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Bioresource Technology 125 (2012) 300–304

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Effects of pyrolysis temperature, time and leaf litter and powder coal ash addition
on sludge-derived adsorbents for nitrogen oxide
Xiaoli Ren ⇑, Baohong Liang, Min Liu, Xiaoyuan Xu, Meihua Cui
Department of Environmental and Safety Engineering, Taiyuan Institute of Technology, Taiyuan 030008, PR China

h i g h l i g h t s

" An adsorbent for NO2 was prepared by pyrolysis of dried sludge mixed with ZnCl2.
" Leaf litter and powder coal ash were used as additives prior to pyrolysis.
" Adsorptive property of sludge-derived adsorbent has been improved by additives.
" Adsorbent with leaf litter showed a strong capacity to adsorb nitrogen oxide.

a r t i c l e i n f o a b s t r a c t

Article history: The objective of this research was to seek a cost effective solution to prepare adsorbents for nitrogen
Received 22 February 2012 oxide from surplus sludge. Leaf litter and powder coal ash were used as cheap and easily available addi-
Received in revised form 21 July 2012 tives. An adsorbent for nitrogen oxide was prepared by pyrolysis of dried sludge mixed with zinc chloride.
Accepted 27 August 2012
Under optimum pyrolysis conditions of 375 °C for 90 min and a zinc chloride content of 30%, the surface
Available online 7 September 2012
area of the adsorbent with leaf litter was 514.41 m2/g, the surface area of the adsorbent with powder coal
ash was 432.34 m2/g, respectively, corresponding to an increase of 90.70% and 60.27% when compared to
Keywords:
the adsorbent without the additives. The saturated adsorption quantity of the adsorbent with leaf litter
Sludge-derived absorbent
Preparation
reached 271 mg/g at 20 °C. The results indicated that the sludge-derived adsorbent was quite promising
Leaf litter for nitrogen oxide removal.
Powder coal ash Ó 2012 Elsevier Ltd. All rights reserved.
Nitrogen oxide

1. Introduction Sludge-derived adsorbents have been investigated for removal


of hydrogen sulfide (Andrey et al., 2001; Lua and Lau, 1996), sulfur
Sewage sludge can contain significant amounts of heavy metals, dioxide and formaldehyde (Wen et al., 2011), heavy metals (Fang
organic toxins and pathogenic microorganisms (Dogru et al., 2002) et al., 2010; Zhang et al., 2005; Rozada et al., 2008; Zhai et al.,
and may cause secondary pollution problems. Sewage sludge is 2004; Otero et al., 2009), dyes (Martin et al., 2003; Chiang et al.,
rich in carbonaceous organic material and can be converted chem- 2009) and various organic substances (Tsai et al., 2008; Pan et al.,
ically into relatively cheap adsorbents for pollutants removal from 2011); however, the influence of pyrolysis temperature, pyrolysis
industrial effluents by chemical activation and pyrolysis. Chemical time and zinc chloride content on iodine number, yield rate, and
activation can be achieved with H2SO4 (Rio et al., 2005; Martin loss rate have never been studied together. So the optimum pyroly-
et al., 2004), ZnCl2 (Liu et al., 2010; Tay et al., 2001a; Moreno sis conditions of the sludge-derived adsorbents prepared by im-
et al., 2006), KOH (Wu et al., 2005), and H3PO4 (Molina-Sabio proved zinc chloride activation were studied in this paper. In
et al., 1995). The most commonly used agents are ZnCl2 and addition, in order to improve the adsorptive capacity of adsorbents,
H2SO4 (Rozada et al., 2005). Activation with zinc chloride was usu- leaf litter and powder coal ash were selected as the additives to
ally done by immersion of the sludge in a solution of the activating sludge prior to pyrolysis, the characteristics of the sludge-derived
agent, removal from the solution and drying before pyrolysising adsorbents after adding the additives were analyzed.
(Chen et al., 2002). In the current study, in order to reduce pyroly-
2. Methods
sis time and consumption of the activating agent, the immersion
method was substituted with a mixing method that consisted of
2.1. Materials
mixing dried sludge with solid ZnCl2.

