Chemical Engineering Science 107 (2014) 1–12

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Quantitative kinetic inhibitor comparisons and memory effect

measurements from hydrate formation probability distributions
Eric F. May a, Reuben Wu a,b, Malcolm A. Kelland c, Zachary M. Aman a, Karen A. Kozielski d,
Patrick G. Hartley b, Nobuo Maeda b,n
a
Centre for Energy, School of Mechanical & Chemical Engineering, The University of Western Australia, M050, Crawley WA 6009, Australia
b
CSIRO Materials Science and Engineering, Ian Wark Laboratory, Bayview Avenue, Clayton VIC 3168, Australia
c
Department of Mathematics and Natural Science, Faculty of Science and Technology, University of Stavanger, N-4036 Stavanger, Norway
d
CSIRO Earth Science and Resource Engineering, Ian Wark Laboratory, Bayview Avenue, Clayton VIC 3168, Australia

H I G H L I G H T S

Quantitative analysis method for gas hydrates nucleation probability distributions.

Quantitative assessment methodology of the efficacy of kinetic hydrate inhibitors.

Quantification of the amount of the memory effect in each sample.

art ic l e i nf o a b s t r a c t

Article history: In contrast with conventional experiments for ranking the performance of kinetic hydrate inhibitors (KHIs),
Received 26 August 2013 the high pressure automated lag time apparatus (HP-ALTA) is not limited by the stochasticity of hydrate
Received in revised form formation because it can make large numbers of formation measurements rapidly. An improved procedure
12 November 2013
for analysing HP-ALTA data is presented here in which formation probability density histograms with
Accepted 26 November 2013
Available online 10 December 2013
uniform temperature bin widths are constructed. Operations such as numerical integration and subtraction
can then be applied to entire formation distributions without the need to regress the data to model
Keywords: analytic functions. This approach enables apparatus effects on the measured formation distributions to be
Gas hydrate quantified and mitigated. Using analogue natural gas mixtures, a demonstration of the improved method is
Nucleation
reported here for six KHIs that were also tested using a conventional rocking cell. The cumulative
Growth
formation probability distribution functions determined by numerical integration of the histograms were
Probability distribution
Kinetics used to quantitatively (1) assess the performance of the KHIs, (2) study the memory effect in pure water,
Inhibitor and (3) assess its impact on the performance of each KHI. The rankings of the KHIs obtained from the
various performance metrics accessible through the HP-ALTA data were generally consistent with the
rocking cell rankings, with the average absolute deviation in net subcooling for the two apparatus being
2 to 3 K. In the quiescent HP-ALTA samples, the three worst performing KHIs still had expected subcoolings
of about 14 K unless the memory effect was present, in which case the expected net subcoolings of the
three worst performing KHIs ranged from 0–6 K. In contrast the memory effect reduced the expected
subcoolings of the three best performing KHIs by only 1–2 K. Using the new method of analysis, hydrate
formation distributions measured with the HP-ALTA can also be used to identify regions of good and poor
performance for a given KHI, which might aid in the determination of improved inhibition strategies or
assist the development of improved hydrate inhibitors.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction carbon dioxide) are trapped in water cages at low-temperature and

Gas hydrates are non-stoichiometric ice-like compounds formed
when certain guest molecules (e.g., methane, ethane, propane and
n
Corresponding author. Tel.: þ 61 3 9545 2388.
E-mail address: Nobuo.Maeda@csiro.au (N. Maeda).
high-pressure conditions (Sloan, 2003). Such conditions are often
encountered in oil and gas pipelines and blockages due to hydrate
formation can lead to major safety and economic concerns. Tradi-
tionally, hydrate problems were addressed using thermodynamic
hydrate inhibitors (THIs) such as methanol or monoethylene glycol,
which shift the hydrate equilibrium phase boundary away from the

