SPE 113313

Development of Surfactants for Chemical Flooding at Difficult Reservoir

Conditions
Julian R. Barnes, Johan P. Smit and Jasper R. Smit, Shell Global Solutions, Amsterdam, Netherlands;
P. Gregory Shpakoff and Kirk H. Raney*, Shell Global Solutions, Houston, Texas, USA;
Maura C. Puerto, Rice University, Houston, Texas, USA

*New address: Shell International Exploration and Production, Houston, Texas, USA

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 19–23 April 2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The production and properties of two families of anionic surfactants (internal olefin sulfonates and branched C16, 17 alcohol-
based alkoxy sulfonates) are described for chemical flooding of oil reservoirs at high temperatures and/or high salinities.
Surfactant properties measured include oil/water micro-emulsion phase behaviour obtained using new glassware-based
procedures appropriate for higher reservoir temperatures. The results obtained relate to oil/water interfacial tension behaviour
and give the “operating window” of the surfactants in terms of their optimal salinity and ability to solubilise oil in the micro-
emulsion. The phase tests also give information on the quality of the micro-emulsions obtained where low viscosity and
absence of gels is desirable. The surfactants described are promising for EOR and can be produced in commercial quantities.
Different IOS products are available with different carbon chain cuts (with range C15 to C28) allowing matching of the IOS to
the temperature, salinity and crude oil type of reservoirs. In addition, both IO carbon chain (degree of branching) and the
degree of sulfonation influence the surfactant properties of the IOS mixture formed which provides a means for tailoring an
IOS surfactant for optimal performance.

1. Introduction

In chemically enhanced oil recovery (EOR) the mobilisation of residual oil saturation is achieved through surfactants that
generate a sufficiently (ultra) low crude oil/water interfacial tension (IFT) to give a capillary number large enough to
overcome capillary forces and allow the oil to flow1. However, reservoirs have different characteristics (crude oil type,
temperature and water composition), and the structures of added surfactant(s) have to be tailored to these conditions to achieve
an ultra low IFT. In addition, a promising surfactant must satisfy other important criteria including low rock retention,
compatibility with the polymer to be used, compatibility with hard water (if present), thermal and hydrolytic stability,
acceptable cost/performance balance and commercial availability in sufficient quantities.
Because of the well-established relationship between the micro-emulsion phase behaviour and IFT2 it is common in the
industry to screen surfactants and their formulations for low IFT through laboratory-based oil / water phase behaviour tests3, 4.
This approach works well for tests carried out at room temperature and slightly higher, but at higher temperatures there may be
safety issues. Specifically, conventional sealed glass tube test methods may be problematic from a laboratory safety
standpoint at higher temperatures due to the vapour pressures from water and crude oil. This paper presents the results of the
evaluation of surfactants using improved phase behaviour experimental methods for higher temperatures (up to 150°C).
Optimal salinities and solubility parameters have been measured.
Two surfactant families have been evaluated, both produced by Shell Chemicals: Internal olefin sulfonates (IOS) which are
part of the ENORDET™ O series and proprietary, branched C16, 17 alcohol-based anionic surfactants which are part of the
ENORDET™ A series. Both families are suitable for EOR because they have a reduced tendency to form ordered
structures/liquid crystals that are undesirable in reservoirs4, IOS products because they are a complex mixture of surfactants of
differing chain lengths and the branched C16, 17 alcohol based surfactants because of their randomly branched structures.
2 SPE 113313

The two families of surfactants have promise in surfactant flooding at “difficult” higher temperature, high salinity reservoir
conditions and with different crude oils, but they can also be tailored to work under a range of conditions. The current industry
situation is discussed with respect to current surfactant availability, largely serving the non-EOR market, and the challenge for
large quantities of surfactants being available for EOR with the appropriate chemical structures.

2. High temperature phase behaviour test methods

The majority of glass tube methods used thus far in the industry for micro-emulsion phase behaviour tests have been relevant
to lower reservoir temperatures (i.e. ambient temperature to 60°C). For higher temperatures (e.g. up to 150°C) the vapour
pressures in a sealed glass tube from water and oil components mean that a specifically designed system is required to prevent
possible rupture and/or explosion.

The following three glassware methods have been developed for phase behaviour tests at high temperatures. More complete
details of the apparatus and test methods are given in a related poster, to be presented at the Tulsa Improved Oil Recovery
Symposium in April 20085. Photos illustrating the three high temperature phase behaviour methods used for an aqueous
saline solution of IOS 2024 (with chain length C20-24) and an alkane (serving as a model crude oil) are shown in Figure 1, 2
and 3. In each the formation of a middle phase micro-emulsion can be seen at intermediate salinities.

2.1. Glass pressure tube test

Glass pressure tubes (20 cm3 total capacity) with special caps have been manufactured in Shell’s laboratory and tested and
certified to operate up to 11 bar (1100 kPa). Each tube is graduated to show relative volumes of phases and has a special
screw-on plastic cap. A specially designed hand-held rack (incorporating a polycarbonate screen) holds 10 of the glass
pressure tubes and is used to provide extra protection in the event that a tube breaks.
Before the tubes are used, the aqueous/oil system to be investigated should first be tested in a separate experiment to
measure actual pressures generated at the temperatures of interest. This step is very important since different crude oils will
generate different vapour pressures as they are heated. In our laboratory we carried out these tests in the autoclave system
described below (section 2.2) though other experimental set-ups can be used. Based on these tests, if the pressures generated
are below the glass tube working pressure of 10 bar (1000 kPa), then it is safe to operate with the aqueous / oil system of
interest.
Aqueous (surfactant in saline or brine)/oil (model alkane or crude oil) mixtures with an oil: water ratio of 1:1 (v/v) are
made up in different tubes. Typically the surfactant solution is at 2.0% active. In some cases this aqueous solution required
heating the solution or the use of a low concentration of a solubilising component to obtain a stable, mainly clear solution (no
precipitation with time). The tubes are placed in the rack that is in turn put in an oven set at the test temperature. As an
additional safety precaution, the oven is purged with nitrogen during the test in the event of a tube breakage and release of
flammable hot oil. Once the rack and tubes have equilibrated at test temperature the rack is removed from the oven, and the
volumes of the surfactant and oil phases are measured and photographs are taken. Then the rack with tubes is thoroughly
shaken for between half to one minute. The rack + tubes is then placed back into the oven and the heights of the interfaces are
measured (and photos taken) at distinct times, typically after 1, 6, 24 hrs and 7 days. At each time interval the “quality” of
micro-emulsions formed are monitored by swaying the rack slightly from side to side. Promising behaviour is often linked to
movement of very fine filaments from the micro-emulsion that has a “sheen”. Less promising behaviour is the potential
formation of viscous gels or large oil globules. The more promising systems (i.e. those that demonstrate Winsor III micro-
emulsion behaviour) are those whose micro-emulsion settle quickly: these are usually kept for several weeks / months and
observed; the less promising ones are disposed of after 7 days.
The method principle is to measure the volumes of water, oil and any emulsion phases at a particular test temperature as
salinity is increased causing a transition in phase behaviour from Winsor type I to type III to type II. The data from these
phases are plotted against salinity and give oil and water solubilisation parameters.

