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Hydrophobic Aerogels for

Oil-Spill Cleanup? Intrinsic
Absorbing Properties
John G. Reynolds, Paul R. Coronado, Lawrence W.
Hrubesh
Published online: 29 Oct 2010.

To cite this article: John G. Reynolds, Paul R. Coronado, Lawrence W. Hrubesh (2001)
Hydrophobic Aerogels for Oil-Spill Cleanup? Intrinsic Absorbing Properties, Energy
Sources, 23:9, 831-843, DOI: 10.1080/009083101316931906

To link to this article: http://dx.doi.org/10.1080/009083101316931906

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 Energy Sources, 23:831 ± 843, 2001
Copyright © 2001 Taylor & Francis
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Hydrophobic Aerogels for Oil-Spill CleanupÐ

Intrinsic Absorbing Properties
JOHN G. REYNOLDS
PAUL R. CORONADO
LAWRENCE W. HRUBESH
University of California
Lawrence Livermore National Laboratory,
Livermore, California
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A hydrophobic , CF3 -functionalized silica aerogel has been applied to water-oil mix-
tures to determine oil absorbing capacity of the solid aerogel. Preliminary tests on
Prudhoe Bay crude oil mixed with salt water, using the aerogel in powder form, show
three regimes for absorbing based on oil to aerogel wt ratios (O/A):1) all oil is
absorbed and the aerogel is dry, O/A 0± 3.5; 2) all oil is involved in an oil± aerogel±
water emulsion, O/A 4.6± 14; and 3) some oil is involved in an oil± aerogel± water
emulsion, but free-phase oil is seen, O/A . 16. For comparison, a silica aerogel that
has not been functionalized shows maximum absorbing capacity without the appear-
ance of free-phase oil at O/A , 0.1. Separation and extraction studies showed good
aerogel recovery and moderate oil recovery. Extraction studies at O/A of 2.3 showed
that the aerogel could be reused at least two times. Infrared studies show that the oil
recovered from the absorbing material and the starting oil are structurally similar.
These results indicate that the CF3 -functionalized aerogel as a powder has the
potential of cleanly separating oil from oil± water mixtures up to 14 times the weight
of the aerogel.
Keywords oil spill, aerogels, absorbing materials, hydrophobic aerogels, oil-spill
remediation

Introduction
Utilization of petroleum for transportatio n fuels has brought about the necessity for
control of accidental and purposeful releases during transportatio n and storage.
Notable releases in recent years have been the Persian Gulf war, where 2.5± 4 million
barrels were purposely dumped into the Gulf of Suez; the EXXON Valdez, where
260,000 bbls were lost in the Gulf of Alaska; and the Monongahel a River, where
24,000 bbls were lost due to a ruptured storage tank. The environmental signi® cance
of these and other releases dictates the need for the developing wide variety of
methods of remediation, particularly when climatic and location conditions preclude
some types of treatment (Air and Waste Management Association, 2000).

Received 23 September 2000; accepted 25 October 2000

This work was performed under the auspices of the US Department of Energy by the
Lawrence Livermore National Laboratory under contract number W-7405-ENG-48.
Address correspondence to John G. Reynolds, University of California, Lawrence
Livermore National Laboratory, Livermore, CA 94551. E-mail: reynolds3@ llnl.gov

831
 832 J. G. Reynolds et al.

Several types of methods for remediation are commonly employed, including

materials that disperse, materials that absorb, booms, and skimmers (Kemnetz and
Cody, 1998; Air and Waste Management Association, 2000). All have positive and
negative characteristics, depending upon the conditions of the spill. Materials that
disperse oil accelerate the natural breakdown by using surfactants and soaps to thin
the oil. Materials that absorb collect the oil and separate it from the water. Booms
and skimmers physically corral the oil for collection.
Materials that absorb oil are attractive for some applications because of the poss-
ibility of collecting and completely removing the oil from the spill site. The material, in
some cases, can be recycled. Some properties that are necessary for good absorbing
materials are: high uptake capacity, high rate of uptake, and hydrophobicity. Several
absorbing materials have been developed that exhibit these properties, such as inor-
ganic powders of clays, lime, and silica (Kemnetz and Cody, 1996; Houston, 1968),
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hydrocarbon and plastic polymers (Faudree, 1980; Falk and Mueller, 1981; Robeson
et al., 1992; Yoshiyuki et al., 1994), cellulose based materials (Patterson, 1999;
Corporate Author, 1983; Starr, 1991; Blaney and Griesbach, 1998), and elastomers
(Gabrick, 1989; Gabrick, 1992; Hepworth et al., 1992). These materials all show
porosity and the ability to absorb oil in the presence of salt water.
Materials that have many of these attractive properties for absorbing are
aerogels. Aerogels are solid metal-oxides with open foam-type structures allowing
for penetration of various sizes of compounds into the solid. They are synthesized
utilizing sol-gel techniques followed by drying techniques, which impart a very high
surface area (up to 1000 m2 /g and greater) and porosity to the material (Hrubesh et
al., 1999). Modi® cation by incorporation of chemical functionality can yield
materials with speci® c chemical properties, such as hydrophobicity (Lu et al.,
1996; Saski et al., 2000; Patterson, 1999; Falk and Mueller, 1981; Hrubesh et al.,
1999; Lee et al., 1995; Yokogawa and Yokoyama, 1995). The per¯ uoro functional
group exhibits excellent properties in this regard (Falk and Mueller, 1981) and has
been incorporated into silica aerogels (Coronado et al., 2001), providing a durable
hydrophobic material usable for separation of organic materials from mixtures of
organics and water. Here we present the screening results of using a per¯ uorinated-
silica aerogel as a powder to absorb oil from oil± saltwater mixtures which simulate
oil-spill conditions.

