TREATMENT OF OIL SPILL BY BUFFING DUST AS AN EFFICIENT ADSORBENT

GALIH RAMADHAN & SYAITS ASYAM CHEMISTRY

INDONESIA

PREFACE

Oil spill has been a major environmental problem and the treatment hasnt always been successful. Sorption by natural organic substrates, inorganic materials or synthetic fibres is one of the most popular methods used for the separation of oily wastes from contaminated water. In this work, the ability of buffing dust of crust leather to remove crude oil from water and natural seawater has been tested. This research project titled: Treatment of Oil Spill by Buffing Dust as an Efficient Adsorbent was carried out since November 2013 to January 2014. The aim of our project was to treat oil spill using industrial waste which is in this case from shoes industry. The authors acknowledge that our project would have not been successful without the support from the following people. Firstly, we would like to express our great appreciation to Mr. Ahmad Tawfiequrrahman Yuliansyah S.T., M.T., D.Eng, lecturer in Department of Chemistry Engineering in Engineering Faculty at Universitas Gadjah Mada, Yogyakarta, for being our supervisor in this project. Secondly, Mr. Angga Yuda Putra Perdana, one of Kesatuan Bangsa High Schools teacher for being our second supervisor. Thirdly, Mr. Eko Andi Hartono, S.Pd for being our third supervisor. Fourthly, Dr. Ir. Bardi Murachman SU. DEA, Head of Chemical Engineering Laboratory in University of Gadjah Mada, Yogyakarta for providing us Laboratory Facility at UGM. Lastly, Mr. Hardi and Ms. Anis as our guides in laboratory. We hope this research project could be useful for wider community, especially in the area of oil waste treatment and can be applied in real wastewater.

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Yogyakarta, January 2014

Authors

Contents

Cover .

Preface ..

Contents

Abstract .

I INTRODUCTION

1.1 Background.

1.2 Research Questions..

1.3 Research Objectives..

1.4. Significance

II LITERATURE REVIEW

2.1 Buffing Dust.

2.2 Adsorption Isotherm Theory..

2.2.1 Langmuir Adsorption Isotherm..

2.2.2 Freundlich Adsorption Isotherm

III MATERIALS AND METHOD

3.1 Adsorbent.

3.2 Adsorbate.

3.3 Research Scheme..

3.3.1 Adsorption of Crude Oil in Water..

3.3.2 Adsorption of Crude Oil in Seawater

3.4 Analysis

IV RESULTS AND DISCUSSIONS

4.1 Adsorption in Water

4.2 Adsorption in Seawater..

4.3 FT-IR Analysis..

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4.4 Analytical Laboratory Result using Scanning Electron Microscope (SEM)

4.4 Further Treatment

V Conclusion

References

Appendix

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AbstractRamadhan, Galih and Syaits Asyam. 2014Treatment of Oil Spill by Buffing Dust as an Efficient Adsorbent.Paper of Kesatuan Bangsa Bilingual Boarding School.First Supervisor : Ahmad Tawfiequrrahman Yuliansyah S.T.,

M.T., D.EngSecond Supervisor : Eko Andi Hartono, S.Pd

This project tested the effectivity and selectivity of buffing dust, a waste from leather industry, as an adsorbent for crude oil. In the initial experiment, 180 mL of seawater and 20 mL of crude oil were mixed in a flask and were adsorbed by buffing dust ranging from 2g to 5g. After the process of adsorption, the mixture was shaken in water bath for 30 minutes and filtered using Bchner funnel. The volume of seawater and crude oil in the filtrate were measured. Amount of oil and water adsorbed by buffing dust were then calculated. Based on experimental data, it can be concluded that the more buffing dust used, the more amount of oil was adsorbed, meanwhile, the amount of water adsorbed became less. It indicated that buffing dust of crust leather can be an efficient adsorbent for oil in oil-contaminated water due to its high selectivity.

Keywords: buffing dust, adsorption, oil spill, crude oil, selectivity

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I Introduction

1.1 Background

Used or spent oils are toxic for the microflora which is responsible

for the biological degradation of organic substances contained in wastewater effluents. This can be explained by the formation of a layer on the water surface limiting energy, heat, moisture, and oxygen exchange between the water reservoir and the atmosphere (Lee et al. 1999; Pushkarev et al. 1983; Haussard et al. 2001). Consequently, the efficiency of microorganisms for the degradation of organic matter in wastewater treatment will be decreased. The spilled oil also contributes to an undesirable taste and odour to drinking water and causes severe environmental damage. Contaminated water cannot be used for municipal water supply, for industry, nor for irrigation (Blumer 1969). Contamination of coastal areas due to oil spills is a tragic event. Under favourable conditions, oil may continue to spread over the water surface and form a thin layer. As a result, marine life is seriously threatened, beaches are polluted and tourism and the fishing industry gravely suffer the effects.

