DESALINATION

ELSEVIER Desalination 140 (2001) 259-264

www.elsevier.com/locate/desal

Investigation of the effectiveness of absorbent materials in oil spills clean up

Ch. Teas, S. Kalligeros, F. Zanikos, S. Stoumas, E. Lois*, G. Anastopoulos
Department of Chemical Engineering, National Technical University of Athens, lroon Polytechniou 9, Athens 157 80, Greece Tel. +30 (1) 772-3190; Fax +30 (I) 619-7750; email: elois@orfeas.chemeng.ntua.gr

Received 8 January 2001; accepted 20 March 2001

Abstract

The present study examines the absorption capacity of five different types of materials for oil spills clean up. The absorbents were a commercial cellulosic material from processed wood, a commercial synthetic organic fiber from polypropylene and three commercial types of local expanded perlite from the island of Milos. The absorption capacities of the above materials were evaluated in a wet as well as a dry environment with different types ofpelroleum products. The results showed that commercial types of perlite, in some cases, have absorption capacities comparable to natural and synthetic organic materials used for clean-up applications. The enhancementof the hydrophobic properties ofperlite can result in better performance in a water bath. The nature of the spilled oil proved to play an important role in the selection of the proper absorbing material. Overall, the results suggested that partial substitution of commercialsynthetic sorbents by mineral materials widely produced in Greece for oil spill clean-up operations is possible, given their friendliness to the environment and their local abundancy.
Keywords: Oil spills; Expanded perlite; Cellulosic fiber; Polypropylene; Sorbents; Greece

1. Introduction

In March 1989 the Exxon Valdez incident spilled 11.2 million gallons o f crude oil into the coastal waters of Prince William Sound, Alaska, causing severe environmental damage [1,2]. The demolition of oil storage tanks in Kuwait during *Corresponding author.

the war in 1991 spilled several hundred million gallons ofoil into the sea. Recent accidents ofoil tankers, for example in the Japan Sea and the Strait of Malacca, have caused serious pollution o f seawater and neighboring coasts, as well as disastrous effects on fishing and great losses of heavy oil. In addition, spills from tanker loading and uploading operations, pipeline rupture and other sources pose serious threats to the

0011-9164/01/$- See front matter 2001 Elsevier Science B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 1 ) 0 0 3 7 5 - 7

260

Ch. Teas et al. / Desalination 140 (2001) 259-264

environment including fisheries and wildlife. In Greece, over 300 accidents were reported yearly during the last 10 years [3,4]. The addition of sorbent materials in an oil spill area facilitates a change from liquid to semisolid phase. Once this change is achieved, the removal of the oil by removal of the sorbent structure is not difficult. While hydrophobicity and oleophilicity are primary determinants of successful sorbents, other important factors include retention over time, the recovery of oil from sorbents, the amount of oil sorbed per unit weight of sorbent, and the reusability and biodegradability of sorbent [5]. Oil sorbents material can be categorized into three major classes: inorganic mineral products, organic synthetic products, and organic vegetable products. Mineral products include perlite, graphite, vermiculites, sorbent clay and diatomite. Synthetic products include polypropylene and polyurethane foam, their main disadvantage being that they degrade very slowly as compared with vegetable products and are not naturally occurring as mineral products [6-8]. Greece's geology favors a potent and dynamic use of mineral resources, which became a major incentive of the country's mining business and economic and social growth. Particular attention is paid to evaluating the development of innovative processing technologies and new industrial and environmental applications. Over the last 10 years, growing awareness has risen concerning the use of naturally occurring industrial minerals in technologies that are much more sustainable with respect to our environment. With this awareness, the interest in industrial minerals increased globally. In particular, the world-class deposits of perlite on Milos Island in the southern Aegean Sea are a possible industrial mineral capable into developing as a low-cost, high-tech solution in order to remediate parts of the oil pollution environmental problem [9].

The purpose of this research was to study the oil absorbency of five different sorbents using three local types of the expanded perlite from Milos with diverse mesh, polypropylene and cellulosic fiber in simulated seawater bath and oil bath containing different types of oil. Three different types of oil were used each time: light cycle oil (LCO), light gas oil (LGO) and Iranian heavy crude oil ( C R U ) - - which are typical types of oils in the majority of actual oil spills. The objective was to examine the relative behavior of these sorbents in oil spills clean up.

