PRELIMINARY STUDY OF THE APPLICATION OF THE CENTRAL COMPOSITE DESIGN

IN THE PRODUCTION OF ACTIVATED CARBON USING BREADNUT (Artocarpus camansi)

PEEL

Balanay, Maria Lovezza S., Mamaril, Gil Stefan S., Rivera, Sherbert L.,
Engr. Andrew Benedict Tengkiat

Department of Chemical Engineering, Faculty of Engineering, University of Santo Tomas

España, Manila, Philippines 1800

Abstract

Breadnut (Artocarpus camansi) peel that was collected from Nepa Q-Mart, Quezon City was used as a low
cost adsorbent in the study by converting it into an activated carbon. The present study deals with the removal of
MB from simulated wastewater by activated carbon from breadnut peel. The activated carbon (AC) was fabricated
by chemical activation and carbonization at temperatures ranging from 494 °C to 706 °C at time 60 to 180 minutes.
The results indicate that carbonization temperature of 607 °C at 119 minutes is the optimum condition to achieve
the maximum yield and a temperature 621 °C at 136 minutes would result to the optimum Y*Q. Economically, this
means that the effectiveness of the product obtained from the activated carbon would be maximized as well as the
yield. However, the optimum parameter of 712 °C at 176 minutes must be met in order to achieve an optimum
adsorption capacity of 125 mg MB per gram of AC. The activated carbon obtained from breadnut peel via chemical
activation has been found to be an efficient material for MB removal from simulated wastewater effluent owing to its
very low cost.

Keywords: Breadnut, Activated Carbon, Methylene Blue, Chemical Activation, Carbonization, Adsorption, Adsorption Capacity

1. Introduction
The fast pace industrialization has become
the contributing factor to the increase in the
environmental problems in our country. The use of
chemicals is one of the reasons why our environment
starts to deteriorate. Organic compounds like dyes are
contaminants which are danger to environment and to
human health. It is toxic and carcinogenic even at
low concentration (El Mouzdahir, et al., 2010).
Pollutants or contaminants are seen from the
wastewater of textile, paper and plastic industries.
These industries use dyes to color their product, and
as a result, they produce a coloured wastewater. The
presence of dye, even in very small amount, in water
is still visible and undesirable due to its harmful
effects to the environment and human beings
(Rafatullah, et al., 2010). The conventional method
for dye removal are coagulation, electrochemical
processes, chemical oxidation, membrane filtration,
adsorption, etc (Weng, et al., 2007).
Adsorption by activated carbon is widely
used in treating effluent which contains organic dyes.
Some waste materials like coir pith, coconut husk,
orange peel, jackfruit peel, etc are used as source of
activated carbon (Kadirvelu, et al., 2001). These
materials are chemically modified with the use of
acid or base (Prahas, et al., 2008) and carbonized at
high temperate to achieve an activated carbon
(Kavitha et al., 2007).
Methylene Blue (MB) is a cationic dye
synthesized as a pure blue dye for cotton and plays an
important role in textile industry (BASF Chemical
Company, 2012). Though it is not regarded as acutely
toxic, it can be harmful to the human body. Its
various harmful effects are short periods of difficulty
in breathing when inhaled which causes burning
sensation, nausea, vomiting, diarrhea and gastritis
when ingested through mouth (Ozer, et al., 2007).
Breadnut (Artocarpus camansi) is native to
New Guinea and possibly the Moluccas (Indonesia)
and the Philippines. The fruit is green, ovoid or Carbonization
somewhat rounded, up to 20 cm in diameter with a
spiny surface, with little pulp. Seeds are numerous, The chemical activated sample was placed
light brown, ovoid, rounded, about 2.5 cm in in crucibles and was carbonized at 494-706°C under
diameter. Artocarpus species are rich in phenolic carbonization time within one hour to three hours
compounds including flavonoids, stilbenoids, using Fishier Scientific furnace. The table 1 below
arylbenzofurons and Jacalin, a lectin. The fruit, shows the temperature and time of carbonization.
particularly the young ones, are boiled and eaten as a
vegetable. While the seeds are rich in starch and Table 1. Parameter Conditions
could be eaten boiled or roasted (Stuart, 2011).
Std Order Run Order Temp, °C Time, min
The purpose of the study is to be able to 4 1 675 160
produce activated carbon, synthesized from breadnut 5 2 494 120
peel, at different carbonization temperatures and
3 3 525 160
time. It also aims to estimate the optimum
carbonization parameters such as temperature and 1 4 525 80
time, and to create a correlation of percent yield, 9 5 600 120
adsorption capacity and weight of removed pollutant 10 6 600 120
per weight of dried sample with respect to 8 7 600 177
carbonization temperature and time. 12 8 600 120
2 9 675 80
The study is limited to the use of Breadnut
peel as raw material for activated carbon by chemical 13 10 600 120
activation and carbonization. The adsorption 7 11 600 63
experiment only performed was a simulated textile 11 12 600 120
wastewater by introducing the produced activated 6 13 706 120
carbon in a MB solution. . The study does not include
the adsorption of other dyes that are usually present The crucibles were cooled down in a room
in a textile wastewater, and the disposal of the temperature after carbonization and were placed in a
activated carbon. The parameters are the desiccator to avoid moisture. The activated carbon
temperatures and time for carbonization. The was taken out from the crucibles and was ground
temperatures and time used range from 494 oC to using mortar and pestle until fine particles of
706oC and 63 to 177 minutes, respectively. These activated carbon were achieved.
parameters are used as references for the
determination of the optimum percent yield and Neutralization of Activated Carbon
adsorption capacity for the study.
The activated carbon was soaked in distilled
water and was stirred in a beaker. A 0.1 M NaOH
was added until the pH of the mixture reached neutral
2. Experimental Procedure level (pH 6.5-7). The mixture was decanted when the
activated carbon had settled to the bottom. The
Raw Materials Preparation
neutral activated carbon was then dried in an oven
and then weighed using analytical balance.
The breadnut peel was cut into pieces and
washed with distilled water. After washing, it was
Reagents / Chemicals
dried in an oven (Scientific Oven 1 Series 2000) at
60°C - 80°C for 5 – 6 hours. The dried sample was
The methylene blue that was used in the
weighed using analytical balance (Sartorius
experiment was supplied by Chryssler Inc. A stock
Analytical Balance 210S). The dried peel was placed solution of 250 ppm was prepared by dissolving 0.5 g
in a beaker and was chemically activated by soaking
of MB in 2000 mL of distilled water. The maximum
it in a 85% w/w H3PO4. It was stirred constantly for 5
wavelength of this dye is 664 nm (Prahas, Kartika et
minutes for 6 hours at 30 minute interval on the fume
al., 2008).
hood. The chemical activated sample was then dried
in an oven.
 Adsorption of Methylene Blue Table 2. Data of Percent Yield

