Fuel 283 (2021) 118624

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Fuel
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Full Length Article

Development of robust models for the prediction of Reid vapor pressure T

(RVP) in fuel blends and their application to oxygenated biofuels using the
SAFT-γ approach
⁎
Alexander Landeraa, Niall Mac Dowellb, Anthe Georgea,
a
Sandia National Laboratories, Livermore, CA 94551, USA
b
Centre for Process Systems Engineering, Dept. of Chemical Engineering, Imperial College London, South Kensington, London SW7 2AZ, UK

A R T I C LE I N FO A B S T R A C T

Keywords: The growing demand for inexpensive, environmentally benign fuels has sparked research into fuel properties
Reid vapor pressure that affect fuel production, handling and engine efficiency. Reid vapor pressure (RVP) has been shown to be one
RVP such important fuel property. Having models that can accurately predict the RVP of a fuel rapidly and robustly
Oxygenates can aid in the design of de novo fuels and increase the value proposition to the refinery. Conventional fossil fuels
Alcohols
typically consist of 100 s of highly non-ideal components, especially when oxygenates are involved, and current
Blend models
methods often fail to predict RVP correctly. The large number of components can render conventional modelling
approaches burdensome and inaccurate. To overcome these barriers, a robust methodology for the rapid and
accurate prediction of the RVP of complex base fuels blended with oxygenated biofuels via surrogate models was
developed. The aim was to minimize the number of components necessary to accurately represent the complex
mixture, whilst retaining the ability to accurately predict RVP of the base fuel. Three models were developed
using the SAFT-γ approach, which varied in complexity and accuracy of prediction. The RVP for a suite of
oxygenates, blended at 10, 20, and 30%, by weight into blendstocks for oxygentated blending (BOB) was studied
in order to evaluate which oxygenate families have potential to reduce RVP. The majority of oxygenates eval-
uated decreased the RVP of the mixture, with the branched alcohols and the ketones showing the largest de-
crease. These results have promising implications for biofuels development and biorefinery economics.

1. Introduction
Whilst the transportation sector is evolving the general consensus is
that liquid fuels will remain dominant for the next several decades [1].
Although commercial sales of electric cars have steadily increased, to
date, in the United States, they still account for less than 2% of all auto
sales [2]. Indeed, annual growth rates for electrified cars has been de-
clining for each of the past 5 years [3]. Globally, the electric car stock is
equivalent to just 0.2% of all Passenger Light-Duty Vehicles (PLDV) [4].
A number of studies have attempted to forecast the market share of
electric vehicles in the United States [5–9]. Forecasts vary, but by the
year 2030, the most optimistic forecasts show a market share, in the
United States, of only 30%. In 2017, the transportation sector ac-
counted for 29% of all the greenhouse gas (GHG) emissions in the
United States. About half of that came from passenger cars and light
duty trucks [10]. The production of crude oil in the United States is
expected to increase for the next several years, plateauing out in the
year 2025 [11]. It is therefore imperative that strategies are developed
to reduce the CO2 intensity of transport fuels, such that GHG emissions
are reduced.
One such strategy is to concentrate on the design of the fuel, its fuel
properties, and how they directly impact its combustion characteristics.
The vapor pressure of a fuel is an important fuel property, as it de-
scribes the facility of fuel volatilization once it is injected into the en-
gine cylinder. When the vapor pressure of a fuel is measured at 37.8 °C,
in a container with a V/L ratio of 4:1, it is referred to as the Reid vapor
pressure (RVP), and is the industry standard measure for vapor pressure
[12]. Low RVP fuels are associated with cold start problems and higher
soot production, while high RVP fuels are associated with vapor lock
[13]. In the United States, in order to be distributed, the maximum RVP
allowed is within a range of 54 and 103 kPa, as a function of location
(primarily altitude) and season [14]. Therefore, fuels vary in compo-
sition based on the region and season in which they are being used. A
‘summer’ fuel, for example, has a low RVP due to higher day time

⁎
Corresponding author.
E-mail address: angeorg@sandia.gov (A. George).