Adsorbent is a material which has the capacity to bind and adsorb another substances (Vankar et.al., 2012). It must have a lot of pores and wide surface area. Sorption by natural organic substrates or inorganic materials or synthetic fibres is one of the most popular methods used for the separation of oily wastes from contaminated water (Fanta et al. 1986; Schrader 1991; Choi and Cloud 1992; Choi et al. 1993; Anthony 1994; Lee et al. 1999; Mackay and Gschwend 2000; Toyoda and Inagaki 2000; Haussard et al. 2001). According to Gregg and Sing (1967) the sorption capacity in a vast range of solids depends on the surface area and pores. Tanned solid wastes generated by the leather industry are very porous and are a good candidate for sorption material.

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Adsorption is preferable because of its effectiveness, operational

simplicity, low-cost and low energy requirement (Jalil et.al., 2010). A low-cost adsorption can be obtained by using industrial waste.

The solid wastes generated from leather industry can be broadly

classified as untanned collagenous, tanned collagenous and non-proteinous wastes. Among the tanned collagenous waste, the one resulting from the finishing operation called buffing dust draws the most attention from the public and pollution control authorities due to its negative impact to public health. Thus, this research project has used buffing dust since such research hasnt been done before.

1.2 Research QuestionsThe general research question asks whether leather industrial

wastes can be utilised as an adsorbent for oil waste. Specifically, the research project will investigate:

1. Whether the buffing dust could be an efficient adsorbent for oil waste.

2. Whether the selectivity of buffing dust could only adsorb oil from the oil-contaminated water.

1.3 Research Objectives1. To investigate whether the buffing dust could adsorb the oil

efficiently.2. To determine the selectivity of buffing dust.

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1.4 SignificanceThis project is significant for three important reasons. Firstly, it is

likely to utilise industrial waste especially buffing dust for wastewater treatment. Secondly, to obtain an low-cost, economical, and environmental-friendly adsorbent for oil waste. Lastly, to obtain a safer alternative way to dispose leather industrys waste especially buffing dust.

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II Literature Review

2.1 Buffing DustBuffing dust is a proteinous solid

waste impregnated with chromium, synthetic fat, oil, tanning agents and dye chemicals which is generated during the manufacture of leather. About 26 kg of buffing dust is liberated as a solid waste per ton of skin/hide processed.

Averagely, a leather industry in Indonesia produce 1 ton of buffing dust every month while there are 388 shoes industries in Indonesia. Buffing dust carries about 2.7% chromium on dry weight basis. This may cause clinical problems like respiratory tract ailments, allergic dermatitis, ulcers, perforated nasal septum, kidney

malfunctions and lung cancer in humans exposed to the environment containing buffing dust particulates. Hence, it is cautioned by pollution control authorities to collect the buffing dust for safety disposal. Hence, one of our objectives is to safely dispose buffing dust and to use the waste as an efficient adsorbent.

2.2 Adsorption Isotherm Theory Langmuir and Freundlich isotherm are theoretically equations to be used to analyse an adsorption process. Since our search on adsorption is

mainly focusing on application, these two isotherms were not further

investigated. They are regarded as beyond the scope of our present

research.

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Figure 2.1 Buffing Dust

2.2.1 Langmuir Adsorption IsothermThis model assumed that adsorption takes place at specific homogenous sites within the adsorbent, and it has been used successfully for many adsorption processes of monolayer adsorption. The linearised form of Langmuir can be written as:

Where qe, is amount of dye adsorbed at equilibrium time (milligrams per litre), qm is maximum adsorption capacity (milligrams per gram), and Ka are determined from plotted between Ce/qe vs Ce (Jaman et.al., 2009)

2.2.2 Freundlich Adsorption Isotherm

This model considers a heterogeneous adsorption surface that has unequal available sites with different energies of adsorption the linearised form of Freundlich can be expressed asIn qe = In Kf + (In Ce)Where qe is the amount of metal ion adsorbed at equilibrium time (milligrams per gram), Ce is equilibrium concentration dye in solution (milligrams per litre). Kf is the capacity of the adsorption constant and n is the intensity of adsorption constant for Freundlich (Yagub et.al., 2012).

