Research Paper Engineering E-ISSN No : 2454-9916 | Volume : 6 | Issue : 9 | Sep 2020

EFFICIENCIES
OF
ORANGE
AND
LEMON
PEEL
IN
THE

REMOVAL
OF
DYE
FROM
TEXTILE
INDUSTRY
EFFLUENT

1 2
Ms. Rini Madhavan Rajeev | Mr. Muhammed Ashik A. S.
1
Faculty of Dept. of Civil Engineering, Vidya Academy of Science and Technology, Technical Campus, Kerala, India.
2
Dept. of Civil Engineering, Vidya Academy of Science and Technology, Technical Campus, Kerala, India.

ABSTRACT
Use of various dyes in order to color the products is a common practice in composite textile industry. The presence of these dyes in water even at low concentration is
highly visible and undesirable. This comparative study was carried out for the utilization of orange peel and lemon peel as adsorbent for the removal of dyes from
wastewater and to establish it as a standard wastewater treatment process for textile industry. This experiment was performed in the laboratory scale and batch
adsorption studies were conducted. The raw materials were obtained and treated for the removal of dyes at different dosages. The use of cheap and ecofriendly
adsorbents were studied in this paper as an alternative substitution of activated carbon for removal of dyes from textile industry effluent. Adsorbents prepared from
orange peel and lemon peel which are domestic wastes which are easily available were successfully tested and used to remove the dye, methylene blue from an aqueous
solution in a batch wise column. This study investigates the potential use of natural materials namely, orange peel and lemon peel pretreated with nominal treatment
method, for removal of methylene blue from simulated wastewater. Treated orange peel and lemon peel were used to study the adsorbtion methylene blue at varies
dosages.

KEYWORDS: dye removal; textile industry; methylene blue; wastewater; adsorbtion; orange peel; lemon peel;UV Visile sprectrometer

