Nanjing Agricultural University

Removal of heavy metal in

solution by modified biochar
immobilizer
RongJun Bian
Institute of resource, Ecosystem and Environment of Agriculture, Nanjing
Agriculture university

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Nanjing Agricultural University

CONTENTS

Background

Materials Methods

Result

Conclusion

Problems

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1. Background
Biochar can significantly reduce the availability of heavy metal in the soil, and
decrease Cd/Pb content in rice grain (Cui et al.,2011). Biochar could stabilize
Pb and improve soil quality in a shooting range soil (Lee, Sung Eun et al.,2011).

The mechanism of biochar heave metal adsorption: electrostatic interactions;

biochar surface functional groups (Minori uchimiya et al.,2010).

Immobilized alginic acid can efficiently adsorb heave metal in the water,
which can be used in wastewater treatment (Choong Jeon et al.,2001).

The immobilization of Zoogloea ramigera in Ca-alginate adsorbed a variety of

metals, after metal adsorption was no longer effective, metal could be
recovered using NTA or concentrated acid (Sabine P. Kuhn et al.,1989).

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2. Materials and methods
a. We used Ca-alginate method to immobilize biochar. The
mass ratio of alginate and biochar was 1/20. The biochar-
alginate bead was washed and dried for using.

b. Hitachi scanning electron microscope S-3000N was

employed to observe the surface of biochar and biochar-
alginate bead.

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c. The sorption experiments were performed by suspending
1g powdered biochar and biochar-aglinate bead in 100ml
of metal solution shaking in a incubator at 25 for 4 h.
--(Different concentration of acid and alkali solution\ interferential ions \ initial
concentration\ pH\ temperature\ reaction time )

d. The final metal concentration was measured using Atomic

Absorption spectroscopy.
e. Langmuir equation: Ce/Qe=1/ (Xm*K) + Ce/Xm
f. First order Kinetic equation : Y=A*e( -k*X ) +B
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3. Result
3.1 The microstructure of biochar-alginate bead

Biochar
Transverse section

Alginate Biochar

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3.2 physical property
Table 1. Physical property of biochar-alginate bead

Physical property Characteristic value

bulk density 0.230.003 g cm-3
diameter 0.450.085 mm
stability to pH 1-14

Table 2. The time of biochar-alginate bead cracked after it was stirred in the acid and alkali solution at 180 rpm

H2SO4 NaOH
concentration(mol L-1) 1 5 10 1 5 10
stirred time (h) 144 75 29 70 44 50
(biochar-aglinate bead:1g , volume:50ml)
Biochar-alginate bead had enough mechanical strength, which was stable in
strong acid and alkali solution.

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3.3 The influence factors to adsorption effect
3.3.1 The influence of Ca2+, mg2+
Table 3. Adsorption capacities of various metal ions in mixed-metal solution by biochar-alginate bead(pH6)

Pb2+ Cu2+ Cd2+ Mg2+ Ca2+

Adsorption capacity
(mg g-1)
3.900.03 2.980.16 0.870.06 0.510.08 0.490.05

Table 4. Heave metal adsorption capacity of biochar-alginate bead with Ca2+ and Mg2+ treatment(pH6, 100mg L-1)

Adsorption capacity (mg g-1)

Coexisting with
Ion only
Ca 2+, Mg2+
Pb2+ 13.600.17 10.470.13
Cu2+ 11.740.20 9.160.02
Cd2+ 5.200.16 2.350.08

Biochar-alginate bead perfered heavy metal ions to alkaline metal ions

such as Ca2+ or Mg2+, so it can be used for the removal of heavy metals
from ground water, which contains much more alkaline metals.

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 3.3.2 The influence of temperature
Cd2+ adsorption capacity (mg g-1)

4.0

Pb2+ adsorption capacity (mg g-1)

19
3.5
3.0 18

2.5
17
2.0
1.5 16
1.0
15
0.5
0.0 14
15 25 35 45 15 25 35 45
)
Temperature(
Cu2+ adsorption capacity (mg g-1)

)
Temperature(
7.0
1. The heavy metal adsorbed by biochar-alginate
6.5 bead was an endothermic process since increased
6.0 uptake capacity occurred as the temperature was
increased.
5.5

5.0
2. The wastewater temperature of municipal
wastewater ranges from 9. 6 to 31 and averages
4.5 at (20.3 6.0)
yearly . (Feng Ye. et al 2010)
4.0
3. The temperature of most real wastewater was
15 25 35 45
)
Temperature( higher than room temperature. (Choone Jeon. et
al 2001)

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 3.3.3 The influence of pH

Pb2+ adsorption capacity (mg g-1)