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III Materials and Method

3.1 AdsorbentBuffing dust was provided by a shoes industry in Jabodetabek area.

These wastes were generated after treating the surface of crust leather (without dyes) by abrasion. The crust leather is, in general, the leather having undergone dressing operations (wet or mechanical) but not yet finished. Wet leather dressing includes neutralisation, retanning and fat liquoring. These operations are carried out after tanning to give certain properties to the leather.

3.2 Adsorbate

For the adsorbate, crude oil, which is a naturally occurring,

unrefined petroleum product composed of hydrocarbon deposits, was used. Crude oil is a fossil fuel, meaning that it was made naturally from decaying plants and animals living in ancient seas millions of years ago.

The crude oil was provided by Coal, Gas and Petroleum Technology Laboratory of Gadjah Mada University and it was obtained from Rantau area in North Sumatra. Crude oil used in this project had characteristics mentioned below:

Specific gravity at 60/60 = 0.8076

Kinematic viscosity at 40/cSt = 1.4248

Flash point PM.C.C. = 39

Pour point = -30

API gravity = 43,5

3.3 Research Scheme

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Adsorption using Buffing Dust

Adsorb Crude Oil in Water

Adsorb Crude Oil in Seawater

With shaking

Without shaking

Figure 3.1 Scheme

3.3.1 Adsorption of Crude Oil in WaterThe adsorption use several mass sample variation of adsorbent,

which were 2g, 3g, 4g and 5g, respectively. Digital balance (CHQ type DJ-B) was used to weigh the adsorbent.

The adsorbent was put into 4 pyrex beakers, respectively. Then, beakers were heated at around 80 - 100 for 4 hours. Lastly, adsorbents were let dripped in a desiccator for an hour. Preparation of adsorbent was now ready.

180mL of water and 20mL of Crude oil were added to each of 4 Erlenmeyer flasks. Then, samples of adsorbent were put in each flask. First test was done without shaking in water bath and the second test was done with shaking in water bath in 30 water temperature for 30, 45, and 60 minutes time variations. Lastly, the adsorbents were filtered using Bchner funnel.

3.3.2 Adsorption of Crude Oil in Seawater

The seawater was obtained independently at Pantai Depok, Bantul,

Yogyakarta. Preparation of adsorbents were the same as before, but the oil was mixed in seawater. Lastly, the flasks were put in a shaker water bath for 1 hour and filtered using Bchner funnel.

3.4 Analysis

After filtered, data were obtained. Volume of water and oil

remaining were measured. To obtain the measure of oil adsorbed, subtractions of the final volume of oil from the initial volume of oil added. This similar calculation was also done to water.

Selectivity measurement was determined by comparing the measure of oil to water adsorbed by the adsorbent.

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IV Results and Discussions

4.1 Adsorption in Water

The experiments were done in 4 different samples of adsorbent.

The result of the experiments are in the figure 4.1, 4.2 and 4.3.

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Flask Initial Volume of Water (mL)

Initial Volume of Oil (mL)

Adsorbent added (g)

Final Volume of Water (mL)

Final Volume of Oil (mL)

Water Adsorbed (mL)

Oil Adsorbed (mL)

1 180 20 2 176 8 4 12

2 180 20 3 178 6 2 14

3 180 20 4 178 4 2 16

4 180 20 5 180 0 0 20

mL

0

5

10

15

20

Adsorbent (g)2 3 4 5

Water Adsorbed (mL) Oil Adsorbed (mL)

Figure 4.1 Experiment without shaking in water bath

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Oil Adsorbed in Time Variation with Shaking

Flask Adsorbent (g) Oil Adsorbed (mL) 30 minutes

Oil Adsorbed (mL) 45 minutes

Oil Adsorbed (mL) 1 Hour

1 2 12 12 12

2 3 14 14 16

3 4 18 18 18

4 5 20 20 20

Oil Adsorbed in Time Variation

0

5

10

15

20

30 minutes 45 minutes 1 Hour

5g Adsorbent 4g Adsorbent 3g Adsorbent 2g Adsorbent

Figure 4.2 Experiment with shaking in water bath (Oil Adsorbed in Time Variation)

