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Removal of Nitrate from Ground Water Using Activated Carbon Prepared from
Rice Husk and Sludge of Paper Industry Wastewater Treatment
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ABSTRACT
Nitrate found in ground waters over the past decades has aroused serious concerns to associated administrators.
Among different methods of removing nitrate, using adsorption technique has drawn attention due to its high efficiency as
well as economic considerations. In this study, the effectiveness of activated carbon absorbents obtained from pyrolysis of
rice husk on nitrate adsorption is explored, and the results of the adsorption by carbon prepared from primary sludge of
wastewater treatment of paper industry have been compared. The results of experiments for both absorbers indicated that
the maximum adsorption occurred in pH equal 4, as the system has reached equilibrium during 4 hour contact time. The
maximum removal of nitrate for activated carbon obtained from rice husk was 93.5 (mg/gr), and for the sludge obtained
from paper industry was 79.5 (mg/gr). The result of tests for both adsorbents suggests a direct relationship between the
level of adsorption run by Zncl2 used to activate adsorbents and the level of adsorbent. Moreover, the results of adsorption
tests for adsorbents were adapted with Langmuir isotherm, and also the kinetics of adsorption was well fitted into pseudo-
second-order model.
Keywords: nitrate, adsorption, activated carbon, rice husk, sludge, paper industry.
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VOL. 10, NO. 17, SEPTEMBER 2015 ISSN 1819-6608
ARPN Journal of Engineering and Applied Sciences
©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
Considering the fact that nitrate adsorption for different c) Testing method
concentrations was studied in this paper, NaNo3 was used DR5000 spectrophotometer and spectroscopic
to increase nitrate concentration in other experiments. method were used to read nitrate concentration in the
solution. In order to investigate the effect of pH on
b) Absorbents and their preparation samples, they were adjusted prior to adding adsorbents to
In this paper, two different types of absorbents the solution. PH adjustment in the samples is conducted
were used for nitrate adsorption, and their results were using hydrochloric acid solution and normal soda. Each
compared in the same condition. To prepare absorbent, test was performed twice in a specific condition, and the
rice husk and sludge of primary settling basin of sewage result of adsorption would be called acceptable in case the
treatment of pulp and paper factories located in Gillan differences between these scenarios were less than 2%.
Province, Iran, were used.
The preparation of absorbents is much the same. d) Adsorption isotherm
In order to prepare activated carbon, the sludge of paper An equilibrium ratio of the quantity of adsorbed
factory sewage is placed in an oven at 110 ° C for 24 substance to mass unit of absorbent and its equilibrium
hours, after partially dried by sunlight, so that it will be state concentration in the liquid phase at constant
completely dried as it is done to avoid weight loss because temperature is called adsorption isotherm. It is one of the
of dryness. Moreover, rice husk was put into the oven after most important parameters to realize the mechanism of
being washed in the same condition. Having been ground adsorption. Langmuir and Freundlich isotherms are the
into powder and passed through a sieve of 600 microns, most applicable isotherms, for which equations 1 and 2
the absorbents were chemically activated in the course of respectively show their relationships.
Zncl2 mixture with different mass ratios for 8 hours (at
ambient temperature). They were then kept in the oven at
110 ° C for 24 hours in order to be completely dry. The
product was ground into powder by pounder. The powder
was put in a furnace under 70 ml per minute nitrogen flow.
The rate of furnace temperature increase was 10 ° C per
minute, as the final temperature was 800 ° C and the
duration for this temperature was 2 hours (pyrolysis
operation was performed in Material and Energy Research
Center in Meshkinshahr, Alborz Province). The
pyrolysised powder was washed in 500 ml of molar ½ e) Kinetics of adsorption
hydrochloric acid solution. Thus, it was washed several It is one of the most important characteristics
times with distilled water, so that its pH reached a constant when dealing with the efficiency of adsorption. Several
value. It was then dried in the oven at 100 ° C for 24 kinetic models have been proposed by researchers until
hours. Finally, the activated carbon was stored in sealed now. In this paper, two models, pseudo-first-order and
glasses to be used for adsorption experiments pseudo-second-order, were assessed for two activated
(U.S.Orlando et al. 2002). carbons, one obtained from rice husk and the other from
Moreover, to increase the efficiency of the sludge of paper industry. In order to obtain kinetic of
adsorption, all the absorbents were activated by Zncl2 with adsorption, we need to plot adsorption graph of proposed
various concentrations, the results of which were equations and build a kinetic model based on whether or
compared with one another. not data correspond. Pseudo-first-order and pseudo-
In order to chemically activate all the absorbents, second-order are respectively shown in equations 1 and 2.
Hcl was used and kept in a mixing scenario along with the
absorbents for 2 hours with respect to the level of
activation.