Experimental

Chemicals
The sources of the chemicals were the following: tetramethylorthosilicate and 13X
molecular sieves (Aldrich Chemical Co., Milwaukee, WI), NH4 OH (EM Science,
Gibbstown, NJ), anhydrous reagent grade CH3 OH (VWR, San Francisco, CA),
and (3,3,3-tri¯ uoropropyl)-trimethoxysilan e (United Chemical Technologies,
Bristol, PA). The CH3 OH was dried over activated molecular sieves before use.

Sol± Gel Synthesis

The synthesis and characterization of the aerogel has been described in detail else-
where (Coronado et al., 2001). The formulation used for this study was as follows:
10.4 g NH4 OH, 44 g DI H2 O, and 90 g CH3 OH were mixed together and left stirring
 Intrinsic Absorbing Properties 833

until cooled to room temperature. In a separate vessel, 75.0 g tetramethylorthosili -

cate were mixed with 37.5 g (3,3,3-tri¯ uoropropyl)-trimethoxysilan e and let stir at
room temperature for 5 min. To this solution, 90 g CH3 OH were added. After the
solution became homogeneously mixed, the NH4 OH solution above was added and
mixed. The solution gelled within 20 min.

Aerogel Formation
The gel produced above was placed in a supercritical exchange reactor system to
form the aerogel by supercritical extraction with CH3 OH at 2000 psig, 295± 300¯ C for
4 h, followed by depressurization at 50 psig/min.
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Crude Oils
Two crude oils were used, a 26.2¯ API gravity Prudhoe Bay and a 14.4¯ API gravity
re® nery mixture from Phillips Petroleum Co. Both crude oils had been desalted prior
to receipt and were used as received.

Oil Absorbing Experiments

Forty grams of 3 wt % NaCl in DI H2 O and varying amounts of crude oil were put
in 200 mL wide mouth bottles. Approximatel y 0.36 g of aerogel were placed in each of
these bottles. Each bottle was sealed with a screw-top cap lined with Te¯ on, and each
was then shaken for 5 min and left to settle. The next day, each bottle was again shaken
for 5 min. The bottles were then left to settle for 30 min or more before separation.

Oil Distribution and Recovery

When settled, the oil± water mixtures were separated. The method depended upon
visible assessment of the mixture. In cases where the aerogel absorbed all the oil, the
aerogel was separated from the water by ® ltration through Watman No. 5 ® lter
paper. The solid was rinsed several times DI H2 O to remove any residual NaCl.
The solid was then left to dry either in air or under vacuum. The dried aerogel was
then soxhlet extracted with a 92 vol % CH2 Cl2 /8 vol % CH3 OH solvent mixture
until the extraction solvent was colorless (approximately 24 h). The solid was then
dried in vacuum and the extracted oil solution was dried under blowing N 2 .
Recoveries were determined by weighing the isolated residual materials.
In cases where an emulsion was formed, the mixture was poured into a tube and
centrifuged for 1 h at 5000 rpm. Free-phase oil (if any) was decanted oŒthe top, and
the emulsion was displaced to allow the water to be poured oŒ. The emulsion was
then broken by adding several mL of CH2 Cl2 . To this mixture, DI H2 O was added
and the tube was shaken. The mixture was centrifuged for 1 h and the H2 O layer was
decanted. This was repeated 2 times to remove any residual NaCl. The solvent layer
was then ® ltered to recover the aerogel through Watman No. 5 ® lter paper. The solid
was left to dry in the air and then extracted as described above. Solvent of the
solution from the ® ltration was removed by blowing N2 .
 834 J. G. Reynolds et al.