https://doi.org/10.1016/j.fuel.2020.118624
Received 30 December 2019; Received in revised form 29 June 2020; Accepted 3 July 2020
0016-2361/ © 2020 Published by Elsevier Ltd.
A. Landera, et al.
temperatures, while a ‘winter’ fuel is allowed to have a higher RVP.
The primary test for RVP is governed by ASTM-D5191, which
measures the RVP of a petroleum product at a V/L ratio of 4:1 [12].
RVP tests are costly and time-consuming to perform, and therefore the
development of a high-throughput screening approach for the reliable
description of RVP is of considerable value for the development of novel
fuels in a high-throughput fashion. A key challenge in this context is the
complexity of the fuel mixtures. Due to the complex nature of fuels, the
development of surrogate fuels for a variety of research applications is a
promising strategy. These surrogates generally have a reduced number
of components, but are designed to be representative of the fully
complex fuel, for the attribute being evaluated; in this study, RVP.
The Research and Motor Octane Number, or RON and MON re-
spectively, are used to describe the knocking tendency of a fuel for use
in a Spark Ignition (SI) engine [15–18]; fuels with a high RON, and low
MON are considered to have the best anti-knocking behavior. Whilst
engine configuration is also important, a fuel that has the aforemen-
tioned qualities is said to display a large Octane Sensitivity (OS), which
is the difference between RON and MON measurements. Therefore, OS
is a useful metric for the evaluation of potential fuels.
Small alcohols, such as methanol and ethanol, blended into BOBs
have several advantages over their non-oxygenated counterparts. They
tend to have better RON, MON, and OS, making them far more suitable
for use in SI engine designs [19]. Chemical kinetics modeling has shown
that this can be explained by their inability to undergo RO2 chain
branching chemistry, which would give rise to Negative Temperature
Coefficient (NTC) behavior [20]. It is for this reason that methanol and
ethanol have an OS of 20, and 19, respectively. In addition, alcohol
fuels, on the basis of ppm in the exhaust, show a decrease in carbon
dioxide (CO2), and hydrocarbon (HC) emissions, with an increase in NO
emissions, as vehicle load increases [21,22]. It may, however, be worth
noting that whilst these fuels show a decrease in CO2 emissions on a
mass basis, owing to their reduced energy density relative to conven-
tional gasoline fuels, alcohol fuels have an increased level of CO2
emissions on the basis of energy service delivered, and thus, in order to
be consistent with a deep decarbonization scenario, the carbon source
for these fuels needs to be ultimately atmospheric [23,24]. In addition,
it has been previously shown that small linear alcohols show marked
non-linear blending behavior, with respect to RVP, when blended into
BOBs. In 2010, Andersen et al. measured the RVP of several alcohol-
gasoline blends from 5 to 85 vol% alcohol [25]. Their results confirmed
the non-linear effects of linear alcohols, with the non-linear effects
decreasing as the size of the alcohol increases. As the size of the alco-
hols increases, they have characteristics more closely resembling linear
alkanes, rather than alcohols, and the non-linear effects caused by the
hydroxyl group are diminished. Several oxygenates beyond alcohols
have been tested as possible additives into fuels. In 2011, Christensen
and others looked at the fuel properties of furans, levulinates, and al-
cohols blended into three BOBs [26]. They observed that most oxyge-
nates decreased the RVP of a BOB, making them suitable for blending
with high RVP BOBs. In addition, McCormick et al. identified several
oxygenates whose properties offer high promise for improving the
performance of high-octane advanced SI engine fuel, when blended into
a conventional or reformulated blendstock for E10 blending [27]. These
oxygenates were identified as ethanol, 2-butanol, and isobutanol.
Oxygenates which can decrease the vapor pressure of fuels may also
find utility in refinery applications, where high vapor pressures can lead
to non-negligible losses, known as fugitive losses, of refinery products
via, for example, evaporative emissions from storage tanks and pipes
[28,29]. In 2008, a team studied the emissions of hydrocarbons from a
typical refinery, and concluded that 0.17% of the mass of the refinery
hydrocarbon were lost due to emissions, a loss in profits by $3.1 million
per year [30], on the basis of a $40 per barrel market value. Minimizing
fugitive losses can therefore clearly improve the economics for re-
fineries, decrease pollutants, and increase the efficiency of refinery
processes.
2
Fuel 283 (2021) 118624
Although, some work has been aimed at reducing emissions from
refineries, this has been primarily focused on improving seals, and
eliminating leaks. An additional way of reducing fugitive losses is to
focus on the refinery product itself, via reducing its vapor pressure.
Recently, for example, it was found that adding ethyl acetate in con-
junction with ethanol decreased the RVP of gasoline [31]. In addition,
the ethyl acetate increased the RON and MON of the original gasoline,
while keeping the OS constant. Ratcliff et al. evaluated the combustion
characteristics of a 12% i-butanol/7% ethanol blend [32]. Their find-
ings show that the resulting RVP does not increase (as it would for
ethanol only blends), showing the benefit of adding other oxygenates to
a petroleum fuel in an effort to decrease fugitive losses. Lastly, An-
dersen et al. tested a 50/50 mixture of ethanol and 1-butanol blended
with gasoline and showed that the resulting RVP curve features a much
smaller increase in RVP, than ethanol alone. [24]. Although, the au-
thors did not evaluate the impact of RVP lowering oxygenates and their
refinery applications, 1-butanol may be used as a refinery additive to
lower the fugitive loss of hydrocarbons. Developing a model, which is
capable of high-throughput screening of fuels is therefore key to ac-
celerating progress in this space.
Efforts to develop models capable of predicting the vapor pressure
of complex mixtures date back to the mid-20th century, with varying
degrees of success. In the 1960s, three methods were available for es-
timating the vapor pressure of petroleum fuels at high temperature and
pressure, namely the British Petroleum, Maxwell, and Edmister
methods [33–35]. The British Petroleum method mimics the distillation
process by using theoretical plates. Using empirical relationships, it
then calculates the partial pressure for each theoretical plate. The sum
of these partial pressures is then considered to be the True vapor
pressure (TVP). Alternatively, the Maxwell and Edmister method both
rely on converting an ASTM distillation curve into either a True Boiling
Point (TBP) distillation curve, or a (pressure, volume, temperature) PVT
phase diagram, respectively. While these methods were reasonably
accurate, they relied on a large number of conversion tables, and were
limited to high temperature and pressure estimations. In 1980, Eg-
gertsen, Nygard, and Nickoley used a gas chromatograph to obtain the
mole fraction of each component in a fuel [36]. They were then able to
estimate the vapor pressure of petroleum distillate fractions by applying
Dalton’s, and Raoult’s laws. For each fuel component, Antoine’s vapor
pressure correlation was used to obtain the saturation pressure. In
1984, Wilhelm and Prausnitz used perturbed hard-chain equation of
state (EoS) methods to estimate the vapor pressure of crude oil fractions
[37]. Their predictions were in reasonable agreement with experi-
mental vapor pressure data. In 1985, Furey examined the volatility
characteristics of oxygenates dissolved in different fuels [38]. Furey
was particularly interested in the sharp boost in RVP that occurs when
some small alcohols are used as the oxygenate. From his work, he de-
veloped a simple relationship, RVP = kCn, which can model the early
rise in RVP, which occurs when the first 1–2% of alcohol is blended. In
his relationship, C is the alcohol concentration, while k and n are
constants dependent on the neat gasoline and alcohol [38]. A few years
later, Chen developed a volatility model for gasoline based on a 10-
component surrogate [39]. The ten components are fuel dependent but
are based on grouping similar-sized species together, and selecting the
compound with the largest wt. % in that group. The surrogate was then
used in isothermal flash calculations, using the Peng-Robinson EoS. The
surrogate performed well for non-oxygenated fuels but led to inaccurate
results when oxygenates were involved. For methanol, the ten-compo-
nent surrogate underestimated the initial rise in RVP by approximately
