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Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 74:1075±1081 (1999)

Water-based non-ionic polymeric surfactants as


oil spill dispersants
Ahmed M Al-Sabagh* and Aiman M Atta
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

Abstract: In this paper, polyisobutylene succinic anhydride adduct (PIB-SA) was modi®ed by esteri-
®cation with polyethylene glycol (PEG 600, 1000 and 2000) to obtain mono- and diterminal polyoxy-
alkynated PIB-SA. The monoterminal products were reacted with pentamethylene-hexamine
(PMHA). The structures were con®rmed by FT±IR and 1H NMR analysis. The surface properties,
interfacial tension and the effectiveness in oil dispersion of the synthesized polymeric surfactants are
reported. The maximum ef®ciency of oil spill dispersants was reached when the surfactant molecule
had two moities (polyoxyalkylene and polyamine units).
# 1999 Society of Chemical Industry

Keywords: polymeric surfactants; dispersants; oil spill dispersants; effectiveness of dispersants; water-based
dispersants

INTRODUCTION solvents, such as kerosene, to water solvents. Petro-


The use of dispersant will generally be preferred over leum-based solvents not only represent the most toxic
other options if there is insuf®cient time for prior component in the dispersant product but also dissipate
mechanical recovery of an oil spill. If the use of most rapidly in the water environment. To reduce
dispersants will prevent environmental damage that toxicity, non-aromatic hydrocarbon water-miscible
could occur if they were not used, the dispersion of solvents (ethylene glycol ethers) have been used in
spilled oil should be strongly considered. Also, if more recent dispersant formulations. The exact details
dispersion of oil can reduce or eliminate hazardous of dispersant formulations are proprietary, but the
conditions, use of dispersants is recommended. The chemical characteristics of these formulations are
theory behind the use of dispersants in oil incidents is broadly known.7,8 The most commonly used disper-
that they provide a means of accelerating the rate of sants are ethoxylated fatty alcohol,9 ethoxylated
natural degradation of oil. Increasing the surface area sorbitan fatty acid esters10 and tall oil esters.11
of the oil by dispersion is thought to increase microbial The present paper deals with preparing water-based
populations and to accelerate the biological degrada- oil spill dispersants to alleviate environmental pollu-
tion of the spilled oil. tion. In this respect, maleic anhydride is reacted with
The use of chemical dispersants as a counter polyisobutylene, PIB (relative molar mass 1000) to
measure to accidental oil spills at sea is now a give product I which is esteri®ed with polyethylene
technique accepted worldwide. In recent years, the glycol (600, 1000 and 2000) to give ethoxylated
commercial availability of dispersants, containing less polyisobutylene succinate. Also, product I reacts with
toxic chemicals and more ef®cient surfactants, has an equi-molar ratio of polyethylene glycol and
renewed interest in basic studies on dispersant effec- pentamethylene-hexamine (PMHA) to produce
tiveness and on the fate of dispersed oil in the marine ethoxylated and amidated polyisobutylene succinate.
environment.1±3 The surface activity of dispersants is The structure of the dispersants, dispersion effective-
of great importance in a wide variety of industrial and ness and interfacial tension are discussed.
technological operations involving foam, froth forma-
tion, dispersion, emulsi®cation, and in determining
biological activity.4±6 EXPERIMENTAL
The role of solvents in the effectiveness of dis- Materials
persants is of primary importance.1 The solvents Polyisobutylene (relative molar mass 1000), maleic
enable the active agent or surfactant to mix with and anhydride, and polyethylene glycols (relative molar
penetrate into the oil slick and thus form an emulsion. mass 600, 1000, and 2000) were purchased from
The solvent usually comprises the bulk of the Aldrich Chemicals Co. Pentamethylene-hexamine
dispersant product and may range from petroleum (PMHA) was supplied by BDH.

