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Journal of Analytical and Applied Pyrolysis 109 (2014) 278282

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Journal of Analytical and Applied Pyrolysis


j o u r n a l h o m e p a g e : w w w.e l s e v i e r. c o m / l o c a te / j a a p

The pyrolysis of multi-component municipal solid waste in xed bed


reactor for activated carbon production
Min Song

, 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

Corresponding author. Tel.: +86 25 83790986.


E-mail address: sm@seu.edu.cn (M. Song).

http://dx.doi.org/10.1016/j.jaap.2014.05.018
0165-2370/ 2014 Elsevier B.V. All rights reserved.

digestion account for only a small percentage. A little of the MSW


is used for incineration (2%), but incineration of MSW is practised
on a large scale overseas [5]. Direct landlling and composting,
because of their disadvantages, are gradually replaced by other
methods. In spite of the advantages derived from incineration of
municipal solid waste, such as heat recovery, there are numerous
disadvantages of incineration, such as production of dioxins,
discarding heavy metal, and wasting heat emitted from burning
[68].
Compared with incineration, pyrolysis method can be used
for resolving the disposal problems and having effective energy
conversion [9]. Pyrolysis is a basic thermo-chemical process for
converting MSW into useful fuel, representing an alternative
process to enhance the energy and economic value of MSW utilization. Solid organic matter pyrolysis has a long-history technology
applied to waste disposal recently.
Activated carbon has been widely used as a versatile adsorbent for separation of gases, removal of organic pollutants, and
so on, due to its large specic surface area, porous structure and
good adsorption properties. Nevertheless, its high cost precludes
its application in most cases. If activated carbons are produced
from the waste, their production costs may be low. Therefore,
many investigators have made efforts in low-cost alternatives to
acti- vated carbon preparation from a range of carbonaceous and
mineral precursors, such as coals (e.g., bituminous coal, lignite),
industrial

M. Song
M. Song
et al.et/ al.
Journal
/ Journal
of Analytical
of Analytical
and and
Applied
Applied
Pyrolysis
Pyrolysis
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27

Table 1
The proximate and ultimate analysis of different components.

Pinewood
Paperboard
Tire
PVC
Acrylic textile

Proximate analysis (%)

Ultimate analysis (%)

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

ad: air dry; daf: dry ash free; d: dry basis.

byproducts (e.g., scraps of polymeric materials, petroleum, coke


pitch), and wood or other biomass sources (e.g., saw dust, coconut
shells, olive stones) [1013].
The pyrolysis of MSW has been studied extensively [1419]
in order to evaluate the inuences of operating parameters (i.e.
temperature, gas phase residence time and catalyst, etc.). However, many literatures focus on the single component MSW. Fewer
researches report the effect of multi component MSW on the
carbon product properties.
Here, according to the differences in the content of volatile matter, xed carbon and ash, we choose ve most representative and
important components of MSW (pinewood, paperboard, waste tire,
polyvinyl chloride (PVC) and acrylic textile) as precursors,
focusing on investigating the effects of different component on
performance
reactor. series
In our study,
the one-step
pyrolpyrolysis
ysis method in
is xed
used bed
to prepare
of activated
carbons.
The
aim of mixing different waste components is to investigate the
syner- getic effect of different components on the adsorption
capability of the carbon products.
2. Materials and methods
2.1. Raw materials
Five kinds of organic components are involved: waste wooden
chopsticks, waste cartons, waste car tire, refectory, and tailors
shop, which are remnants in the experiments: pinewood, paperboard, waste tire, polyvinyl chloride (PVC) and acrylic textile
respectively. Table 1 shows the proximate and ultimate analyses
measured according to ASTM standards. The original waste components are dried under the sun on the ground oor in order to
reduce the moisture content. And then the sufciently dried raw
materials are crushed and milled before the experiment is
started.
2.2. Preparation of the activated carbons
Activated carbon (AC) samples are prepared by one-step activation methods, using ve kinds of waste components and their
respective mixtures as raw materials. Detailed procedures are
described as follows. 10 g of raw materials are impregnated with
KOH aqueous solution in the optimal ratio, and then stirred for 6
h
at 40 C. Subsequently, the above samples are dried under 105 C
for 24 h.
The pre-treated samples are loaded in quartz pipe, and then
they are activated at different temperatures for different activation times under nitrogen atmosphere. After that, the products
are cooled down to the room temperature and then washed with
deion- ized water until the pH value is changed from 6 to 7, and
nally
dried at 60 C to the constant
weight.
2.3. Characterization of the activated carbons
Specic surface areas and pore volumes are measured on a
Micromeritics ASAP 2020 sorptometer using nitrogen adsorption