2.2. Glass autoclave

The glass autoclave used was manufactured in Shells’ laboratory and comprises an inner-jacketed vessel used to contain
aqueous solution and oil (model alkane or crude oil). The aqueous solution of the surfactant dissolved in sodium chloride or
simulated reservoir brine is prepared is a similar way to that described in section 2.1 above, i.e. typically at 2% active
concentration of surfactant and using an oil: water ratio of 1:1 (v/v).
The total liquid volume in the inner vessel is 100 cm3 with a 30 cm3 gas cap. The outer jacket is circulated with heating oil
to maintain a test temperature, the heating oil being heated via an external heater. The autoclave is graduated vertically to
measure phase volumes. Its maximum working pressure is 11 bar (1100 kPa) and in our working experience with the
apparatus to date, aqueous/oil systems (including alkanes and “dead” crudes) generate pressures below 10 bar (1000 kPa) in
the temperature range ambient to 150°C. The autoclave constructed is certified to operate up to 160°C therefore covering
almost all possible reservoir temperatures relevant to EOR. Nevertheless a user using the same or similar apparatus should be
SPE 113313 3

aware that high pressures could occur with particular crude oils and check this pressure relative to the upper limit possible for
the apparatus. As additional precautions, the autoclave is equipped with a pressure relief valve (set at 11bar) and is contained
in a polycarbonate box, the latter ensuring that, should a breakage or explosion occur, any flying glass fragments and hot
liquids are safely contained. The use of polycarbonate has the advantage that it allows a clear view of phase behaviour.
In this test method, a 1:1 (v/v) oil: aqueous system (or other ratios) is “temperature scanned”. Other ratios can be used, this
being relevant for screening tests for alkaline surfactant floods. Heating oil is circulated to take the system up to particular test
temperatures whilst the aqueous/oil system is mixed vigorously with a magnetic stirrer. At a particular test temperature, the
aqueous/oil system is allowed to mix via the magnetic stirrer for several additional minutes, after which time mixing is stopped
and the phase behaviour observed as described in section 2.1. Phases are observed (with photos) at 1, 6 and 24 hours. In some
cases the phase volumes are measured again after several days.

2.3. Glass pipette method

In this method developed at Rice University, the high-temperature tests are carried out in baths filled with appropriate fluids,
silicone or high-molecular weight oils. The volume of fluids required to accurately determine surfactant properties is about 2
cm3 in heat-sealed pipettes. Water, oil and surfactant are weighted into pipettes using an analytical balance, taking into
account their densities. These sealed pipettes, containing water/surfactant (1 cm3) and either octane or decane (1 cm3) are
placed inside a 10 cm3 test tube filled with same fluid in bath. Inserting the sealed pipette in a test tube filled with the bath
fluid has the following advantages:
(a) If the sealed pipette leaks, the alkane in the sample will be diluted by about 10 times and this mitigates the hazard of
handling alkanes such as octane at high temperature,
(b) The presence of the outer liquid oil jacket that will contain any leak or rupture of the glass pipette,
(c) Contamination of bath fluid is contained, and
(d) The outer-hot fluid mitigates temperature losses. This makes it practicable to visualise and photograph the surfactant
phase behaviour at high temperature.

Samples are manually mixed and left to equilibrate in the bath. The mixing and equilibration is repeated over time until phase
volumes are constant. Photographs are taken at these time intervals. This method has been used to determine optimal salinity
and solubilisation ratio at that salinity for a range of surfactants in models alkanes, including n-octane and n-decane.

3. Laboratory screening: Sulfonate surfactants for chemical EOR

In EOR chemical flooding processes for sandstone reservoirs, anionic (negatively-charged) surfactants have been found to
give the best performance/cost profile3. They are known to show a low tendency to adsorb on reservoir rock surfaces arising
from negative-negative charge repulsion between the surface and the surfactant3. The use of alkali further reduces the
tendency for surfactants to adsorb and reduced losses means a lower concentration of the surfactant can be used making the
process more economic3. Two families of surfactants, internal olefin sulfonates (IOS) and sulfonates based on a proprietary,
branched C16, 17 alcohol, have been evaluated. Their synthesis and average molecular structures are summarised in the next
sections.

3.1. IOS synthesis and structures

A description of the synthesis steps and chemical structures of IOS is given in reference 6. Using this approach, internal
olefins with carbon number cuts C15 to C18, C20 to C24 and C24 to C28 were produced and then sulfonated via a laboratory-
based falling film sulfonation method. Reaction with SO3 produces a variety of twin-tailed products since SO3 reacts with the
double bond on the internal olefin that is randomly positioned along the carbon chain. The first intermediates of sulfonation
are β-sultones, which undergo transformation to predominantly hydroxyalkane sulfonates on immediate neutralisation. If the
β-sultones are aged γ- and δ- sultones are formed. Subsequent neutralisation/hydrolysis steps convert the β-, γ- and δ- sultones
to mixtures of alkene and hydroxyalkane sulfonates. The proportion of alkene sulfonates to hydroxyalkane sulfonates varies
and can be tailored according to the aging and neutralisation/hydrolysis conditions.
In summary, the main surfactant species formed are a range of twin-tailed isomers of alkene sulfonate and a range of twin-
tailed isomers of hydroxyalkane sulfonates, each of these having a range of overall carbon numbers depending on the IO
feedstock (e.g. C15-18). Low concentrations of di-sulfonated molecules are also formed. IOS is thus a complex surfactant
mixture and would be expected to have advantages in EOR through minimising the formation of ordered structures such as
liquid crystals and gels. Changing IOS structure through the internal olefin (IO) feed and the sulfonation process means that
an IOS can in principle be tailored for different reservoir conditions, based on phase behaviour results.
Figure 4 shows the main generic structures present in IOS.
Table 1 shows the typical properties of the IOS surfactants studied. The carbon number range and average carbon number
of the IOS was measured by GC analysis of the internal olefin (IO) feedstock. Branching index (number of branches per
molecule) was measured by 13C NMR analysis of the IO feedstock. The sulfonated species distribution was obtained by an
4 SPE 113313

LC-MS method. In order to investigate the link between IOS structure and its properties / performance, three batches of IOS
with C20-24 (termed IOS 2024) were prepared, as indicated by batch A, B and C in Table 1. Batches A and B were prepared
from the same IO feedstock and differed in the conditions and degree of sulfonation. In contrast, batches A and C had the
same conditions and degree of sulfonation but had different IO feedstocks (which differed in degree of branching).