I. INTRODUCTION: carbons can be produced from different carbon-containing raw

The presence or introduction of unwanted materials in the environment which materials like wood, wood charcoal, coconut shells, and sawdust.
have harmful or poisonous effects is called Pollution. With the advancement in For organic raw materials like wood, a preliminary carbonization
technology, the luxury of human life has enhanced considerably and so has the process is necessary to transform the cellulose structures into a car-
degradation of ecological systems. Instance of such advancement is the use of bonaceous material [3].
dyes in various fields of textiles, food, cosmetics, paper, paints, pharmaceuticals
and several other industries. Most synthetic dyes are aromatic in nature which ii. Polymeric adsorbents:
makes them physically, chemically, thermally, biologically and optically stable Polymeric adsorbents, also referred to as adsorbent resins, are
[1]. Upon degradation, the dye products are toxic, carcinogenic and mutagenic to porous solids with considerable surface areas and distinctive
life forms .The effluents containing dyes are difficult to be treated because of adsorption capacities for organic molecules. They are produced by
high chemical oxygen demand, color of the water which is easily recognizable copolymerization of styrene, or sometimes also acrylic acid esters,
and high structural stability of these molecular dyes. Numerous studies have with divinylbenzene as a cross-linking agent [2].
been conducted to assess the harm impacts of colorants on the ecosystem. A vari-
ety of physical, chemical and biological treatment methods have been reported. iii. Natural and low-cost adsorbents:
The choice of method is limited by cost, efficiency, release of secondary effluents Among the natural and low-cost adsorbents, clay minerals are
and simplicity in design for operation. Among the treatment methods, adsorption important. Their adsorption properties are related to the net nega-
is the most preferred method because it is simple & efficient [5]. The commer- tive charge of the mineral structure. This property allows clays to
cially available granulated activated carbon provides an excellent adsorption sur- adsorb positively charged species – for heavy metal cations such as
face but is expensive. Natural materials that are available in large quantities may Cu2+, Zn2+ etc. [2]. Relatively high adsorption capacities were
have high adsorption potential as an inexpensive adsorbent. also reported for organic dyes during treatment of textile
wastewater.
II. ADSORPTION AND IT’S TYPES:
Adsorption is the process in which matter is extracted from one phase and con- III. MATERIALS USED IN THE EXPERIMENT:
centrated at the surface of a second phase (Interface accumulation). This is a sur- i. Orange peel and lemon peel:
face phenomenon The adsorption process is used to remove colour and other The natural adsorbents used in the present work are dried peels of lemon and
soluble organic pollutants from effluent [1]. The process also removes toxic orange. The materials are easily available and natural. They also act as cheap
chemicals such as pesticides, phenols, and organic dyes that cannot be treated by adsorbents due to the presence of large no of pores. These materials are pol-
conventional treatment methods [2]. Dissolved organics are adsorbed on the sur- lution free and eco – friendly [3].
face when waste water containing these are made to pass through adsorbent.
Most commonly used adsorbent for treatment is activated carbon.. The pores ii. Methylene blue:
need to be large enough for soluble organics compounds to diffuse in order to Adsorbates are substances which are adsorbed or removed. They mainly
reach the abundant surface area. include colour dye and dissolved solids. The adsorbate removed here is meth-
ylene blue dye.
A. Exchange adsorption (ion exchange): Electrostatic due to charged
sites on the surface. Adsorption goes up as ionic charge goes up and as Methylene blue (MB) is a cationic dye and is regarded as significant threat to
hydrated radius goes down. human and eco system due to its carcinogenic and mutagenic properties that
forms a deep blue solution when dissolved in water [3]. Methylene blue has
B. Physical adsorption: Van der Waals attraction between adsorbate and been widely used in coloring paper, wools, as biological stains and dying cot-
adsorbent. multilayer adsorption. The attraction is not fixed to a specific tons. It is a heterocyclic aromatic chemical compound with the chemical for-
site and the adsorbate is relatively free to move on the surface. mula C16H18N3Cl. Though MB is not strongly hazardous it can cause some
harmful effects [1]. It can cause eye injury to both human and animals. On
C. Chemical adsorption: Some degree of chemical bonding between inhalation, it can give rise to short periods of rapid or difficult breathing
adsorbate and adsorbent characterized by strong attractiveness. while ingestion through the mouth produces a burning sensation and may
Adsorbed molecules are not free to move on the surface. cause nausea, profuse sweating, diarrhea, gastritis, mental confusion and
methemoglobinemia. Acute exposure to methylene blue can cause increased
Some of the common adsorbents are described below: heart rate, vomiting, and tissue necrosis in humans. Fig. 1 shows the molecu-
lar structure of MB.
i. Activated carbon:
The adsorption properties of carbon-rich materials like wood char-
coal have been improved by special activation processes. Activated
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International Education & Research Journal [IERJ] 67

Research Paper E-ISSN No : 2454-9916 | Volume : 6 | Issue : 9 | Sep 2020
4. Preparation of lemon and orange peel:
Orange and lemon are used mainly in soft drinks industries all over the
world. They discard a huge amount of orange peels. At first, the peels were
cleaned with distilled water to remove dust particles and water-soluble impu-
rities. The peels were dried in sunlight for 2 days and kept in oven for 8
hours. After drying, the pieces were crushed in a mixer grinder until
they became fine powder. Finally the orange peel powder was stockpiled in
air tight packets so that they can be used in future without any further treat-
Fig. 1: Molecular structure of Methylene Blue ment [5]. The orange peel should be thoroughly washed and dried properly
or else it imparts colour after removal of methylene blue and leads to adverse
1. Model water: result and increase in chemical oxygen demand (COD) [6]. Fig. 4 shows the
Wastewater which was used in the experiments was prepared by dissolving lemon and orange peels used as adsorbents.
methylene blue in distilled water concentration 2.5 ppm. A stock solution of
methylene blue dye was prepared by dissolving 0.1 g of dye powder in 100
water (1000 ppm).The batch adsorption studies were carried out by prepar-
ing various concentration of 0.5ppm, 1ppm, 1.5ppm, 2ppm, 2.5ppm and the
calibration was carried out. The concentrations of residual MB dye were
measured using UV visible spectrophotometer equipment at 664 nm. The
aqueous solutions of varied concentrations of methylene blue dye were pre-
pared by dilution from its stock solution and the studies were done by vary-
ing different parameters. The stock solution prepared for the study is shown
in Fig. 2.
Fig. 4: Orange and lemon peel samples