10 kPa, or an error of 12.5%. The authors suggest this may be due to the
polar nature of methanol. In 1999, Gahbri et al. used a Neural-Network
model to estimate the bubble point pressure of crude oil and gas mix-
tures. Their neural network was trained using 5200 PVT datasets, and
obtained a correlation coefficient of 0.9891 [40]. The maximum abso-
lute relative error was reported to be 19.93%, while the average ab-
solute relative error was 6.48%. In 2014, Albahri used a neural network
A. Landera, et al.
algorithm to predict the RVP of 362 different petroleum fractions. Of
these, 300 were used in the training set, and 62 were used as a testing
set. For the training set, the average deviation was 2.29 kPa, and the
maximum deviation was reported to be 13.85 kPa. For the testing set,
the average deviation was 2.24 kPa, and the maximum deviation was
reported to be 13.85 kPa. In total, Albahri’s work resulted in a corre-
lation coefficient of 0.995, equivalent to a relative deviation of 5.09%
[41]. However, petroleum fractions do not contain oxygenates, and it is
as yet uncertain how well this method will fare when including oxy-
genated blendstocks. Later, Adlene and coworkers used a fitting pro-
cedure to predict the RVP of a fuel. They validated the resulting model
using a variety of fuels, with a correlation coefficient of 0.87 [42]. Plots
of the measured RVP vs. the predicted RVP show large deviations, with
the largest deviations being about 50%. In 2019, several oxygenates
were blended into a CARBOB (California reformulated BOB), with
subsequent RVP measurements taken [43]. Predictions using five EoS
methods demonstrated reasonable accuracy in being able to reproduce
experimental measurements for oxygenated blends. Of the five EoS
methods used, the two best performing were UNIFAC-Dortmund, and
the CPA (Cubic Plus Association), which have a Root Mean Square
Errors (RMSE) of 5.2 and 5.5%, respectively. While these RMSE are
relatively good, it is interesting to note that all of the methods tested
show deteriorating results towards the high end of their RVP mea-
surements. In addition, when blended with ethanol, neither of the five
EoS produce accurate results, with the best performing EoS being de-
viating by more than 10% (~5.1 kPa). In 2011, the Vapor Liquid
Equilibrium (VLE) of binary and ternary mixtures of long-chain me-
thylesters was modeled using the SAFT-VR EoS [44]. Predictions
slightly underestimated the experimentally derived VLE of the methyl
palmitate/methyl linolenate binary mixture, and nearly perfectly re-
produced the experimentally derived VLE of the methyl oleate/methyl
linolenate binary mixture. A residue curve map was generated for the
ternary mixture, consisting of methyl palmitate, methyl linolenate, and
methyl oleate. Predictions of the bubble pressure, using the SAFT-VR
EoS, are nearly identical to previous predictions using an empirical EoS.
In 2014, Oliveira and coworkers published predictions on the vapor
pressure of several pure Fatty Acid Methyl Esters (FAME), using the
soft-SAFT EoS [45]. Overall 14 different FAMEs were chosen. Predic-
tions were nearly identical to experimental measurements at tempera-
tures beyond about 350 K but tended to slightly over predict the vapor
pressure at lower temperatures. A %AAD total for all of their vapor
pressure data was calculated to be 5.8%. It is suggested by the authors
that one reason for the low temperature deviation may be due to the
low inherent vapor pressures of FAMEs, which may be accompanied by
larger experimental errors. In the same year, Perdomo, Millan, and
Aragon published vapor pressure predictions of several saturated and
unsaturated FAMEs, using the SAFT-γ EoS [46]. While their predictions
were always in good agreement with the available research, they al-
ways slightly underpredicted the vapor pressure by a few kPa. Predic-
tions were slightly worse as the degree of unsaturation increased, and
the authors propose that the inclusion of more unsaturated FAMEs into
their objective function could improve predictions.
Most previous work in this area has focused on developing models
suitable for only very specific fuels. Each new fuel requiring a new
model. This is laborious and inefficient. If a general model could be
developed capable of accurately estimating RVP, while retaining ease of
use, fuels could be screened in a high-throughput fashion. Novel fuels
could be screened in silico before production begins, and lead times to
more functional fuels can be reduced.
The present study aims to develop a set of rules, which will enable
customized RVP prediction models for a target fuel. Three sets of rules
were developed. The first set of rules leads to the creation of a “small
surrogate model”, while the second and third set of rules correspond to
a “moderate” and “large” surrogate model, respectively. These models
increase in complexity and precision, therefore for each target blend-
stock one of the three models can be used depending on the level of
3
Fuel 283 (2021) 118624
precision required. These models differ in the number of components
chosen to represent a given BOB, with the small model employing the
fewest number, and the large model employing the largest number of
components. These surrogate models can then be used with the SAFT-γ-
mie EoS, which has been shown to reliably predict thermophysical
properties of complex fluid mixtures. These models are validated using
seven BOBs, with varying chemical compositions, and RVPs. This study
then goes on to evaluate the performance of these models in predicting
the RVP of oxygenated BOBs. To this end, the models are validated
using two BOBs (a summer and a winter), each with data on blends with
several oxygenates. A physical interpretation of the interaction of aro-
matics with alkanes and alcohols is then given. Appealing to previous
excess thermodynamic measurements reported in the literature, an
explanation for why these interactions are important in understanding
RVP is made. Lastly, predictions are then made on the RVP of several
oxygenates blended into a Summer BOB, at 1 vol% increments, ending
at 30% by volume. These predictions are made using the large surrogate
model.
The novelty of this contribution lies in the development of a gen-
erally applicable approach for the development of reliable surrogate
models, including when oxygenates are present. These surrogate
models will aid the development of novel fuels by providing a platform
for high- throughput screening, and also help identify oxygenates with
promising refinery applications.
Theory/calculation
The method used to predict the RVP is the SAFT-γ-Mie EOS. SAFT-γ-
Mie’s robustness relies on an efficient and reliable way to construct the
Helmholtz free energy of a system. Here, only a brief overview is pro-
vided, and interested readers are directed to the original papers for
more details [47–49]. SAFT-γ-Mie calculates the Helmholtz free energy
of a given fluid by decomposing it into specific and meaningful com-
ponents. This is represented below as:
A = Aideal + Amono + Achain + Aassoc (1)
where Aideal
is the Helmholtz free energy obtained through the ideal gas
law, Amono is the residual accounting for monomeric Mie segment in-
teractions, Achain is the residual accounting for molecule formation, and
Aassoc is a term that accounts for association interactions. With the ex-
ception of the ideal term, these terms can be obtained by using per-
turbation theory as applied by Barker and Henderson [50], or Wer-
theim’s first order perturbation theory (TPT1) [51–54]. The Mie
potential, Φ , which offers more flexibility than the Lennard Jones po-
tential, describes the interaction between segments. The interaction
potential between two identical segments is given by the following
formula:
r
λkk a
λkk
⎡ σ σ ⎤
Mie
Φkk (rkk ) = Ckk εkk ⎢ ⎛ kk ⎞
⎜ ⎟ − ⎛ kk ⎞
⎜ ⎟
⎥
r ⎝ rkk ⎠
⎣ ⎝ kk ⎠ ⎦ (2)
where rkk is the center of mass to center of mass distance between the
two segments, σkk is the diameter of each segment, εkk is the depth of the
r a
potential well. λkk , and λkk are repulsive and attractive factors. Ckk is a
normalization factor designed to ensure that the magnitude of the po-
tential minimum coincides with εkk . It is defined as:
r
λkk
λr λ r ⎞ λkk
r −λ a
Ckk = r kk a ⎛⎜ kk a ⎟
kk
λkk − λkk ⎝ λkk ⎠ (3)
Values for Mie potential parameters can be obtained by regression
to appropriate pure component data, such as density, or vapor pressure.
Unlike interactions (also known as cross interaction parameters), i.e.,
those interactions between two segments of different types, may be
obtained by simple combining rules, which involve the individual like
interactions. These combining rules are summarized below.
σkk − σll
σkl =
2 (4)
A. Landera, et al. Fuel 283 (2021) 118624

