REMOVAL OF METHYLENE BLUE AND METHYLENE ORANGE FROM AQUEOUS

SOLUTION BY CARBON ACTIVE MEMBRANE AND FUEL CELL APPLICATION

NANO – TECHNOLOGY COURSE

By : Asst. Prof. Stephan Thierry Dubbas

Members of Group :

1. Febri Putri Batama EX617005

2. Silvi Nursukmaindri EX617009

PETROLEUM AND PETROCHEMICAL COLLEGE

CHULALONGKORN UNIVERSITY
BANGKOK, THAILAND
2019
 INTRODUCTION

Dyes are usually emitted from various kind of industries, mainly from dye manufacturing
and textile – industries. Dyes are one of the most common pollutants in the world. Dyes also may
spread toxic and carcinogenic metabolites in anaerobic conditions. Dyes can be treated by
physical and chemical methods to prevent pollution in the aquatic environment, however, the
cost is extremely high. Methylene Blue (MB) is cationic dye and Methylene Orange (MO) is a
anionic dye which are commonly used for dyeing acrylic, nylon, silk and wool. They have
various harmful effects on human beings and animals if it is once inhaled, such as heart rate
increasing, nausea and vomiting. (Eren E. and Afsin B., 2008).
Adsorption becomes the most successful process or technique which has been used for
removing dyes from aqueous solution. Besides, it doesn’t need high cost for dye removal, and
also very quick and easy. Many adsorbents have been tried and tested to reduce dye
concentrations from aqueous solution. Activated carbon membrane is the most preferred
adsorbent because of high adsorption capacity.
In this study, activated carbons were used to remove Methylene Blue and Methylene
Orange from an aqueous solution by batch adsorption process and the parameter affecting the
adsorption capacity of the activated carbon, including concentration variation was investigated.
 EXPERIMENT

1. Materials
- Activated carbon powder
- Poly(Styrene Sulfonate-co-maleic) or PSS as P-
Molecular Weight : 206 gr/mol
- Poly (DiAllyDimethylammonium Chloride) or PDAD as P+
Molecular Weight : 161 gr/mol
- Sodium Chloride (NaCl)
Molecular Weight : 58,5 gr/mol
- Methylene Blue
- Methylene Orange
- Deionized Water (DI Water)

The materials above are prepared from Polymer Laboratory in PPC Building,
Chulalongkorn University.

2. Tools
- Erlenmeyer
- Beker glass
- Spoon
- Measuring Glass

The tools above are borrowed from Polymer Laboratory in PPC Building,
Chulalongkorn University.

Procedures :
1. Preparation of Carbon Active Membrane
To make a membrane from activated carbon powder, 0,1 gr; 0,3 gr; 0,5 gr of activated
carbon powder were collected from Polymer Laboratory in PPC Building. Activated
carbon is a small particle, with a dominant size of less than 0.075 mm.

Then, make two kinds of solution. The first solution is a mixture of PSS (P-) as an
activator of activated carbon as much as 1,854 gr, and NaCl as a stabilizer as much as
5,265 gr then diluted with 90 ml DI Water.
 The second solution is a mixture PDAD (P+) (material to form a “ball”) as much as
7,245 gr and 5,265 gr of NaCl diluted with 90 ml water. Then separate each solution
into 3 smaller beaker glass (@ 30 ml). So, we have 6 samples (3 P+ solutions and 3 P-
solutions).

Put 0,1 gr of activated carbon powder into the first solution (PSS + NaCl) and stir
them with magnetic stirrer around 1 minute. Then, pour all the second solution
(PDAD + NaCl) into activated carbon + PSS + NaCl solution, then stir them for 2
minutes until all of the materials are homogeny. Do the same steps for 0,3 gr and 0,5
gr of activated carbon.

Next, take the balls out and put them into centrifuge tube and add 36 ml of solution
from all of these samples (0,1; 0,3; 0,5 gr) in order to get a perfect form of ball for 20
minutes. The last step is press the 3 balls with 60℃ and 1000 atm for 5 minutes and
2000 atm for 5 minutes to form a membrane.

2. Adsorption Test
The activated carbon membranes were used to adsorb Methylene Blue (MB) and
Methylene Orange (MO) in aqueous solution.
Methylene Blue (MB) is a cationic dye, was collected from Polymer Laboratory in
PPC Building. MB has empirical formula C16H18ClN3S.xH2O and its molecular
weight is 319,85 gr/mol. The maximum adsorption wavelength of this dye is 618 nm.
The structure of MB is shown in Figure 1 :

Figure 1. Chemical Structure of Methylene Blue

Methylene Orange (MO) is an anionic dye, was collected from Polymer Laboratory
in PPC Building. MO has molecular formula C14H14N3NaO3S and its molecular
weight is 327,34 gr/mol. The maximum wavelength is 467 nm. The structure of MO
is shown in Figure 2 :
 Figure 2. Chemical Structure of Methylene Orange

To test the ability of adsorption, put the activated carbon membrane into diluted
methylene blue solution and methylene orange solution and left them for 2 days.
Then to analyze the wavelength peak, we used UV- Visible Spectroscopy.