Spectroscopy
The infrared spectra were taken on a Nicolet Impact 400d Infrared Spectrometer.
The samples were prepared as either KBr pellets or evaporated CH2 Cl2 solutions on
NaCl disks.

Results
Table 1 shows the weights of starting materials and product fractions for experi-
ments using the CF3 -functionalized aerogel to absorb Prudhoe Bay crude oil from a

Table 1
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Weights (g) of oil and aerogel in experiments using CF3 -functionalized aerogel to
absorb oil from mixtures of crude oil and salt water (starting quantities are 0.36 g
aerogel powder, 40 g H2 O containing 3 wt % NaCl)

Spent Extracted Extracted Emulsion Free-phase O/A

Exp. Oil Aerogel a Aerogel b Oilc Oild Oile Ratio
1f 0.21 0.50 0.30 0.16 ± ± 0.55
2f 0.22 0.52 0.34 0.29 ± ± 0.60
3f 0.41 0.66 0.31 0.31 ± ± 1.2
4f 0.41 0.67 0.34 0.18 ± ± 1.2
5f 0.81 1.1 0.34 0.72 ± ± 2.3
6f 0.82 1.0 0.34 0.69 ± ± 2.3
9f 1.3 1.3 0.35 1.0 3.5
10f 1.6 0.40 0.28 0.12 1.3 ± 4.6
11f 2.0 0.60 0.34 0.35 0.9 0.27 5.6
13f 3.1 0.85 0.34 0.52 1.6 0.31 8.5
15f 3.2 0.35 0.31 0.05 2.4 nag 9.1
16f 5.0 0.68 0.33 0.32 4.3 0.07 14.0
17f 5.7 0.47 0.32 0.15 2.8 1.5 16.0
18f 6.4 0.67 0.33 0.28 2.4 3.4 18.0
19f 10.0 0.27 0.15 0.14 2.6 5.8 28.0
7f,h 0.80 1.0 0.34 0.66 ± ± 2.4
8f,i 0.80 0.96 0.33 0.56 ± ± 2.4
12f,j 2.0 2.1 0.34 1.7 ± ± 5.7
14k 3.3 0.67 0.36 0.30 1.4 0.30 9.0
a
Wt. of aerogel after isolation from mixture, before soxhlet extraction.
b
Wt. of aerogel after soxhlet extraction with CH2 Cl2 /CH3 OH solvent mixture.
c
Oil recovered from extraction in note b.
d
Amount of oil recovered from breakdown of emulsion.
e
Amount of oil not absorbed by aerogel or aerogel± oil± water emulsion.
f
Prudhoe Bay crude oil.
g
Oil lost in work-up.
h
Reuse of extracted aerogel from Experiment 5 (0.34 g aerogel).
i
Reuse of extracted aerogel from Experiment 7 (0.34 g aerogel).
j
Aerogel large chunks, not powder.
k
Phillips crude oil substituted for Prudhoe Bay crude oil.
 Intrinsic Absorbing Properties 835

3 wt % salt solution. The salt solution was used to mimic ocean water. Experiments
are numbered by increasing starting oil wt to aerogel wt ratios, O/A.
The experiments were performed as a screening study to establish the ability of
the aerogel to absorb oil and were not meant for accurate mass balances and process
stream evaluation. The small quantities used prevented accurate mass balances, so
mass losses in Table 1 vary greatly. However, a full listing of the mass balances are
shown and discussed in the Appendix.

Oil Absorbing Behavior

Based on the behavior of the oil± aerogel± water mixtures, the data is divided into
roughly three regimes. These regimes were determined by visual inspection of the
mixture and containers, noting the appearance of an emulsion or an emulsion and
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free-phase oil. The division between regimes has not been examined in detail, so the
O/A value ranges are only approximate.

Regime 1. In this regime, all the oil is absorbed into the aerogel, and there are no
visible signs of oil on the container or the surface of the water. The aerogel is dry to
the touch and is separated from the water by simple ® ltration. Experiments 1± 6 and 9
in Table 1 fall into this category. The O/A goes from 0 to 3.5.

Regime 2. In this regime, all the oil and aerogel form an emulsion with some of the
water. There are no visible signs of free-phase oil on the sides of the container or on the
water surface. The emulsion can be isolated simply by scooping it out of the container.
Experiments 10, 11, 13, 15, and 16 in Table 1 fall into this regime. This regime goes
between O/A of 4.6 to 14.0. As in Regime 1, exact O/A values where the regime
changes were not determined, so the transition from Regime 1 to Regime 2 is some-
where between O/A of 3.5 and 4.6. Table 1 does show that a little free-phase oil is
observed for many of these samples in this regime. This material is a very small
amount, appears to be around 0.3 g for most of the samples, and is not proportional
to the amount of starting oil. We believe this to be either a small amount that becomes
entrained as the emulsion is formed or a small amount of the emulsion that is broken
down during the centrifuge step used for work-up. Experiment 10 was separated in a
diŒerent way, without the centrifuge step, and did not show free-phase oil.