3 3
σkk σll
εkl = εkk εll
σkl3 (5)

λkl = 3 + (λkk − 3)(λll − 3) (6)

With these parameters, the interaction between different molecules
can be determined, as well as the Helmholtz free energy. Once the
Helmholtz free energy is constructed, it is the derivative with respect to
volume that gives the pressure:
∂A
P=
∂V (7)
The default dispersion energy (ε) parameters are regressed from
experimental data spanning a wide range of experimental conditions.
RVP values however are measured specifically at 37.8 °C. Any model
created can therefore benefit from re-optimizing these ε values for use
in estimating RVP. The SAFT-γ-Mie default ε parameters are useful in
describing many physical properties, at varying conditions. Here, the
Fig. 1. Composition of the BOBs used in the validation of the new models based
interest is in ε parameters specifically for the estimation of RVP. The
on the categorization of the components in a BOB into 5 groups: paraffins, i-
optimization of ε values were made in response to SAFT-γ-Mie’s, with
paraffins, aromatics, olefins, and naphthenes. The y-axis is in mole percent. The
its default parameters, ability to reproduce experimental VLE data for plot shows a wide distribution of chemical classes within the 7 BOBs used in this
binary mixtures involving isooctane, toluene, n-heptane, and 1-hexene, study.
at conditions of 40 °C, close to the RVP temperature of 37.8 °C [55–62].
VLE data at 40 °C is plentiful, while data at 37.8 °C is scarce, or not
variance in composition of these seven BOBs. In terms of mol%, n-
available. It is anticipated that using VLE data at 40 °C will still yield
paraffins vary from 8.4 to 25.8, while i-paraffins vary from 27.2 to 63.4.
good estimates of ε parameters. These 4 components chosen make up
Meanwhile, aromatics vary from 14.9 to 39.8, olefins vary from 0.9 to
the components involved in a four-component surrogate used ex-
29.7, and naphthenes vary from 1.5 to 30. In addition, the RVP reported
tensively in the fuel industry [63]. As a simplified model, this four-
for these BOBs also vary from 27.64 to 89.71 kPa, covering a large
component surrogate has been used to investigate several combustion
swath of the RVP spectrum for non-oxygenated BOBs. As RVP is a
engine characteristics [63,64]. Additionally, these four components
function of chemical composition, comparison of the models in this
include the majority of the SAFT groups used in spark ignition fuels.
study to these seven BOBs should yield confidence in their ability to
The default ε values were refined to obtain an adequate description of
predict RVP.
the fluids studied. The new models provide a reliable representation of
As most commercially sold fuels contain 10% ethanol, the model
the fluids, with all %AADs < 8. Plots illustrating these results can be
must also be validated using oxygenated BOBs. For this, data were
found in the supplementary materials section, along with a list of the
obtained from a Fuel Property Database developed as a data repository
parameters which were changed, along with their default values. The
for properties of oxygenated fuels [74]. It contains oxygenate blend
default SAFT parameters are wholly unable to reproduce VLE data for
data for two BOBs, one summer and one winter, with oxygenates from
the toluene + isooctane system. This stems from the CCH3 group used
different chemical classes. The summer and winter BOB chosen corre-
in modeling isooctane, and the unreliability of combining rules to
spond to BOB 1 and BOB 2 in Fig. 1 and Table 2, respectively. They
correctly estimate unlike dispersion energy parameters (εkl) [65,66].
make up two of the 7 BOBs used to validate the models for non-oxy-
The SAFT-γ-Mie group parameters for the CCH3 group were taken from
genated BOBs. For the Summer BOB, the following oxygenate data were
Chremos et al., and are important in the modeling of tert-butyl con-
available: 2-butanol, 1-butanol, ethanol, methanol, butyl acetate, cy-
taining groups. [67] In addition, the parameters for a cyclic ketone
clopentanone, anisole, 2-methyl-1-butanol, 2,4-dimethyl-3-pentanone,
group were estimated using vapor pressure, and saturated liquid den-
3-methyl-1-butanol, 2-pentanone, methyl acetate, ethyl acetate, 2-
sities for a homologous series of cyclic ketones from C4 to C7. Cross
pentanol, and tetrahydrofuran. For the winter BOB, the following
interaction parameters between the cyclic ketone group and CH3, CH2,
oxygenate data were available: 2-butanol, isobutanol, ethanol, n-pro-
aromatic CH, and CH3 bonded to an aromatic carbon were also esti-
panol, cyclopentanone, isopropanol, and isopropyl acetate. In total,
mated using appropriate vapor pressure, bubble temperature and excess
these data contained 39 data points for the summer BOB, and 21 data
enthalpy data [68–72]. These results are available in the supplementary
points for the winter BOB. The exact details of this data can be found in
material to this paper.
the supplementary materials section. The data available can validate
All calculations were carried out using the gPROMS software [73].
the RVP models for a variety of functional groups including alcohols,
Comparisons with experimental data are quantified in this paper by the
ketones and esters blended into BOBs.
use of the %AAD (percent Average Absolute Deviations), which is de-
fined as follows:
nR 2.2. Model rules and descriptions
1 Riexp − Ricalc
%AAD =
nR
∑ Riexp
× 100
i=1 (8)
In a search for a quick and predictive model for physical properties
many research groups have turned toward surrogate models [75–77].
2. Results and discussion These models contain no more than about 10 components and are
tested and validated using experimental measurements [78]. These
2.1. BOBs used for model validation surrogate models tend to work for very specific BOBs, and in general,
cannot be used or extrapolated to other BOBs. A different approach
The RVP models developed in this study for non-oxygenates were must be taken if a suitable model that works for a majority of BOBs is to
validated using seven BOBs. These BOBs were selected such that there be developed. Experimental testing of BOBs has recently become fairly
was high variability between their compositions, and in addition that routine and obtaining a detailed hydrocarbon analysis (DHA) of any
they were representative of a broad range of base fuels. Fig. 1 shows the BOB can be done with little effort. A DHA gives a list of all the