0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.11.048
2 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12
pipeline operating condition. Typical concentrations of THIs used are
around 15–50 wt% (Sloan et al., 1998). However, in deep water
production, which is becoming increasingly common, even higher
concentrations are needed to prevent hydrate formation leading to
increased operating costs. Hence, alternative methods of avoiding
hydrate blockages, such as kinetic hydrate inhibitors (KHIs) and anti-
agglomerants (AAs) are being investigated. Unlike THIs, KHIs function
by delaying hydrate nucleation and/or growth while AAs prevent
agglomeration of hydrate particles (Kelland, 2006). The use of KHIs
and AAs is increasing because they can be used in much lower
dosages (about 0.5–1 wt%) (Kelland, 2006), which increasingly makes
them a more cost-effective inhibition option in comparison with
traditional THIs.
A key stage in the development of new kinetic inhibitors is
laboratory testing, which is used to screen KHI performance and
identify which inhibitors may be suitable for field deployment.
Probably the most common apparatus used for KHI screening is a
rocking cell (Lederhos et al., 1996). This apparatus is usually made
up of a number of test tubes, each filled with a hydrate-forming
solution and containing a small stainless steel ball. The sample
cells are continually rotated and hydrate formation is recorded as
having occurred when the stainless steel balls are no longer able to
move freely through the sample cells. Another method of testing
KHIs is the high-pressure cell or autoclave (Svartaas et al., 2000;
Chua and Kelland, 2012), where hydrate formation is inferred from
the time when a sudden pressure drop is observed, caused by the
uptake of gas into the hydrate cages. Daraboina et al. (2011a,
2011b, 2013) have used both stirred autoclaves and rocking cells to
investigate the impact of KHIs on both hydrate formation and
decomposition, as well as the impact of other compounds such as
NaCl on KHI performance. Recently Daraboina et al. (2013) used
nuclear magnetic resonance (NMR) microscopy and a stirred
autoclave to study the formation kinetics of methane/ethane/
propane mixed gas hydrate in the presence of KHIs. The KHI
performance ranking from the NMR results were shown to match
the ranking obtained from conventional autoclave experiments.
Ohno et al. (2012) used NMR and in-situ powder X-ray diffraction
to determine the impact of growth kinetics on the structure and
stability of hydrates formed with gas mixtures in the presence
of various KHIs. To enable the use of small samples, they dispersed
the KHI solution in a silica gel housed in a pressurised but
unstirred autoclave. Linga and co-workers (Linga et al., 2012;
Babu et al., 2013; Daraboina and Linga 2013) have found that
formation rates in dispersed systems could be higher than in
mechanically agitated systems, making them suitable for KHI
testing: silica sand was found to be even more effective than silica
gel. High pressure differential scanning calorimetery (HP-DSC) has
been used to study the effect of KHIs on hydrate formation in
emulsions (Lachance et al., 2009; Daraboina et al., 2011a, 2011b),
while Yang and Tohidi (2011) used an ultrasonic testing technique
to study the inhibition characteristics of two commercial KHIs.
Kvamme et al. (2005) employed molecular dynamics simulations
to investigate the likely performance of several KHIs in a multi-
phase hydrate-water system with a rigid hydrate interface. On a
larger scale, KHI testing can be carried out in high-pressure flow-
loops Talaghat et al., (2009a, 2009b). Visual studies of the effect of
KHIs on the morphology of methane hydrate formed on water
droplets have been carried out by Bruusgaard et al. (2009).
Hydrate formation is stochastic (Kashchiev and Firoozabadi,
2002), and consequently the results of KHI screening tests usually
show some scatter. Duchateau et al., (2009) proposed a method
that used the memory effect (Vysniauskas and Bishnoi, 1983) to
increase the repeatability of results in KHI tests and allowed a
ranking of KHI effectiveness based on the degree of subcooling
achieved in the system prior to hydrate formation. The memory
effect is a phenomenon whereby hydrate reformation occurs at
shorter induction times and/or lower subcooling temperatures
because the water sample has previously formed a hydrate phase
and not been subject to significant superheating (Vysniauskas and
Bishnoi 1983). Tohidi et al., (2012) used a rather extreme version of
the memory effect by re-cooling the system prior to complete
dissociation of the methane hydrates to characterise the inhibi-
tion effect of PVCap (Lederhos et al., 1996) based solely on the
inhibition of hydrate growth (as opposed to nucleation). However,
a KHI can inhibit both nucleation and growth and a complete
assessment of its inhibition performance should characterise both
aspects. The improved repeatability of KHI testing achieved
through use of the memory effect comes at the expense of weight-
ing the KHI performance test towards growth only rather than
nucleation plus growth.
While it is obviously not a thermodynamic effect, the exact
cause of the memory effect is unclear. One hypothesis is that
the presence of residual hydrate structures in the water after
incomplete dissociation provides a framework for easier hydrate
reformation. (Sloan et al., 1998; Sefidroodi et al., 2013). However,
Buchanan et al., (2005) reported not finding any evidence of
residual hydrate structure upon melting. Rodger, (2000) hypothe-
sised that the memory effect was caused by the supersaturation of
the gas in the water after the hydrate had melted. Clearly more
quantitative study of the memory effect is needed to understand
its underlying mechanism. If the memory effect is caused by
residual hydrate structures, variations in the affinity of different
KHIs to the hydrate phase could cause the ‘strength’ of the
memory effect to vary when all samples are dissociated at the
same superheating temperature (Chua and Kelland, 2012; Del
Villano and Kelland 2011). In such cases it is possible that the
inhibitor ranking achieved by using the memory effect would be
significantly different to that found without it.
Maeda et al. (2011, 2012) recently reported the development of
a high pressure automated lag time apparatus (HP-ALTA), which
they used to study the statistics of hydrate formation. The HP-ALTA
design was based on that of the ambient version originally used by
Heneghan and Haymet (2002). The main advantage of the HP-
ALTA is its ability to perform a large number ( 4100) of experi-
mental runs in a relatively short period of time as compared to the
number viable (  10) with conventional KHI testing methods like
rocking cells or autoclaves. This means that the HP-ALTA can
access and measure the entire probability distribution for hydrate
formation in a reasonable time frame, and collect a sufficient
number of measurements that statistical uncertainties can usually
be reduced in comparison to those of other techniques.
The HP-ALTA was first used to study the probability distribu-
tions of the formation of hydrates of pure methane, a gas mixture
of 90% methane þ 10% propane and a synthetic natural gas
mixture. Maeda et al., (2012) and Wu et al., (2013) used the HP-
ALTA to investigate probability distributions measured either in
terms of an induction time at constant subcooling or in terms of a
subcooling achieved at a constant cooling rate. They showed that
the two distributions are equivalent representations of the same
information, which is important for KHI testing, particularly when
measuring relative performance. Lou et al., (2012) used the HP-
ALTA to investigate the performance of six novel polymer-based
KHIs. However, the concentrations of the novel KHI solutions used
by Lou et al., (2012) were only 0.05 wt%, due to the low solubility