3.2
Cd2+ adsorption capacity (mg g-1)

16.5

3.0
16.0
2.8
15.5
2.6
15.0
2.4
2.2 14.5

2.0 14.0
3 4 5 6 7 8 3 4 pH 5 6
pH
Cu2+ adsorption capacity (mg g-1)

7 The adsorption capacity of heavy

metal was effected by pH, and the
5
adsorption capacity went to maximum
value when pH was 6.
3

1
2 3 pH 4 5 6

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 3.4 Kinetic process of adsorption effect
100
Equilibrium concentration (mg L-1)

90 2+ 2+ 2+
Pb Cd Cu
80
70
60
50
40
30
20
10
0
0 25 50 75 100 125 150 175 200 225 250
Time (min)
Fig1. Adsorption kinetic changing curve

First-order kinetics equation R2

Pb2+ y=102.022*exp(-0.078*x)+2.581 0.992
Cd2+ y=30.275*exp(-0.036*x)+17.522 0.972
Cu2+ y=75.869*exp(-0.066*x)+26.872 0.994

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3.5 The Adsorption capaticy of heavemetal
3.5.1 The adsotption capacity of Cd2+
Adsorbed Cd2+ capacity (mg g-1)

10 biochar
biochar-alginate bead
8

0
0 100 200 300 400 500
Final concentration (mg L-1)
Fig 2. Cd2+ sorption isothermal curve

Langmuir equation R2 Xm(mg g-1)

Biochar-alginate bead y=x*0.04*8.66/(1+x*0.04) 0.974 8.67
Biochar y=x*0.67*4.71/(1+x*0.67) 0.978 4.71

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3.5.2 The adsotption capacity of Pb2+
Absobed Pb2+ capacity (mg g-1) 35
30
25
biochar
20 biochar-alginate bead
15
10
5
0
0 100 200 300 400 500 600 700 800
Final concentration (mg L-1)
Fig 3. Pb2+ sorption Isothermal curve

Langmuir equation R2 Xm(mg g-1)

Biochar-alginate bead y=x*0.02*31.34/(1+x*0.02) 0.888 31.34
Biochar y=x*7.25*32.119/(1+x*7.25) 0.991 32.12

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3.5.3 The adsotption capacity of Cu2+
Biochar-alginate bead
Absobed Cu2+ capacity (mg g-1) 18 Biochar
15

12

0
0 100 200 300 400 500 600
Final concentration (mg L-1)
Fig 4. Cu2+ sorption Isothermal curve on biochar and biochar-alginate bead

Langmuir equation R2 Xm(mg g-1)

Biochar-alginate bead y=x*0.02*16.95/(1+x*0.02) 0.931 16.95
Biochar y=x*0.07*8.04/(1+x*0.07) 0.928 8.04

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3.6 The adsorption efficiency
100
Pb
90 Cu
Cd
Adsorption ratio %

80
70
60
50
40
30
20
10
0
5 20 50 100 200 300 400
-1
mg L
Initial concentration
Fig 5. The adsorption ratio of heavy metal by biochar-aglinate bead in solution with different initial concentration

(biochar-aglinate bead:1g , volume:100ml)

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3.7 The desorption of heave metal
Table 5. Desorption effciency of heave metal for different desorption agents

Desotption effciency(%)
Desortbent Concentration(mol L-1) Cd Pb Cu

Cacl2 0.01 0.130.01 0.030.01 0.220.01

0.01 0.480.10 0.140.01 0.790.04

HNO3 0.1 0.940.03 0.720.00 0.810.01
0.2 0.950.02 0.780.01 0.900.04

HNO3(0.2mol L-1) gave the best result while Cacl2 desorption efficiency
was not significant.

After heave metal adsorption was no longer effiective, heave metal

could be recovered by HNO3 solution.

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 4. Conclusion
The porous structure of biochar gave itself high internal surface, and the
ability to adsorb heave metal;
The biochar alginate bead had enough mechanical strength, which was
stable in strong acid and alkali solution;
Biochar-alginate bead had a higher affinity to heavy metals compared to
alkaline metals;
The adsorption reaction of biochar-alginate bead was an endothermic
reaction, and the uptake capacity was increased to a high temperature;
Compare with biochar the biochar-alginate bead had higher adsorption
capacity to Cd2+ and Cu2+ and its adsorption process fitted Langmuir
model;
Heavymetals on biochar-alginate bead could be desorbed effectively
over 90% by HNO3(0.2mol L-1).

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5. Problems
How it works in real waste water

The mechanism of heave metal

adsorption
(fuctional groups, electrostatic interactions, specific surface area ? )

How to cope with the biochar-alginate

bead after it was used.
(recover heave metal by concentrated acid, then the biochar used as
stroma for municipal lawn or trees ?)

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Thanks for your attention!

Biochar make the world healthy