3.2. Branched C16, 17 alcohol alkoxy sulfonates: synthesis and structures

The branched C16, 17 alcohol, known commercially as NEODOL™ 67 alcohol, was used to synthesise several surfactants
based on the alcohol hydrophobe, propylene oxide and/or ethylene oxide linking groups and a sulfonate end group. These
surfactants are part of the ENORDET A series. NEODOL 67 alcohol is produced via a proprietary process that results in a
mixture of C16 and C17 chains (in approximate ratio 1:2) with a randomly positioned methyl group (or groups) along the
molecule, on average 1.5 methyl groups per molecule4, 7, 8. The alcohol alkoxylate was prepared via ethoxylation or
propoxylation reaction of the alcohol using conventional catalytic techniques. The sulfonate derivatives were synthesised by
reaction of the alcohol alkoxylate with epichorohydrin, followed by reaction with sodium hydroxide and with sodium
bisulfite9, 10.
Alternatively, sulfate derivatives can be made by reaction of the alcohol alkoxylate with SO3 (via a falling film sulfonation
rig), or by reaction with chlorosulfonic acid or sulfamic acid. However they suffer from low hydrolytic stability at higher
temperatures and are not discussed in this paper.
Figure 5 shows the main generic structure for the branched C16, 17 alcohol alkoxy sulfonate (strictly speaking termed a
glycidyl sulfonate which refers to the bridging group linking the sulfonate group to the alkoxylate chain) and, for comparison,
the structure of the alcohol alkoxy sulphate is shown. The C16, 17 alcohol alkoxy glycidyl sulfonate has three chemical
structure variants, each with three functional groups (sulfonate, hydroxyl and “X” where X can be hydroxyl, chloride or
sulfonate). The main chemical species will be with a sulfonate end group and two hydroxyl groups.

3.3. Phase behaviour test results

In micro-emulsion phase behaviour tests it has been established that the following variables will strongly influence the
suitability (or match) of a candidate surfactant to a particular crude/reservoir condition3:
• Surfactant carbon number
• Salinity (electrolyte) concentration
• Temperature
• Crude oil Effective Alkane Carbon Number (EACN), where EACN typically varies from octane (C8) to dodecane
(C12)

To investigate the range of applicability of IOS surfactants, phase behaviour tests were carried out with several alkanes
(octane, decane and dodecane) over a range of salinities and temperatures (up to 150°C). Some specific tests were also carried
out with “dead” crudes oils with sodium chloride solutions. The surfactant concentrations used (usually around 2% active)
are higher than those to be practically used in a surfactant slug for EOR but allow the laboratory phase behaviour (particularly
formation of the middle phase micro-emulsion) to be more easily visualised.

3.3.1. IOS surfactants

Before the phase behaviour tests are discussed, comments on our experience of solubility of IOS surfactants in saline and
reservoir brine are given.

Solubilisation of IOS in saline and reservoir brine solutions

As the IOS carbon chain length is increased and hydrophobicity increases solubility in saline and reservoir brine solutions
can be difficult, particularly at higher salinities. An aqueous solution of surfactants to be injected into a reservoir needs to be a
single phase and exhibit with no precipitation with time. The approach traditionally used to aid solubility has been to use co-
solvents such as sec-butanol, isopropanol and others4. Such co-solvents also play a useful role in preventing the formation of
high viscosity phases and gels4 that can be an issue for some surfactants. We have used an alternative method to aid
solubilisation of the IOS family, via addition of a low concentration of a non-ionic surfactant as a solubiliser. There is a
precedent for this approach that was used in 1984 by Nelson et al for the technically successful White Castle field trial in
Louisana in 1984 where an IOS with C17-20 carbon chains was solubilised with a low concentration of an alcohol
ethoxylate11. Based on further work in our laboratory we think this is a promising alternative approach for solubilising some
surfactants, compared to the use of co-solvents such as alcohols, since it requires lower concentrations.
Several alcohol ethoxylates were screened and it was found that certain structures gave the bests results for solubilisation
in high salinity aqueous solutions at room temperature, including for solutions containing divalent ions. Based on solubility
SPE 113313 5

tests it was found that this component could be used at low concentrations, at around 10-25% of the active concentration of the
surfactant. Our approach has been to use the solubiliser for those surfactants, such as IOS, that have a low tendency to align
and form viscous phases and gels though its use may not be appropriate for those surfactants that require co-solvents to
prevent the formation of gels and viscous phases. Other tests would need to be carried out in these cases to judge the
solubiliser’s applicability. Since the level of non-ionic solubiliser used is low, its effect on micro-emulsion phase behaviour
tests is relatively small. Nevertheless, our approach has been to carry out phase behaviour tests with and without the
solubiliser, for example to identify a surfactant system optimal for a particular reservoir (in terms crude oil, brine salinity and
temperature). Since, chemically, the non-ionic solubiliser will tend to adsorb to the rock surface once the aqueous solution is
injected, the phase behaviour results “without solubiliser” are considered the best to judge behaviour in the real situation. In
addition, in our laboratory test experience, the IOS surfactants tested remained dissolved in the salinity range of interest
(around each surfactants optimal salinity) due to the higher temperatures. In summary, the main role of the solubiliser is to aid
surfactant solubilisation up to the point of injection.