⇑ Corresponding author. Tel.: +86 0351 3566125; fax: +86 0351 3566100. Potassium hydroxide, iodine (GB/T 675), potassium iodide (GB/
E-mail address: renxiaoli4915@126.com (X. Ren). T 1272), zinc chloride, sodium thiosulfate {Na2S2O35H2O} (GB/

0960-8524/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.08.123
X. Ren et al. / Bioresource Technology 125 (2012) 300–304 301

T637), soluble starch (GB/T3095), potassium dichromate (GB 1259) 3. Results and discussion
were purchased from sinopharm chemical reagent Co. Ltd. The
commercial activated carbon (AC) was bought from Shanxi Xinhua 3.1. Optimization of production
Chemical Co., Ltd., and its technical data: iodine value >1050 mg/g,
moisture <5% and ash content 8–12%. 3.1.1. Single-factor experimental
Deionized water was employed for preparation of all required The influence of pyrolysis temperature, pyrolysis time and zinc
solutions. chloride content on iodine number, yield rate and loss rate of the
Dewatered surplus sludge (SS) was collected from the Northern adsorbents are shown in Fig. 1.
Suburb Municipal Wastewater Treatment Plant of Taiyuan, PR Chi- The iodine number, which is the amount of iodine adsorbed per
na. Proximate analysis of the raw materials showed a water con- gram of adsorbent at 0.02 mol/L, achieved a maximum of 332 mg/g
tent of 76%, an ash content of 47.1%, a volatile mass of 47.55% with sludge-derived adsorbent prepared at 300–450 °C (Fig. 1a).
and fixed carbon of 5.35% (dry basis). The iodine number decreased with increasing pyrolysis tempera-
ture. When the pyrolysis temperature was 700 °C, the iodine num-
ber was only 103 mg/g, but when the temperature was higher than
2.2. Preparation of adsorbents 700 °C, the iodine number increased slightly again, likely because
higher temperature probably made some ingredients decompose
The sludge sample was dried in the sun or in an oven at 105 °C, and release gaseous substance, which might bring about new
and crushed to an average particle size of 75 lm. The dried sample pores, the formation of new pores increased the iodine number
was mixed with solid ZnCl2 to a final concentration of 5% to 30% again.
(w/w) and pyrolyzed in a stainless steel container (60 mm i.d.) in Fig. 1b shows the influence of pyrolysis time on iodine number,
a hypoxic environment at 375 °C for 90 min. The product was yield rate, and loss rate of sludge-derived adsorbents pyrolyzed at
washed several times with 3 M HCl and rinsed with deionized 350 °C. The iodine number rapidly increased with time and
water until the pH of the washing effluent reached 6–7. The prod- reached a maximum at 80 min. The yield rate of the adsorbents de-
uct was dried at 150 °C for 2 h, ground and sieved to 100 mesh. creased with time. Conversely, the loss rate increased, but yield
rate and loss rate of the adsorbents remained almost the same after
100 min.
2.3. Orthogonal experiment design
Fig. 1c shows the influence of the zinc chloride content on io-
dine number, yield rate, and loss rate of the adsorbents prepared
In order to investigate the influence of pyrolysis temperature
at 350 °C for 90 min. With the increase in the content of zinc chlo-
(A), pyrolysis time (B) and zinc chloride content (C) on adsorptive
ride, the iodine number reached a maximum of 489 mg/g at a zinc
property, an orthogonal test scheme with 3 factors and 3 levels for
chloride content of 15–25%. The iodine number was about 47.3%
each factor was used with iodine number as evaluation index.
higher in comparison with that of adsorbent without zinc chloride.
According to the single factor experiments, three levels of each fac-
The yield rate of the adsorbents remained almost unchanged, and
tor are selected in the test range, L9(34) orthogonal table was
the loss rate dropped down slightly as the zinc chloride content
employed.
increased.