Regime 3. In this regime, free-phase oil is observed on the edges of the container as
well as on the surface of the water. This is seen for experiments having O/A of 16 and
greater. As above, the exact transition from Regime 2 to Regime 3 has not been
determined and is somewhere between O/A of 14 and 16. Experiments 17± 19 fall
into this regime.
For comparison, to demonstrate the oil a nity of the CF3 -functionalized
aerogel, a normal silica aerogel was prepared (Hair et al., 2000) without the CF3 -
functionality and tested in the same manner, above. Only 0.06 g of oil were recov-
ered, giving an O/A of , 0.1 for saturation.

Oil Distribution
Table 2 summarizes the distribution for the oil recovered from experiments using
Prudhoe Bay crude oil. These values have been normalized to 100% to account for
 836 J. G. Reynolds et al.

Table 2
Distribution of oil (% , normalized) in experiments using CF3 -functionalized aerogel
to absorb oil from mixtures of Prudhoe Bay crude oil and salt water (starting
quantities are 0.36 g aerogel powder, 40 g H2 O containing 3 wt % NaCl)

Oil from Oil from Free-phase O/A

Exp. Aerogel Emulsion Oil Ratio
1a 100 ± ± 0.55
2a 100 ± ± 0.60
3a 100 ± ± 1.2
4a 100 ± ± 1.2
5a 100 ± ± 2.3
6a 100 ± ± 2.3
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9a 100 ± ± 3.5
10b 8 91 ± 4.6
11b 10 82 8 5.6
13b 21 66 13 8.5
15b 2 98 ± 9.0
16b 7 91 2 14.0
17b 4 63 34 16.0
18b 5 40 55 18.0
19b 2 30 68 28.0
a
Oil in aerogel isolated by soxhlet extraction with 92% CH2 Cl2 /8% CH3 OH.
b
Oil in aerogel isolated by ® rst rinsing with CH2 Cl 2 , followed by soxhlet extraction as in
footnote a.

the loss of volatile oil components in the isolation of the fractions (see Appendix for
evaluation). For Experiments 1± 6 and 9, 100% of the oil was absorbed by the CF3 -
functionalized aerogel and was recovered through soxhlet extraction of the dried
aerogel solid. These samples spanned the O/A range of 0.55 through 3.5 (Regime 1).
Experiments 10, 11, 13, 15, and 16 show that oil is recovered from soxhlet extraction of
the aerogel, from break-up of the emulsion, and as free-phase oil. These samples
spanned O/A 4.6 through 14.0 (Regime 2). The majority of the oil is recovered
from the emulsion with little extracted from the aerogel. As noted, part of this is
due to the preliminary rinse of the aerogel with CH2 Cl2 in cases where emulsions
were formed. The little amounts isolated as free-phase oil are thought to be artifacts
of the isolation procedure using the centrifuge. Experiments 17± 19 show the majority
of the oil was isolated as free-phase oil. These samples spanned the O/A 16 through 28
(Regime 3).

Aerogel Behavior
Table 3 shows analysis of the residual CF3 -functionalized aerogels from the oil-
absorbing experiments. For Experiments 1± 9, the theoretical values (from starting
materials) match the measured values (from recoveries) fairly well. In some cases, the
measured oil also matches the theoretical oil value. These experiments are for O/A
values that fall in Regime 1, where no emulsion or free-phase oil is observed.
Experiments 10, 11, and 13± 19 show a diŒerent behavior, where the theoretical
 Intrinsic Absorbing Properties 837

Table 3
Aerogel± oil behavior (% distribution) in experiments using CF3 -functionalized
aerogel to absorb oil from mixtures of Prudhoe Bay crude oil and salt water (starting
quantities are 0.36 g aerogel powder, 40 g H2 O containing 3 wt % NaCl)

Theoretical Theoretical Measured Measured O/A

Exp. Aerogel a Oila Aerogel b Oilb ()c Ratio
1d,g 65 35 60 40 (31) 0.55
2d,g 62 37 65 35 (84) 0.60
3d,g 47 53 47 53 (47) 1.2
4d,g 46 54 51 49 (04) 1.2
5d,g 31 69 32 68 (69) 2.3
6d,g 30 70 33 67 (67) 2.3
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7d,e,g 30 70 34 66 (65) 2.4