Influence of IOS carbon chain length and different model oils

Initial phase behaviour tests were carried out for IOSs with C20-24 and C15-18 chain lengths (termed IOS 2024 and IOS 1518
respectively in the discussion that follows). Tests were carried out at 80-84°C and over a range of salinities using n-octane as
model oil. The IOS 2024 initially tested had sample batch “A”. Figure 6a shows a typical plot of equilibrium phase volumes
for IOS 2024 that were used to plot oil and water solubility parameters as shown in Figure 6b. A comparable result for IOS
1518 is shown in Figure 7. The intersection of the oil and water solubility parameters gives the optimal salinity and oil
solubilisation parameter at the optimal salinity condition. Solubilisation parameters at optimal salinity greater than
approximately 10 typically signify an ultra-low oil-brine IFT (and below 0.003 dyne/cm).
Further phase behaviour tests were carried out for IOS 2024 (batch A) with n-octane at the higher temperature of 96°C.
Plots of the resulting optimal salinity and solubilisation parameter data as a function of temperature together with the IOS 1518
data point are shown in Figure 8a and 8b. Comparing data at the same temperature (say 84°C) shows that, as expected, an
increased chain length (from C15-18 to C20-24) results in an optimal salinity decrease (from 13% to 4%) in line with the
increased hydrophobicity of the surfactant, and the solubilisation parameter increases (from 7 to around 19). Changing
temperature from 84°C to 96°C, the IOS 2024 system, although showing about the same optimal salinity, provides a lower
solubilisation parameter. Further data will be shown in relation to the reduction in the solubilisation parameter with
temperature that sometimes occurs. Such trends give information about oil solubilisation by an IOS at its optimal salinity, and
how this changes with temperature.
Phase behaviour tests were then carried out for IOS 2024 (batch A) and an IOS 2428 (with carbon chain C24-28) with n-
dodecane between 70 and 150°C: the optimal salinity and solubilisation parameter data are plotted in Figure 9a and 9b. This
shows, as expected, that the longer chain IOS 2428 hydrophobe gives the lower optimal salinity at 150°C (around 1%) and a
higher solubilisation parameter (close to 50). Thus the more hydrophobic IOS 2428 gives much more effective heavier oil
solubilisation, this having been reported elsewhere4, 12, 13.
IOS 2024 (batch A) was further tested with n-octane, n-decane and n-dodecane over a range of salinities and temperatures.
The measured optimal salinities and solubilisation parameters are plotted in Figure 10a and 10b. These alkanes cover the
range of EACNs relevant to different crude oils. As the alkane becomes heavier, the optimal salinity increases whereas
solubilisation parameter follows the reverse trend, becoming lower. Figure 10a also shows an interesting trend in that optimal
salinity decreases as temperature is increased to 150°C. This effect runs counter to that reported in the industry3, although it
should be noted that the previously reported measurements were, we assume, at temperatures only slightly higher than ambient
temperature. In principle, as an aqueous solution of an anionic surfactant is heated from ambient temperature, its solubility
will increase and so it’s optimal salinity would be expected to increase. However, at higher temperatures, enhanced solubility
for the hydrophobe part of the surfactant in the oil phase might occur, causing the opposite effect, i.e. reduced optimal salinity.
The suggested mechanism, although plausible is only a hypothesis. We plan to explore this in future high temperature phase
tests.

Influence of IOS chemical structure

As mentioned earlier we have synthesised variants of the IOS 2024 surfactant to investigate how changes in a) degree of
sulfonation, and b) branching in the hydrophobe feedstock changes surfactant phase behaviour. Although this study focuses
on the IOS 2024 surfactant the resulting findings will apply to other IOS chain lengths. Table 1 shows the analytical data of
the surfactants, in terms of the IO carbon chain and the sulfonated species.
Figure 11a and 11b show the influence of change in the degree of sulfonation (at constant IO feedstock structure) on
optimal salinity and phase behaviour properties with n-octane. In these figures, batch A (the IOS 2024 discussed earlier) was
sulfonated with a higher than stoichiometric SO3/alkene ratio and at higher temperature compared to batch B which was
sulfonated at a lower ratio and at a lower temperature. The most striking feature is the change in optimal salinity between the
two samples (ca. 4 versus 1%) with the lower temperature sulfonation IOS giving a lower optimal salinity suggesting a more
hydrophobic surfactant. Referring to Table 1 this difference might potentially be attributed to the fact that batch B does not
6 SPE 113313

contain any of the very hydrophilic di-sulfonate species. Despite the difference in optimal salinity, Figure 11b shows that both
samples yielded very good oil solubilisation, with solubilisation parameters greater than 10.
Figure 12a and 12b show the influence of change in the IO feedstock (at constant degree of sulfonation) on IOS 2024
optimal salinity and phase behaviour. Batch C (based on a highly branched IO feedstock) is compared to batch A (low
branching level). Interestingly, the more branched IOS gave the higher optimal salinity. This effect might be explained by
two contributions: a) branching in the IO carbon chain aids IOS solubility, and b) branching in the IO chain influences the
reaction with SO3 and resulting the sulfonated structures that are formed. Referring to Table 1, batch C had a relatively high
concentration of alkenesulfonate and the hydrophilic di-sulfonate species. The overall result is to form a product that is both
more hydrophilic (with higher optimal salinity) and has a higher solubilisation parameter at higher temperatures (it is close to
25 at 120°C, Figure 12b).

Summary IOS study

Table 2 summarises the optimal salinity data generated with IOSs with different carbon chains and includes additional tests
with a Chinese crude oil tested at high temperatures. The data in Table 2 show that the IOS family (IOS 1518, 2024 and 2428)
cover a range of optimal salinities (1% to 13%) at higher temperatures and gives moderate to very high (in the case of IOS
2428) solubilisation parameters. This level of oil solubilisation is appropriate for EOR. In addition, reviewing the
solubilisation parameter data for the different IOS surfactants (Figures 8 to 12) shows that temperature sensitivity is in most
cases not large: this could be viewed as a positive feature, e.g. for reservoirs with temperature gradients.
This study also showed that both IO carbon chain (degree of branching) and the degree of sulfonation influence the
surfactant properties of the IOS mixture formed. With such information, an IOS such as IOS 2024 can be tailored to give
optimal performance.
Overall, the IOS family of surfactants is promising for use over a range of reservoir conditions, covering moderate to high
reservoir temperatures and from low to high salinity conditions. The IOS family is particularly appropriate for very high
temperature reservoirs due to the temperature-stable sulfonate group. Other work by Shell has shown that IOS 1518, IOS 2024
and IOS 2428 can be mixed to obtain optimal performance IFT and phase behaviour performance for particular reservoir
conditions.

