180 oC. Biochar pellets with 30%
lignin at 180 oC had sharper water uptake slop than other biochar pellets within the first 4h and
thereafter gradual uptake (90 92 wt%). The sharp water uptake in the second stage in biochar
pellets with 20 and 30% lignin and dried at 180 oC may result from production of high porosity
among the biochar particles and lignin, which is produced by removing volatile matter from
lignin (Table 1), decreasing density (Table2) and increasing lignin condensation and crosslinking (Fig. 2) at 180 oC.

13

60
40
20
0

100

4
Time (hr)

80
60
40
20
0

100

4
Time (hr)

20
0

60
40
20
0
4
Time (hr)

4
Time (hr)

4
Time (hr)

4
Time (hr)

80
60
40
20
0
0

(d) 20-180

100

80

40

(e) 30-105

60

100

(c) 20-105

(b) 10-180

80

Adsorbed H2O/pellet (w/w%)

Adsorbed H2O/pellet (w/w%)

Adsorbed H2O/pellet (w/w%)

80

Adsorbed H2O/pellet (w/w%)

100

(a) 10-105

Adsorbed H2O/pellet (w/w%)

Adsorbed H2O/pellet (w/w%)

100

(f) 30-180

80
60
40
20
0
0

Fig. 3. Water uptake of biochar pellets. Lines presented triplicate runs of each sample. (a) 10-105,
(b) 10-180, (c) 20-105, (d)20-180, (e) 30-105, and (f) 30-180 represent biochar pellets produced
with 10, 20 and 30% lignin and dried at 105 and 180 oC respectively.

14

2. Nutrient release
2.1. Nutrient release from biochar pellets
The cumulative nutrients (sum of all nutrients released at a particular time) naturally
present in raw biochar and biochar pellets were rapidly released within the first 24 h followed by
a more gradual release rate within 432 h (Fig.4). Raw biochar released 49.8 % of total K (3622
mg kg-1) within 24 h and 82 % by 432 h. Biochar pellets blended with 10, 20 and 30% lignin and
dried at 105 oC released 79, 82 and 76% within 24 h, respectively. All biochar pellets released
more than 97% of total K within 432 h. Biochar pellets dried at 105 oC demonstrated higher K
release rates than raw biochar. This difference in K release may be attributed to smaller particle
sizes generated by the pellet mill during the pelletization step. This could imply that nutrients
present in smaller particle sizes of biochars are released faster than in larger particle sizes.
However, biochar pellets dried at 180 oC showed a significant decrease of release rate of K with
increasing lignin amount. Biochar pellets with 10% lignin released 74.1% of total K (4368 mg
kg-1) while biochar pellets with 30% lignin released only 39.5% of total K (2852 mg kg-1) within
24h, and then released 97 and 75% within 432h, respectively. Therefore, by controlling the
amount of binder, one can control the amount of K that is being released in biochar pellets.
The cumulative release percentage of P from raw biochar was 46.3% within 24 h and
56.4% within 432 h. Biochar pellets with 10% lignin and dried at 105 and 180 oC possessed
similar release pattern with 65% within 24 h and 95% within 432 h. This result could also be
attributed to smaller particle sizes of biochar in the pellets with low lignin content. P release % in
biochar pellets with 20 and 30% lignin and dried at 105 oC was lower than P release in the
biochar pellets with 10% lignin and higher in raw biochar. However, when biochar pellets were
dried at 180 oC, P release % was 41.5% in biochar pellets with 20% lignin and 39.1% in biochar
pellets with 30% lignin within 24 h, and then 57 and 48.4% in 432 h, respectively.
The cumulative release percentage of Ca and Mg from raw biochar and biochar pellets by
time showed similar trend than K and P. Total release % was 31% of total Ca and 45.3% in raw
biochar within 432 h. Biochar pellets with increasing lignin % released lower amount of Ca (3 6%) and Mg (12.9 - 20%) within 432 h. These findings could be explained by the fact that Ca
and Mg have lower solubility than K and these elements may be bonded with surface negative
functional groups present in biochar and lignin.