8d,f,g 30 70 35 65 (62) 2.4
9d,g 22 78 25 75 (62) 3.5
10d,h 18 82 70 30 (30) 4.6
11d,h 15 85 57 43 (57) 5.6
12d,g,i 15 85 16 84 (81) 5.7
13d,h 11 89 40 60 (61) 8.5
14j,h 10 90 53 47 (44) 9.0
15d,h 10 90 86 14 (01) 9.0
16d,h 7 93 48 52 (48) 14.0
17d,h 6 94 67 33 (32) 16.0
18d,h 5 95 49 51 (42) 18.0
19d,h 3 97 55 45 (50) 28.0
a
Based on starting weights of oil and aerogel.
b
Based on weights of extracted aerogel/aerogel isolated after absorbing oil.
c
Based on weight of isolated extracted oil.
d
Prudhoe Bay crude oil.
e
Reuse of extracted aerogel from Experiment 5.
f
Reuse of extracted aerogel from Experiment 7.
g
Aerogel soxhlet extracted with 92% CH2 Cl2 /8% CH3 OH.
h
Aerogel washed with CH2 Cl 2 ® rst, then extracted as in footnote f.
i
Aerogel in chunks, not powder.
j
Phillips crude oil substituted for Prudhoe Bay crude oil.

values do not match the measured values in most cases. This results from the aerogel
not absorbing all the oil and from some oil being partitioned in the emulsion
(Regimes 2 and 3) and some as free-phase oil (Regime 3). In addition, the work-
up procedure for these samples included a preliminary CH2 Cl2 washing step before
extraction. Experiment 12 was a special case (see below).

Aerogel Reuse
As a screening eŒort to determine whether the CF3 -functionalized aerogel can
be reused after absorbing oil, the spent, extracted aerogel from Experiment
 838 J. G. Reynolds et al.

5 was reused for Experiment 7 and the spent, extracted aerogel from Experiment 7
was reused for Experiment 8. In both reuse cases, 100% of the oil was absorbed by
the aerogel and no oil was seen on the side of the containers or on the surface of the
water. Both Tables 1 and 3 show the behavior of the aerogels in all three experiments
to be the same.

Limiting Oil Uptake of the Aerogel

In Tables 1 and 3, Experiment 12 is from an experiment where the CF3 -functionalized
aerogel was not ground into a powder, but was used in the form of several large
chunks. Experiment 11 is of the same conditions except that the aerogel is ground.
The O/A of both experiments are very close. In the case where the aerogel was used as
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chunks, no free-phase oil or emulsion was observed, as in Regime 1. In the experiment

where the aerogel was powder, the product is an emulsion, as in Regime 2. Table 3
shows the behavior of the aerogel in both cases also. For Experiment 12, the measured
values of aerogel and oil distribution match the theoretical values, exhibiting Regime 1
behavior. For Experiment 11, the measured values of aerogel and oil distribution do
not match the theoretical values, exhibiting Regime 2 behavior.
The saturation level of the CF3 -functionalized aerogel was also determined by
adding the aerogel directly into Prudhoe Bay crude oil with no salt water present.
Solid mixtures with the oil were produced with 0.557 g of the aerogel indicating the
aerogel has 100% absorbing capabilities at an O/A of 3.6 in the absence of water. At
O/A levels higher than this, the mixture appeared thixotropic.

Aerogel with Other Oil

To determine whether the CF3 -functionalized aerogel performs with other crude oils,
a re® nery mixture crude from Phillips Petroleum Co. was also tested at O/A of 9.0.
The results are listed as Experiment 14 in Tables 1 and 3. The behavior falls into
Regime 2 and the product distributions are very similar to those of Prudhoe Bay
crude oil at O/A of 8.5.

Infrared Analysis
Prudhoe Bay crude oil and isolated oils from various fractions above were examined
by FTIR to determine if any structural changes occurred to the oil when using CF3 -
functionalized aerogel for absorbing oil. The same bands were seen in all the samples,
except the oil extract from Experiment 15, and are assigned as follows from literature
values (Rashid et al., 1989; Reynolds et al., 1997; Yang et al., 1988; Bunger et al., 1979;
Peterson et al., 1971): 2959, 2931, and 2853 cm¡ 1 (C-H stretching vibrations of ali-
phatic hydrocarbons) ; 1699 cm¡ 1 (CˆO); 1605 cm¡ 1 (aromatic or CˆC); 1460 cm¡ 1
(methyl and methylene bridge); 1382 cm¡ 1 (CH3 on aromatics); and 1034 cm ¡ 1 (aro-
matics). The sample from Experiment 12 did show evidence of a higher concentration
of carbonyl functionality. This material, along with the aerogel solids, are being ex-
amined in more detail and the results will be reported elsewhere.
 Intrinsic Absorbing Properties 839

