Application of biochar produced
from wood and seaweed for the
removal of dye in wastewater
Mi Nam Lee and Seung Han Woo*
Hanbat National University, Korea
2nd FORBIOM Workshop
Potentials of Biochar to Mitigate Climate Change
Outline
1
2
Application for Corn Cultivation
1
Biomass Resources
Biomass
Terrestrial
1st generation
2nd generation
Agriculture
crops
Lignocellulosic
biomass
Aquatic
3rd generation
Microalgae
Macroalgae
2
Energy Production from Biomass
Agriculture
Crops
Lignocellulosic
Algae
Production
interval
1~2/yr
>~8 yrs
4~6/yr
Production
yield
(ton/ha)
180
9
565
Energy
conversion
30~35%
20~25%
> 45%
3
Types of Macroalgae
Brown Algae
Sea mustard
Red Algae
Kelp
Sea string
Purple laver
Agar
Green Algae
Hijikia
Gulfweed
Gom Pi
Green
laver
Greyblue
Spicebush
Seaweed
fulvescens
4
Objectives
 Application for dye adsorption
 Textile industries discharge large amounts of colored wastewater
containing various dyes, some of which are mutagenic and carcinogenic to
human beings.
 The adsorption of Congo red and Methylene blue using biochars produced
with four different biomass sources was investigated.
 Application for crop cultivation
 Mostly, it is known that biochar augmentation increases crop yield due to
water and nutrient retention, etc. However, it has sometimes been reported
to have negative effects on crop yield.
 In order to know the effect of the seaweed biochars on crop growth, corn
was cultivated in the field with or without the biochars and/or compost
fertilizer.
6
1
7
Pyrolysis System
Bio-gas
N2
Bio-oil
Bio-char
8
Biomass Materials
Drying
(120 ℃, 100 h)
Oak tree
Bamboo
Drying, Grinding
Kelp
Green laver
 Pyrolysis conditions
 Temperature: 200, 300, 400, 500 oC
 Heating rate: 3, 6, 9 min
 Holding time: 0, 20, 60 min
 N2 flow rate: 100 mL/min
9
Effect of Temperature
100
Biooil
Biochar
Biogas
Yield (%)
80
60
40
20
0
200
300
400
500
Temperature (oC)
Fig. 1. The effect of temperature on the yield of pyrolysis prod
ucts with oak tree.
10
Yields of Pyrolysis Products
60
50
Bamboo
Oak tree
Kelp
Green laver
Yield (%)
40
30
20
10
0
biooil
biochar
biogas
Fig. 2. The yield of pyrolysis products with different biomass
(400 oC, 9 oC/min, 60 min).
11
FE-SEM Images
Oak tree
Bamboo
Kelp
Green laver
Fig. 3. FE-SEM images of the surfaces of biochars made from
different biomass sources (400 oC, 9 oC/min, 60 min).
12
CHONS Analysis
Table 1. Elemental analysis for various biochars (400 oC, 9 oC/min, 60 min)
N (%)
C (%)
H (%)
S (%)
O (%)
Oak tree
0.00
79.46
2.91
ND
13.28
Bamboo
0.21
77.86
2.92
ND
12.56
Kelp
1.10
37.56
3.23
0.64
24.74
Green laver
1.99
27.65
1.62
1.10
19.60
13
Target Dye Chemicals
Anionic Dye
Congo red
Cationic Dye
Methylene blue
14
Adsorption Experiments
Congo red solution
10 ml
Methylene blue solution
10 ml
Bio-char (0.2 g, 300~500 µm)
Shaking
(25℃, 125 rpm, 24 h)
Spectrophotometer (DR5000, HACH)
λ max : 497 nm
λ max : 665 nm
(congo red)
(methylene blue)
15
Isotherm Study (Congo Red)
Congo Red adsorption (Bamboo)
Congo red adsorption (Oak tree)
Experimental data
Langmuir isotherm
Freundlich isotherm
6
qe (mg/g)
40
qe (mg/g)
8
Experimental data
Langmuir isotherm
Freundlich isotherm
50
30
20
4
2
10
0
0
0
200
400
600
800
1000
0
200
400
600
Ce (mg/l)
Ce (mg/l)
(a)
(b)
800
1000
Fig. 4. Isotherms for the adsorption of congo red with various biochar sorbents.