15

3000
2000
1000
0
6000

K_Biochar

0 (c)

100

5000

200

300

400

-1

KTime
4368(hr)
mg kg

4000
3000
2000
1000
0
6000 0
(e)
5000

K_10-100
105
K_10-180

100

200

300

400

Time (hr)

4000

K 3266 mg kg-1

3000
2000
1000
0
6000 0
(g)
5000

105
K_20-100
K_20-180

100

200

300

400

Time (hr)

4000

K 2852 mg kg-1

3000
2000

105
K_30-100
K_30-180

1000
0
0

100

200

300

Cumulative release (mg/kg)

K 3622 mg kg-1

4000

Cumulative release (mg/kg)

5000

Cumulative release (mg/kg)

(a)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

6000

400

(b)

1200
1000

P 815 mg kg-1

800
600
400
200
0
1400

1200

P_Biochar

0(d)

100

200

16

300

400

Time (hr)

P 836 mg kg-1

1000
800
600
400

P_10-100
105
P_10-180

200
0
1400 0
(f)
1200

100

200

300

400

Time (hr)

1000

P 801 mg kg-1

800
600
400

P_20-100
105
P_20-180

200
0
1400 0
(h)
1200

100

200

300

400

Time (hr)

1000

P 722 mg kg-1

800
600
400

105
P_30-100
P_30-180

200
0
0

100

200
Time (hr)

Time (hr)

1400

300

400

Ca (4055 mg/kg)

1000
800
600
400
200
0
1400 0
(c)
1200

Ca_Biochar

100

200

300

400

Time (hr)

1000

Ca (4308 mg/kg)

800
600
400

Ca_10-105
Ca_10-180

200
0
1400 0
(e)
1200

100

200
Time (hr)

300

400

Ca_20-105
Ca_20-180

1000
800
600

Ca (3996 mg/kg)

400
200
0
1400 0
(g)
1200

100

200
Time (hr)

1000

300

400

Ca_30-105
Ca_30-180

800
600

Ca (3432 mg/kg)

400
200
0
0

100

200

300

400

Time (hr)

3000
2500

(b)
Mg (2504 mg/kg)

2000
1500
1000
500
0
3000

Mg_Biochar

0(d)

2500

100

200

300

400

Time (hr)
Mg (2713
mg/kg)

2000
1500
1000
Mg_10-105
Mg_10-180

500
0
3000
2500

0(f)

100

200

300

Mg (2457 mg/kg)

400

Time (hr)

2000

Mg_20-105
Mg_20-180

1500
1000
500
0
3000 0
(h)
2500

100

200

300

400

Time (hr)
Mg (2174
mg/kg)

2000
Mg_30-105
Mg_30-180

1500
1000
500
0
0

100

200
Time (hr)

17

Cumulative release (mg/kg)

1200

Cumulative release (mg/kg)

(a)

Cumulative release (mg/kg)

1400

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Fig. 4. Nutrient release (K and P) from biochar pellets with lignin content 10, 20 and 30% and
dried at 105 and 180 oC.

300

400

Fig. 5. Nutrient release (Ca and Mg) from biochar pellets with lignin content 10, 20 and 30% and
dried at 105 and 180 oC.
2.2. Nutrient release from biochar pellets embedded with K and P fertilizer
Biochar pellets embedded with K fertilizer (8366 8499 mg kg-1) dried at 105 oC
released 74 - 77% of K with 10, 20 and 30% lignin. Subsequently, all biochar pellets released 87,
85, and 77%, respectively. Biochar pellets dried at 180 oC and containing 10, 20 and 30% lignin,
released 62, 59 and 53% of K, respectively within 24 h. After 432 h, K released was 87, 85 and
78% for pellets with 10, 20 and 30% lignin, respectively. Biochar pellets with P fertilizer dried at
105 oC released 77 85 % of total P (2049 2323.5 mg kg-1) within 24 h and 89 - 95% within
432 h. However, biochar pellets dried at 180 oC released only 49 62 % within 24 h and 73 78%
within 432 h. These findings demonstrate that the release of fertilizers embedded in biochar
pellets can also be regulated by controlling the amount of binder.
As Indulin AT lignin, containing high amounts of Na (6397 mg kg-1) and S (10381 mg
kg-1), was added to biochar pellets (Table 1), amount of Na in biochar pellets increased from
1202 to 2816 mg kg-1 with increasing lignin content from 10 to 30 wt%. All biochar pellets dried
at 105 oC released abruptly 68 75% of Na within the first 24h. However, biochar pellets dried
at 180 oC released 59 and 50% in biochar pellet with 10 and 30% within 24 h and thereafter
released 78 and 71% of Na with 10 and 30% of lignin within 432 h. The release pattern of S was
also similar with that of Na, but release % of S in 432 h was significantly lower than that of Na,
which is attributed to the covalently bound S with lignin derived from the kraft process (Beis et
al., 2010). These findings demonstrate that nutrient-release rates can be controlled by binder
amount and by drying temperature.