V. EXPERIMENTAL PROCEDURE:
1. Calibration of Methylene Blue:
Stock solution of methylene blue was prepared by taking 0.1g of dye powder
in standard flask and diluted to 100 ml (1000ppm). After that take 1 ml of
stock solution in measuring jar and diluted to 100 ml (10ppm) and was kept
as a working standard for calibration. Take adsorbate concentration as 0.5
ppm, 1ppm, 1.5ppm, 2ppm and 2.5ppm.Each of the sample was detected in
spectrometer and the calibration graph was plotted [4]. From the graph a suit-
able concentration was chosen for further adsorption batch studies.

2. Adsorption of methylene blue using orange peel:

The adsorption of methylene blue dye using orange peel powder was studied
using the batch techniques. To assess the removal efficiency of orange peel
under various adsorbent dosages, methylene blue standard sample in the
range 2.5 ppm was prepared by taking appropriate quantities of standard
methylene blue solution with distilled water. The experiments were con-
ducted in 250 ml Erlenmeyer flasks containing different amount of bio
adsorbents 0.2g, 0.4g, 0.6 g, 0.8g, 1g, 1.4g, 1.8g, 2.2g, 2.4g and 100ml of
MB solution at desired concentrations (2.5ppm). First the stock solution was
Fig. 2: Methylene blue stock solution prepared from which 25ml was taken and balance 75ml was added to pre-
pare the solution of required concentration for batch adsorption study. The
various doses of orange ranging from 0.2g to 2.4g were added in the flask
2. Ultra – Violet Visible Spectrometer: containing methylene blue solution. The flasks were agitated using a shaker
Ultraviolet–visible spectroscopy or ultraviolet-visible spectrophotometry at 150rpm for different time intervals. After agitation allow the sample to set-
(UV-Vis or UV/Vis) refers to absorption spectroscopy or reflectance spec- tle and is filtered using filter paper & residual MB concentration using UV
troscopy in the ultraviolet-visible spectral region. This means it uses light in visible spectrometer at 664nm is determined. Based on various studies con-
the visible and adjacent ranges. The absorption or reflectance in the visible ducted, colored particles have the property of absorbing light in visible
range directly affects the perceived color of the chemicals involved [2]. In region [4]. Here methylene blue particles absorb radiation of 664nm. Here
this region of the electromagnetic spectrum, atoms and molecules undergo the monochromatic source is emitted from monochromator and strikes the
electronic transitions. Absorption spectroscopy is complementary to fluo- particles and sends it to photo detector. The results obtained from the spec-
rescence spectroscopy, in that fluorescence deals with transitions from the troscopy confirmed that the considerable amount of dye was adsorbed on
excited state to the ground state, while absorption measures transitions from adding orange peel powder. Absorbance readings were compared with stan-
the ground state to the excited state. Molecules containing π-electrons or dard curve [6].
non-bonding electrons (n-electrons) can absorb the energy in the form of
ultraviolet or visible light to excite these electrons to higher anti-bonding The same procedure was repeated with lemon peel samples.
molecular orbitals. The more easily excited the electrons, the longer the
wavelength of light it can absorb [4]. The basic parts of a spectrophotometer
are a light source, a holder for the sample, a diffraction grating in a mono-
chromator or a prism to separate the different wavelengths of light, and a
detector. The radiation source is often a Tungsten filament (300-2500 nm), a
deuterium arc lamp, which is continuous over the ultraviolet region (190-
400 nm), Xenon arc lamp, which is continuous from 1602,000 nm; or more
recently, light emitting diodes (LED) for the visible wavelengths. Fig. 3 rep-
resents a double beam Ultra – Violet Visible Spectrometer

