Professional Documents
Culture Documents
, Mei Tang, Shifeng Lv, Xia Wang, Baosheng Jin, Zhaoping Zhong, Yaji Huang
Ministry of Education of Key Laboratory of Energy Thermal Conversion and Control, School of Energy and Environment, Southeast University, Nanjing
210096, China
a r t i c l e
i n f o
Article history:
Received 5 December 2013
Accepted 28 May 2014
Available online 5 June 2014
Keywords:
Municipal solid waste
Pyrolysis Fixed
bed Activated
carbon
a b s t r a c t
The ve representative components (pinewood, paperboard, waste tire, polyvinyl chloride (PVC) and
acrylic textile) in municipal solid waste (MSW) were selected as raw materials to prepare the activated
carbon. Single component, double component, and triple component mixtures were pyrolyzed in a xed
bed reactor. The optimal preparation condition was acquired with a reaction temperature of 800 C
and reaction time of 60 min. The inuence of different components on the adsorption performance of
pyrolysis product was investigated under the optimum condition. Among the different single
components, the pinewood showed the best adsorption capacity. As for the four kinds of double
components mixture, the mixture of pinewood and tire showed the highest methylene blue adsorption
performance. To approach the actual proportion of MSW, the triple components mixtures were further
investigated. Four kinds of the triple components mixtures were pyrolyzed under the same
preparation conditions under nitrogen atmosphere. The mixture of pinewood, tire and acrylic textile
showed the best adsorption performance, which exhibited high surface area (646.32 m2 /g) and pore
volume (0.52 m3 /g), suggesting the potential application as adsorbent.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Generation of the municipal solid waste (MSW) has greatly
increased in recent years, so that reducing of waste mass,
making it innocuous, and converting it into fuel have become
important issues. MSW is mainly composed of high percentage
of organic compounds, such as paper, plastic, wood, and textile.
Most Chi- nese MSW usually includes residential, institutional,
commercial, street cleaning and non-process waste from
industries [1]. The pro- portion of organic substances (food waste,
paper, plastic, wood and ber) increases gradually. Plastic and
paper occur in relatively high proportions, taking over 10% and
20%, respectively [2]. Food waste makes up the largest fraction
(50%) of MSW in most cities in China [3]. As such, the waste
contains a high proportion of renewable materials which can be
used for energy recovery or the production of solid, liquid and
gaseous fuels. Hence, the treatment of MSW is not only a
recovery process of energy, but also a major environ- mental
problem.
A greater proportion of the MSW is dumped to landll in China
[4]. Other waste disposal options such as composting and
anaerobic
http://dx.doi.org/10.1016/j.jaap.2014.05.018
0165-2370/ 2014 Elsevier B.V. All rights reserved.
M. Song
M. Song
et al.et/ al.
Journal
/ Journal
of Analytical
of Analytical
and and
Applied
Applied
Pyrolysis
Pyrolysis
109109
(2014)
(2014)
278282
278282
27
27
Table 1
The proximate and ultimate analysis of different components.
Pinewood
Paperboard
Tire
PVC
Acrylic textile
Vdaf
FCad
Ad
Mad
Cad
Had
Nad
Sad
Oad
76.2
75.5
55.9
94.8
82.8
17.9
9.7
34.3
4.9
16.7
0.8
7.4
8.3
0.0
0.2
5.1
7.4
1.5
0.3
0.3
48.5
38.6
69.4
40.3
62.2
6.1
5.0
4.8
4.3
5.9
0.3
0.2
0.5
0.1
20.8
0.14
0.19
0.23
0.11
0.35
44.96
56.01
25.07
55.19
10.75
Components
600
500
400
300
200
100
0
0
Alkali/carbon ratio
Activation time
Activation temperature
3
1
2
3
4
5
400
Pine wood
Tire
Paperboard
Acrylic textile
PVC
1
2
3
4
5
40
Yield / %
300
20
200
10
100
0
Pine wood
Tire
Paperboard
Acrylic textile
PVC
30
50
500
Fig. 2. The methyleneblue adsorption value (left) and yield (right) of ve different kinds of component based activated carbon at the optimum preparation conditions.
Table 2
The preparation conditions of four samples.