18

K 8366.1 mg kg-1

8000
6000
4000
2000

K_10-105
K_10-180

0
0

100

200

300

Cumulative release (mg/kg)

Cumulative release (mg/kg)

10000

2500

P 2323.5 mg kg-1

2000
1500
1000
500

P_10-105
P_10-180

400

100

K 8499.6 mg kg-1

8000
6000
4000
2000

K_20-105
K_20-180

Cumulative release (mg/kg)

100

200

300

Cumulative release (mg/kg)

10000

K 8428.1 mg kg-1

8000
6000
4000
2000

K_30-105
K_30-180

0
0

100

200

300

2500

400

P 2250 mg kg-1

2000
1500
1000
500

P_20-100
105
P_20-180

0
0

400

Time (hr)

10000

300

Time (hr)

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Time (hr)

200

400

200

300

400

Time (hr)

2500

P 2049.6 mg kg-1

2000
1500
1000
500

P_30-105
P_30-180

0
0

Time (hr)

100

100

200

300

400

Time (hr)

Fig. 6. Nutrient release (K and P) from biochar pellets embedded with K and P fertilizer, lignin
content 10, 20 and 30 %, and dried at 105 and 180 oC.

19

Cumulative release (mg/kg)

(a)

150
100

Na (87 mg/kg)

50

200

300

400

Time (hr)

3000
2000

Na (1202 mg/kg)
1000
0
4000

Na_10-105
Na_10-180

0 (e)

100

200

400

Time (hr)

3000

Na (1980 mg/kg)

2000
1000
0
4000

300

Na_20-105
Na_20-180

0(g)

100

200

300

400

Time (hr)

Na (2816 mg/kg)

3000
2000
1000

Na_30-105
Na_30-180

0
0

100

200

300

Cumulative release (mg/kg)

100

Cumulative release (mg/kg)

0
4000 0
(c)

Na_Biochar

Cumulative release (mg/kg)

Cumulative release (mg/kg)

Cumulative release (mg/kg)
Cumulative release (mg/kg)

Cumulative release (mg/kg)

200

(b)

500

S (498 mg/kg)

400
300
200
100

0
4000 0

S_Biochar

(d)

100

200

2000

400

S_10-105
S_10-180

S (1630 mg/kg)

1000
0
4000 0

(f)

100

200

300

Time (hr)

3000

400

S_20-100
105
S_20-180

S (2595 mg/kg)

2000
1000
0
4000 0
(h)

100

200

300

400

(hr)mg/kg)
STime
(3745

3000

S_30-105
S_30-180

2000
1000
0
100

200
Time (hr)

20

300

Time (hr)

3000

400

Time (hr)

600

300

400

Fig. 7. Nutrient release (Na and S) from biochar pellets with lignin content 10, 20 and 30% and
dried at 105 and 180 oC.

Conclusions
This study concludes that when switchgrass-derived biochars produced by fast pyrolysis are
blended with fertilizer and lignin followed by pelletization and then a drying process at
temperature higher than lignins glass transition temperature, the resulting biochar pellets are
more durable and have higher porosity and surface functionality. These properties in biochar
pellets contribute in holding nutrients for a longer time in the biochar pellets and participate in
their slow release. Therefore, nutrient-rich biochar pellets may be a potential candidate for a
cost-effective slow-release fertilizer in soil.