A 50 mL of MB stock solution was placed Std Run Temp, Time, % Yield

in an Erlenmeyer flask followed by the addition of Order Order °C min
0.1 gram of activated carbon. The mixture was placed 4 1 675 160 29.74
in a water-bath shaker (Thermo Scientific MaxQ™ 5 2 494 120 34.79
2000 Water Bath Shaker) at 200 rpm for two hours, 3 3 525 160 23.80
and then was subjected to centrifugation for 3-5
1 4 525 80 26.02
minutes to separate the activated carbon from the
solution. The carbonized samples at different 9 5 600 120 35.40
carbonization temperature and time were used to 10 6 600 120 37.82
adsorb methylene blue. The absorbance of the 8 7 600 177 31.07
methylene blue solution was measured using the UV- 12 8 600 120 44.91
Vis spectrophotometer (Hitachi U-5100 UV-Vis 2 9 675 80 30.63
Spectrophotometer). The calibration curve was used
13 10 600 120 36.86
to determine the concentration of the solution.
7 11 600 63 29.07
Calibration Curve and Concentration 11 12 600 120 40.15
6 13 706 120 22.88
Methylene Blue solution of concentrations
of 30, 25, 20, 15, 12.5, 10, 7.5, 5, and 2.5 ppm were The data was treated using Minitab ® 15
prepared by dilution from the stock solution of 250 response surface regression of percent yield against
ppm. The absorbance of different methylene blue temperature and time. As a criterion, p-values should
solution was measured using UV-Vis be below 0.05 in order to attest the correctness of the
Spectrophotometer at maximum wavelength. The experiment. Standard order 5 and 9 were removed
equipment was calibrated before measuring the since these two were considered as outlier and
absorbance of the solution. The plot of absorbance temp*time (Tt) term was deleted due to a low p-
versus concentration was used as calibration curve to value.
determine the final concentration. Solution with
concentration exceeding 10 ppm (or its color is much An equation was generated using the final
darker than the color of 10 ppm solution) was to be response surface regression analysis.
diluted with distilled water, and its absorbance was
measured using the UV-Vis spectrophotometer. %𝒀 = −𝟓𝟎𝟐. 𝟐𝟕𝟔 + 𝟏. 𝟔𝟕𝟔𝟑𝑻 + 𝟎. 𝟒𝟖𝟕𝒕
– 𝟎. 𝟎𝟎𝟏𝟑𝟖𝑻𝟐 – 𝟎. 𝟎𝟎𝟐𝟎𝟒𝒕𝟐