Preparation conditions
Alkali/carbon ratio
Activation temperature ( C)
Activation time (h)
Sample
1
0.5
500
30
1
600
45
2
700
60
3
800
90
The results illustrate that with the increase of the activation temperature, the methylene blue adsorption values show the
increasing trend. As for the activation time and alkali/carbon
ratio, the adsorption capability increases rstly, and then
decreases. Based on
the
above results, the
optimum
conditions for KOH
chemical activation are selected. Therefore, in our study, the raw
materials are impregnated with KOH aqueous solution (precursor/KOH = 1:2, in weight), and then activated for at 800 C for 60
min
under nitrogen ow by one step process. The above optimum
con- ditions are maintained/followed in the following studies.
3.2. The effect of different single- and multi-component MSW on
adsorption performance
The methylene blue number (mg of methylene blue adsorbed/g
of carbon) is considered as a measure of adsorption capability of
activated carbon, denoting the amount of mesopore of activated
carbon. During the activation process, the pyrolysis and
precipita- tion of volatiles are the key factors for the formation of
mesopore.
Under the optimum experiment condition, any one of the single components, such as paperboard, waste tire, polyvinyl chloride
(PVC) and acrylic textile, can be selected as precursor to produce
the carbon materials. The methylene blue adsorption values are
used to evaluate the adsorption performance of carbon
adsorbents. And the yield is used to illustrate the production
efciency. The effects of different single component on the
methylene blue value and carbon yield are shown in Fig. 2.
Different components show the differ- ent adsorption values.
The paperboard precursor shows the best adsorption capacity. It
can be seen that adsorption capacity has the sequence of
paperboard > tire > PVC > acrylic textile. However, the tire shows
the higher yield than the other components could do. The sequence
of yield can be listed as follows: tire > paperboard > acrylic textile
> PVC.
MSW is a multi-component mixture, and its composition can
be very complex. The study of single-components cannot cover
the characteristics and mechanisms of fast pyrolysis of MSW.
There- fore, to investigate the synergetic effect of the mixture
components, the different mixture components are selected as
the precursor to produce the carbon materials. Different mixtures
of pinewood, tire,
500
400
1:1
1:2
300
200
100
0
Fig. 3. The effect of different double components mixture on the methylene blue
adsorption values.
PVC and acrylic textile are pyrolyzed. Fig. 3 shows the effect of different two components mixture on adsorption properties under
the same preparation condition.
The co-pyrolysis of PVC with pinewood has an effect on the
car- bon formation. As for the mixture of pinewood and PVC,
comparing with these results obtained from only pinewood, it can
be observed that the addition of PVC to the mixture could
decrease the adsorp- tion capability. In addition, it shows a
decrease trend of methylene blue adsorption values, when higher
contents of plastics are used. According to the former report [20],
the dehydrochlorination of PVC increases the reactivity of
pinewood. The liberated HCl may interact chemically with the
cellulose, catalyzing an acid hydrolysis type of reaction making it
less stable. However, the pore could be occupied and blocked by
the volatile residue to form obdurate.
As for the mixture of pinewood and tire, the similar
experiment results are observed. The addition of tire to the
mixture decreases the adsorption capability, comparing to the only
pinewood. In addi- tion, methylene blue adsorption values
decrease with the increase of tire content, but are higher than the
mixture of pinewood and PVC. The results show that component
interactions affect each other. The effect of PVC and tire on
pinewood is quite remarkable.
As for the mixture of pinewood with PVC or tire, the role
of pinewood is dominant. The methylene blue adsorption value
increases with the enhancement of pinewood ratio. In the meanwhile, as for the mixture of acrylic textile with PVC or tire, the
polymers play the key role on the adsorption values. With the
increase of the polymer, the adsorption values increase.
To approach the real proportion of municipal solid waste, the
triple components mixtures are further investigated. Four kinds
of the triple components mixtures are prepared with the ratio of
400
350
300
250
350
300
Adsorption
Desorption
250
200
200
150
150
100
100
50
50
0.0 0.1
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Fig. 4. The effect of different triple components mixture on the methylene blue
adsorption values.
1:1:1, and then the mixtures are impregnated with KOH in mass
ratio of 1:2, which is same as the above in the experimental condition; subsequently the mixtures were pyrolyzed under nitrogen
atmosphere. Fig. 4 shows the effect of different triple components
mixture on methylene blue adsorption properties. According to
the results, the mixture of pinewood, tire and acrylic textile
shows the best adsorption performance, whereas the mixture of
pinewood, tire and paperboard is better than the rest of mixed
materials. However, both of adsorption properties of these two
kinds of the triple components mixture are lower than the
mixture of pinewood and tire, suggesting the decrease effect on
the adsorption with the addition of the other component. The
mixture of pinewood, acrylic textile and PVC and the mixture of
paperboard, pinewood and tire show the weaker adsorption.