Fig. 5: Samples prepared for batch adsorption studies

3. Chemical Oxygen Demand (COD) Analysis:

The COD determination is a measure of the oxygen equivalent of that por-
tion of the organic matter in a sample that is susceptible to oxidation by a
strong chemical oxidant. It is an important, rapidly measured parameter for
Fig. 3: Schematic of a double beam Ultra – Violet Visible Spectrometer industrial waste water studies and for control of waste water treatment pro-

68 International Education & Research Journal [IERJ]

Research Paper E-ISSN No : 2454-9916 | Volume : 6 | Issue : 9 | Sep 2020
cess. So we have to analyze the COD before and after adsorption using concluded that dye and peels should be in contact for 120 minutes in order to
orange and lemon peel. get maximum removal percentage as shown in Fig.7

The reagents used are Potassium dichromate, Sulphuric acid 3. Effect of adsorbent dosage (lemon peel):
Adsorbent dose represents an important parameter due to its strong effect on
Silver sulphate, Mercuric sulphate, Ferroin indicator and organic free dis- the capacity of an adsorbent at given initial concentration of adsorbate.
tilled water. Effect of adsorbent dose on removal of MB was monitored by varying adsor-
bent dose from 0.2g/100ml to 2.4g/100ml. It was seen that the removal of
3. a. Procedure: methylene blue increases with an increase in an amount of adsorbent and
reached on equilibrium value after 1.6g of absorbent of PH-7. For all the
Ÿ Take 10 ml samples of methylene blue, maximum adsorbent capacity experiment, initial MB concentration was fixed at 2.5 mg/l. The most impor-
dosage samples of lemon & orange peel & blank sample in 250 ml of tant factors is that adsorption site remains unsaturated during the adsorption
refluxing flask. reaction. The decrease in adsorption capacity with increase in adsorbent
dose is mainly attributed to non-saturation of the adsorption sites during the
Ÿ Add 0.1g of mercuric sulphate, 5 ml of potassium dichromate by pipette, adsorption process as shown in Fig.8.
14 ml of concentrated sulphuric acid reagent by measuring cylinder.

Ÿ Acid should be added in controlled manner with mixing of the sample. If

the sample color changes to green, dilute the sample and repeat the pro-
cedure for diluted sample. Connect the reflux flask through the con-
denser and reflux for a minimum period of 2hrs at 150°C.

Ÿ After that the condenser is taken out and cooled as room temperature. It
is then titrated with standard 0.1 N ferrous ammonium sulphate using 2
to 4 drops of ferroin indicator.

Ÿ Let the titrate value be ‘A’ End point is the sharp color change from blue
green to brick red, even though blue green reappears within minutes.

Ÿ Let the titrate value be ‘V’ ml. In same manner, a blank with distilled
water 10 ml and follow the procedure from previously. Let the titrate
value be ‘B’ ml. Calculate the COD (mg/l) as follows:

COD = (B-A) xNx8000/V mg/l

Fig. 8: Graph showing efficiency vs dosage for lemon peel
where, B = ml of ferrous ammonium sulphate used for titrating against
blank.
4. Optimal contact time for adsorbent dosages (lemon peel):
A = ml of ferrous ammonium sulphate used for titrating against sam- In the case of lemon peel the contact time is less than the orange peel Initial
ple removal occurs rapidly as soon as the dye and peels come in contact but after
that when some of the easily available active sites engaged by dye needs
N = Normality of ferrous ammonium sulphate.
time to find out more active sites for building. Removal percentage is
V = Volume of sample used increased steadily over the period of experiment .It is concluded that dye
and peel should be in contact for 120 minutes in order to get maximum
VI. RESULTS AND DISCUSSIONS: removal percentage as shown in Fig. 9.
1. Effect of adsorbent dosage (orange peel):
Adsorbent dose represents an important parameter due to its strong effect
son the adsorption capacity of an adsorbent on given initial concentration of
adsorbate. Effect of adsorbent dose on removal of MB was monitored by
varying adsorbent dose from 0.2 g/100ml to 2.4g/100ml at different PH. It
was seen that the removal of methylene blue increases with an increase in the
amount of adsorbent used. For all the experiments, initial MB concentration
was fixed at 2.5 mg/l. At low amount of dosage higher uptake was obtained.

Fig. 9: Effect of contact time on the removal of dye by adsorption

5. Results of COD Analysis:

The analysis the COD before and after adsorption using orange & lemon
peel was done. In the result, MB dye shown a COD content of 16 mg/l. After
using orange peel as an adsorbent there was no reduction in the COD con-
tent. In the case of lemon peel as an adsorbent there was a reduction in the
COD value compared to orange peel. So that in the COD analysis, lemon
peels as an adsorbent was effective in the reduction of COD.
Fig. 6: Graph showing efficiency vs dosage for orange
Volume of COD
Material A (Sample) ml B (Blank) ml
sample (ml) (mg/l)
2. Optimal contact time for adsorbent dosages (orange peel):
The removal efficiency is increases with increase in contact time between Methylene Blue 10 13.1 13.3 16
adsorbate and adsorbent. It can be attributed to the fact that more time Orange Peel 10 12.8 13.3 40
becomes available for the dye to make an attraction complex with orange
peels. The graph shows that, Initial removal occurs rapidly as soon as the dye Lemon Peel 10 13.2 13.3 8
and peels in contact but after that when some of the easily available active
sites engaged, dye needs time to find out more active sites for building.so, VII. CONCLUSION:
removal percentage is increased steadily over the period of experiment . It is Removal of methylene blue dye from aqueous solution using orange peel &

International Education & Research Journal [IERJ] 69

 Research Paper E-ISSN No : 2454-9916 | Volume : 6 | Issue : 9 | Sep 2020
lemon peel was done and following conclusion were arrived:

Ÿ Lemon peel was found to have better adsorbing capacity than orange
peel

Ÿ The adsorption of dyes onto orange peel & lemon peel are influenced by
amount of adsorbents, pH and contact time. As adsorbent dose increases
adsorption increases due to the availability of free sites. As we increase
adsorbent dose more than the optimum, the removal efficiency
decreases.

Ÿ Removal of methylene blue from textile wastewater by adsorption on

lemon peels has been found to be useful than orange peel for controlling
water pollution due to dyes.

Ÿ In COD analysis lemon peel was found to reduce COD and has higher
adsorption capacity, hence found superior.

Ÿ The permissible exposure of methylene blue is 0.4ppm and the after

adsorption solution contained only 0.13ppm of methylene blue, thus it
is safe to dispose into the environment.

Based on the present study it can be concluded that the use of the lemon peel pow-
der as bio adsorbent for removal of methylene blue is feasible and the removal by
adsorption increases with increase in adsorbent dose. After optimum dosage the
removal efficiency decreases. In these study adsorbent dosage (orange & lemon)
increases from 0.2g to 2.4 g per 100 ml of 2.5 ppm concentrated methylene blue
solution. Optimum dosage obtained is 2.2 g and maximum efficiency is88.4 % in
orange peel and optimum dosage obtained is 1.6 g and maximum efficiency is
94.8% in lemon peel. Results confirm that the adsorption is a very effective pro-
cess for the decolourisation of wastewater. Thus it can be concluded that lemon
peel is better than orange peel for the removal of methylene blue dye from waste
water.

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