3.3.2. Branched C16, 17 alcohol alkoxy sulfonates

As mentioned earlier, the branched C16, 17 alcohol hydrophobe discussed here is a mixture of C16 and C17 chains with a
methyl group randomly positioned along the molecule. This makes the molecule and its derivatives less likely to align and
form ordered structures associated with liquid crystals and gels compared with linear and regularly branched hydrophobes. In
addition, its long carbon chain makes it more compatible with more hydrophobic crude oils than alcohol-based surfactants
with lower carbon numbers.
Several propoxy and/or ethoxy sulfonates based on this alcohol hydrophobe were screened in specific crude oil/reservoir
conditions for their oil/water IFT by the spinning drop method using a University of Texas model tensiometer. Two examples
are shown to illustrate the approach. In this well-known industry method, the IFT, derived from the diameter of a spinning
drop of oil in an aqueous medium, is measured as function of time. The IFT takes some time (typically 20-25 minutes) to drop
to a minimum as the system reaches an equilibrium temperature and it is after this time that the IFT results should be judged.
The study focused on sulfonate derivatives since reservoir conditions of interest were moderate to high temperature. Due
to the labile C-O-S bond for the sulfate, the sulfonate derivative is appropriate for use with higher temperature reservoirs
where higher hydrolytic stability is required. Sulfated surfactants start to decompose rapidly at temperatures above about
60°C14.
Figure 13 shows the results obtained for the ENORDET A772 surfactant (a branched C16, 17 alcohol alkoxy glycidyl
sulfonate) that was tested in two crude oil/reservoir environments: the first (Crude A) at 98°C with a reservoir brine of 18.2%
total dissolved solids (TDS), the second (Crude B) at 72°C with the appropriate seawater reservoir brine of 3.1% TDS. Both
brines had significant levels of divalent ions. In the case of Crude A, the actual reservoir temperature to be screened was
120°C but since the spinning drop IFT test method could only be carried at temperatures up to 100°C, tests were carried out at
the practically achievable temperature of 98°C to give data indicative of 120°C. The IFT results in Figure 13 show that the
ENORDET A772 surfactant gave a low IFT of around 0.01 dyne/cm with Crude B showing it to be better matched to
conditions of this reservoir than those of Crude A. In addition, Figure 13 illustrates that the test method gives repeatable
results.
The Crude A reservoir conditions are very challenging, combining high temperature (120°C) and a very high salinity, high
divalent ion content brine (18.2% TDS). IFT tests were carried out on a range of surfactants within the ENORDET A series
(branched C16, 17 alcohol alkoxy sulfonates) for the Crude A conditions (though at a test temperature of 98°C) where the
alkoxy group was varied. Several of the results are shown in Figure 14. This Figure shows that the type and number of alkoxy
groups (PO, EO or PO/EO) needs to be carefully selected to obtain a surfactant active in this high temperature and high saline,
hard water environment. One particular surfactant (ENORDET A092) gave the best result, with an IFT below 0.01 dyne/cm;
others had significantly higher IFTs for the very severe conditions of this reservoir.
SPE 113313 7

This initial screening by the spinning drop IFT method is exactly that, an initial screening and it should be borne in mind
that several factors can influence the result, including the time for the temperature to stabilise during the test (typically 20-30
minutes) and the variability of the observed oil drop shapes used for the measurements. In addition, IFT is measured at non-
equilibrium conditions and micro-emulsions can form during the measurement that can influence the result. Furthermore, our
in-house IFT test method can only test up to 98°C. On the other hand, the IFT test method can be used to quickly determine
the IFT between a crude oil with brine at conditions that approximate to the reservoir. It is also a particularly useful when only
very small quantities of an experimental surfactant are available. The more promising surfactants based on the spinning drop
IFT method would need to be tested in phase behaviour tests to see how easily a Winsor III micro-emulsion forms and how
this emulsion is visually judged (lower viscosity and absence of gels is required).
The spinning drop IFT examples shown here illustrate the sensitivity of the IFT (between a crude oil and reservoir water)
to the structures of alcohol-based surfactants. It also suggests that the ENORDET A family of surfactants are promising for
higher temperature and higher salinity reservoirs. Future work will report a more comprehensive evaluation of this family of
surfactants.

4. Discussion: Technical and industry requirements for EOR surfactants

This section will discuss the technical requirements for IOS and branched C16, 17 alcohol based surfactants based on our
experience of screening such structures for particular reservoirs. It will also discuss the potential market demand for
surfactants for EOR relative to the supply of suitable molecules available.

4.1 Technical requirements

Based on our own test results and other data15, 16, Table 3 shows which surfactant families are best suited for particular
reservoir conditions (temperature, salinity and hardness) and the EOR process (surfactant-polymer or alkaline-surfactant-
polymer floods, SP or ASP). The Table highlights the fact that different chemical structures have different strengths and the
importance of selecting surfactant structure for optimal performance. The Table also highlights the fact that ASP floods are
not currently considered feasible in very hard water environments (i.e. containing high concentrations of divalent ions such as
calcium and magnesium) due to scaling issues.
Future work will investigate how a) the presence of divalent ions influence performance of the IOS and branched C16, 17
alcohol based surfactants, and b) blending of these two surfactant types can be used for particular reservoir conditions: other
workers have found that this approach looks promising4, 7. It has been reported, for example, that the presence of PO chains in
the connecting group of branched alcohol-based surfactants aids in tolerance to calcium and magnesium ions4 which makes
these surfactants particularly interesting for higher salinity and harder water reservoir brines.
This paper has focused on the primary requirement for an EOR surfactant, namely that it must generate an ultra low IFT as
measured by phase behaviour tests at conditions simulating the reservoir. These tests also provide information about the
suitability of a candidate surfactant or surfactant mixture through observation of the micro-emulsion formed and any presence
of undesirable viscous phases.
There are other important criteria for a suitable surfactant or surfactant formulation including a) the tendency to adsorb on
the rock surface (and the influence of water chemistry), and b) compatibility with polymer used in chemical floods. Carrying
out tests associated with these other properties is required before continuing with core flood tests on front-running
formulations. A successful core flood test is considered a pre-requisite before injecting a surfactant slug in a pilot field trial.
Finally, a surfactant must meet environmental criteria and associated regulations, these being particularly important for use
with offshore reservoirs. Reference 17, for example, gives a good overview of this subject for the North Sea area.