limit of some of the KHIs. As a result of this low concentration the
inhibitive effect of the KHIs was comparable to or smaller than the
stochastic uncertainty of the measured formation temperatures,
despite the large number of data measured with the HP-ALTA.
In this current work, we used the HP-ALTA to assess quantita-
tively the performance of six KHIs with greater concentrations
(0.5 wt%) for which the effectiveness of inhibition was signifi-
cantly greater than the measurement uncertainty. To achieve the
 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12
detailed, quantitative measures of inhibitor performance described
here a new more comprehensive framework for analysing
and interpreting formation probability distributions measured
with the HP-ALTA is presented. While the data analysis approach
described previously (Maeda et al., 2012) is satisfactory for con-
structing survival probability curves, the new method facilitates an
extended quantitative analysis of the measured distributions that
was not previously achievable. The new method starts by con-
structing a histogram that is a discretised approximation to the
probability density distribution function (PDDF) for hydrate
formation and which can be numerically integrated to obtain the
cumulative probability distribution function (CPDF). The new
method allows various numerical operations to be performed
directly on the measured distributions without recourse to fitting
the data to an analytical model.
The new method for analysing HP-ALTA data is demonstrated
through the comparison of the hydrate formation distributions
measured for six kinetic inhibitors with and without the memory
effect. The six KHIs were also ranked using a conventional rocking
cell, allowing comparison of two very different techniques.
Explaining the reasons for the differences in KHI performance is
not the purpose of this paper: for this the reader is referred to
references (Chua and Kelland, 2012; Duchateau et al., 2010; Lone
and Kelland, 2013; Reyes and Kelland, 2013; Nakarit et al., 2013).
The rest of the paper demonstrates how the rocking cell results
can be obtained from a subset of the information measured with
the HP-ALTA and how additional insight about the KHI per-
formance can be obtained through analysis of the complete
formation distributions. Methods for identifying and mitigating
apparatus effects, quantification of the memory effect and ways to
potentially improve inhibition strategies and KHI development are
also presented.
2. Materials and rocking cell results
The performance of six KHIs was tested using both a conven-
tional rocking cell approach to measure onset temperatures and,
subsequently, using an HP-ALTA to measure the formation prob-
ability distributions associated with each inhibitor. Both sets of
experiments used gas mixtures, with mole fraction compositions
listed in Table 1, to ensure that sII hydrates would form.
The rocking cell experiments used a multi-component synthetic
natural gas. Unfortunately this mixture was not available for use in
the HP-ALTA experiments, which instead used a binary mixture
with a mole fraction composition of 0.9 CH4 þ0.1 C3H8. Table 1
also lists the operating pressure utilised in the two sets of
experiments, the hydrate equilibrium temperature calculated for
Table 1
Gas compositions, operating pressures, and hydrate equilibrium temperatures for
the mixtures used to rank KHI performance in the rocking cell and HP-ALTA
experiments. Cooling rates and maximum run duration are also listed for both
methods.
Component Rocking cell
Mol%
CH4 80.67
C2H6 10.2
C3H8 4.9
i-C4H10 1.53
n-C4H10 0.76
N2 0.1
CO2 1.84
Pexpt 7.6 MPa
Teqbm at Pexpt (Multiflash for Windows 4.0 2011) 293.2 K
Cooling rate 0.0003 K s  1
Maximum run duration 18.5 h
3
the gas composition and pressure using Multiflashs 4.1 with the
cubic plus association model set, (Multiflash for Windows 4.0
2011) as well as the experiment cooling rates and maximum
durations. The operating pressure of the HP-ALTA experiments
was chosen to ensure that the differences between the pressures
and equilibrium temperatures of the two sets of experiments were
small. The results obtained from the two sets of experiments
indicate that the differences caused by variations in gas composi-
tion and pressure were negligible in comparison with the effects
associated with stochastic formation.
The details of the six KHIs studied in this work are provided in
Table 2. The KHIs were chosen to give a variety of structures, some
known to be primarily anti-nucleators, and some which were good
at both inhibiting nucleation and crystal growth. Another objective
was to demonstrate the HP-ALTA method using a set of KHIs which
had exhibited a range of performance levels during the rocking cell
tests. The KHIs were tested by preparing aqueous solutions with
an inhibitor concentration of 0.5 wt% using 18 MΩ de-ionised
water. The change in hydrate equilibrium temperature caused by
this concentration was assumed to be negligible. Although this
assumption is very likely to be robust given the low KHI concen-
trations, testing it experimentally can be difficult because many
KHIs also retard the kinetics of hydrate dissociation. Consequently,
equilibrium temperatures inferred from dissociation measure-
ments in the presence of KHIs can be systematically high
(Duchateau et al., 2010). Table 2 also lists the results of the rocking
cell experiments. Kelland and co-workers (Chua and Kelland,
2012; Lone and Kelland, 2013; Reyes and Kelland 2013) present
pictures of the rocking cell and the details of the procedures used
for the rocking cell tests. Briefly, each test comprised of having a
sample of the KHI solution in five cells that were rocked at a rate of
20 times per minute. The onset temperature of hydrate formation,
To, in each cell was determined from the location of the slope
change in the pressure–temperature curve measured as the cell
was cooled at a rate of 1 K/h. Each test was conducted twice, with
a fresh solution, so that a total of at least 10 onset temperatures
were measured for each KHI. The ranking of the inhibition
performance of each of the KHIs listed in Table 2 was determined
using the average To from the tests (the lower the average To, the
more effective the KHI). The standard deviation of the measured To
values was about 1 K and the p-values determined from statistical
t-tests of the measurements were all lower than 0.05.
The results of rocking cell tests using pure water indicated that
a subcooling of only 2.1 K was required to initiate hydrate forma-
tion in this apparatus, which reflects the significant mixing of the
sample that occurs in rocking cell experiments. The KHIs in Table 2
are listed in order of their inhibition performance, with subcool-
ings of 17.8 K and 3.3 K achieved by KHI-1 and KHI-6, respectively.
Given the standard deviations of the T0 measurements, the
difference between KHI-2 and KHI-3 is likely smaller than the
resolution of the rocking cell experiments. This resolution could in
principle be increased by conducting more tests but given the time
required per run the practicality of doing so is limited.
HP-ALTA
Mol%
3. HP-ALTA measurements and results
90
0 A schematic of the HP-ALTA used to measure the hydrate
10 formation probability distributions is shown in Fig. 1. Detailed
0
descriptions of the apparatus and the method followed to obtain
0
0 the raw data used to construct the formation probability distribu-
0 tions have been given previously (Maeda et al., 2011; Maeda
7.2 MPa et al., 2012) so only a brief summary is given here together
293.9 K with a description of any differences in the method followed.
0.025 K s  1
0.6 h
About 150 μL of the sample solution to be tested was placed in a
custom-made glass ‘boat’ about 30 mm in length and 4 mm in
4 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12