4
A. Landera, et al. Fuel 283 (2021) 118624

components identified in a BOB along with the quantity of each com- Table 1
ponent present. In addition, a particular BOB is described in terms of Vapor pressure at 37.8 °C for a homologous series of par-
the proportion of chemical classes present. Typically, these chemical affin, i-paraffin, aromatic, olefin, and naphthene chemical
classes are n-paraffins, i-paraffins, aromatics, olefins, and naphthenes. groups. Vapor pressure is given in units of kPa.
Using the DHA of a fuel, three sets of simple rules for the inclusion Paraffin
of components into an RVP model were developed. They lead to the Chemical name VP, 37.8 °C
development of a small, moderate, and large surrogate model. These propane 1301.96
butane 354.65
models developed also give insight into the predicted RVP as more
pentane 107.45
components are added to the model. The rules used to develop the hexane 34.20
models are as follows, with a detailed procedure shown in the supple- heptane 11.18
mentary materials: I-Paraffin
Chemical name VP, 37.8 °C
2.2.1. Rules for small surrogate model i-butane 498.90
The small surrogate model includes all those components which i-pentane 142.86
i-hexane 46.69
make at least a 1 mol% contribution to the composition of the BOB. The i-heptane 15.67
composition of the components, within a chemical class, is then nor-
Aromatics
malized to the fraction of the chemical class present in the fuel, ac-
Chemical name VP, 37.8 °C
cording to the DHA. The chemical classes used here are n-paraffins, i- benzene 22.24
paraffins, aromatics, naphthenes, and olefins. This normalization step toluene 7.12
ensures that the proportion of each chemical class is preserved. In m-xylene 2.24
general, implementing the small surrogate models will include ~10–15 Olefin
components. Chemical name VP, 37.8 °C
1-hexene 41.45
1-heptene 14.36
2.2.2. Rules for the moderate surrogate model
The moderate surrogate model, includes all those components Naphthene
Chemical name VP, 37.8 °C
which make at least a 0.5 mol% contribution to the composition of the
cyclopentane 68.41
BOB, and normalization undertaken as with the small surrogate model. methylcyclopentane 31.07
In general, these models include ~30 components. In general, the small
and moderate models are easy to implement, and represent a very small
fraction of the total number of components present in a typical BOB. If Table 2
this threshold is decreased further from 0.5 mol% to 0.1 mol% a typical Predicted and measured values for the seven BOBs used in this study, using the
model would include more than 80 components. Such a model would small, moderate, and large surrogate model. Values are in kPa.
be cumbersome to produce, and difficult to calculate; and so, a slightly Small Moderate Large Measured
different set of rules for obtaining the large surrogate model have been
developed. BOB 1 35.21 38.35 38.47 37.43
BOB 2 104.60 98.01 87.34 89.71
BOB 3 23.76 26.38 25.76 27.64
2.2.3. Rules for the large surrogate model BOB 4 57.25 51.72 50.35 52.46
The large surrogate model includes those n-paraffins and i-paraffins BOB 5 66.97 61.52 58.62 54.16
that make at least a 0.1 mol% contribution to the BOB. A 1 mol% BOB 6 43.35 42.19 40.12 41.45
threshold is used for aromatics, and only the most abundant naphthene BOB 7 57.82 58.73 54.84 56.44
%AAD 10.59 5.302 4.36
is included. Olefins are included, as α-olefins, and only those that make
at least a 1 mol% contribution are included. In order to ensure that
some aromatics are included in each model the three isomers of xylene used in each model, for each BOB, can be found in the supplementary
are treated as one component, and the same normalization procedure materials section of this paper. For convenience, a Standard Operating
followed in the development of the small and moderate surrogate Procedure (SOP) for the development of the models outlined in this
model is used. On average, the large surrogate model employs 39.6 section has been written. It can be found in the Supplementary
components. This is only slightly larger than the 30 components re- Materials Section.
quired to use the moderate model. The advantage of the large surrogate
model is not only in the number of components used to model RVP, but
also in the type of components used. It draws heavily on paraffins, 2.3. Model validation
while de-emphasizing aromatics. This works because the range of RVPs
present in paraffins is much greater than that which is present in aro- Fig. 2 graphically illustrates the performance of these three models
matics. Table 1 illustrates this idea by showing the RVP of a homo- using the seven BOBs available for validation. Table 2 shows both the
logous series of paraffins, i-paraffins, aromatics, olefins, and naph- predicted, and measured RVP values. All three models perform well,
thenes [79]. In this study, when the terms small surrogate model, with the %AAD of the moderate and large surrogate model both cal-
moderate surrogate model, or large surrogate model are used, it is in culated to be < 6%. The small surrogate model is less accurate, with a
reference to the model developed from the corresponding set of rules. %AAD of 10.59%. On average, 19.8 components are included in the
When analyzing Table 1, it can be observed that for any surrogate small surrogate model. This means that the small surrogate model can
model to succeed at predicting RVP it must contain most of the low produce modestly accurate results, with very few components.
molecular weight paraffins and i-paraffins. Propane, butane, and pen- By percentage, all models performed less well when trying to model
tane all have RVPs above 100 kPa. If they are not included large errors BOB 5. BOB 5 is anomalous, because it contains a very large amount of
in RVP predictions are likely to occur. For aromatics, and naphthenes, naphthenes, 29.98 mol%. The dispersion energy parameter (εkk) for the
the difference between successive members of the homologous series is cyCH2 (cyclic methene) group was not optimized for RVP predictions,
much smaller thereby making them less important in RVP surrogate and was kept at its default SAFT-γ-Mie value. Optimization of the
models. Although the smallest olefins do have large RVPs, the propor- cyCH2 εkk parameter for RVP predictions would likely improve the
tion of olefins in most BOBs are very small. Tables of the mole fractions performance of the model when applied to BOB5. However, the large