4.2 Industry requirements

The block diagram in Figure 15 shows the manufacturing routes to the large volume surfactants used in several industries. To
start at the bottom there a number of different surfactant types and a large number of companies are active in the industry.
Moving up one level, the number of surfactant structures is reduced since the generic hydrophobes are shown.
Correspondingly, the number of companies active in hydrophobe manufacturing is also significantly lower since hydrophobes
are manufactured on a large scale by processes that are exceedingly capital intensive. At the top level the specific feedstock is
shown to produce hydrophobes. The raw material source of hydrophobes today is mainly paraffin and ethylene. Paraffin has
the disadvantage that most commercially available paraffins produced in large volumes are highly linear and are only available
in the range C10-16. Ethylene is a widely produced commodity chemical and can be converted into branched internal olefins
and alcohols. Natural oils and fats (derived from plant or animal sources) are another feedstock to surfactants but have the
disadvantage that the resulting chemicals (such as oleo alcohols) have carbon chains that are almost 100% linear.
Thus, ethylene is likely to be the principal raw material of choice as it allows production of branched long chain
hydrophobes through internal olefins. It also allows the production of branched long chain alcohols through hydroformylation
of suitable olefins.
8 SPE 113313

It is notable that current availability of carbon chains in the range of interest for EOR (C14-28) is limited and most
surfactant molecules are in the C10 – C16 range where they are used in household, personal care and industrial applications.
The current total surfactant market size is around 6 million metric tons per year. Shell Chemicals uses ethylene and a
proprietary process that makes it the largest producer of high carbon number olefins and alcohols. It is thus well positioned to
serve the industry.
Considering surfactants for EOR and taking the estimate of recoverable oil by chemical EOR recently reported in an SPE
Distinguished Lecturer Series (750 Billion BBL)18. If it is assumed that 50% of cases will use surfactant whose consumption
will be 1 kg surfactant / bbl incremental oil recovered over a flood period of 30 years yields a surfactant demand of 12.5
million metric ton of surfactant per year (underlined figures are assumptions for this calculation). This figure may turn out to
be lower but the requirement will still be very large indeed relative to the currently produced volumes of surfactants.
It is therefore key that future users of surfactants for EOR understand the surfactant supply chain to ensure that the
appropriate surfactants are selected that can be made available in large quantities and with satisfactory product consistency.
An effective surfactant will thus be one that both a) fulfils the technical criteria (discussed in this paper), and b) can be made
on a large scale at a satisfactory price. This is the challenge to both surfactant suppliers and surfactant users.
Finally, it is clear from the figures given here that if EOR is widely implemented with surfactants the demand for EOR
surfactants will have a dramatic effect on the surfactants market. The effect will be felt both in terms of the volume demand
and the required chemical structures.

5. Conclusions

Three new methods are reported for carrying oil/water phase tests for screening surfactants at temperatures relevant to higher
temperature reservoirs. These methods have certain safety-features related to higher temperature use that, in our view, offer
advantages over methods commonly used in industry and academia.
Phase behaviour tests carried out with different internal olefin sulfonates (IOS) shows that they a) can be used over a range
of salinities, and b) give high oil solubilisation at their optimal salinities. The latter being particularly so for a longer chain
IOS, e.g. with C24-28. These properties and the fact that they are chemically stable at higher temperatures make them very
versatile surfactants for EOR and promising for reservoirs up to 150°C. Different IOS products are available with different
carbon chain cuts (with range C15 to C28) allowing matching of the IOS to the temperature, salinity and crude oil type of
reservoirs.
Both IO carbon chain (degree of branching) and the degree of sulfonation influence the surfactant properties of the IOS
mixture formed. This gives two processing methods to tailor an IOS for optimal performance.
The IOS family of surfactants are part of the ENORDET™ O series. They have chemical features that are advantageous for
EOR: its twin-tailed structure and the fact that it contains a mixture of hydroxyalkane sulfonate / alkene sulfonate and di-
sulfonate structures means that it will have less tendency to form regularly ordered structures that can give viscous phases.
A family of anionic surfactants based on a branched C16/C17 alcohol (part of the ENORDET A series) has promise for
reservoir conditions of higher salinity and containing hard water. In this family a connecting group (of EO and/or PO) links
the alcohol hydrophobe to the anionic sulfonate or sulfate and is used to change the HLB (hydrophile/lipophile balance) of the
molecule and match it to reservoir conditions in terms of salinity and crude oil.
An effective surfactant for EOR should fulfil technical criteria, the key one being ultra-low oil / water interfacial tension as
judged by phase behaviour test. However, it should also be capable of being made on a large scale at a satisfactory price.
Currently there are only limited volumes available in the market of surfactant hydrophobes in the preferred carbon change
range of C14-C28. In a continuing high crude oil price environment and a likely resurgence of interest in EOR, surfactant
suppliers and users will need to work closely together to meet this challenge.
Future work will investigate how a) the presence of divalent ions influence performance of the IOS and branched C16, 17
alcohol based surfactants, and b) blending of these two surfactant types can be used for particular reservoir conditions.
SPE 113313 9