Table 2
Details of the kinetic hydrate inhibitors (KHIs) studied in this work and results of rocking cell experiments. The rocking cell ranking of the KHIs is based on the average onset
temperature, T0, measured for at least 10 runs with the corresponding subcooling ΔT below the calculated equilibrium temperature also listed.

Label Sample name To ΔT Reference and comment

(K) (K)

KHI-1 Polymer: synergist blend 275.4 17.8 Duchateau et al., (2010)

KHI-2 Low molecular weight PVCap (Lederhos et al., 279.7 13.5 Average of 15 tests: five by Lone and Kelland (2013) (with average of 279.6 K) and 10 by
1996) in Butyl Glycol Ether (BGE) solvent Duchateau et al., (2010) (with average of 279.8 K).
KHI-3 Luvicap 55 W 280.1 13.1 Lone and Kelland (2013)
KHI-4 Polyaspartamide 282.3 10.9 Chua and Kelland (2012)
KHI-5 Polyvinylpyrrolidone (PVP 15k), 15k Mw 284.8 8.4 Reyes and Kelland (2013)
KHI-6 Polyvinylimidazole 289.9 3.3 A T0 of 290.1 K was reported by Nakarit et al. (2013) for a 0.25 wt% solution. This value was
obtained for a 0.5 wt% solution of that KHI with the same rocking cell.
Water 291.1 2.1 Average of more than 30 tests

ranged between 75 and 293: as discussed below, one advantage of

6 mm diameter
cross bore
Fig. 1. Schematic of the HP-ALTA used for measuring hydrate formation probability
distributions.
width. The gas pressure in the sample chamber was set and
maintained using a pneumatically-driven, non-lubricated gas
booster and measured using a capacitance diaphragm type trans-
ducer. The sample was cooled at a constant rate of 0.025 K/s using
two Peltier modules located on either side of the stainless steel
pressure vessel that housed the boat. Temperature was measured
using a platinum resistance thermometer located about 5 mm
from the sample boat on the outside of the pressure vessel.
The transmission of light through the sample from an LED was
monitored using a photodetector. The formation of a solid phase in
the boat was detected when the photodetector signal dropped
below a certain threshold as a result of the increased light
scattering. The temperature resolution with which solid formation
could be measured was 0.1 K. Following the detection of solid
formation, the sample was heated to a specified superheating
temperature where it was held for 300 s to ensure the solid was
completely dissociated. In this work the superheating temperature
was set to either 6 K or 16 K (absolute temperatures of 300 or
310 K, respectively) so that the impact of the memory effect
(Vysniauskas and Bishnoi, 1983) on the measured formation
probability distributions could be investigated. The number
of measurements made to construct the formation probability
distributions for a given sample and superheating temperature
the new analysis method presented here is it allows an assessment
of whether the number of trials conducted is likely to be sufficient.
The choice of the two dissociation temperatures used here was
based on the results of Duchateau et al. (2010) who reported that
the memory effect was discernible at superheating temperatures
of less than 5.6 K for experiments involving the KHI PVCap
(Lederhos et al. 1996). In the current work, the clear differences
between the hydrate formation distributions measured at the two
dissociation temperatures (Fig. 2) demonstrate that the memory
effect was significant in all cases (water and each KHI) when the
superheating temperature was only 6 K. To distinguish between
the two sets of HP-ALTA measurements, we denote those mea-
sured with a superheating of 6 K as “ME” and those measured with
a superheating temperature of 16 K as “NME” where we have
assumed that the latter were not influenced by the memory effect.
The results of this work indicate that the HP-ALTA could be a
useful tool for future quantitative studies of the memory effect.
An improved method of analysing the data acquired with the
HP-ALTA and using them to construct formation probability
distributions was developed in this work, which has some advan-
tages over the method described previously by Maeda et al., (2012)
The information content of the data is of course unchanged and
both methods produce formation probability distributions; how-
ever the new method allows a more extensive analysis of the data
and, thus, a more comprehensive and generalised interpretation of
the results. The first step in the new method is to construct from
the HP-ALTA data a histogram of formation events as a function of
subcooling, ΔT. This is achieved by selecting a bin size, δTf, and
converting the number formation events recorded within the
interval (ΔT to ΔTþ δTf) into a fraction of the total number of
formation events measured over the range 0 o ΔT r ΔT(max),
where ΔT(max) corresponds to the lowest temperature at which a
formation event was observed. The resulting histogram is a
discretised approximation to the probability density distribution
function (PDDF) of hydrate formation in the system being studied.
The NME-PDDFs and ME-PDDFs measured in this work are shown
in Fig. 2(a) and (b), respectively.
The choice of δTf is important and can impact the shape of
resulting histogram. For a continuous variable such as subcooling,
the bin size should be as small as justifiable given the measur-
ement's resolution. Following de Podesta et al. (2010) we selected
δTf on the basis of the Nyquist theorem related to sampling.
Usually, the Nyquist theorem is expressed in terms of critical
frequency for data sampled at discrete time intervals, with a
critical sampling rate of two samples per cycle. In this work since
the hydrate formation temperature in a given HP-ALTA run could
be measured with a resolution of 0.1 K, we took δTf ¼ 0.2 K.
One advantage of the new method over the one described by
Maeda et al. (2012) is that a common set of values for δTf and
ΔT(max) can be chosen for use in the data analysis for each KHI. As
 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12 5