3. Discussion of Results The optimum temperature and time were

solved by taking the partial derivative of the equation
Determination of Percent Yield and equate it to zero. The estimated optimum
temperature and time are 607.35°C and 119.36
Percent yield is the weight after minutes respectively. Substituting the optimum
carbonization, washing and drying divided by the values in the equation, the estimated maximum
weight before activation and carbonization. The percent yield is 35.84%. Figure 1 illustrates the
experiment showed that the lowest yield came from optimum percent yield obtained in the analysis.
the highest temperature which is 706°C with duration
of 120 minutes of carbonization. In contrast, the
lowest yield gained came from the 494°C with the
same period of carbonization. Table 2 shows the
result of the percent yield with their corresponding
time and temperature.
 Table 3. Data of Adsorption Capacity

Std Run
Order Order Temp, C Time, min Q (mg/g)
4 1 675 160 123.59
5 2 494 120 59.33
3 3 525 160 86.40
1 4 525 80 61.52
9 5 600 120 104.27
10 6 600 120 93.76

Figure 1. Surface plot of %Y versus temperature, 8 7 600 177 113.36

time 12 8 600 120 98.81
2 9 675 80 118.33
Determination of Adsorption Capacity 13 10 600 120 101.17
7 11 600 63 63.90
Adsorption capacity is the amount of solute
from aqueous solution that is adsorbed per mass of 11 12 600 120 103.46
adsorbent. The adsorption capacity (Q) was 6 13 706 120 124.72
calculated by:
The p-values for all the terms in the initial
(𝐶𝑜 − 𝐶)𝑉
𝑄= response surface regression were below 0.05.
𝑊 Standard order 7, 10 and 12 were detected by the
software as outliers. After removing the residual
Where: values and time*time (t2) term, the final response
Q = amount of solute from aqueous solution surface regression showed a good result. The p-
that is adsorbed per mass of adsorbent values are higher than the criterion and there’s no
Co = initial concentration of MB solution standard residual in the analysis.
C = final concentration of MB solution
V = Volume of solution An equation was generated using the final
W = mass of adsorbent response surface regression analysis.
From the experiment, the AC that has the 𝑸 = −𝟓𝟕𝟐. 𝟒𝟑𝟑 + 𝟏. 𝟔𝟔𝟗𝟑𝑻 + 𝟏. 𝟏𝟔𝟖𝟐𝒕
lowest adsorption was from the temperature −𝟗. 𝟔𝟖𝟔 × 𝟏𝟎−𝟒 𝑻𝟐 − 𝟎. 𝟎𝟎𝟏𝟔𝟒𝑻𝒕
494.934°C carbonized for 120 minutes. The AC
produced from 706°C for 120 minutes had the The optimum temperature and time were
highest adsorption of MB. Table 3 shows the data of solved by taking the partial derivative of the
adsorption capacities based on the experiments. correlation and equate it to zero. The estimated
optimum temperature and time are 712.32°C and
176.46 minutes respectively. Substituting the
optimum values in the equation, the estimated
optimum adsorption capacity (Qopt) is 125.174
milligram of solute that is adsorbed per gram of
activated carbon. Figure 2 below illustrates the
surface plot of adsorption capacity with respect to
carbonization temperature and time. It also shows the
optimum adsorption capacity obtained in the analysis.
 residual present in the analysis and the p-values for
all the term are below 0.05.

A correlation for Y*Q with respect to

carbonization temperature and time was generated
using the final response surface regression analysis.