2. Experimental
2.1. Oil samples

The specifications of the three different types of oil used in the experimental procedure are listed in Table 1. These oils were chosen because they exhibit similar properties with the oil types proposed by ASTM F-716 and F-726. Both methods are approved by Greek legislation for absorbent performance [ 10].
2.2. Absorbent materials

Descriptive characteristics of the materials used in this study are given in Table 2. Expanded perlite 3 is expanded perlite 1, with increased hydrophobicity, as a result of chemical treatment. The use ofpolypropylene and cellulosic materials allowed comparison of mineral absorbents with common sorbent materials.
2. 3. Procedure

A 500-ml sample of artificial seawater [11] was placed in an 800-ml glass beaker. The desired amount ofoil (10, 20, 30, 40, 50g) was added to the beaker. The beaker containing crude oil and artificial seawater was mounted in a shaking apparatus. Approximately l g of a

Ch. Teas et al. / Desalination 140 (2001) 259-264 Table 1 Specifications of the oil samples Property Density, g/ml o API gravity Viscosity, 40C, cST Light cycle oil (LCO) 0.9550 16.66 3.85 Iranian heavy (CRU) 0.8692 31.00 11.05 Light gas oil (LGO) 0.8411 36.73 3.36 Method ASTM D-1298 ASTM D-1298 ASTM D-445

261

Table 2 Specifications of sorbent materials Type Expanded perlite 1 Expanded perlite 2 Expanded perlite 3 Cellulosic fiber Polypropylene Description of material Granular form Granular form Granular form Wooden chips Non woven web Mesh 0-5 1-6 0-5 20 Density, g/1 0.20 0.20 0.20 0.11 Application Insulation material Horticultural applications Insulation material (waterproof) Absorbent material for liquid wastes Absorbent material for liquid wastes

sorbent material was added in the system, which was shaken for 10 min at 98 cycles/min. The wetted sorbent material was weighted after being drained for 1 min in the sustainer. Water content of the sorbent was analyzed by the distillation technique described in ASTM D 95 [12]. A mixture of toluene and xylene (20/80, v/v) was used as the carrier solvent. The amount o f oil sorbed by the sorbent was determined by subtracting the water content and the initial sorbent weight from the total weight of the wetted sorbent. Oil quantity absorbed is S r - S w - SA (1)

Often sorbents are used for clean up in areas where water is not involved. Oil sorption is expected to be different because o f the different sorption environment. To model the case where only sorbent and oil are present, similar experiments were carried out with no water present. One hundred ml of oil were placed in a 200-ml beaker before any sorbent was immersed in the bath. After addition of the sorbent, shaking and drainage as described above the amount o f oil sorbed by the material were determined gravimetrically, using Eq. (1) where Sw equaled zero.

3. Results and discussion

where Sr is the total weight (g) of oil, water and absorbent material as determined gravimetrically, Sw is the water weight (g) as determined by distillation and SA is the absorbent material weight (g). The quantity of oil was recorded as grams per gram of sorbent.

3.1. Sorption in artificial seawater The oil sorption capacities o f the sorbents in the artificial seawater bath, containing different amounts ofoil, are shown in Figs. 1-3 for LCO, CRU and LGO, respectively.

262

Ch. Teas et al. /Desalination 140 (2001) 259-264

==

-= 1

Expanded perlltel

Expanded perHte2

Expanded parllle3

Celtuloslc fiber Polypropylene

Fig. 1. Absorption capacity of materials for LCO.

8
Expanded pexlitel Expanded petlite2 Expanded perllte3 Cellulosic fiber Polypropylene

Fig. 2. Absorption capacity of materials for CRU.

4."

.=_ O. Expanded perlltel Expanded parllte2 Expanded perllte3 Cellulosic fiber Pnlypropylene

sorption values of expanded perlite 1 and 2 were generally lower compared to the other materials used. Despite the fact that expanded perlite 1 and 3 have similar physical properties, the hydrophobicity of the latter due to chemical alteration makes them perform totally different in a water medium. Expanded perlite 2, intended for horticultural applications, has natural hydrophilic performance, absorbing twice as much water than oil in all cases. Expanded perlite 3 sorption capacity was greater than the other two types of perlite because it is waterproof. In the case of crude oil, the absorption capacity of cellulosic fiber was the highest of all materials used, being able to absorb the whole amount of oil in the seawater bath. Similar high absorptions of natural organic sorbents have been reported by other researchers; the reason may be the hydrophobic interaction and Van der Waals forces, which would occur between the crude oil in the bath and wax in the natural sorbent [6,13]. An alternative explanation is that the cellulosic material acted more like a solidifier for the crude oil forming a cohesive solid mass with no dripping effect [14]. Crude oil as more viscous was highly absorbed by all materials. Although increased oil viscosity reduces the rate of absorption within the pores and capillaries of materials, it increases the adherence on the surface of the material and within the pores during drainage. Low-viscosity oils are released by the sorbent while being lifted out of water and during drainage lowering the oil sorption. This is probably the reason that maximum absorption is observed for 30 or 40 g of oil in the bath, as oil drainage combined with small sorbent integrity allows more oil quantity to lose adhesion with the sorbent.

