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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
⇑ 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.
Table 1
L9(34) orthogonal testing program and results.
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-
4. Conclusions
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.
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