Methylene blue value / mg/g

Components

600

500

400

300

200

100
0
0

Alkali/carbon ratio
Activation time
Activation temperature
3

Fig. 1. The effect of preparation parameters on the methylene blue adsorption


per- formance of four samples (the samples illustrations are shown in Table 2).

at 77 K. BrunauerEmmettTeller (BET) is an equation used for the


determination of specic pore volume (s(BET)). The compositions
of carbon materials are analyzed using Fourier transform infrared
spectroscopy (FTIR) (Bruker Tensor 27 spectrometer in the range of
5004000 cm1 on KBr pellets.
2.4. The methylene blue (MB) adsorption value
The methylene blue (MB) capacity value is determined by China
National Standards
(GB/T12496.8-1999) to examine the
adsorption capability of the prepared activated carbons.
3. Results and discussion
The ve most representative and important components of
MSW are selected as raw materials, focusing on investigating the
effects of different component properties on pyrolysis performance
(with reference to adsorption composition) in xed bed reactor.
3.1. The optimum of preparation parameters
The activated carbons are prepared by one-step chemical
activa- tion method. The raw materials are impregnated with
potassium hydroxide rstly, and then pyrolyzed in an inert
atmosphere. In order to optimize the reaction conditions, we
take pinewood as a sample to test the effect of activation
temperature, activation time and alkali/carbon ratio on the
adsorption characterization of the prepared, activated carbons.
A series of activated carbons preparation experiments are
carried out with different reaction conditions. For each factors
(activation temperature, activation time and alkali/carbon ratio),
four points are investigated to test. Fig. 1 shows the relationship
between preparation parameters and the methylene blue
adsorption performance of four
samples. The meanings of
abscissa are shown in Table 2.

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

Methylene blue value /mg/g

Methylene blue value / mg/g

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

Wood + PVC Wood + tire Textile + PVC Textile + tire

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

Quantity Adsorbed (cm2/g STP)

Methylene blue value /mg/g

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

Wood+textile+PVC Wood+tire+textile Paperboard+textile+PVC Paperboard+wood+tire

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

Relative Pressure (P/Po)


Fig. 6. The nitrogen adsorption isotherm of the activated carbon prepared by
pinewood, tire and acrylic textile under the optimum conditions.

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

Smic (m2 /g)


134.045

Vmic (m3 /g
0.0544

a profound effect on the surface properties of activated carbons


and thus inuence their adsorption characteristics.
The most important property of the activated carbon is its
adsorptive capacity that is related to the specic pore surface
area. The main pore structural characteristics of adsorbent are
obtained from its nitrogen adsorption isotherms. As shown in
Fig. 6, the nitrogen sorption isotherms of the carbon materials
derived from pinewood, tire and acrylic textile are of typical type
I in the IUPAC classication. A large amount of nitrogen adsorption
occurs in a rel- ative low pressure range, and the adsorption
capacity increases as the enhancement of the pressure.
Hysteresis is detected between adsorption and desorption
isotherms, indicating the presence of a little proportion of
mesopores and macropores. Table 3 gives the BET surface area
(SBET ), micropores surface area (Smicr ), total pore
volume (Vt ), micropores volume (Vmicr ), and average pore diameter (Dp ) of the activated carbons. It can be seen that the prepared
carbon materials are characteristic of predominantly mesoporous
solids with some contribution by the micropores. It is found that
the activated carbon prepared while using pinewood, tire and
acrylic textile may have a remarkable BET surface area (646.32 m2
/g). The average pore diameter is 3.2 nm, indicative of its
mesoporous char- acter. Therefore, the high BET surface areas of
the activated carbons
render them to be suitable as effective adsorbents for the
potential application of pollutants removal.

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.

nents and triple components mixtures based carbon materials


and the adsorption properties of carbons are
investigated.
Among the four kinds of double components mixture, the mixture
of pinewood and tire shows the highest methylene blue
adsorption values. In

addition, the mixture of pinewood, tire and acrylic textile shows


the best adsorption performance among the four kinds of the
triple components mixtures, which exhibit high surface area
(646.32 m2 /g) and pore volume (0.52 m3 /g).
Acknowledgements
The authors are grateful for the nancial support of the
National Hi-tech Research and Development Program of China
(973) (2011CB201505 and 2010CB732206). This work was supported by Program for New Century Excellent Talents in University
(NCET-12-0118), the Fundamental Research Funds for the Central
Universities and Qing Lan Project of Jiangsu Province.
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