𝒀 ∗ 𝑸 = −𝟓𝟒𝟒. 𝟗𝟗𝟕 + 𝟏. 𝟔𝟕𝟕𝟒𝑻 − 𝟏. 𝟎𝟖𝟗𝟖

−𝟎. 𝟎𝟎𝟏𝟑𝟓𝑻𝟐 − 𝟎. 𝟎𝟎𝟒𝟎𝟐𝒕𝟐

The optimum temperature and time were

Figure 2. Surface Plot of Q versus
temperature, time
Determination on the Amount of Removed
Pollutant per Weight of Dried Material, Y*Q
For the estimation of the amount of pollutant
that can be removed per weight of dried material
(Y*Q), the percent yield was multiplied with the
adsorption capacity and then plotted with its
temperature and time. Table 4 shows the data of the
amount of removed pollutant per weight of dried
material.
solved by taking the partial derivative of the
correlation and equate it to zero. The estimated
optimum temperature and time are 621.26 °C and
135.55 minutes respectively. Substituting the
estimated optimum values in the correlation, the
estimated optimum Y*Q is 39.913 milligram of
removed pollutant per gram of dried breadnut peel.
Figure 3 illustrates the surface plot of Y*Q versus
temperature and time.

Table 4. Data of amount of removed

pollutant per weight of dried sample (Y*Q)

Std Run Time,

Order Order Temp, C min Y*Q
4 1 675 160 36.75
5 2 494 120 20.64
3 3 525 160 20.57
1 4 525 80 16.01
Figure 3. Surface plot of Y*Q versus
9 5 600 120 36.91 temperature, time
10 6 600 120 35.46
8 7 600 177 35.22
4. Conclusion and Recommendation
12 8 600 120 44.38
2 9 675 80 36.24 Based on the analyses drawn together, the
13 10 600 120 37.29 research proved that breadnut peels can be an
7 11 600 63 18.58 alternative raw material for preparation of activated
carbon.
11 12 600 120 41.55
6 13 706 120 28.54 The activated carbon fabricated has showed
an optimum yield of 35.84% at the optimum
In the initial surface analysis, the p-values conditions at 607.36 °C for 119.36 minutes.
for time (t) and temp*time (Tt) is beyond the Correlation for the %yield is given by:
criterion and standard order 2 is considered an
outlier. After deleting standard order 2 and %𝒀 = −𝟓𝟎𝟐. 𝟐𝟕𝟔 + 𝟏. 𝟔𝟕𝟔𝟑𝑻 + 𝟎. 𝟒𝟖𝟕𝒕
temp*time (Tt) term, the final response surface – 𝟎. 𝟎𝟎𝟏𝟑𝟖𝑻𝟐 – 𝟎. 𝟎𝟎𝟐𝟎𝟒𝒕𝟐
regression showed a good result. There is no standard
 The produced AC that can have the highest
adsorption capacity can be derived with the optimum
temperature and time estimated which is at
712.317oC for 176.46 minutes. The correlation for the
adsorption capacity is given:
𝑸 = −𝟓𝟕𝟐. 𝟒𝟑𝟑 + 𝟏. 𝟔𝟔𝟗𝟑𝑻 + 𝟏. 𝟏𝟔𝟖𝟐𝒕
−𝟗. 𝟔𝟖𝟔 × 𝟏𝟎−𝟒 𝑻𝟐 − 𝟎. 𝟎𝟎𝟏𝟔𝟒𝑻𝒕
In terms of amount of removed pollutant per
weight of dried material, the optimum parameters are
621.26°C and 135.55 minutes. Using the computed
parameters, the optimum amount of pollutant
removed per weight of dried raw material is 39.913
milligram of MB of dried raw material derived from
the equation:
𝒀 ∗ 𝑸 = −𝟓𝟒𝟒. 𝟗𝟗𝟕 + 𝟏. 𝟔𝟕𝟕𝟒𝑻 − 𝟏. 𝟎𝟖𝟗𝟖
−𝟎. 𝟎𝟎𝟏𝟑𝟓𝑻𝟐 − 𝟎. 𝟎𝟎𝟒𝟎𝟐𝒕𝟐
Since the obtained estimated optimum time
and temperature for adsorption capacity is beyond the
parameter conditions that were set in the experiment,
it is recommended to further refine the study by
setting the conditions near the estimated values to
justify the correlation.
It is recommended to sieve the activated carbon
derived from breadnut (Artocarpus camansi) to
obtain the uniform particle size of the product.
Comparison with the commercially available
activated carbon can be done using the available data
to assess the efficacy of the produced activated
carbon with respect to yield (%Y), adsorptive
capacity (Q) and amount of removed pollutant per
dried raw material (Y*Q).
It is suggested to study the effects of
concentration on the adsorption isotherm of the
activated carbon derived from breadnut peel. It is also
suggested to conduct further tests on metals and
industrial effluent as well as considering factors such
as cost and equipment.
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