Discussion

Oil Saturation of the Aerogel

Clearly, Table 1 shows that the CF3 -functionalized aerogel absorbs all the oil at least to
O/A of 3.5, leaving no oil on the water surface or on the side of the container± Regime 1

Table 4
Oil uptake of selected materials

Material Oil type Oil uptakea Form ref.

c
Bregoil (waste-wood ® bers) crude 7X sponge
d
Urethane-isocyanate-alcohol motor 34.4 X granular
polymer
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e
Acrylate-nitrile-alcohol crude 12 X device
polymer
e
Polypropylene crude 7X device
f
Exfoliated graphite crude 80 X device
g
Berthinate (hydrophobic crude 6X granular
treated peat)
Gum rubber 1 polyole® n crude 4X powder h,i

Clay ‡ NR4 ‡ ATFb 6X powder j,k

j,k
Clay ‡ NR4 ‡ mineral 0.4 X powder
l
Cellulose crude 18 to 22 X device
m
Polyvinyl alcohol/ motor 2X powder
polypropylene
n
Cellulose acetate crude 9X device
o
CH3 SiCl3 treated gear 0.5 X powder
¯ y ash
o
Hydrous calcium silicate gear 4.9 X powder
o
Hydrous calcium silicate crude 6.3 X powder
p
CF3 -functionalized silica crude 4 to 16 X powder
aerogel
Silica aerogel crude , 0.1 X powder p

a
Oil wt times absorbing material wt.
b
Automatic transmission ¯ uid.
c
Corporate Author 1983.
d
Faudree 1980.
e
Yoshiyuki et al. 1994.
f
Toyoda et al. 1998.
g
Fransham and Lynch 1991.
h
Gabrick 1989.
i
Gabrick 1992.
j
Kemnetz & Cody 1996.
k
Kemnetz & Cody 1998.
l
Blaney & Griesbach 1998.
m
Robeson et al. 1992.
n
Patterson 1999.
o
Houston 1968.
p
This report.
 840 J. G. Reynolds et al.

behavior. No eŒort was made to ® nd the exact O/A where the emulsion starts to form±
Regime 2 behavior. This seems to occur somewhere between O/A of 3.5 and 4.6.
However, this may be an artifact of the powdered nature of the aerogel used in
these experiments and may not re¯ ect the intrinsic absorbing capacity. Experiments
11 and 12 demonstrate this, both at O/A of 5.6, where the whole (not powdered)
aerogel completely absorbs oil, while the powdered aerogel forms an emulsion. This
emulsion may be a consequence of physical properties of the powder instead of the
intrinsic oil absorbing limit of the aerogel and suggests that utilization of the aerogel
solely as a powder is not optimal.
For Experiments 10, 11, 13, 15, and 16, which produced primarily emulsions,
the free-phase oil isolated is suspected to be an artifact of the isolation procedure,
where centrifuging forces oil out of the samples. The amounts isolated are very
small, around 10% of the starting amount of oil. In addition, for Experiment 10,
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the isolation procedure did not include centrifuging and no free-phase oil was
observed. In Experiments 17± 19, the free-phase oil was clearly isolated
and accounted for the majority of the oil. The O/A where this occurs is between 16
and 18.

Comparison with other Absorbing Materials

Several absorbing materials for oil spills have been developed and tested over the
years. Some are used directly as powders and some as coatings on devices that aid in
the absorption and separation of the oil. Table 4 shows some of these materials and
compares their uptake ability based only on the weight of the absorbing material.
Note that some of these absorbing materials are used on devices and some were not
tested on crude oils, but other types of oil.
From the table, the CF3 -functionalized aerogel performs relatively well com-
pared to some of the materials, particularly when considering some materials have
the advantag e of being designed into devices. As mentioned in the Results section,
the whole or chunk form of the CF3 -functionilized aerogel out performed the
powder for absorbing capacity. This observation, combined with the general success
that absorbing materials have when designed into a device suggests that the CF3 -
functionalized aerogel should have even better performance than shown in Table 4
when used as a coating on a device. We are in the process of demonstrating this, and
these results will be reported elsewhere.