Fig. 3. Absorption capacity of materials for LGO.

Polypropylene showed the highest oil sorption capacity for LCO and LGO followed by expanded perlite 3 and cellulosic fiber. The oil

3.2. Sorption without the water medium

The oil sorption capacities of different sorbents in a pure oil bath are shown in Fig. 4.

Ch. Teas et al. / Desalination 140 (2001) 259-264

263

Expanded periitel

Expanded perlite2

Expanded Cellulosicfiber Polypropylene perlite3

Fig. 4. Absorption capacity of materials in an oil bath. In dry conditions expanded perlite 1 exhibited higher absorption than in wet conditions, performing better than the other two types of perlite. As sorption on clay materials depends on the molecular size, highly polar water molecules that are generally smaller than organic compounds cover the clay surfaces reducing the attraction of organic molecules [15]. In the absence o f water, expanded perlite 1 had better efficiency-absorbing organic constituents. As it was calculated by the distillation technique in the previous paragraph, expanded perlite 1 absorbed nearly 1 g o f water each time while hydrophobic expanded perlite 3 absorbed 0.1 g o f water. The best performing material was proven to be polypropylene in CRU.

2. In the presence ofwater and LCO, one type o f hydrophobic perlite had comparable absorption efficiencies with polypropylene and cellulosic material. 3. In a dry environment, polypropylene exhibited the best absorption characteristics, whereas all expanded perlites had similar absorbing efficiencies with the cellulosic material for all oils used. 4. The results suggest that substitution o f commercial synthetic oil sorbents in oil spill clean-up and wastewater purification from organic molecules is possible by naturally occurring minerals with regional interest, given their friendliness to the environment and their local abundancy.

References

4. Conclusions In this series of experiments, we examined the oil sorption capacities of five sorbents - expanded perlites 1, 2 and 3 from the island of Milos, cellulosic fiber and polypropylene - - in three types o f oil, to determine the potential use in oil spill clean-up, with and without the presence o f seawater. The results can be summarized as follows: 1. In wet environments, the best performing materials were polypropylene and cellulosic fiber.

[1] W.E. Westermeyer,Environ. Sci.Technol.,25 (1991) 196. [2] J.M. Weber and R.E. Crew Jr., J. Environ. Mgrnt., 58 (2000) 161. [3] F. Yando, Oil Spill Intelligence Report, Cutter Information Corp., 28 Dec. 1995. [4] Marine Environmental Protection Division, Greek MinistryofMercantileMarine,<http://www.yen.gr>. [5] J.W. Doerffer, Oil Spill Response in the Marine Environment, Pergamon Press, 1992. [6] H.M. Choi and R.M. Cloud, Environ. Sci. Technol., 26 (1992) 772. [7] The InternationalTankerOwner PollutionFederation Limited,Measuresto Combat Oil Pollution, Graham & Trotman, London, 1980. [8] M. Toyoda, J. Aizawa and M. Inagaki, Desalination, 115 (1998) 199. [9] N. Arvanitidis, J. Geochem. Exploration, 62 (1998) 217. [10] GreekGovernmentGazette, 951/131997, 1997. [1 l] ASTM, D 1141, Annual Book of ASTM Standards, American Society of Testing and Materials, Philadelphia, PA, Vol.11.02, 1998. [12] ASTM D95, Annual Book of ASTM Standards, American Society of Testing and Materials, Philadelphia, PA, Vol. 05.01, 1998.

264

Ch. Teas et al. / Desalination 140 (2001) 259-264

[13] H.M. Choi, J.H. Kwon and J.P. Moreau, Textile Res. J., 63 (1993) 211. [14] R.D. Delaun, C.W. Lindau and A. Jugsujinda, Spill Sci. Tchnol. Bull., 5 (1999) 357.

[15] S. Gitipour, M.T.Bowers, W.Huff and A. Bodocsi, Spill Sci. Technol. Bull., 4 (1997) 155.