2.4. Characterization of adsorbents


3.1.2. Orthogonal experimental
The dried sludge and adsorbents were gold-coated and ob- Results of the 3-factor, 3-level experiment involving pyrolysis
served under a scanning electron microscope (KYKY-3800 SEM, temperature (A), pyrolysis time (B) and zinc chloride content (C)
China). are shown in Table 1, where Kij denotes the average of the numer-
The physical characteristics of the adsorbents, including the ical values for the same level in each column, Rj denotes the range,
specific surface area, pore volume distribution and pore diameter, and the subscripts i and j are for the number of levels and columns.
were measured with a surface area analyzer (ASAP 2020 M, The analysis of variance (Rj and Kij) showed that the main influ-
Micromeritics Instrument Co., USA) by using the adsorption iso- encing factor on the iodine number was pyrolysis temperature, fol-
therms for gas adsorption (N2, 77 K). The specific surface area lowed by zinc chloride content and pyrolysis time. The optimal
was calculated by the Langmuir equation. Micropore volume combination was A2B2C3, corresponding to a pyrolysis temperature
(Vmi) was obtained by the t-plot method. Macropore and meso- of 375 °C for 90 min, and a zinc chloride content of 30% (by mass).
pore volume as well as pore size distribution were calculated by Rio et al. (2006) have optimized experimental conditions of the
the Barrette Joynere Halenda (BJH) method (Chiang et al., 2009). sludge-derived adsorbents prepared by chemical activation with
The iodine number (IN, mg/g), defined as the amount of iodine sulfuric acid using experimental design methodology. The follow-
adsorbed per gram of activated carbon at an equilibrium concen- ing optimal conditions, 1.5 g of H2SO4/g of sludge, 700 °C and
tration of 0.02 mol/L, was calculated from the adsorption isotherm 145 min were obtained. Jindarom et al. (2007) reported that the
as described by Martin et al. (2002). maximum surface area of the char was achieved at 750 °C under
the CO2 atmosphere, 60.7 m2/g with mainly mesopores. Tay et al.
(2001b) studied the preparation of activated carbon from digested
2.5. Adsorption of nitrogen oxide sewage sludge and coconut husk, the optimum conditions were
5 M ZnCl2 solution, 500 °C and 2 h. Yu and Qin (2006) obtained
Nitrogen dioxide from a nitrogen oxide cylinder were mixed the optimum preparation conditions as follows: concentration of
with air from an air compressor in a gas mixing container to obtain two activators 5 mol/L (the ratio of ZnCl2 and H2SO4 was 2:1), tem-
simulated flue gas. The inlet concentration of nitrogen dioxide was perature of 500 °C, the proportion of solid to liquid 1:2.5, and a per-
1234 mg/m3, the gas flow rate was 60 mL/min. Nitrogen oxide iod of 2 h. The above results showed that the optimum preparation
adsorption was conducted in a 15-mm i.d. and 150-mm long conditions for sludge-derived adsorbents were not identical using
adsorption column in an incubator (HS-100, China), the outlet different methods. In the current study, the adsorbents were pre-
gas was purified in a wash bottle containing 10% (by mass) NaOH pared by mixing dried sludge with zinc chloride prior to pyrolysis,
solution. the optimum pyrolysis conditions were 375 °C for 90 min, superior
302 X. Ren et al. / Bioresource Technology 125 (2012) 300–304

Table 1
L9(34) orthogonal testing program and results.

No. A (°C) B (min) C (wt.%) Iodine number (mg/g)


1 1(300) 1(60) 1(10%) 398.21
2 1 2(90) 2(20%) 422.16
3 1 3(120) 3(30%) 440.58
4 2(375) 1 2 468.63
5 2 2 3 489.37
6 2 3 1 476.2
7 3(450) 1 3 460.95
8 3 2 1 457.62
9 3 3 2 446.43
K1j 420.317 442.597 444.010
K2j 478.067 456.383 445.740
K3j 455.000 454.403 463.633
Rj 57.750 13.786 19.623

3.2. Characterization of sludge-derived adsorbent with additives

Leaf litter and powder coal ash were selected as the additives
because both of them could be used to prepare adsorbents
although they were solid wastes as the same as surplus sludge.
The carbon content of the leaf litter was 45.2% (by mass) and the
ash content was 1.06%. The main components of powder coal ash
were SiO2, 40–60%; Al2O3, 15–40%; Fe2O3, 4–20%; and CaO, 2–10%.
Table 2 gives pore volume (PV), micropore volume (MV), as well
as pore size (PS) and surface area (SA) of the adsorbents. Adsorbent
SA1 was sludge adsorbent without additives, adsorbents SA2 and
SA3 were the modified-sludge adsorbents with leaf litter and pow-
der coal ash, respectively. The activation conditions for adsorbents
SA1, SA2 and SA3 were 375 °C for 90 min.
As shown in Table 2, adding additives to the sludge improved
the properties of the sludge-derived adsorbents. The surface area
of the adsorbent SA2 was 514.41 m2/g, 90.70% larger than that of
absorbent SA1. The surface area of adsorbent SA3 was 432.34 m2/
g, 60.27% larger than that of absorbent SA1. The pore volumes of
adsorbents SA2 and SA3 were 0.321 and 0.192 cm3/g, respectively
and the corresponding micropore volumes were 0.106 and
0.104 cm3/g. This result indicated that the pore volume increase
of adsorbent SA2 was mainly caused by the increase in meso-
and macropores. The pore volumes of adsorbent SA1 and SA3 were
0.178 and 0.192 cm3/g, respectively and the corresponding micro-
pore volumes were 0.049 and 0.104 cm3/g. This finding indicated
that the pore volume increase of the adsorbent SA3 was mainly
caused by micropores.
Fig. 2 shows the adsorption and desorption isotherms of the
adsorbents. The isotherm of the adsorbent SA3 resembled that of
a type I adsorbent as defined by IUPAC classification. Correspond-
ing to the Langmuir monolayer adsorption process, the adsorption
was reversible and occurred mainly within micropores, which indi-
cated that the adsorption capacity of the adsorbent was affected by
the micropore volume. The isotherms of adsorbents SA1 and SA2
resembled those of type IV adsorbents since they were up-convex
curves at lower P/P0. Similar to type II adsorbents, the capillary
Fig. 1. Influence of Pyrolysis temperature (a), Pyrolysis time (b) and zinc chloride
adsorbate condensation did occur at higher P/P0 and the adsorp-
content (c) on iodine number, yield rate and loss rate of adsorbents.
tion isotherm rose rapidly. Due to capillary condensation, the hys-