Water Adsorbed in Time Variation with Shaking

Flask

Adsorbent (g) Water Adsorbed (mL) 30 minutes

Oil Adsorbed (mL) 45 minutes

Oil Adsorbed (mL) 1 Hour

1 2 2 2 2

2 3 0 0 0

3 4 0 0 0

4 5 0 0 0

Figure 4.1 shows that the amount of adsorbed water cannot be determined by amount of adsorbate added, but it is concluded that the amount of oil adsorbed is linear to the amount of adsorbent added. Figure 4.2 and 4.3 shows that the selectivity of adsorbent increased due to the shaking in water bath. The time variation doesnt make a significance difference for the oil or water adsorption. The amount of adsorbate adsorbed was not affected by the shaking in water bath.

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0

0.5

1

1.5

2

30 minutes 45 minutes 1 Hour

5g, 4g, 3g 2g

Figure 4.3 Experiment with shaking in water bath (Water Adsorbed in Time Variation)

4.2 Adsorption in Seawater

Figure 4.4 shows that in seawater more buffing dust means better selectivity and more efficient adsorption. It is also concluded that the amount of oil adsorbed is directly proportional to the amount of buffing dust used and the amount of water adsorbed is inversely proportional to the adsorbent used.

The difference in selectivity of buffing dust in seawater and that in water was not significant.

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Figure 4.4 Adsorption in Seawater

Flask Initial Volume of Water (mL)

Initial Volume of Oil (mL)

Adsorbent added (g)

Final Volume of Water (mL)

Final Volume of Oil (mL)

Water Adsorbed (mL)

Oil Adsorbed (mL)

1 180 20 2 178 10 2 10

2 180 20 3 180 6 0 14

3 180 20 4 180 2 0 18

4 180 20 5 180 0 0 20

mL

0

5

10

15

20

Adsorbent (g)2 3 4 5

Water Adsorbed (mL) Oil Adsorbed (mL)

4.3 FT-IR Analysis

To understand changes in functional groups during adsorption, FT-

IR analysis of buffing dust before and after adsorption were performed. FT-IR spectra for buffing dust were shown in figure 4.5 and 4.6.

FT-IR spectra (figure 4.5 and 4.6) indicated that aliphatic CHn Groups (Wave Number 2924) contained in buffing dust increased after adsorption. The result showed that percent peak area for aliphatic CHn Groups changed from 0.9 to 9.4%. This change was caused by the adsorption of oil, which is rich in hydrocarbon, by the buffing dust.

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CHn Groups

CHn Groups

Figure 4.6 Buffing dust (after adsorption)

Figure 4.5 Buffing dust (before adsorption)

4.4 Analytical Laboratory Result using Scanning Electron

Microscope (SEM)

The effectiveness of buffing dust was checked microscopically using a scanning electron microscope (SEM) with the same magnification. The pictures obtained are presented in figure 4.7 and 4.8. As can be seen, comparison between the adsorbent before (figure 4.7) and after the adsorption (figure 4.8), shows that after adsorption the adsorbent seems to be covered extensively with small particles. It is very likely that these particles are contaminants adsorbed from the crude oil.

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Figure 4.7 Buffing dust before adsorption

4.5 Further TreatmentOil adsorbed by buffing dust can increase its calorific value.

Consequently, these wastes can be easily treated by incineration. The heat liberated during incineration could be used for supplementary heating fuel in several industries, such as the cement industry. Formation of toxic substances in buffing dust incineration could be avoided by thermal treatment above 1000. The ashes obtained, which may contain chromium oxide, could be immobilized and solidified into concrete blocks.

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Figure 4.8 Buffing dust after adsorption process

V Conclusion

The results obtained prove the utility of using buffing dust for resolving an environmental problem. We have demonstrated that oil can be efficiently removed from water and seawater by buffing dust as adsorbent. The use of industrial waste materials for the removal of pollutants from effluents prior to their treatment could decrease the cost of operation.

It is also concluded that the selectivity of buffing dust is effective due to only small amount of water was absorbed in the experiments.

Used buffing dust is also useful for cement industry as supplement for fuel in heating, which means that alternative disposal for buffing dust is proved.

In conclusion, this project has proved the efficiency and selectivity of buffing dust as an adsorbent for oil spill treatment. Also, used buffing dust could be disposed and is useful as supplement in cement industry.