0.25 1.0
Water
KHI-1
KHI-2 Water
KHI-3 KHI-1
0.20 KHI-4 0.8 KHI-2
KHI-5 KHI-3
Fraction of Total Runs

Formation Probability
KHI-6 KHI-4
KHI-5
0.15 0.6 KHI-6
Ice

0.10 0.4

0.05 0.2

0.00 0.0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35

0.25 1.0
Water
KHI-1
KHI-2 Water
0.20 KHI-3 KHI-1
KHI-4 0.8
KHI-2
Fraction of Total Runs

KHI-5 KHI-3

Formation Probability
KHI-6 KHI-4
0.15 KHI-5
0.6
KHI-6

0.10
0.4

0.05
0.2

0.00
0.0
0 5 10 15 20 25 30 35
0 5 10 15 20 25 30 35
Subcooling, T/K
Subcooling, T/K
Fig. 2. Probability density distribution histograms for hydrate formation estimated
from the HP-ALTA experiments with pure water and each of the KHIs. (a): Fig. 3. Cumulative probability distribution functions for hydrate formation
Distributions obtained from measurement with no memory effect (NME). (b): obtained by numerical integration of the histograms shown in Fig. 2. (a): Distribu-
Distributions obtained from measurements influenced by the memory effect (ME). tions obtained from measurement with no memory effect (NME). The ice formation
curve for the apparatus, which was determined from N2 measurements to occur in
the temperature range 263 to 269 K, is also shown. (b): Distributions obtained from
a result, the histograms derived from each data set are of the same measurements influenced by the memory effect (ME).

length and have the same spacing, which means that subsequent
numerical operations on the data sets, such as integration and
subtraction, can be performed in a straightforward manner. In the
previous method, cumulative probability distribution functions
(CPDF) were constructed directly from the measured data,
by-passing the PDDF histograms and the spacing of the data
within the so-constructed CPDFs was determined by the (varying)
difference between each measured formation event. Each resulting
CPDF would consequently have non-uniform spacing and the total
number of points in the vector representing the CPDF would vary.
The only way numerical operations such as subtraction or integra-
tion of the entire distribution could then be conducted was
through the use of model analytic functions that could be
regressed satisfactorily to each data set. The new method of data
analysis still permits such an approach but does not require it and
is thus more flexible and convenient.
Fig. 3 shows the cumulative probability distribution functions
for hydrate formation obtained by numerical integration of the
PDDF histograms shown in Fig. 2. These CPDFs contain the
equivalent amount of information to that contained the survival
curves produced using the method described by Maeda et al.
(2012) (a survival curve is the complement of the formation
distribution, i.e. the survival probability is 1 p, where p is the
formation probability). However, the choice of a consistent δTf in
the histogram construction combined with the integration of the
histograms to produce the CPDF means that the formation
distributions obtained with the new method are smoother and
have a higher point density than the survival curves constructed
previously.
In addition to allowing the performance of the various KHIs to
be evaluated and the impact of the ME to be quantified, the
measured distributions allow some limitations of the experimen-
tal measurements themselves to be identified, particularly at the
lowest subcoolings. For the NME experiments, all of the KHIs
tested enabled subcoolings of 28 K to be achieved in more than
half of the experiments; in comparison, the hydrate formation
probability with pure water in the HP-ALTA was over 98% at this
subcooling. However, for an increase in subcooling of only 2 K, all
of the KHI distributions for the NME experiments reach a forma-
tion probability of over 90% and none of those distributions extend
beyond a subcooling of 33 K. Such an increase in formation
probability over a small range of subcooling indicates that the
hydrate formation distribution measurement was being limited
by the formation of ice. To confirm this, an experiment was
conducted using N2 gas at 7.3 MPa and pure water. The hydrate
6 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12