5
A. Landera, et al.
Fig. 2. Performance of the small, moderate, and large surrogate models vali-
dated using seven BOBs. Units are in kPa. From top to bottom: small, moderate,
and large surrogate model.
surrogate model only overestimates the RVP of BOB 5 by 8.23%.
Conversely, one of the best performing BOBs is BOB 6. BOB 6 may
benefit from having its percentage of olefins represented by two olefins.
Due to this, an unusually large percentage of olefins are automatically
included in the small surrogate model, and that may lead to excellent
RVP estimates, even when using the small surrogate model.
The large surrogate model also performs well. It outperforms the
moderate surrogate model, even though it includes a similar number of
species. Rather than simply including all species with at least a certain
threshold concentration the large surrogate model considers the im-
portance of molecular classes as well. Recognizing that aromatics are
less important than paraffins, the large surrogate model includes sev-
eral more paraffins than aromatics. On average, the % error for the
large surrogate model is 4.36%, and the absolute deviation is 2.11 kPa.
According to ASTM D5482-07, the repeatability, and reproducibility of
RVP measurements for samples within 14 to 100 kPa is 1.31–1.79, and
2.69–4.14 kPa, respectively [12]. This places the average absolute de-
viation of the large surrogate model squarely within the noise of ex-
perimentally measured RVP values. Because the large surrogate model
is easy to implement its potential as a screening tool cannot be ignored.
2.4. Oxygenated BOBs
Most commercially sold fuel in the United States is E10, meaning
that it is made up of 10% by volume ethanol, and 90% hydrocarbons
[80]. Oxygenates offer a number of advantages, including better RON
and MON values, as well as a general lowering of soot [19]. These are
important qualities in a fuel, and therefore, for any model to be useful,
it must also be predictive of the RVPs of oxygenate blends. To that end,
Fig. 3 show the performance of the small and moderate surrogate model
in predicting the RVP of oxygenates. The data used include 60
6
Fuel 283 (2021) 118624
Fig. 3. Performance of the small and moderate surrogate model validated using
oxygenate blending data from a summer and winter BOB. Values are in kPa. The
data show that these models tend to over-predict RVPs for oxygenate containing
BOBs.
oxygenate blending data points. Of these, 39 are oxygenates blended
into a summer BOB, while the remaining 21, are oxygenates blended
into a winter BOB. The summer and winter BOB correspond to BOB 1
and BOB 2 in Table 2, and are part of the 7 BOBs used to validate the
non-oxygenate models earlier.
Table S21 includes a detailed list of these oxygenate blending data
points. While these results are not generally promising, a few things are
worth noting. The %AAD for the summer and winter data are 19.72%
and 15.50% for the small surrogate model, respectively. While, for the
moderate surrogate model, these values are found to be 14.90% and
12.16%, respectively. These results are worse than each model’s per-
formance with non-oxygenated BOBs and serves to highlight the diffi-
culty involved in predicting the behavior of non-linear properties, such
as the RVP of oxygenated blends. It is noteworthy that, except for a few
outliers, both the small and moderate model tend to overestimate the
RVP of oxygenated blends. This suggests that these models are weighted
too heavily towards light molecular weight species, and therefore, a
better model can be achieved if higher molecular weight species are
included. One reason why the large surrogate model performs well may
be that it includes larger molecular weight paraffins (linear and bran-
ched). It does so by including those paraffins which make a contribution
of at least 0.1 Mol% to the composition of the BOB. These components
reduce the importance of low molecular weight species, leading to a
more balanced description of RVP. This is borne out by the results
depicted in Fig. 4, in which the performance of the large surrogate
model is validated using the same sixty blending data points used in the
validation of the small and moderate model.
With respect to the summer and winter data, the %AAD is 4.40%
and 1.55%. Additionally, the RMSE for the summer data is 1.79%,
while for the winter data it is 1.45%. In comparison to the previous
work by this team lead by Gaspar et al., in which the best performing
EoS had an RMSE of 5.2%, this work represents a substantial im-
provement [43]. Furthermore, in addition to having a lower RMSE, this
study spans an RVP range of 63 kPa, while Gaspar’s work spans an RVP
range of ~10 kPa (as measured from their Fig. 7). The lowest RVP
measured in Gaspar’s work is ~26 kPa, while the largest RVP measured
is ~36 kPa. This work, using EoS, also allows for greater insight than
methods which rely on neural networks. This is true, because with EoS
methods specific molecular interactions can be correlated to physical
properties, and can thus yield a physical understanding of why a par-
ticular RVP measurement occurs. An example comes from the work of
Mac Dowell et. al., in which they used SAFT-VR to model the phase
behavior of CO2 and monoethanolamine in aqueous solutions, as a
potential method of carbon capture [81]. They were able to make
A. Landera, et al. Fuel 283 (2021) 118624

