Bashir 2009
Bashir 2009
Bashir 2009
Waste Management
journal homepage: www.elsevier.com/locate/wasman
a r t i c l e i n f o a b s t r a c t
Article history: This study investigated the electrochemical oxidation of stabilized leachate from Pulau Burung semi-aer-
Accepted 7 May 2009 obic sanitary landfill by conducting laboratory experiments with sodium sulfate Na2SO4 (as electrolyte)
Available online 11 June 2009 and graphite carbon electrodes. The control parameters were influent COD, current density and reaction
time, while the responses were BOD removal, COD removal, BOD:COD ratio, color and pH. Na2SO4 con-
centration was 1 g/L. Experiments were conducted based on a three-level factorial design and response
surface methodology (RSM) was used to analyze the results. The optimum conditions were obtained as
1414 mg/L influent COD concentration, 79.9 mA/cm2 current density and 4 h reaction time. This resulted
in 70% BOD removal, 68% COD removal, 84% color removal, 0.04 BOD/COD ratio and 9.1 pH. Electrochem-
ical treatment using graphite carbon electrode was found to be effective in BOD, COD and color removal
but was not effective in increasing the BOD/COD ratio or enhancing biodegradability of the leachate. The
color intensity of the treated samples increased at low influent COD and high current density due to cor-
rosion of electrode material.
Ó 2009 Published by Elsevier Ltd.
H2 O $ Hþ þ OH ð4Þ narrower ranges of the process variables before conducting the fac-
2H2 O þ 2e $ H2 þ 2OH ð5Þ torial design experiments. The three process variables and their
respective levels are presented in Table 2. Each factor was varied
Bulk reactions :
over three levels numerically. The number of experiments in this
Oxidation of SO2
4 ; study was 27 plus another five replications of the center point.
HSO4 þ OH ! SO
4 þ H2 O ð6Þ Thus, a total of 32 experiments were conducted. Since there are
SO þ SO ! S2 O2 ð7Þ only three levels for each factor, the appropriate model is the qua-
4 4 8
dratic model Eq. (9), where Y is the response, Xi and Xj are variables,
Oxidation of organics (A represents some other products): b0 is a constant coefficient, bj, bjj and bij are interaction coefficients
of linear, quadratic and the second order terms, respectively, k is
Organics þ S2 O2
8 ! intermediates ! H2 O þ CO2 " þA: ð8Þ
the number of studied factors and ei is the error.
X
k X
k XX
k
2.3. Experimental design and analysis Y ¼ b0 þ bj X j þ bjj X 2j þ bij X i X j þ ei : ð9Þ
j¼1 j¼1 i <j¼2
A three-level factorial design was established with the help of
Generally, the quadratic model is used for predicting the opti-
the Design Expert 6.0.7 software for the statistical design of exper-
mal conditions. Analysis of variance (ANOVA) was used for graph-
iments and data analysis. Response surface methodology (RSM)
ical analyses of the data to obtain the interaction between the
was used to determine the optimum process parameter levels.
independent (process) variables and the dependent variables (re-
The three significant process variables considered in this study
sponses). The quality of the fit polynomial model was expressed
were: initial COD concentration (A), current density (B) and reac-
by R2 (coefficient of determination) and its statistical significance
tion time (C). BOD removal, COD removal, color removal, BOD:COD
was checked by the F-test. Model terms were estimated based on
ratio and pH were chosen as response parameters. Some experi-
probability (P-value) with 95% confidence level (Ghafari et al.,
ments were conducted as a preliminary study in order to estimate
2009). Three dimensional plots with their contours were obtained
for BOD removal, COD removal, color removal and pH. Further-
Table 2 more, the optimum region was identified based on the process
Independent variables of the three-level factorial design. parameters in the overlay plot.
Level of value Initial COD (mg/L) Current density (mA/ Reaction time (h)
cm2) 3. Results and discussion
1 500 40 2
0 1185 60 3 Table 1 shows that the stabilized landfill leachate had high COD
+1 1870 80 4
(1870 mg/L) and low BOD (80 mg/L) which resulted in a very low
Table 3
Response values for different experimental conditions.