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References

Aidina, Shafira Raudya and Vania Erriza. 2013. Powder of Dry Teak (Tectona grandis sp.)Leaves as Effective Adsorbent for Liquid Textile Waste. Semarang: SMA Semesta.

Albizane, Abderrahman, Amal Gammoun, Miguel de la Guardia, Mohammed Azzi and Soufiane Tahiri. 2007. Decontamination of water polluted with oil through the use of tanned solid wastes. J. Environ. Eng. Sci. 6: 553559. doi:10.1139/S07-006.

Anthony, W.S. 1994. Absorption of oil with cotton products and kenaf. Appl. Eng. Agric. 10: 357361.

Blumer, M. 1969. In Oil on the sea. Edited by D.P. Hoult. Plenum Press, New York, N.Y. p. 6.

Choi, H.M., and Cloud, R.M. 1992. Natural sorbents in oil spill cleanup. Environ. Sci. Technol. 26: 772776. doi:10.1021/ es00028a016.

Choi, H.M., Kwon, H., and Moeau, J.P. 1993. Cotton nonwovens as oil spill cleanup sorbents. Text. Res. J. 63: 211218. doi:10. 1177/00405175930630040.

Fanta, G.F., Burr, R.C., and William, W.M. 1986. Oil absorbency of graft copolymers from softwood pulp. Polym. Sci. Technol. 33: 107114.

Gregg, S.J., and Sing, K.S.W. 1967. Adsorption, surface area and porosity. Academic Press Inc. New York, N.Y. pp. 1, 45, 252 253.

Haussard, M., Gaballah, I., De Donato, P., Barre`s, O., and Mourey, A. 2001. Removal of hydrocarbons from wastewater using trea- ted bark. J. Air Waste Manag. Assoc. 51: 13511358. PMID:11575889.

Jaman, H., Chalraborty, D., & Saha, P. 2009. Study about thermodynamic and kinetic copper adsorption using modified-riceplant chemically.

Lee, B.G., Han, J.S., and Rowell, R.M. 1999. Oil sorption by lignocellulosic fibers. In Kenaf Properties, Processing and Products. Mississippi State University, Ag & Biol. Engineering. ISBN 0 96705590-3. Chapter 35, pp. 423433.

Mackay, A.A., and Gschwend, P.M. 2000. Sorption of monoaromatic hydrocarbons to wood. Environ. Sci. Technol. 34: 839 845. doi:10.1021/es9900858.

Pushkarev, V.V., Yuzhaninov, A.G., and Men, S.K. 1983. Treatment of oil containing wastewater. Allerton Press, Inc., New York, N.Y. pp. 35.

Schrader, E.L. 1991. Remediation of floating, open water oil spills: Comparative efficacy of commercially available polypropylene sorbent booms. Environ. Geol. 17: 156166.

Toyoda, M., and Inagaki, M. 2000. Heavy oil sorption using exfoliated graphite. New application of exfoliated graphite to protect heavy oil pollution. Carbon, 38: 199210. doi:10.1016/S0008- 6223(99)00174-8.

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Vankar, P.S. et. al., 2012, Biosorption of Zinz Ions from Aqueous Solutions onto Natural Dye Waste of Hibiscus rosa sinensis: Thermodynamic and Kinetic Studies. Environmental Progress and Sustainable Energy, vol. 1, no. 31, pp. 89-99.

Yagub T, Mustafa and Tushar Kanti Sen. 2012. Equilibrium, Kinetic, and Thermodynamics of Methylene Blue Adsorption by Pine Tree Leaves. WA: Springer Science+Business Media.

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Appendix

Photos of project activities:

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The AuthorGalih Ramadan

galihramadan@me.com

Co-AuthorSyaits Asyam

syaitsasyam@icloud.com

Summary

Spilled oil is a waste which is caused by a tragic

event and the treatment hasnt always been

successful. Leather industry waste (buffing dust)

has also been a major problem due to its vast

production. This project tested the capability of

buffing dust to adsorb spilled oil in seawater. The

experiments proved that the buffing dust is capable

and highly efficient to adsorb the oil and the

selectivity of buffing dust is also high due to no

seawater is adsorbed. Lastly, the mixture of buffing

dust and oil due to adsorption is still useful for

starved air incineration supplement in cement

industry. This project has treated both wastes and

made them useful.

mailto:galihramadan@me.commailto:syaitsasyam@icloud.commailto:galihramadan@me.commailto:syaitsasyam@icloud.com