* Correspondence to: Ahmed M Al-Sabagh, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
(Received 12 November 1998; accepted 22 May 1999)

# 1999 Society of Chemical Industry. J Chem Technol Biotechnol 0268±2575/99/$17.50 1075


AM Al-Sabagh, AM Atta

Synthesis of product I immediately increased, maintained at a maximum rate


Maleic anhydride (2 mol) was reacted with polyiso- of 2000 rpm over a 60 s period and then stopped. The
butylene at 180 °C in a nitrogen atmosphere for 24 h. level of oil dispersion in the water was visually
The mixture was then poured into an excess of estimated after a 1 min rest. The classi®cation A was
propanone to remove the unreacted maleic anhydride. attributed to the resulting brown-black mixture when
The precipitate (polyisobutylene succinate) was col- all the oil was dispersed in the water, leaving no slick at
lected by ®ltration and dried. The molar solution of the surface, whereas the classi®cation E was used to
the precipitate in xylene was stored under a nitrogen describe a total lack of dispersion, ie all the oil was
atmosphere. returned to the surface a few seconds after the end of
the stirring, leaving the aqueous phase nearly trans-
Esterification of product I parent. The letters B±D represent intermediate situa-
From product I 0.1 mol was reacted with 0.22 mol tions.
polyethylene glycol (600, 1000 and 2000) respectively
in the presence of 1% p-toluene sulfonic acid as The surface tension and O/W interfacial tension
catalyst. The re¯ux of the reaction mixture was measurements
continued until the theoretical amount of water was In order to correlate the dispersion effectiveness of the
collected azeotropically by a Dean and Stark trap. At individual and mixed surfactants with basic physico-
the end of the reaction the solvent was distilled off chemical properties of the O/W interface, the inter-
under reduced pressure. The reaction product was facial tension (y in mN mÿ1) was determined using a
dissolved in propan-2-ol and then extracted with 5% spinning drop tensiometer.14 All tests were performed
sodium carbonate solution. Propan-2-ol was distilled using asphaltenic crude oil (Ras Budran Gulf Suez)
off and the polyoxyethylenated-polyisobutylene succi- and waxy crude (Um Baraka, E Western Desert). The
nate esters (non-ionic surfactants) were isolated after general speci®cations of the crude oils are shown in
repeating the puri®cation process. Table 1.

Amidation and esterification of product I


Product I (0.1 mol) was reacted with 0.1 mol PMHA RESULTS AND DISCUSSION
and 0.1 mol polyethylene glycol (600 or 2000). The Structure and surface properties of dispersant
amidation and esteri®cation were carried out at 110± The reaction of PIB-1000 with MA was completed
140 °C in the presence of 1% p-toluene sulfonic acid in and characterized by FT±IR analysis. The spectrum of
xylene, with continuous stirring under a nitrogen the product is presented in Fig 2(a). The spectrum
atmosphere. The reaction was complete when the shows two characteristic peaks of anhydride groups at
theoretical amount of water was collected. The 1865 cmÿ1 and 1780 cmÿ1. The disappearance of the
prepared compound-surfactants were puri®ed as peak at 1680 cmÿ1, which represents C=C stretching,
described previously. The scheme of the synthesis is indicates the formation of the structure of product I as
shown in Fig 1. The structures are con®rmed by 1H shown in Fig 1. In view of this structure PEG, having
NMR and FT±IR spectral analysis. different relative molar mass (PEG 600, 1000 and
2000), can be esteri®ed on the anhydride groups. The
Effectiveness measurements structures of the compounds produced are identi®ed
Labo®na inverting ¯ask method by FT±IR analysis. The spectra of these compounds
The labo®na method has been adopted by the UK are the same and the spectrum of product I with two
government for approval test purposes and a detailed moieties of PEG 600 (n = 13) is selected to illustrate
description of it is contained in the Warren Spring the structures of esteri®ed products. The spectrum of
Laboratory (WSL) speci®cation.12 Dispersant is this compound is shown in Fig 2(b). The appearance
added to 5 cm3 of oil placed on 250 cm3 of water of the broad band at 3450 cmÿ1 (representing the OH
contained in a speci®ed shaped ¯ask. It is rotated at stretching vibration band) and the strong band at
34 rpm for 2 min, followed by a static period of 1 min. 1745 cmÿ1 (for C=O stretching vibration of ester
A 50 cm3 sample is withdrawn. The oil is solvent- groups) indicates the formation of esteri®ed products
extracted and the quantity present in the sample is for compound I. Basically, the characteristic features
determined colorimetrically. are observed in FT±IR spectra recorded for amidation
of monoesteri®ed products of I with PEG. The IR
b-The screen test procedure spectrum for amidation of compound I with PEG
A quick comparative test method using small vials 2000 monoester, and with PMHA was selected and is
(25 cm3) was developed from the beaker test,13 and shown in Fig 2(c). The appearance of the new band at
was used for visual determination of the effectiveness 1670 cmÿ1 for O=CNHÐ stretching con®rms the
of the dispersant. The crude oil sample (100 mm3) was amidation of unreacted carboxylic groups in PIB-
carefully added to the surface of seawater (20 cm3) and SA45.
a 1 cm deep vortex was created by slow magnetic A further con®rmation of the complete esteri®cation
stirring. The dispersant mixture (5.0 mm3) was added and amidation of product I with PMHA and PEG is
to the centre of the vortex and the stirring rate was given by 1H NMR. The spectra of the esteri®ed