16
Isotherm Study (Congo Red)
Congo red adsorption (Kelp)
Congo Red adsorption (Green laver)
60
80
Experimental data
Langmuir isotherm
Freundlich isotherm
60
Experimental data
Langmuir isotherm
Freundlich isotherm
50
qe (mg/g)
qe (mg/g)
40
40
30
20
20
10
0
0
0
200
400
600
Ce (mg/l)
(c)
800
1000
0
200
400
600
800
1000
Ce (mg/l)
(d)
Fig. 4. Isotherms for the adsorption of congo red with various biochar sorbents.
17
Long-term Adsorption (Congo Red)
25
500 mg/l
1000 mg/l
20
qe (mg/g)
Fig. 5. Long-term adsorption of congo red
with various sorbents.
Oak tree
15
10
5
0
0
Kelp
1
2
3
4
5
6
7
8
9
10 11 12 13 14
Day
250
600
100 mg/l
500 mg/l
1000 mg/l
200
Activated
carbon
100 mg/l
500 mg/l
1000 mg/l
500
qe (mg/g)
qe (mg/g)
400
150
100
300
200
100
50
0
0
0
1
2
3
4
5
6
7
Day
8
9
10 11 12 13 14
0
1
2
3
4
5
6
7
Day
8
9
10 11 12 13 14
18
Isotherm Study (Methylene Blue)
Methylene blue adsorption (kelp)
Methylene blue adsorption (Oak tree)
25
300
Experimental data
Langmuir isotherm
Freundlich isotherm
250
200
15
qe (mg/g)
qe (mg/g)
20
Experimental data
Langmuir isotherm
Freundlich isotherm
10
5
150
100
50
0
0
0
200
400
600
Ce (mg/l)
(a)
800
1000
1200
0
100
200
300
400
500
600
Ce (mg/l)
(b)
Fig. 6. Isotherms for the adsorption of methylene blue with various biochar sorbents.
19
Isotherm Parameters
Isotherm model
Langmuir isotherm
qe 
qmax K LCe
1  K LCe
Freundlich isotherm
qe  K F Ce1/ n
biochar
sorbent
Dye
Oak tree
Bamboo
Kelp
Green laver
Oak tree
Kelp
Congo red
Congo red
Congo red
Congo red
Methylene Blue
Methylene Blue
Oak tree
Bamboo
Kelp
Green laver
Oak tree
Kelp
Congo red
Congo red
Congo red
Congo red
Methylene Blue
Methylene Blue
parameter value
kL (dm3 mg-1) qm (mg g-1)
0.0011
85.20
0.0063
5.56
0.0018
95.12
0.0611
35.78
0.0127
15.29
0.0202
243.32
KF (dm3 g-1)
1/n
0.35
0.708
0.56
0.306
1.05
0.595
8.60
0.228
2.15
0.279
18.39
0.450
R2
0.9950
0.1896
0.9793
0.9839
0.6458
0.9868
R2
0.9892
0.3969
0.9969
0.9839
0.7444
0.9310
20
Summary
 The highest production yield was achieved with green laver and kelp for biochar
and biooil, respectively.
 In case of oak tree, many pores were formed during pyrolysis, but not in case
of seaweed biomass.
 The carbon content was much lower in seaweed biomass than wood biomass,
while nitrogen and sulfur content were higher in seaweed biomass.
 The biochar of kelp and oak tree showed higher Langmuir adsorption capacity
for congo red compared to that of bamboo and green laver.
 In case of methylene blue, kelp biochar showed much higher adsorption
capacity (243 mg/g) than oak tree biochar.
 Kelp biochar showed slow but high adsorption capacity in the long-term
adsorption.