Figure 3. Process of Making Activated Carbon Membrane

3. Fuel Cell Application

Fuel cells are electrochemical devices that convert chemical energy from the
reactants directly into electricity and heat. The device consists of an electrolyte layer
in contact with a porous anode and cathode on either side. An illustration of a fuel cell
with reactant/product gasses and the ion conduction flow directions through the cell is
shown in Figure 4 below :
In a standard fuel cell, gaseous fuels are fed continuously to the anode (negative
electrode), while an oxidant (oxygen from the air) is fed continuously to the cathode
(positive electrode). Electrochemical reactions take place at the electrodes to produce
an electric current. Some of the advantages of fuel cell systems are:
 A high operating efficiency that is not a function of system size.
 A highly scalable design.
 Several types of potential fuel sources are available.
 Zero or near-zero greenhouse emissions.
 There are no moving parts in the fuel cell stack, which provides reliable,
vibration-free operation. (There may be pumps or compressors in some
fuel cell plant subsystems).
 Nearly instantaneous recharge capability when compared to batteries.

Figure 4. Fuell Cell Application

 RESULT

A. ACTIVATED CARBON MEMBRANE

Figure 5. Adsorption Result

Methylene Orange
0.1
0.08
0.06
0.04
0.02
0
-0.02
-0.04
-0.06
-0.08

Figure 6. Wavelength of Methylene Orange

Note: Blue line showed the wavelength of 0,1 gram of activated carbon.
 Red line showed the wavelength of 0,3 gram of activated carbon.

Green line showed the wavelength of 0,5 gram of activated carbon.

Methylene Blue
0.2

0.15

0.1

0.05

-0.05

-0.1
Wavelength

Figure 7. Wavelength of Methylene Blue

Note: Blue line showed the wavelength of 0,1 gram of activated carbon.

Red line showed the wavelength of 0,3 gram of activated carbon.

Green line showed the wavelength of 0,5 gram of activated carbon.

Explanation :

Adsorption experiments were carried out by using activated carbon as adsorbent.

We turned activated carbon powder into membrane by mixing PSS, PDAD and NaCl
as well. NaCl was used as a stabilizer. We used UV – Vis Spectroscopy to determine
the wavelength peak of Methylene Orange and Methylene Blue after be adsorbed by
activated carbon membrane.

Methylene blue is a cationic dye which has 618 nm of wavelength. From the
graph, we can conclude that activated carbon membrane couldn’t adsorb the
methylene blue well, the graph also shows that the wavelength peak of the 3 samples
were increased more than the maximum wavelength of the diluted methylene blue
before it was adsorbed by activated carbon membrane. The maximum wavelength
peak had 638-639 nm, while the maximum wavelength of methylene blue is only 618
nm. Also, from the graph we can conclude that the more concentration of activated
 carbon in a membrane, made it became more saturated so it couldn’t adsorb the dyes
well.

Methylene orange is an anionic dye which has around 467 nm of wavelength. In 2

days, the methylene orange solution turned from orange color into transparent like
clear water, while the color of methylene blue solution turned into light blue, but did
not transparent yet like methylene orange solution. From the graph, we may conclude
that 0,5 gr of activated carbon could adsorb more dyes, or in this case was methylene
orange. Wavelength peak was decreased into around 366 – 389 nm.

B. ACTIVATED CARBON MEMBRANE FOR FUEL CELL APPLICATION

Figure 8. Activated Carbon Membrane After Be Tested On Fuel Cell (left); Activated
Carbon Membrane 10% AC and 30% AC (right)
 10% OF ACTIVATED 30% OF ACTIVATED
CARBON CARBON

0,025 V 0,021

-0,015 V -0,005

-0,011 V 0,026

0,043 V 0,041

Result :

From 10% AC membrane, we can conclude that the voltage decreased around 20
seconds, but then increased from -0,011 V into 0,043 V at the end. While from 30% AC
membrane, the voltage decreased also into -0,005 V but then increased highly into 0,026
V and became 0,041 V at the end.

CONCLUSION

1. Activated carbon membrane has cationic, while methylene orange has anionic. That’s
why the wavelength peak on MO decreased than before (from 467 nm, became 366-389
nm)
2. Activated carbon membrane couldn’t adsorb methylene blue wee, because MB has
anionic. The wavelength peak increased from 618 nm into 639 nm.
3. The more AC in a membrane, it could block the proton to go passed through the
membrane and it made less proton conductivity.