1076 J Chem Technol Biotechnol 74:1075±1081 (1999)


Water-based oil-spill dispersants

Figure 1. Scheme of modification of


PIB-SA.

product of I with PEG 600 and amide derivatives of product I. The appearance of new peaks at 5 ppm,
PIB-SA45 are presented in Fig 3 (a and b respec- 2.9 ppm and 2.1 ppm in Fig 3(b), which represent
tively). The disappearance of this peak above 10 ppm, amide ÐNH proton, CH2 proton in PMHA and NH2
which relates to hydrogen proton for ÐCOOH in the amine protons respectively, indicates the amidation of
MA group, in the spectra of two compounds indicates I with PMHA. Moreover, the presence of the strong
the complete esteri®cation and amidation of product I. band at 3.5 ppm in both spectra, which represents
The observed peaks at 0.98 ppm and 1.4 ppm, repre- CH2 proton in PEG, indicates the formation of
senting methyl protons and methylene protons in PIB esteri®ed products of I with PEG.15
respectively, can be used to illustrate the structure of The hydrophile±lipophile balance (HLB), surface

Ras Budran
asphaltenic Umbaraka
Speci®cation Method crude waxy crude

Speci®c gravity, 60/60 IP 160/87 0.8730 0.8266


Kinematic viscosity 40 °C (mm2 Sÿ1) IP 71/80 9.69 3.96
Total sulfur content (wt%) ASTM S1266/87 1.67 0.10
Asphaltene (wt%) IP 143/84 9.56 0.81
Wax (wt%) MOP 46/64 1.3 20.50
Table 1. Characteristics of investigated crudes

J Chem Technol Biotechnol 74:1075±1081 (1999) 1077


AM Al-Sabagh, AM Atta

Figure 3. 1H NMR spectra of (a) PIB-SA (eo 13) and (b) amide derivatives
of PIB-SA (eo 45).

to an increase in the solubility of surfactants as n is


increased and (n) amine is introduced.16
Figure 2. IR spectra of (a) PIB-SA (I), (b) PIB-SA (eo 13) and (c) amide
derivatives of PIB-SA (eo 45). Dispersion capability of non-ionic polymeric
surfactants alone
In order to evaluate the dispersion capability of indi-
tension at critical micelle concentration (gCMC), CMC vidual non-ionic surfactants (D1±D5) they were tested
and designation for the prepared surfactants were on asphaltenic and waxy crude oils. The surfactants to
measured and are listed in Table 2. It can be observed oil ratio (SOR) ranged from 1:10 to 1:100. Figures 4
that the CMC value decreases with an increasing and 5 show the results of WSL measurements. Figure
number of ethylene oxide units (n). On the other hand 4 illustrates the relationships between dispersed oil
the CMC value increases when PHMA (D2 and D4) ratios (DOR) for asphaltenic crude and interfacial
replaces the PEG chain (D1 and D5). This may be due tension. The data show that D5 has the maximum

Surface tension gCMC, CMC  104


Surfactants Designation HLB mN mÿ1 (25 °C) (mol dmÿ3) (25 °C)

PIB-SA (eo 13)2 D1 10.4 36.2 2.24


PIB-SA (eo 13) PMHA D2 9.23 37.5 4.47
PIB-SA (eo 22)2 D3 12.9 34.7 1.78
PIB-SA (eo 22) PMHA D4 16.2 31.2 1.26
Table 2. Designation and some surface
PIB-SA (eo 45)2 D5 17.58 30.5 0.79
properties for the prepared surfactants

1078 J Chem Technol Biotechnol 74:1075±1081 (1999)


Water-based oil-spill dispersants

Figure 4. The relationships between


dispersed oil ratio for asphaltenic crude and
interfacial tension for D1 to D5.