3.3. The physico-chemical prosperity of prepared carbon
materials
FTIR and BET are further carried out to analyze the composition and structure of the samples. Fig. 5 gives the FTIR spectrum
of the three components (pinewood, tire and acrylic textile) mixture based carbon adsorbents. The absorption bands and peaks
provide the evidence of the presence of some surface functional
groups. As shown in the FTIR spectrum, the strongest peak at
3410 cm1 reects the hydroxyl stretching vibration. Furthermore,
the spectrum of the activated carbon sample
has several other
bands, which are
assigned to C C (1570 cm1 ), CO (1020 cm1 ),
CN (1115 cm1 ). Therefore, the prepared materials are mainly
composed of amorphous carbons with different oxygen containing
surface groups. These carbonoxygen surface groups may
exercise
105
100
2330
T/ %
95
3740
Table 3
The BET surface area and pore parameters of activate carbons prepared by
pinewood, tire and acrylic textile under the optimum conditions.
SBET (m2 /g)
Vt (m3 /g)
646.32
0.52
Dp (nm)
3.2
Vmic (m3 /g
0.0544
90
4. Conclusions
1570
85
1115
3410
80
75
1020
70
4000
3000
2000
1000
In this work, we focus on the utilization of different components as raw materials for the preparation of activated carbons by
one-step KOH chemical activation methods. The optimum preparation conditions are followed at a reaction temperature of 800 C
and reaction time of 60 min with ratio of precursor/KOH = 1:2 in
weight. For single component, the precursor of pinewood shows
the best adsorption capacity among ve
representative
components
in MSW. In addition, the relationship between the double compoWavenumber/cm -1
Fig. 5. The FTIR spectra of the activate carbons prepared by pinewood, tire and
acrylic textile under the optimum conditions.
[4] H.F. Cheng, Y.G. Zhang, A.H. Meng, Q.H. Li, Environ. Sci. Technol. 41 (2007)
7509.
[5] H. Wang, Dioxins Zero Emission Technology for Incineration with Municipal
Solid Waste, Yejin Industry Press, Beijing, 2001.
[6] K. Tuppurainen, I. Halonen, P. Ruokojarvi, J. Tarhanen, J. Ruuskanen, Chemosphere 36 (1998) 1493.
[7] S.B. Qiao, W.T. Liu, Energy Conserv. Technol. 1 (2003) 38.
[8] S.Y. Li, R.S. Bie, Tech. Equip. Environ. Pollut. Cont. 3 (2003) 63.
[9] A.M. Li, X.D. Li, S.Q. Li, Y. Ren, N. Shang, Energy 24 (1999) 209.
[10] S. Sircar, T.C. Golden, M.B. Rao, Carbon 34 (1996) 1.
[11] P. Davini, Carbon 40 (2002) 1973.
[12] J. Hayashi, A. Kazehaya, K. Muroyama, A.P. Watkinson, Carbon 32 (2000)
1873.
[13] C. Sunho, H.D. Jeffrey, W.J. Christopher, ChemSusChem 2 (2009) 796.
[14] A. Bjorklunda, M. Melaina, G. Keoleian, Int. J. Hydrogen Energ. 26 (2001) 1209.
[15] M.Y. He, B. Xiao, Z.Q. Hu, S.M. Liu, X.J. Guo, S.Y. Luo, Int. J. Hydrogen Energ. 3
(2009) 1342.
[16] M.Y. He, B. Xiao, Z.Q. Hu, J.F. Li, X.J. Guo, S.Y. Luo, Int. J. Hydrogen Energ. 34
(2009) 195.
[17] L. Sorum, M.G. Gronli, J.E. Hustad, Fuel 80 (2001) 1217.
[18] T.H. Kwak, S. Lee, S. Maken, H.C. Shin, J.W. Park, Y.D. Yoo, Energy Fuels 19 (2005)
2268.
[19] C.H. Wu, C.Y. Chang, C.H. Tseng, J.P. Lin, J Anal. Appl. Pyrol. 67 (2003) 41.
[20] R. Miranda, J. Yang, C. Roy, C. Vasile, Polym. Degrad. Stab. 72 (2001) 469.