 The biochars, more preferably seaweed biochars, could be effective and low cost
adsorbents for the removal of anionic or cationic dyes from wastewater.
21
2
Application for Corn Cultivation
22
Production of Biochar
(a)
(b)
 Biomass resource: (a) Fir pellet 500 g, (b) kelp 500 g
 Pyrolysis system: Traditional can (40 L), heating for 3 hrs
23
CHON Analysis
Table 1. Elemental analysis data of raw biomass and its biochar
Biomass
C
H
O
N
Others
Fir wood pellet
47.24
5.45
42.25
1.77
3.29
Fir biochar
82.4
2.92
9.97
0.57
4.14
Kelp
27.5
2.81
36.19
2.32
31.18
Kelp biochar
27.42
0.59
12.08
1.28
58.63
24
Element Concentration
Table 2. Element concentration in biochars measured by ICP.
The elements Ag, Be, Cd, Co, Cr, Li, Mo, Ni, Pb, Se, Si, W, and Zr were not found.
Fir biochar
Kelp biochar
Element
mg/kg
RSD(%)
mg/kg
RSD(%)
Al
289.00
1.72
225.40
3.25
As
0.00
210.90
42.61
40.25
B
17.60
3.39
498.60
3.73
Ba
0.00
3.72
230.11
0.52
Ca
5032.00
1.57
21851.00
2.36
Cu
0.00
3.64
308.70
3.45
Fe
344.60
0.86
317.20
0.31
K
3585.00
1.91
382300.00
2.42
Mg
985.10
1.4
16270.00
2.17
Mn
126.60
1.51
11.84
0.33
Na
1323.00
1.53
63260.00
2.29
P
183.30
2.65
4101.00
0.64
S
187.40
46.6
11630.00
1.38
Sr
12.61
1.95
814.40
2.25
Ti
13.51
12.63
0.00
11.83
V
0.00
59.41
13.26
1.87
Zn
31.08
0.76
82.39
0.8
25
Corn Cultivation
 Biochar addition: The 20g of biochar powders after grinding was added
with or without compost fertilizer sold in a local market.
 Planting: young tree of corn (10cm)
 Multiplicity: n = 4
 Planting conditions: without compost (A), with compost (B),
without biochar (1), with fir biochar (2), with kelp biochar (3)
B3
B2
B1
A3
A2
A1
Biochar
kelp
fir
X
kelp
fir
X
Compost
O
O
O
X
X
X
27
Effect of Biochar on Crop Yield
5d
B3
B2
B1
A3
A2
A1
A3
A2
A1
12d
B3
B2
B1
B3
B2
B1
A3
A2
A1
Biochar
kelp
fir
X
kelp
fir
X
Compost
O
O
O
X
X
X
28
Effect of Biochar on Crop Yield
27d
B3
B2
B1
A3
A2
A1
B3
B2
B1
A3
A2
A1
Biochar
kelp
fir
X
kelp
fir
X
Compost
O
O
O
X
X
X
29
Effect of Biochar on Crop Yield
63d
A1
A2
A3
B1
B2
B3
B3
B2
B1
A3
A2
A1
Biochar
kelp
fir
X
kelp
fir
X
Compost
O
O
O
X
X
X
30
Effect of Biochar on Crop Yield
10 %
Application rate (t/ha)
177
treatments
 sewage sludge
(-28%)




Jeffery et al., Agr. Ecosyst. Environ., 2011
Acidic soil (14%)
Large soil (10%)
Large amount (39%)
Poultry waste (28%)
26
Summary
 Biochar was positively effective but only when compost fertilizer was
added together in the soil for the corn growth, which is reasonable
because biochar plays a role in the retention of nutrients.
 Kelp seaweed biochar has lower carbon storing effects than woody
biomass on the basis of the total weight of raw biomass.
 Kelp seaweed biochar showed significant inhibition of corn growth
probably due to toxicity caused by higher contents of heavy metals.
 The toxic effect of kelp biochar was serious in the initial phase, but
recovered at some extent with time, indicating soil minerals might have
mitigated the toxicity.
32

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