to others. The experiments were conducted five times under the


optimum conditions, the iodine number of the absorbents were Table 2
in the range of 478.16–495.69 mg/g. Pore characteristics of the sludge-derived adsorbents (SA1: without additives, SA2:
with leaf litter, SA3: with powder coal ash).

Adsorbents PV (cm3/g) MV (cm3/g) PS (nm) SA (m2/g)


3.1.3. Surface morphology of the adsorbent
In comparison with the surplus sludge, the sludge-derived SA1 0.178 0.049 4.86 269.75
SA2 0.321 0.106 3.96 514.41
adsorbent showed a very large number of pores (Supplemental
SA3 0.192 0.104 2.77 432.34
Fig. 1). This demonstrates that the sludge can form well-developed
pore structures after carbonization and activation. PV: pore volume, MV: micropore volume, PS: pore size, SA: surface area.
X. Ren et al. / Bioresource Technology 125 (2012) 300–304 303

Fig. 4. Saturated adsorption capacity of commercial activated carbon and sludge-


Fig. 2. Adsorption and desorption isotherms of sludge-derived adsorbents (SA1: derived adsorbents for nitrogen oxide at different temperatures (AC: commercial
without additives, SA2: with leaf litter, SA3: with powder coal ash). activated carbon, SA1: without additives, SA2: with leaf litter, SA3: with powder
coal ash).

tion quantity of SA2 was 15% lower than that of commercial


activated carbon, but the potential lower cost of the sludge-derived
adsorbent might make it still attractive for practical applications.

4. Conclusions

Adsorbents for nitrogen oxide were prepared by pyrolysis of


dried surplus sludge mixed with zinc chloride. Analyses of pore
volumes and pore size distributions showed that the adsorption
performance could be improved by adding leaf litter and powder
coal ash into the sludge prior to pyrolysis. The sludge-derived
adsorbent had a good adsorptive property for nitrogen oxide. Thus
sewage sludge, leaf litter and powder coal ash as cheap and easily
available materials can be used to prepare adsorbents for nitrogen
oxide as a better replacement for commercial activated carbon.

Acknowledgements
Fig. 3. HJB mesopore size distributions of sludge-derived adsorbents (SA1: without
additives, SA2: with leaf litter, SA3: with powder coal ash). This work was financially supported by Shanxi Science and
Technology Agency Research Project (No. 20100321086), Scientific
Research Foundation of the Shanxi Education Department (No.
teresis of adsorption could be observed in this region. The desorp-
20111029), Innovation and Entrepreneurship Training Program
tion isotherm was not coincident with the adsorption isotherm,
for Shanxi College Students (No. 2011372).
and a hysteresis loop appeared between them. This demonstrates
that the adsorption by SA1 and SA2 occurred mainly in mesopores.
Fig. 3 shows HJB mesopore size distributions of SA1, SA2 and Appendix A. Supplementary data
SA3. SA2 and SA3 exhibited a narrow mesopore distribution, with
a peak around 1.9 and 2.0 nm, respectively. SA1 exhibited a wilder Supplementary data associated with this article can be found, in
mesopore distribution, with a peak around 4.2 nm. the online version, at http://dx.doi.org/10.1016/j.biortech.2012.08.
123.
3.3. Nitrogen oxide adsorption

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