equilibrium temperature calculated for N2 þ water at 7.3 MPa is
248.3 K, (Multiflash for Windows 4.0 2011) which corresponds to a
subcooling of 48 K in Fig. 3 whereas the equilibrium ice tempera-
ture for this system (273.15 K) corresponds to a subcooling of
20.8 K. The cumulative formation distribution measured with the
HP-ALTA for N2 þwater at 7.3 MPa is shown as a dashed curve in
Fig. 3(a) and had absolute temperature bounds of 267.3 K–263.9 K
(subcooling range of 26.6 K–30.0 K). This confirms that in the NME
experiments the formation probability distributions measured for
the KHIs at subcoolings of 26 K and below were corrupted by ice
formation: for KHI-1 and KHI-3, hydrate formation had occurred in
less than 5% of the runs at this subcooling.
Another limitation present in several of the current measure-
ment sets is that at the highest subcoolings the histogram values
are not close to zero (e.g. KHI-3 in the ME experiments). This is
also reflected by the corresponding CPDF not approaching p ¼ 1
asymptotically and indicates that, in those cases, a significant
fraction of formation events were still occurring at the highest
subcoolings, implying that the full-width of the distributions may
not have been completely sampled. Future measurements with the
HP-ALTA should therefore construct the histogram as soon as
possible to establish whether additional measurements are neces-
sary to completely map the formation PDDF (it may be in some
cases that ice formation means that extending the HP-ALTA
measurements will not be effective).
These limitations are, however, only apparent because of the
significant increase in information about each hydrate formation
distribution produced by the HP-ALTA. Such information is gen-
erally inaccessible through conventional methods of testing KHI
performance because it requires execution of a much larger
number of formation measurements than is usually feasible with
those methods. The HP-ALTA allows a much more extensive
comparison of KHI performance because in general it allows the
entire formation distribution associated with each inhibitor to be
measured. The entire formation distribution can then be used to
compare the performance of each KHI on a quantitative basis and,
furthermore, various weighting criteria can be used to determine
the inhibitor's quantitative ranking in accordance with the user's
requirements.
4. KHI Performance quantification
The CPDFs shown in Fig. 3 can be used in several ways to rank
quantitatively the performance of KHIs. The most straightforward
of these may be called the subcooling-probability threshold (SPT)
method in which either a threshold cumulative probability, pt, is
set and the CPDF is used to determine the subcooling, ΔTt,
corresponding to pt or, equivalently, a threshold subcooling is
selected and the corresponding cumulative probability is deter-
mined. The physical interpretation of this method is that the KHIs
are being compared on the basis of the probability that they will
allow hydrates to form for a selected subcooling. For a given
threshold, the higher the corresponding subcooling or the lower
the probability determined from the CPDF, the better the perfor-
mance of the KHI. Of course, the probability of achieving that
subcooling is specific to the quiescent HP-ALTA measurement and
will not necessarily correspond to the probability of achieving that
subcooling in a turbulent system. Nevertheless, the measurements
provide a clear indication of the comparative performance of
several KHIs under the same conditions.
In previous HP-ALTA studies, Maeda and co-workers (Maeda
et al., 2012; Wu et al., 2013) used the median of the measured
distribution as the basis of comparison. This approach is a specific
case of the SPT method in which a threshold probability of 0.5 is
selected. This choice of threshold is, however, somewhat arbitrary
and other reasonable choices may be made: for example, a ΔTt
corresponding to the ice point might be considered (20.8 K in
these experiments). In different contexts, others have proposed
(Klomp, 2008) that pt should be chosen to be as small as possible
(e.g. 0.01); the level chosen would presumably reflect not only an
engineering risk tolerance but also the resolution of the measure-
ment technique.
However, the choice of threshold to be used in the SPT method
can have a significant effect on the ranking likely to be obtained.
For example, in the case of the NME experiments, the use of
the median method with pt ¼0.5 as the ranking criteria leads to
the result that all six KHIs are essentially equivalent because the
difference between their ΔTt values is less than 1 K at an average
subcooling of 29 K. This reflects the fact that the efficacy of all of
the KHIs was sufficient to reach the ice-formation boundary of the
present HP-ALTA measurements, beyond which any resolution to
hydrate inhibition performance was lost. Similarly use of the
equilibrium temperature for ice formation (ΔTt ¼20.8 K) provides
little useful discrimination as the cumulative formation probability
at this condition was still zero for four of the KHIs.
By first considering the entire range of each measured forma-
tion distribution, it is possible to choose thresholds for which the
SPT method provides a quantitative discrimination between the
inhibitors. Table 3 shows quantitative measures of each KHI's
performance for both the NME and ME experiments, which
includes measures based on the SPT method for several different

Table 3
Quantitative measures of inhibitor performance in terms of either net subcooling (K) or formation probability (%) of the six KHIs measured in this work. For the HP-ALTA
experiments, the non-memory effect (NME) and memory effect (ME) experiments were assessed using either the integrated quantile function (IQF) method to determine the
expected net subcooling 〈ΔT ðnetÞ 〉 from the measured formation distribution, or using the subcooling-probability threshold (SPT) method, to determine the net subcoolings
corresponding to chosen probability thresholds, pt, of 50% or 1%, or to determine the formation probabilities corresponding to (absolute) subcooling thresholds, ΔTt, of 26 K
or 16 K.