BOD:COD ratio of 0.043. It also shows that the color intensity was lack-of-fit was non-significant as the P-values were greater than
very high (dark black–green color) at 2970 Pt–Co. The responses 0.05; except for color removal where the lack-of-fit was significant
obtained under different experimental conditions are tabulated (P < 0.0001).
in Table 3. The results show COD removal to be from 19.2% to Fig. 2 shows the normal probability plots of the studentized
70.0%, BOD removal from 23.6% to 74.2%, color removal from residuals for: (a) BOD removal, (b) COD removal, (c) color removal
421.2% to 80.3%, BOD/COD ratio from 0.026 to 0.051and pH from and (d) pH. A normal probability plot indicates whether the resid-
8.35 to 9.54. uals follow a normal distribution, in which case the points will fol-
low a straight line. Some scatter is expected even with normal
3.1. Analysis of variance (ANOVA) data. It can therefore be concluded from Fig. 2 that the data is nor-
mally distributed.
The application of RSM offers an empirical design to relate the
response and test variables based on parameter estimation. By 3.1.1. BOD removal
applying the factorial regression analysis on the experimental data The effect of experimental conditions (influent COD, current
given in Table 3, responses and factors can be related by polyno- density, reaction time) on BOD removal efficiency is shown as 3D
mial equations. Quadratic models obtained for each response, after surface plots in Fig. 3. This figure indicates that the BOD removal
neglecting statistically non-significant terms, are presented in Eqs. efficiency increased when the current density and reaction time
(10)–(14). A, B and C are model terms that represent the operating were increased. The initial COD concentration has limited effect
factors influent COD, current density and reaction time, on BOD removal; with maximum removal efficiency being 69.2%,
respectively. 72.7% and 76.2% at initial COD concentrations of 500, 1185 and
1870 mg/L, respectively (sodium sulfate concentration 1 g/L, reac-
BOD removal ¼ 57:02 þ 3:51A þ 10:48B þ 11:46C
tion time 4 h and current density 80 mA/cm2). The minimum
5:62B2 6:39C 2 þ 5:80BC ð10Þ BOD removal (22.4%) was obtained with influent COD 500 mg/L,
COD removal ¼ 43:14 þ 10:11B þ 14:08C þ 1:99B2 current density 40 mA/cm2 and reaction time 2 h.
Table 4
ANOVA results for significant model terms.
Model Sum of squares Degree of freedom Mean square F-value Prob > F
Table 5
ANOVA results for response surface quadratic model.
Source Sum of squares Degree of freedom Mean square F-value Prob > F
Fig. 2. Design–expert plot; normal probability plot of the studentized residuals for the: (a) BOD removal, (b) COD removal, (c) color removal and (d) pH.
due to electrode corrosion at increased current density and tem- words, under the present parameter ranges, electrochemical treat-
perature of the solution (which reached 80 °C at maximum cur- ment was found to be not suitable for increasing the BOD:COD ra-
rent). The effect was so severe that even negative values of color tio and enhancing biodegradability of the stabilized leachate.
removal efficiencies were observed. At influent COD 1870 mg/L,
reaction time 4 h and current density 80 mA/cm2, the maximum 3.1.5. pH
color removal efficiency was 83%. The pH variation for all experimental conditions tested in this
study was small (8.35–9.54). Fig. 6 shows increase in pH when
3.1.4. BOD/COD ratio influent COD and current density were increased (due to the in-
Table 1 shows that the BOD:COD ratio varied between 0.026 creased OH ion production at high current). This can be repre-
and 0.051 for all the experimental conditions tested. In other sented by the following equation (at cathode):
M.J.K. Bashir et al. / Waste Management 29 (2009) 2534–2541 2539
furic acid. The water is broken at the interface into its component
ions: hydrogen and hydroxyl ions that migrate towards the cath-
ode and anode, respectively. During their migration they react with
the target salt to yield its acid and base.
Fig. 4. 3D surface plot for COD removal efficiency (initial COD = 500–1870 mg/L).
Table 6
Optimum response results from overlay plot and laboratory.
4. Conclusions
Acknowledgement
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