Conclusions
A hydrophobic aerogel synthesized through the combination of tetramethylortho -
silicate and (3,3,3,tri¯ uoropropyl)-trimethoxysilan e was tested for oil absorb-
ing properties on oil± salt water mixtures. The CF3 -functionalized aerogel was
found to:
° completely absorb oil at O/A ratios up to 3.5, producing a dry solid when
separated from the water,
° form an emulsion at O/A ratios of 4.6 to 14, which was easily separated from
the water,
° absorb only part of the oil at O/A ratios 16 and greater, with free-phase oil
being observed,
 Intrinsic Absorbing Properties 841

° be extractable and reusable for at least 2 times additionally,

° absorb oil 40 to 140 times better than the nonfunctionalized silica aerogel,
° have a higher oil absorbing capacity when in a nonpowder form, and
° perform equally well with two diŒerent crude oils.

References
Air and Waste Management Association. 2000, Oil Spills.
http://www.awma.org/awma/educate/oilspills.htm
Blaney, C. A., and H. L. Griesbach, III. 1998. Oil-Sorbing Article and Methods for Making
and Using Same. U. S. Patent 5, 834, 385.
Bunger, J. W., K. P. Thomas, and S. M. Dorrence. 1979. Compound types and properties of
Utah and Athabasca tar sand bitumens. Fuel 58:183± 195.
Downloaded by [University of Louisville] at 12:39 20 September 2013

Coronado, P. A., L. W. Hrubesh, and J. G. Reynolds. 2000. Hydrophobic aerogels± Synthesis

and characterization of per¯ uorinated silica aerogels. J. Non-Crystal. Solids, submitted.
Corporate Author. 1983. Absorbent sponge material slurps up oil spills. Chem. Eng. 90(7):49.
Falk, R. A., and K. F. Mueller. 1981. Per¯ uoroalkylthioethyl Ether Derivatives. U. S. Patent,
4, 266, 080.
Faudree, III, T. L. 1980. Foamaceous Hydrocarbon Adsorption Medium and Method and
System for Making Same. U. S. Patent 4, 230, 566.
Fransham, P. B., and D. Lynch. 1991. Development of a Mobile Fluid-Bed Pyrolysis Unit for
Waste Disposal-Energy Recovery. Symp. Pap. Energy Biomass Wastes, Inst. Of Gas
Technology, Chicago, IL, pp. 895± 906.
Gabrick, A. 1989. Controlling and Recovering Oil Spills From the Environment. U. S. Patent
4, 941, 978.
Gabrick, A. 1992. Controlling and Recovering Oil Spills from the Environment. U. S. Patent
5, 104, 548.
Hair, L. M., P. R. Coronado, and J. G. Reynolds. 2000. Mixed-metal oxide aerogels for
oxidation of volatile organic compounds. J. Non-Crystal. Solids 270:115± 122.
Hepworth, M. T., W. Reindl, H. Han, and G. Fell. 1992. Rubber tires, A potentially eŒective
sorbent for oil spills. J. Resour. Manage. Technol. 20(2):88± 93.
Houston, B. J. 1968. Investigation of Materials and Methods for Use in Removing Surface
Layers of Oil on Water. Defense Technical Information Center report AEWES-MISC-
PAPER-C-68-5.
Hrubesh, L. W., J. F. Poco, and P. R. Coronado. 1999. Method for Producing Hydrophobic
Aerogels. U. S. Patent 6, 005, 012.
Kemnetz, S., and C. A. Cody. 1996. Oil Spill Flocculating Agent and Method of Remediating
Oil Spills. U. S. Patent 5, 558, 777.
Kemnetz, S., and C. A. Cody. 1998. Composition of Matter Useful as an Oil Spill Flocculating
Agent. U. S. Patent 5, 725, 805.
Lee, K. -H., S. -Y. Kim, and K. -P. Yoo. 1995. Low-density, hydrophobic aerogels. J. Non-
Cryst. Solids 186:18± 22.
Lu, Y. F., L. Han, C. J. Brinker, T. M. Niemczyk, and G. P. Lopez. 1996. Chemical Sensors
based on Hydrophobic Porous Sol-Gel Films and ATF-FTIR Spectroscopy. Sensor.
Actuat. B-Chem. 36(1± 3):517± 521.
Patterson, J. A. 1999. Oil Spill Recovery Articles and Method. U. S. Patent 5, 971, 659.
Peterson, J. C., R. V. Barbour, S. M. Dorrence, F. A. Barbour, and R. V. Helm. 1971.
Molecular interactions of asphalt. Tentative identi® cation of 2-quinolones in asphalt
and their interactions with carboxylic acids present. Anal. Chem. 43:1491± 1495.
Rashid, H. A., S. B. Dekran, N. A. Fakhri, H. J. Aziz, and N. A. Hamoudi. 1989.
Determination of several physical properties of light petroleum products using IR. Fuel
Sci. Tech. Int’l. 7(3):237± 250.
 842 J. G. Reynolds et al.