21

Reference
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Produced from the Pyrolysis of Mallee Wood under Slow-Heating Conditions. Energy &
Fuels, 23(8), 4174-4181.
Beis, S.H., Mukkamala, S., Hill, N., Joseph, J., Baker, C., Jensen, B., Stemmler, E.A., Wheeler,
M.C., Frederick, B.G., van Heiningen, A., Berg, A.G., DeSisto, W.J. 2010. FAST
PYROLYSIS OF LIGNINS. Bioresources, 5(3), 1408-1424.
Cantrell, K.B., Hunt, P.G., Uchimiya, M., Novak, J.M., Ro, K.S. 2012. Impact of pyrolysis
temperature and manure source on physicochemical characteristics of biochar.
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Cantrell, K.B., Martin II, J.H. 2012. Poultry litter and switchgrass blending and pelletizing
characteristics for biochar production. 2012 ASABE Annual International Meeting, 2012,
Dallas, Texas. American Society of Agricultural and Biological Engineers. pp. 121337605.
Fernndez-Escobar, R., Benlloch, M., Herrera, E., Garca-Novelo, J.M. 2004. Effect of
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by leaching. Scientia Horticulturae, 101(12), 39-49.
Hua, L., Wu, W.X., Liu, Y.X., McBride, M., Chen, Y.X. 2009. Reduction of nitrogen loss and
Cu and Zn mobility during sludge composting with bamboo charcoal amendment.
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Husk, B., Major, J. 2008. Commercial scale agricultural biochar field trial in Quebec, Canada,
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Kim, P., Johnson, A., Edmunds, C.W., Radosevich, M., Vogt, F., Rials, T.G., Labbe, N. 2011.
Surface Functionality and Carbon Structures in Lignocellulosic-Derived Biochars
Produced by Fast Pyrolysis. Energy & Fuels, 25(10), 4693-4703.
Kim, P., Johnson, A.M., Essington, M.E., Radosevich, M., Kwon, W.T., Lee, S.H., Rials, T.G.,
Labbe, N. 2013. Effect of pH on surface characteristics of switchgrass-derived biochars
produced by fast pyrolysis. Chemosphere, 90(10), 2623-2630.
Lehmann, J., Rillig, M.C., Thies, J., Masiello, C.A., Hockaday, W.C., Crowley, D. 2011. Biochar
effects on soil biota A review. Soil Biology and Biochemistry, 43(9), 1812-1836.
Major, J., Lehmann, J., Rondon, M., Goodale, C. 2010. Fate of soil-applied black carbon:
downward migration, leaching and soil respiration. Global Change Biology, 16(4), 13661379.
Mortain, L., Dez, I., Madec, P.J. 2004. Development of new composites materials, carriers of
active agents, from biodegradable polymers and wood. Comptes Rendus Chimie, 7(6-7),
635-640.
Reza, M.T., Lynam, J.G., Vasquez, V.R., Coronella, C.J. 2012. Pelletization of Biochar from
Hydrothermally Carbonized Wood. Environmental Progress & Sustainable Energy, 31(2),
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Ro, K.S., Cantrell, K.B., Hunt, P.G. 2010. High-Temperature Pyrolysis of Blended Animal
Manures for Producing Renewable Energy and Value-Added Biochar. Industrial &
Engineering Chemistry Research, 49(20), 10125-10131.
Siebold, A., Walliser, A., Nardin, M., Oppliger, M., Schultz, J. 1997. Capillary rise for
thermodynamic characterization of solid particle surface. Journal of Colloid and
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Stelte, W., Sanadi, A.R., Shang, L., Holm, J.K., Ahrenfeldt, J., Henriksen, U.B. 2012. RECENT
DEVELOPMENTS IN BIOMASS PELLETIZATION - A REVIEW. Bioresources, 7(3),
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23

Final (actual) budget

1. Actual Dollars Spent:

BUDGET ITEM

SUN GRANT $

a. Total Salaries & Wages

$35,000

b. Fringe Benefits

$16,884

c. Supplies

$10,000

COST SHARE $

d. Equipment
e. Travel

$5,000

f. Publications

$2,000

g. Other (Subcontractors, Consultants)

$3,000

$20,000

Total DIRECT COSTS (Sum of A-G) $74,884

Total INDIRECT (i.e. F&A) COSTS $18,721
(IDC Usually = Total Direct Costs*.25)
h. Graduate Student Tuition
i. Permanent Equipment ($5,000 or More)
j. Other Costs Not Requiring Indirect
Total DOLLARS SPENT
(Total Direct + Total Indirect + H + I + J)

2. Describe all Cost Share:

a) Sources
b) Proton Power supported the project by making in-kind contribution in the optimization of
the pyrolysis system, the production of the biochars, and the pellets.

24

Publication and Presentations

Kim, P. et al. (2012), Poster presentation, Characterization of nutrient-embedded biochar pellets
as a slow release fertilizer material, 2012 National conference, Science for biomass feedstock
production and utilization, October 2-5, 2012, New Orleans, LA. USA.
Labb, N. and Kim, P. (2013), Poster presentation, Nutrient release of biochar pellets embedded
with fertilizers, 2013 BIO Pacific Rim Summit on Industrial Biotechnology and Bioenergy, Dec.
8-11, 2013, San Diego, CA, USA.
Kim, P. and Labb, N. (2013) Nutrient release from switchgrass-derived biochar pellets
embedded with fertilizers, in preparation.

Contracts Related to this Project since Project Inception

Nicole Labb, Screening of biomass and processes to upgrade bio-fuels, supported by Proton
Power Inc. 10/2012 - 04/2013 ($174,000).
Nicole Labb and Pyoungchung Kim, Characterization and upgrade of bio-oils and
development of activated carbons from biochars, supported by Proton Power Inc. 05/201305/2015 ($285,879).

25