ef®ciency (70%) at DOR from 1:20 to 1:10 whilst D1 and D4 were 32%, and 63%, respectively at 1:40
exhibits the minimum ef®ciency (50%) at DOR 1:40. DOR.
The dispersion ef®ciencies for D2, D3 and D4 are 58%, The dispersion ef®ciency of D1 to D5 on the waxy
49% and 64% at DOR 1:20, 1:40 and 1:40, re- crude oil is illustrated in Fig 5. The values of WSL
spectively. From the data presented in Fig 4 D1 and D5 percentages at DOR 1:40 are 70%, 63%, 45%, 80%
were selected to investigate the role of interfacial and 90% for D1 to D5, respectively. This observation
tension in its dispersion capability. The interfacial indicates a good dispersion effectiveness of D1 to D5
tension data are plotted for D5 and D1, as shown in Fig on waxy crude. The wide difference in the dispersion
4, against DOR. It was observed that the dispersability capability of D1 to D5 for waxy and asphaltenic crude
for D5 and D1 increases with decreasing interfacial may be due to the large differences in chemical
tension. The effect of polyethylene oxide units (n) on composition between the two crude oils.17 This means
the dispersability of D1, D3 and D5 is observed in Fig that the ethoxylated and aminated PIB are more
4. In this respect, increasing (n) increases dispers- compatible with waxy than asphaltenic crudes.
ability. Moreover, the effect of PMHA on the dis-
persability of D2 is noticed from the increase in WSL Dispersion capability of a blend of two non-ionic
percentage from 54% for D1 to 57% at 1:20 DOR. On surfactants
the other hand, the increasing of (n) in the presence of Hydrophile±lipophile balance, HLB, and the chemical
PMHA increases the dispersion capability of D2 and structure of the surfactants exert a large in¯uence on
D4, as shown in Fig 4. The WSL percentages for D2 the rate of coalescence of emulsions containing blends

Figure 5. The dispersion efficiency (WSL)


for D1 to D5 on the waxy crude oil.

J Chem Technol Biotechnol 74:1075±1081 (1999) 1079


AM Al-Sabagh, AM Atta

Figure 6. The dispersion efficiency (WSL)


for D5 with sorbitan mono-, di- and tri-oleate
blends against HLB on asphaltenic crude
oil at DOR 1:30.

of non-ionic surfactants. The best stability is obtained hydrocarbon chains is increased by their proximity.18
by mixing surfactants which vary in HLB values.18±20 The most effective non-ionic surfactant blends, as
In order to estimate the validity of this observation shown in Fig 6, appear to be good with an HLB of
with asphaltenic crude oil dispersions D5 was selected 8±10, these having long hydrophobic chains and long
(HLB = 17.6) due to its good dispersability. The D5 is polyoxyethylene chains. So the maximum dispersion
blended in pairs with sorbitan mono, di- and trioleate power can be arranged in sequence D5 ‡ sorbitan
in proportions giving a resultant HLB range from 12 to trioleate > D5 ‡ sorbitan dioleate > D5 ‡ sorbitan
16. The blends were tested by WSL at ®xed DOR 1:30 monooleate. Under these conditions the interfacial
and the results are shown in Fig 6. tension is generally quite low and the surface viscosity
A real improvement in the percentage of dispersed is high since these long chains add rigidity to the
oil is observed for the blends when compared with the interface, making it more gel-like.18
individual D5 performances. The maximum WSL The screen test, ST, was used as a technique in this
ef®ciency of D5 is 70%, as shown in Fig 4, where the investigation to support the data obtained from WSL.
values reached were from 90 to 100% for blends, as Figure 7 shows the effectiveness from ST against DOR
shown in Fig 6. The interactions between D5 and for D5 and their blends on asphaltenic crude. The data
sorbitan trioleate are favourable to the interface obtained from ST, as shown in Fig 7, agree with those
stabilization and give a quite good dispersion test, as exhibited by using WSL as is shown in Fig 6. In all
shown in Fig 6, since the repulsion between sorbitan cases of blends, interfacial tensions (g) were measured
rings is minimized and the attraction between the and are shown in Fig 8. The lowering of g and the

Figure 7. The dispersion efficiency (ST) for


D5 with sorbitan mono-, di- and tri-oleate
blends against HLB on asphaltenic crude
oil.