Reynolds, J. G., A. K. Burnham, and P. H. Wallman. 1997. Reactivity of paper residues

produced by a hydrothermal pretreatment process for municipal solid wastes. Energy &
Fuels 11(1):98± 106.
Robeson, L. M., R. J. Axelrod, and T. A. Manuel. 1992. Fibrous Material for Oil Spill Clean-
up. U. S. Patent 5, 120, 598.
Sasaki, D. Y., C. J. Brinker, C. S. Ashley, C. E. Daitch, K. J. Shea, and D. J. Rush. 2000.
Molecular Receptors in Metal Oxide Sol-Gel Materials Prepared via Molecular
Imprinting. U. S. Patent 6, 057, 377.
Starr, T. F. 1991. Oil Absorbent. U. S. Patent 5, 067, 984.
Toyoda, M., J. Aizawa, and M. Inagaki. 1998. Sorption and recovery of heavy oil by using
exfoliated graphite. Desalination 115(2):199± 201.
Yang, P. W., H. H. Mantsch, L. S. Kotlyar, and J. R. Woods. 1988. Characterization of
athabasca tar sand maltenes by diŒuse re¯ ectance infrared spectrometry. Energy & Fuels
2:26± 31.
Yokogawa, H., and M. Yokoyama. 1995. Hydrophobic silica aerogels. J. Non-Cryst. Solids
Downloaded by [University of Louisville] at 12:39 20 September 2013

186:23-29.
Yoshiyuki, H., I. Toru, G. Tomoki, G. Takakiyo, U. Toro, and R. Kenji. 1994. Oil-Absorbent
Polymer and Use Therefor. European Patent 0, 441, 512, B1.

Appendix
This study was for screening purpose only. Because of the very small quantities of
material and techniques utilized for isolation, the mass balances were not particu-
larly close to 100% . However, to obtain a qualitative understanding of potential
process streams, Table A shows the mass recovery for each of the experiments based
on the initial starting weights of oil and aerogel. The raw data is shown in Table 1.
Several sources for losses can be identi® ed. The aerogels have very low densities
(0.03 g/ ml) and are di cult to handle when dry because of static electricity.
However, Table A shows that aerogel recovery is relatively good. The recovery of
the oil was generally by dilution with CH2 Cl2 or extraction with CH2 Cl2 /CH 3 OH
mixtures followed by removal of the solvent with blowing N2 . This process will
remove volatile oil components. For example, Prudhoe Bay crude oil has about
20 vol % of the crude, which distills below 400¯ F. This crude when left under a
blowing N2 stream for 24 h looses 15 wt % and when mixed with 300 vol %
CH2 Cl2 and left under a blowing N2 stream for 48 h loses 18 wt % . These are the
type of losses generally seen in Table A.
 Intrinsic Absorbing Properties 843

Table A
Recovery of aerogel and oil

Oil/aerogel Aerogel ‡ oil Aerogel Oil

Experiment ratio a recovery b recovery c recoveryd
1e,f 0.55 85.4 79.3 75.7
2e,f 0.60 90.0 94.0 131.8
3e,f 1.2 85.4 86.4 75.5
4e,f 1.2 87.0 95.9 43.9
5e,f 2.3 94.6 93.9 88.8
6e,f 2.3 86.9 95.4 84.7
7e,f,g 2.4 88.4 100.4 82.4
8e,f,h 2.4 79.8 92.7 70.1
Downloaded by [University of Louisville] at 12:39 20 September 2013

9e,f 3.5 83.7 96.9 79.4

10e,i 4.6 nai 77.0 85.8
11e,i 5.6 nai 94.7 73.5
12e,f 5.7 87.3 94.5 83.4
13e,i 8.5 nai 95.2 79.1
14i,j 9.0 nai 99.4 62.3
15e,i 9.1 nai 85.1 75.1
16e,i 14. nai 92.2 95.4
17e,k 16. nai 88.5 78.0
18e,k 18. nak 91.6 95.4
19e,k 28. nak 41.8 85.6
a
Starting oil wt/starting aerogel wt.
b
Wt. of isolated aerogel with absorbed oil/(wt. of starting oil ‡ wt. of starting aerogel).
c
Wt. of extracted aerogel/wt of starting aerogel.
d
§ of wt. of oil recovered from aerogel extraction, emulsion break-up, and free-phase oil/wt.
of starting oil.
e
Prudhoe Bay crude oil.
f
Regime 1.
g
Extracted aerogel from Experiment 5 used.
h
Extracted aerogel from Experiment 7 used.
i
Regime 2.
j
Phillips crude oil.
k
Regime 3.