Fig. 5. Excess enthalpy data for a series of n-alkane + toluene binary systems.
Excess enthalpies are given in J/mole. Excess enthalpies increase as the n-al-
Fig. 4. Validation of the large surrogate model: Plot of the predicted vs. mea-
kane size increases.
sured RVP of oxygenates blended into the Winter and Summer BOB. RVPs are
given in units of kPa. This plot illustrates the statistically superior performance
of the large surrogate model vs. the small and moderate surrogate model.

accurate predictions of the fluid composition as a function of pressure,

an important characteristic for measuring the amount of CO2 captured.
They did so, in part by accurately estimating the appropriate Binary
Interaction Parameters (BIPs), and thus understanding the type of in-
teractions responsible for their results. An approach which relies solely
on neural networks would have given a result without an explanation.
The small and moderate surrogate models are unsuitable for RVP
predictions of oxygenated BOBs. They only capture some of the changes
in RVP involved with the introduction of an oxygenate. Nevertheless,
the large surrogate model, being validated against the same 60 oxy-
genate data points, is statistically more robust and accurate than the
small and moderate models.

2.4.1. Physical explanation Fig. 6. Excess enthalpy data for a series of cycloalkanes + toluene binary
Although having models that correctly predict the RVP of BOBs is mixtures. Excess enthalpies are given in J/mole. Cycloalkanes weaken the
important, it would be complimentarily interesting to understand some aromatic interactions between toluenes.
of the important interactions which give rise to the RVP observed for a
given BOB. To do this, it is important to examine excess thermodynamic
properties. Excess thermodynamic properties are derived from the ap-
propriate excess thermodynamic function and is the difference between
the observed thermodynamic function of mixing and the function for an
ideal solution. Excess properties can give insight into the physical in-
teractions occurring in a mixture. There are many excess thermo-
dynamic properties; here the focus is mainly on the excess enthalpy
(HE). Figs. 5 and 6 show the HE of several n-alkane + toluene, and
cycloalkane + toluene mixtures at 298.15 K [82–91]. The n-alkanes
range from n-hexane to n-hexadecane [82–91]. Interactions with to-
luene are of interest because there are sufficient measurements of to-
luene, and it represents an aromatic with a side chain. Benzene could
have also been considered, but it would not have been a good proto-
typical aromatic found in fuel. From Fig. 5, HE increases with the size of
n-alkane indicating that larger n-alkanes are more capable of disrupting
toluene-toluene interactions. Fig. 7. Excess enthalpies of alcohols + toluene at 298.15 K. Excess enthalpies
In 2011, using two-color resonant two-photon ionization spectro- are in J/mole.
scopy, as well as ab initio calculations, Fujii et al. investigated the non-
covalent interactions of benzene-paraffin clusters [92]. A correlation
This computational study found a correlation between the average
between the strength of the interaction energy, and average polariz-
polarizability of the alkane and the interaction energy. Larger alkanes,
ability of the paraffin was found, and based on this, it was determined
given their higher polarizabilities, are capable of larger dispersion
that these interactions between benzene and paraffins (normal/bran-
forces, and thus larger strengths of interaction. This is in accord with
ched) were mainly due to dispersion. These results are reinforced by
the results shown in Fig. 5. It is important to note that these compu-
computational results carried out on saturated hydrocarbon - benzene
tational results, and the resulting correlation between polarizability and
complexes. The saturated hydrocarbons studied were propane, iso-
strength of interaction were also found to extend to iso-alkanes, and
butane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cy-
naphthenes. Indeed, these findings are also in agreement with the data
clooctane, and bicyclo[2.2.2]octane [93].

7
A. Landera, et al. Fuel 283 (2021) 118624

shown in Fig. 6, which show an overall weakening of interactions when

cycloalkanes are combined with toluene. Islam and Ibrahim, based on
observations of positive VE values for the toluene + cyclohexane
system, suggest that the difference in geometrical shapes (toluene is flat
while cyclohexane is not) may be important to understanding the
nature of this interaction. [94]. Further, they posit, based on excess
viscosity data, that a mixture of 2:1 and 1:1 (cyclohexane:toluene)
complex may form at low temperatures. This complex formation may
weaken toluene-toluene interactions. Literature sources for HE data
involving non-aromatic binary mixtures can be easily found. While an
exhaustive search of the literature cannot be claimed, an HE value in the
literature above 200 J/mole for such binary mixtures could not be
found [95–100]. One exception to this is cyclohexane + heptane,
whose maximum HE value was reported to be 228 J/mole [100].
Compare this to data from Fig. 5, where the maximum HE value for the
toluene + n-hexane system (the system with the smallest maximum HE
value) is 469 J/mole. This is larger by more than a factor of two. Here it
is posited that one of the important interactions responsible for RVP is
Fig. 8. Predictions of the RVP of several alcohols blended into the Summer
that between aromatics and alkanes (normal, branched, and cyclic).
BOB, at 1 vol% increments, up to 30 vol%. Most alcohols decrease the RVP. The
The possibility that other interactions may be important is not ruled out plot on the right shows antagonistic blending behavior. This illustrates the RVP
but it is clear that, when aromatics are present, the aromatic-alkane suppression of many alcohols.
interaction is significant. These interactions weaken aromatic-aromatic
interactions, and that may have a noticeable impact on RVP.
Alcohols can have profound influences on the observed RVP of a
BOB [25,26,43]. Fig. 7 shows HE data for a series of linear alcohols with
toluene at 298.15 K [101–106]. Their HE data is similar to that of the
alkanes in the previous paragraph, in that they are similarly large.
However, unlike those alkanes, the HE curves in Fig. 7 are un-
symmetrical, indicating the stronger polar nature of alcohols. Recent
literature, focusing on excess entropic factor (TSE) data between an
alcohol and an aromatic molecule, show that these binary interactions
feature a bond breaking and bond forming event, at low temperatures
[101,103]. This is borne out by excess VE data, as well [104]. As the
concentration of alcohol increases the weakening of aromatic-aromatic
interactions gives way to stronger hydrogen bond formation. However,
at higher temperatures relevant to RVP, VE measurements are positive
throughout the binary composition, indicating that hydrogen bonding
may be less effective, and a weakening of interactions in the mixture
occurs when alcohols combine with aromatics [107]. This, in con-
junction with the data in Fig. 7 indicate that alcohols strongly disrupt
the aromatic-aromatic interactions, but at some concentrations may Fig. 9. Predictions of the RVP of several esters and ketones blended into the
Summer BOB, at 1 vol% increments. The plot on the right shows antagonistic
lead to more structured fluids.
blending behavior. This illustrates the RVP suppression of many ketones and
esters.
2.5. RVP predictions