Label Rock. Cell ΔT ðnetÞ HP-ALTA

NME ME

IQF, SPT: ΔT ðnetÞ for SPT: ΔT ðnetÞ for SPT: p for IQF, SPT: ΔT ðnetÞ for SPT: ΔT ðnetÞ for SPT: p for
〈ΔT ðnetÞ 〉 pt ¼ 0.5 pt ¼ 0.01 ΔTt ¼ 26 K (%) 〈ΔT ðnetÞ 〉 pt ¼0.5 pt ¼0.01 ΔTt ¼ 16 K (%)

KHI-1 15.7 14.3 15.4 14.8 2 12.1 12.7 12.9 0

KHI-2 11.4 13.6 15.2 11.8 21 11.4 12.1 9.7 3
KHI-3 11 14.3 15.7 15.8 0 13.9 15.3 8 2
KHI-4 8.8 13.6 14.9 10.8 15 6 6.5 7.6 39
KHI-5 6.3 13.4 15.1 8.2 15 3.8 4.5 3.9 95
KHI-6 1.2 13.1 15.4 7.2 27 -0.9 -0.2 2 100

Water 0 0 0 0 99 0 0 0 97
 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12
thresholds. For a threshold formation probability of 1%, the best
performing KHIs (KHI-1 and KHI-3) achieve subcoolings 7 K larger
than the worst performing KHIs (KHI-5 and KHI-6). One problem
with this choice of threshold, however, is that its proximity to the
start of each inhibitor's CPDF maximises the sensitivity of the
results obtained to the stochastic nature of hydrate formation.
This stochastic sensitivity is present and affects measurements of
formation at all subcoolings equally; it is an implicit uncertainty in
the level of the PDDF histogram at any given subcooling. Never-
theless, in terms of the CPDF, the relative size of this statistical
uncertainty decreases with increasing cumulative probability, and
therefore the further removed the chosen threshold is from the
low probability limit of the CPDF, the more robust the measure of
performance obtained with the SPT method will be.
A better threshold choice, therefore, for use with the SPT
method is the subcooling at which the best performing KHI
achieves a non-zero (but appreciable) formation probability. With
this choice the corresponding cumulative formation probabilities
for many of the KHIs will have a reduced statistical relative
uncertainty. A potentially even better choice is to select a sub-
cooling threshold at which the worst performing KHI achieves a
cumulative formation probability of nearly 100%, which would be
an improvement if the best performing KHI had a formation
probability significantly greater than zero at this subcooling.
Two such subcooling thresholds are shown in Table 3: ΔTt ¼26 K
for the NME experiments and ΔTt ¼16 K for the ME experiments. In
the former case, the formation probabilities for KHI-1 and KHI-3 are
0% and 2%, respectively, and thus stochastically sensitive with the
formation probabilities for the other KHIs ranging from 15% to 27%
at this threshold subcooling, with pure water having a formation
probability of 99%. Choice of a higher subcooling threshold for these
NME experiments is not helpful because of the ice formation
boundary that starts from 26.6 K; it is likely that the anomalous
ranking via this metric of KHI-2 as the second worst perform-
ing inhibitor, (compared with any other of the ranking methods
considered here) was a result of ice formation affecting the
measured distribution. For the ME experiments it was possible to
choose ΔTt ¼16 K at which the worst performing KHI-6 had a
cumulative formation probability of 100%. We note that ME experi-
ments with pure water had a formation probability of 97% at this
subcooling, which suggests that the statistical uncertainty of any
given probability might be about 3–5%, and/or KHI-6 may act as a
hydrate promoter in the presence of the ME. At ΔTt ¼16 K for the
ME experiments the best performing inhibitors, KHI-1, -2 and -3
have formation probabilities between 0% and 3%, while KHI-4 and
KHI-5 have formation probabilities of 39% and 95%, respectively.
This ranking is very similar to that obtained in the rocking cell
experiments.
However, while a judicious choice of threshold can enable the
SPT method to produce robust rankings of the inhibitors, that
choice will inevitably involve a degree of subjectivity and possibly
be somewhat arbitrary. Furthermore, a judicious threshold selec-
tion requires consideration of the entire CPDFs measured for all of
the KHIs being ranked, which means that the chosen threshold
may need to shift when a subsequent batch of KHIs is tested.
A better approach would be one that utilises all of the information
available about the KHI's performance that is available through the
entire CPDF in a systematic way.
The most statistically robust method of evaluating KHI perfor-
mance is to calculate the expected (or mean) subcooling value,
〈ΔT〉, for each KHI using
Z 1
〈ΔT〉  ΔTf dΔT ð1Þ
0
where f is the PDDF for hydrate formation and the integration is
over all possible subcoolings, ΔT. To evaluate Eq. (1), we use the
7
relationship f ¼dp/dΔT, where p is the CPDF, to write
Z 1  
dp
〈ΔT〉  ΔT d ΔT ð2Þ
0 d ΔT
The variable and bounds of the integration can then be changed
Z 1
〈ΔT〉  ΔTdp ð3Þ
0
To evaluate Eq. (3) it is therefore convenient to calculate the
inverse function of the CPDF, which is known as the quantile (or
percentile) function, QF, to express the subcooling as a function of
probability. The SPT method implicitly uses the QF if a cumulative
probability threshold is specified.
The expected subcooling value of each KHI may be calculated
from HP-ALTA experiments by converting numerically the mea-
sured CPDF to a QF and integrating it over the full range of
formation probabilities. The expected subcooling for each KHI
then provides a quantitative means of ranking their performance
that does not require a choice of a particular threshold. We call
this the integrated quantile function (IQF) method and, assuming
sufficient data are obtained in the measurement of the probability
distribution, it is the most robust method of quantifying inhibitor
performance with the least stochastic sensitivity. The rankings of
the KHIs obtained via the IQF method for both the NME and ME
experiments are listed in Table 3.
Geometrically, the IQF method calculates the area between the
probability axis and the CPDF over the probability bounds 0 to 1:
for the CPDFs shown in Fig. 3 the expected subcooling for each KHI
corresponds to the area between the left vertical axis and the
corresponding CPDF. As discussed in Section 6 below, additional
quantitative insight into the performance of the different KHIs can
also be obtained by integrating over a sub-domain of probability
from 0 to pmax o1, which corresponds to the area between the
vertical probability axis and the CPDF up to a horizontal stripe at
the chosen pmax.
5. Net subcoolings and memory effect quantification
The HP-ALTA is a quiescent system which results in formation
occurring at higher subcoolings than is found in rocking cell or
autoclave tests of KHI performance. The effects of apparatus
artefacts can be reduced in a straightforward way if the perfor-
mance measure is a single temperature, such as T0 in rocking cell
tests, by simply subtracting the average onset temperature mea-
sured in the control experiment with pure water from the average
onset temperatures obtained for each KHI. However, the correction
of apparatus effects is not as straightforward when the entire
formation distribution is measured as occurs with HP-ALTA
experiments. A second advantage of the new method of analysing
the HP-ALTA data presented in this work over that reported
previously is that because the CPDFs obtained with it have the
same length and uniform spacing, they can be subtracted from one
another in a straightforward manner. The additional, or net
subcooling, that is achieved due to the KHI only can therefore be
determined by subtracting its CPDF from that obtained with pure
water. The net integrated subcooling achieved by that KHI is
equivalent to the area between the CPDFs for pure water and for
that KHI and evaluation of this area by integration gives its
expected net subcooling, 〈ΔT ðnetÞ 〉. Fig. 4(a) illustrates this geome-
trical interpretation using the CPDFs measured for KHI-5 and pure
water in the ME experiments.
Fig. 5 shows calculated net subcoolings, ΔT(net) ¼ ΔT(KHI) 
ΔT (water)
for the NME and ME experiments, plotted as a function
of cumulative formation probability. In making the abscissa the
cumulative probability, the curves shown in Fig. 5 correspond to
8 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12