References

1. I. Chatzis and N.R. Morrows, “Correlation of capillary number relationships for sandstone”. SPE Journal (October 1989), Volume
29 (5), pp 555-562
2. C. Huh, "Interfacial tensions and solubilizing ability of a microemulsion phase that coexists with oil and brine, Journal of Colloid
and Interface Science (September 1979), pp 408426
3. “Surface Phenomena in Enhanced Oil Recovery”, edited by D.O. Shah. Compilation of papers presented at the symposium on
surface phenomena in Enhanced Oil Recovery , Stockholm, Sweden, 20-25 August 1979. Plenum Press, New York, 1981.
Referring to Chapter 1 on the fundamental aspects of the oil displacement process
4. D.B. Levitt, A.C. Jackson, C. Heinson, L.N. Britton; T. Malik; V. Dwarakanath, G.A. Pope, “Identification and Evaluation of High
Performance EOR Surfactants”. SPE-100089. And other references cited here with author G.A. Pope.
5. J.R. Barnes, J.P. Smit, J.R. Smit, P.G. Shpakoff and K.H. Raney, “Phase behaviour method for the evaluation of surfactants for
chemical flooding at higher temperature reservoir conditions”. SPE-113314-PP. Poster to be presented at the Improved Oil
Recovery symposium, Tulsa, April 2008
6. “Anionic Surfactants: Organic Chemistry”. Surfactant Science Series Vol 56 edited by H.W. Stacke. Marcel Dekker, Inc., New
York, 1996. Chapter 7: Olefinsulfonates by N.M. van Os, R. van Ginkel, A. van Zon, F.W. Heywood, E.L. Berryman and J.K.
Borchardt, page 363
7. D.L. Zhang, S. Liu, W. Yan, M. Puerto, G.J. Hirasaki, C.A. Miller, “Favorable attributes of alkali-surfactant-polymer flooding”.
SPE 99744. Presented at the 2006 SPE/DOE Symposium on Improved Oil Recovery, Tulsa, USA, April 2006
8. P.G. Shpakoff and K.H. Raney. “Method and composition for enhanced oil recovery”. U.S. Patent nos: US 7,055,602 B2, US
7,262,153 B2, US 7,137,447 B2
9. “Anionic Surfacants”, edited by W.M. Linfield. Surfactant Science Series, Volume 7. Referring to Chapter 14: Alkyl glyceryl
ether sulfonates
10. E.F. Lutz , “Polyalkoxy sulfonate, CO2 and brine drive process for oil recovery”. U.S. Patent 4,502,538
11. A.H. Falls, D.R. Thigpen, R.C. Nelson, J.W. Ciaston, J.B. Lawson, P.A.Good, R.C. Ueber and G.T. Shahin. “Field test of co-
surfactant enhanced alkaline flooding”. SPE Reservoir Engineering, August 1984, pp 217-223
12. M. Bourrel and R. S. Schechter, "Microemulsions and Related Systems", Marcel Dekker, Inc., New York, NY (1988)
13. M. Aoudia, W. H Wade and V. Weerasooriya, "Optimum Microemulsions Formulated with Propoxylated Tridecyl Alcohol
Sodium Sulfates," Journal of Dispersion Science and Technology (16(2) 1995), 115
14. “Anionic Surfactants: Organic Chemistry”. Surfactant Science Series Volume 56, edited by H.W. Stache, Marcel Dekker, Inc.,
New York, 1996. Chapter 5, Alcohol and Alcohol Ether Sulfates by Xavier Domingo, page 233
15. W.W. Gale, M.C. Puerto, T.L. Ashcraft, R.K. Saunders and R.L. Reed, “Propoxylated ethoxylated surfactants and method of
recovering oil therewith”. U.S. Patent no: 4,293,428
16. M.C. Puerto, “Propoxylated surfactants for enhanced oil recovery in the range between high and low salinities”. U.K. Patent no:
GB 2 168 095 A
17. J. Killaars and P. Finley. “ Move to environmentally acceptable products: How the OSPARCOM legislation affects the
introduction of new products”. SPE 65044
18. S. Thomas, “Chemical EOR – The past, does it have a future?” SPE Distinguished Lecturer Series. SPE-108828-DL.

Acknowledgements

The authors would like to thank Professors Clarence Miller and George Hirasaki, Rice University, Houston for supervision and interpretation
of much of the phase behaviour work. In addition, we are grateful to Arie van Zon (Amsterdam laboratory) and to Tom Semple and Bob
Ellison (Houston laboratory) for the synthesis of surfactants and valuable discussions on their structure. Finally, we are grateful to Wim
Genuit (Amsterdam laboratory) and Pierre Tutunjian (Houston laboratory) for the LS-MS analysis and 13C NMR analysis respectively of the
IOS surfactants.
10 SPE 113313

Table 1: Typical properties of IOS samples tested

IOS 1518 IOS 2024 IOS 2024 IOS 2024 IOS 2428
(batch A) (batch B) (batch C)
Carbon Number Range 15-18 20-24 20-24 20-24 24-28

IO average C no: 16 21 21 21 26

IO branching index: Medium Low Low High High

SO3/alkene ratio: Low High Low High Low

Hydoxyalkanesulfonate, %* n.m. 92 87 61 66
Alkenesulfonate, %* n.m. 5 13 27 29
Di-sulfonates, %* n.m. 2.5 0 4 0

*Measured by a semi-quantitative LC-MS method

n.m. = not measured
SPE 113313 11

Table 2: IOS family: Summary of optimal salinity and solubilisation parameter results
IOS* Oil** Optimal Solubilisation
salinity (%m) parameter
Medium temperature (70-90°C)
IOS 1518 C8 13 7

IOS 2024 C8 4 21
IOS 2024 C10 5 14
IOS 2024 C12 8 6-10

IOS 2428 C12 3 46-48

High temperature (120-150°C)
IOS 2024 C12 6-7 6
IOS 2024 Chinese Crude 4 -

IOS 2428 C12 1 46-48

IOS 2428 Chinese Crude 2.5 -

*IOS 1518 refers to carbon number range C15-18, IOS 2024 to C20-24 and
IOS 24-28 to C24-28
**C8 is n-octane, C10 is n-decane and C12 is n-dodecane

Table 3: Overview of surfactant, reservoir condition and EOR type

Reservoir Condition*
Low Temp; Low Salinity
Process Surfactant Choices
Choices**
ASP/SP Alcohol ethoxy/propoxy sulfate,
Alkylaromatic sulfonate, Internal
olefin sulfonate

Low Temp; High Salinity ASP/SP Alcohol ethoxy/propoxy sulfate,

Internal olefin sulfonate

Low Temp; High Hardness SP Alcohol ethoxy/propoxy sulfate

High Temp; Low Salinity ASP/SP Alcohol ethoxy/propoxy

High Temp; High Salinity
sulfonate, Alkylaromatic
sulfonate, Internal olefin
sulfonate
ASP/SP Internal olefin sulfonate, Alcohol
ethoxy/propoxy sulfonate

High Temp; High Hardness SP Alcohol ethoxy/propoxy

sulfonate

*Low Temp = ambient to 60°C; High Temp = >60°C.

*Low Salinity = 0 - 3% NaCl; High Salinity = >3% NaCl
*High Hardness = >1,700 ppm divalent ion concentration (that of sea water)
**ASP = Alkaline Surfactant Polymer flood; SP = Surfactant Polymer flood
12 SPE 113313

Figure 1: Glass pressure tube method: Phase behaviour of 2% IOS 2024 and n-dodecane at 150°C (after one hour equilibration).
Salinity varies from left to right 0.5, 3, 6 and 9%w

3.4% NaCl 6.5% NaCl 8.3% NaCl

Figure 2: Glass autoclave method: Phase behaviour of 2% IOS 2024 and n-dodecane at 120°C at different salinities (after one hour
equilibration)
SPE 113313 13

Figure 3: Glass pipette method: IOS 2024 mixed with n-octane at 96°C. Salinity is scanned from left to right (2.6, 3.5, 4.3 and 5.2%).