Using the large surrogate model, predictions were made for dif-
ferent oxygenates blended into the Summer BOB. These predictions will
aid researchers in their understanding of how different oxygenates,
when blended into a BOB, effect the RVP of that BOB. The first set of
predictions were performed for alcohols. Fig. 8 shows the results of
these predictions. The RVP predictions are plotted on the left panel, and
on the right panel, the predicted RVP minus the RVP taken from the
linear interpolation blend model are plotted. The goal in this study was
to find RVP suppression i.e. that the RVP is lowered with addition of an
oxygenate. If values on the right panel are negative, they correspond to
synergistic lowering of the RVP, and the RVP predicted is lower than
what the linear interpolation blend model predicts. Conversely, if those
values are positive, they indicate antagonistic blending, i.e. and the
RVP predicted is higher than what the linear interpolation blend model
predicts. A synergistic lowering of the RVP is favorable for refinery
applications, because lower RVP fuels lead to less fugitive losses.
Fig. 8 shows that, in general, only the higher molecular weight al-
cohols tend to decrease the RVP of the BOB they are blended into. All
alcohols showed antagonistic blending behavior with 2-pentanone and
2-hexanone behaving the most linearly (Fig. 9).
Fig. 8 shows the same type of predictions made for esters and
ketones. The overall trend in both of these groups is to lower the RVP
when blended into a BOB. In comparison to alcohols, esters and ketones
lower the RVP of a BOB by a further 1 to 2 kPa. While still exhibiting
antagonistic blending, esters and ketones show more linear blending
behavior than alcohols. Fig. 10 shows the same type of predictions, but
applied to cyclic ketones. It is clear that synergistic blending occurs for
all cyclic ketones, with cyclooctanone exhibiting large synergistic
blending behavior.
Overall, it was found that higher molecular weight oxygenates
tended to decrease the RVP of a BOB more than lower molecular weight
oxygenates.
The lowering trend of many of the oxygenates tested shows the
potential for reducing the RVP of refinery products, especially cyclic
ketones. As highlighted in Section 1, this lowering can account for in-
creased profits, and reduced GHG emissions emitted into the atmo-
sphere. Even at 10% blend levels, many of the oxygenates tested show
decreases of the neat BOB RVP by at least 1 kPa, a substantial reduction
which can reduce costs over the long run. There is also an opportunity
for some of these oxygenates to be used in the development of better
performing vehicle fuels. As an additive, they can take the RVP of an
otherwise good performing fuel and lower it so that it meets

8
A. Landera, et al.
Fig. 10. Predictions of the RVP of several cyclic ketones blended into the
Summer BOB, at 1 vol% increments. The plot on the right shows synergistic
blending behavior for all cyclic ketones studied.
regulations. Additionally, several of these oxygenates have the added
benefit of increasing RON and S in a blend, while decreasing harmful
emissions.
3. Concluding remarks
In this paper, three models for rapidly predicting RVP have been
developed, a small, medium, and large surrogate model. They were
rigorously validated using a series of non-oxygenated and oxygenated
BOB data. The three models were shown to have excellent agreement
when compared to experimentally determined RVPs of seven BOBs. The
small surrogate model achieved a %AAD of 10.59, while the medium
and large surrogate models achieved a %AAD of 5.30 and 4.36, re-
spectively. These models were then validated using 60 oxygenate
blending data points. 39 of these data points were oxygenates blended
into a Summer BOB, while the remaining 21 data points were oxyge-
nates blended into a winter BOB. It was found that the small and
moderate surrogate models could not model the RVP of these oxygenate
data well. When compared to both the Summer and Winter RVP data,
the small and medium surrogate model achieved %AADs in excess of
10. The large surrogate model achieved much better results, with
%AADs of 4.40 and 1.55, for the Summer and Winter RVP data, re-
spectively. This study also concluded that alkanes and alcohols interact
with aromatics, weakening aromatic-aromatic interactions. This was
supported by excess thermodynamic data. Finally, predictions were
made for a series of homologous oxygenates including alcohols, esters,
ketones, and cyclic ketones, many of which were found to lower the
RVP and therefore have applications in refineries. In particular, the
research concludes that cyclic ketones achieve synergistic lowering of
the RVP when blended into Summer BOB, increasing their potential for
use in refinery applications.
CRediT authorship contribution statement
Alexander Landera: Investigation, Data curation, Formal analysis,
Methodology, Writing - original draft. Niall Mac Dowell:
Conceptualization, Visualization, Supervision, Methodology, Writing -
review & editing. Anthe George: Conceptualization, Visualization,
Supervision, Funding acquisition, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to
9
Fuel 283 (2021) 118624
influence the work reported in this paper.
Acknowledgments
This research was conducted as part of the Co-Optimization of Fuels
& Engines (Co-Optima) Project sponsored by the Bioenergy
Technologies and Vehicle Technologies Offices, Office of Energy
Efficiency and Renewable Energy (EERE), U.S. Department of Energy
(DOE). Co-optima is a collaborative project of multiple national la-
boratories initiated to simultaneously accelerate the introduction of
affordable, scalable, and sustainable biofuels and high-efficiency, low-
emission vehicle engines. Sandia National Laboratories is a multi-pro-
gram laboratory managed and operated by National Technology and
Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of
Honeywell International, Inc., for the U.S. Department of Energy’s
National Nuclear Security Administration under contract DE-
NA0003525.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118624.
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