1080 J Chem Technol Biotechnol 74:1075±1081 (1999)


Water-based oil-spill dispersants

Figure 8. The HLB scanning against


interfacial tension for D5 with sorbitan
mono-, di- and tri-oleate blends at DOR
1:30.

improved stability of O/W emulsions combining sur- 3 Mackoy D, Chau A, Hossain K and Bobra M, In Oil Spill
factants with high and low HLB have been explained Chemical Dispersants Research Experience and Recommendations,
STP 840, Ed by Allen TE, ASTM, Philadelphia. pp 38±54
on the basis of some speci®c molecular association of
(1984).
surfactants at the interfaces.18,21 The minimum 4 Preston WC, J Phys Colloid Chem, 52:84 (1948).
interfacial tensions of blends against asphaltenic crude 5 Ginn ME and Haris JC, J Am Oil Chemists Soc, 38:605 (1961).
oil (Fig 8) are obtained at the HLB range from 8 to 10. 6 Shinoda K, J Phys. Chem, 58:1136 (1954).
This may give indirect evidence that the HLB and 7 Brochu C, Pelletier E, Caron G and Desnoyers JE, Dispersion of
interfacial tension are linked in the same way by their crude oil in sea water. The role of synthetic surfactants, Oil and
dispersion capability. Chemical Pollut, 3:2567±279 (1986/87).
8 Wells PGS, Abernethy and Mackay D, Acute toxicity of solvents
and surfactants of dispersants to two crustaceans, in 8th Annual
Arctic Marine Oil Spill Program Technical Seminar Ottawa,
CONCLUSIONS
Environment, Canada. pp 228±240 (1985).
The following conclusions are drawn from the present 9 Brit Pat 1 361 179 (1974).
investigation: 10 Belg Pat 886 656 (1975).
11 Fr Pat 2 479 251 (1980).
(1) Polyisobutylene succinic anhydride adduct, PIB-
12 Morris PR and Martinelli F, A speci®cation for oil spill
SA, can be converted to water-soluble polymeric dispersants, Warren Spring Laboratory Report, LR 448 (OP)
surfactants having different HLB by varying the (1983).
relative molar mass of the grafted PEG. 13 Canevari GP, Development of the next generation of chemical
(2) The dispersion ef®ciency of the prepared surfac- dispersants, in Proceed 1973 Conf Prevention Control Oil Spills,
tants on asphaltenic crudes increases with increas- API, Washington, DC. pp 231±240 (1973).
ing relative molar mass of the PEG used for 14 Quirion F and Desnoyers JE, Effects of alcohol and surfactants
on the lowering of the interfacial tension between water and
grafting.
benzene, a correlation with phase diagrams. AOSTRA J Res
(3) The ethoxylated aminated PIB-SA gives good 1:121±126 (1984).
dispersion capability with waxy crude oil. 15 Johansson M, Trollsas M and Hult A, J Polym Sci Part A: Polym
(4) The blending of sorbitan trioleate with the pre- Chem, 30:2203 (1992).
pared surfactants increases dispersion ef®ciency to 16 Youssed AM, Gendy JS, Mohamad AI and Barakat Y, British
about 100%. Polymer Journal 22:339±346 (1990).
17 Ismail M, El-Gamal and Al-Sabagh AM, Fuel 75(6):743±750
(1996).
18 Boyd J, Parkinson C and Sherman PJ, Colloid Interface Sci
REFERENCES 41:359±370 (1972).
1 Canevari GP, The effect of crude oil composition on dispersant 19 Al-Sabagh AM, Nael Z and Abdel-Fattah MB, J Chem Technol
performance. in Proceed 1985 Oil Spill Conf, API, Washington, Biotechnol 69:350±356 (1997).
DC. pp 441±444 (1985). 20 Nael Z and Al-Sabagh AM, Tenside Surf Det 34:1 (1997).
2 Lewis A, Byford DC and Laskey PR, Proc (1985) Oil Spill Conf, 21 Takamura A, Minowa T, Novo and Kubo T, Chem Pharm Bull
API, Washington, DC. pp 433±440 (1985). 27:2921±2926 (1979).

J Chem Technol Biotechnol 74:1075±1081 (1999) 1081

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