OH SO3Na SO 3Na

n n

n=0-2 n=0-2

Hydroxy alkane sulfonate Alkene sulfonate

Na SO SO 3Na Na SO 3 OH SO 3Na
3

m n m n

m=0-2 m=0-2
n=0-2 n=0-2

Olefin disulfonate Hydroxy disulfonate

Figure 4: Internal olefin sulfonate chemical structures

O O
O a b
O c
SO3Na
OH

X = OH, SO3Na or Cl

Branched C16, 17 alcohol-PO/EO-glycidyl sulfonate

O O SO 3Na
O a b

Branched C16, 17 alcohol-PO/EO-sulfate

Figure 5: Chemical structures of branched C16, 17 alcohol alkoxy sulfonate and sulphate derivatives
14 SPE 113313

25

Solubilisation Parameter, v/v

20 Vo/Vs
100
90 Excess n-octane
80 15
Phase Volume, cc

70
60
50 Microemulsion 10
Vw/Vs
40
30 5
20
10 Excess Brine
0 0
2 3 4 5 6 12 13 14 15 16

Salinity, % NaCl Salinity, %NaCl

Fig 6a: Phase volumes measured for IOS 2024 at 84°C Fig 7: Solubilisation parameters vs salinity, IOS 1518 at 80°C

25
Solubilisation Parameter, v/v

Vo/Vs
20

15

10

5
Vw/Vs
0
2 3 4 5 6
Salinity, %NaCl

Fig 6b: Solubilisation parameters vs salinity, IOS 2024 at 84°C

 SPE 113313 15

20 25

Solubilisation Parameter at Cø, v/v

IOS 1518, n-octane
IOS 2024, n-octane
20
Opt. salinity Cø, %NaCl

15

15
10
IOS 1518, n-octane
IOS 2024, n-octane
10
5

5
0 75 80 85 90 95 100
75 80 85 90 95 100 Tem perature, °C
Temperature, °C

Fig 8a and b: Optimal salinity and solubilisation parameter vs temperature for IOS 2024 and IOS 1518

50
15

Solubilisation Paramter at Cø, v/v

IO S 2024, n-dodecane 40
IO S 2024, n-dode cane
Opt. salinity Cø, %NaCl

IO S 2428, n-dodecane
IO S 2428, n-dode cane
10 30

20
5
10

0
0 0 50 100 150 200
50 60 70 80 90 100 110 120 130 140 150
Tempe rature , °C
Temperature , °C

Fig 9a and 9b: Optimal salinity and solubilisation parameter vs temperature for IOS 2024 and IOS 2428

10 IO S 2024, n-octane
IO S 2024, n-de cane
Solubilisation Parameter at Cø, v/v

25 IO S 2024, n-dode cane

Opt. salinity Cø, % NaCl

20
6

4
15
IO S 2024, n-octane
IO S 2024, n-de cane
2 10
IO S 2024, n-dode cane

0 5
50 60 70 80 90 100 110 120 130 140 150 50 60 70 80 90 100 110 120 130 140 150
Te mpe rature , °C
Te mpe rature , °C

Fig 10a and b: Optimal salinity and solubilisation parameter vs temperature for IOS 2024 in different alkanes
16 SPE 113313

Batch
87B Batch
131B
A B
8

Solubilisation Parameter at Cø, v/v

Batch
87B 131B
Opt. salinity Cø, % NaCl

7 Batch
A B 25
6
5 20
4
3 15
2
10
1
0 5
60 70 80 90 100 110 120 130 60 70 80 90 100 110 120 130
Temperature, °C
Te mpe rature , °C

Fig 11a and b: Optimal salinity and solubilisation parameter vs temperature for chemically different IOS 2024 samples (with differing
sulfonation)

Solubilisation Parameter at Cø, v/v

8
25
7
Opt. salinity Cø, % NaCl

6 20
5
4 15
3
81C
Batch 87B
Batch
2 10 Batch
81C Batch
87B
C A
1 C A

0 5
60 70 80 90 100 110 120 130 60 70 80 90 100 110 120 130
Te mpe rature , °C
Te mpe rature , °C

Fig 12a and b: Optimal salinity and solubilisation parameter vs temperature for chemically different IOS 2024 samples (with differing
IO feedstocks)
SPE 113313 17

10

Crude A
1
0.3% ENORDET A772, test1
IFT, dyne / cm

0.3% ENORDET A772, test 2

0.1
Crude B

0.01

0.001
0 10 20 30 40 50 60 70 80 90
Time, minutes

Figure 13: ENORDET A772 (a branched C16,17 alcohol alkoxy glycidyl sulfonate) tested at 98°C with Crude A (with
18.2% brine) and at 72°C with Crude B (with 3.1% Seawater Brine)

10
< 98°C

1
IFT, Dyne / Cm

0.1

0.3% ENORDET A552

0.01
0.3% ENORDET A092

0.3% ENORDET A792

0.3% ENORDET A372

0.001
0 20 40 60 80 100 120 140
Time, Minutes

Figure 14: Different ENORDET A series surfactants (branched C16,17 alcohol alkoxy glycidyl sulfonates) tested at 98°C with Crude A
with 18.2% brine, showing ENORDET A092 to give the lowest IFT result
18 SPE 113313

Starting Ethylene
Natural Fats Paraffin Normal
Materials and Oils waxes Paraffins

Ethylene Detergent
Raw Alpha / Benzene
Oxide range Fatty
Materials Internal
PO alcohols Acids Toluene
Olefins
Xylene

Alcohol
alcohol ethoxy- Alkyl Fatty Fatty Alpha Linear Paraffin
sulfates
Alcohol glyceryl Alkyl sulfonate
ethoxylate alkanol amine Internal
Surfactants sulfates ether aromatic
Sulphon- amides oxides olefin
ates sulfonate sulfonate sulfonate
Carboxyl
-ates

Figure 15: Different routes to surfactants (shaded = Shell Chemical commercial routes and surfactants)