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VOL. 10, NO. 17, SEPTEMBER 2015 ISSN 1819-6608
ARPN Journal of Engineering and Applied Sciences
©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
Figure-1. Nitrate adsorption versus contact time for activated carbon obtained from rice husk
activated by Zncl2 with 1 to 1 ratio.
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©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
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ARPN Journal of Engineering and Applied Sciences
©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
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ARPN Journal of Engineering and Applied Sciences
©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
Table-2. Coefficients of Langmuir and Freundlich isotherms and the regression coefficient of rice husk activated carbon
and paper industry sludge activated carbon at a modified state by Zncl2 in a 1 to 2 ratio in pH=4.
Table-3. Fixed values and regression coefficients of the adsorption kinetics of pseudo- first and second- order model for
nitrate adsorption by activated carbon activated by Zncl2 in a 1 to 2 ratio obtained from rice husk at various nitrate
concentrations.
In order to explore the consistency of kinetic adsorption equilibrium state qe(real) and concentration obtained based
model, we need to consider regression coefficient factor on qe(real).
(R2) and difference in nitrate adsorption level at
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ARPN Journal of Engineering and Applied Sciences
©2006-2015 Asian Research Publishing Network (ARPN). All rights reserved.
www.arpnjournals.com
In a study conducted on nitrate adsorption by activated 20%, while it was less than 14% in this paper, which truly
carbon obtained from coconut shell at two activated and confirm that the result of the experiments correspond with
non-activated states, the maximum difference between pseudo-second-order adsorption level.
qe(cal) and qe(real) for pseudo-second-order model was
Table-4. Fixed values and regression coefficients of the adsorption kinetics of pseudo- first and second- order model for
nitrate adsorption by paper industry sludge activated carbon activated by Zncl 2 in a 1 to 2 ratio at various nitrate
concentrations.
As can be noticed from the above table, as for the [2] Abbas Afkhami, Tayyebeh Madrakian and Ziba
absorbent, the results of the experiments correspond more Karimi. 2007. The effect of acid treatment of carbon
with pseudo-second-order adsorption model. cloth on the adsorption of nitrite and nitrate ions,
The results of the tests performed by other Journal of Hazardous Materials Vol. 144, pp. 427–
researchers also indicate that pseudo-second-order 431.
adsorption level can finely interpret adsorption process in
the most tests (Amit Bhatnagar et al. 2008). [3] Amit Bhatnagar, Minkyu Ji, Yang‐Hun Choi, Woosik
Jung, Sang Hun Lee, Sun Joon Kim, Giehyeon Lee,
4. CONCLUSIONS Heejun Suk, HyoungSoo Kim, Booki Min,
The results of the studies demonstrated that both SeongHeon Kim, Byong Hun Jeon and JoonWun
activated carbon adsorbents, obtained from rice husk and Kang. 2008. Removal of Nitrate from Water by
sludge of paper industry wastewater treatment, have high Adsorption onto Zinc Chloride Treated Activated
efficiency in adsorbing nitrate. Given a partially low Carbon, Separation Science and Technology, Vol. 43,
equilibrium contact time and partially high adsorption No. 4, pp. 886-907.
level as against other relevant studies, both adsorbents
exhibited quite reasonable functionality for removal of [4] Amit Bhatnagar, Eva Kumar and Mika Sillanpaa.
nitrate. 2010. Nitrate removal from water by nano-alumina:
The use of Zncl2 has a positive effect on nitrate Characterization and sorption Studies, Chemical
adsorption level. As adsorbent concentration rises, so does Engineering Journal Vol. 163, pp. 317–323.
nitrate adsorption; however, this is limited.
The results of adsorption by both adsorbent [5] Chinnaiya Namasivayam and Wolfgang H Holl. 2005.
correspond with Langmuir adsorption isotherm, and Quaternized biomass as an anion exchanger for the
pseudo-second-order kinetic model could reasonably removal of nitrate and other anions from water, Chem
delineate adsorption speed run by both adsorbents. Technol Biotechnol, Vol. 80, pp. 164–168.
However, as for each groundwater sample which requires
decreasing nitrate concentration and bringing it to the [6] Dong-Wan Cho, Chul-Min Chon, Yongje Kim, Byong-
permissible level, it is imperative to choose the best Hun Jeon, Frank W. Schwartz, Eung-Seok Lee and
adsorbent, pH, and economical contact time with respect Hocheol Song. 2011. Adsorption of nitrate and Cr(VI)
to primary concentration, and essential adsorption level, as by cationic polymer-modified granular activated
well as economic considerations. Carbon, Chemical Engineering Journal Vol. 175, pp.
298– 305.
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www.arpnjournals.com
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