1.0 20

0.8 15
Water

/K
KHI-5
Formation Probability

(net)
T
0.6 10

Net Subcooling,
0.4 5

0.2 0

KHI-1 KHI-2 KHI-3

KHI-4 KHI-5 KHI-6
0.0 -5
0.0 0.2 0.4 0.6 0.8 1.0
0 5 10 15 20 25 30 35

1.0 20
KHI-1 KHI-2 KHI-3
KHI-4 KHI-5 KHI-6

0.8 15

/K
Formation Probability

(net)
T
10
0.6
Net Subcooling,

Memory Effect
No Memory Effect
5
0.4

0
0.2

-5
0.0
0.0 0.2 0.4 0.6 0.8 1.0
0 5 10 15 20 25 30 35
Formation Probability
Subcooling, T/K
Fig. 5. Net sub-cooling curves plotted as a function of cumulative formation
Fig. 4. Quantification of (a) the inhibitive effect of KHI-5 and (b) the memory effect probability (i.e. net quantile functions) for each of the KHIs. (a): Net subcoolings
in pure water by calculation of the net integrated subcooling shown as the shaded obtained from measurements with no memory effect (NME). (b): Net subcoolings
areas between the CPDFs. In (a) the distributions for pure water and KHI-5 obtained from measurements with the memory effect (ME).
measured during the ME experiments are shown. In (b) the distributions shown
are for pure water as measured in the ME and NME experiments

level either slightly worse or equal to them depending on the

the net subcooling quantile functions. These were integrated
directly to determine the expectation values of net subcooling
for each KHI listed under the IQF method in Table 3. The threshold
subcoolings obtained using the SPT method for pt ¼0.5 and
pt ¼0.01 are also listed on a net-basis in Table 3.
Calculation of the net subcoolings allows a direct comparison of
the rankings achieved from the rocking cell tests with those
obtained by the IQF and SPT methods from the HP-ALTA data
that is both qualitative and quantitative. Qualitatively, there is a
reasonable similarity between the rankings derived from the
rocking cell onset formation tests and those obtained via the
various methods of analysing the HP-ALTA distributions: all
methods ranked KHI-4, KHI-5 and KHI-6 as the fourth, fifth and
sixth best inhibitors, respectively, except when the method
applied to the HP-ALTA data focussed on measurements affected
by ice formation (SPT with pt ¼ 0.5 or ΔTt ¼ 26 K for the NME
experiments). For the three best performing inhibitors, the rocking
cell results indicate that KHI-1 performed significantly better than
KHI-2 or KHI-3, which had performed similarly. The HP-ALTA
experiments found that KHI-1 and KHI-3 were effectively the
equal best performers for all methods, with KHI-2 performing at a
chosen method.
Any further analysis of the quantitative differences between the
methods should include an estimate of their respective uncertain-
ties. Such estimates are difficult to make because of the significant
impact that each technique's systematics can have on the mea-
surement, such as the differences between quiescent and agitated
systems or the impact of the memory effect on an inhibitor's
performance. Given these differences it is interesting that across
all the experiments considered (rocking cell, HP-ALTA with and
without ME) both the inhibitor performance rankings and the
measured net subcoolings are so similar. Estimating the statistical
uncertainties associated with the various methods is a more
tractable problem because these are essentially determined by
the resolution of the measurement to a formation event, the
number of measurements that are made with that technique and
the extent to which further averaging occurs during the analysis
used to a quantitative performance metric. According to these
criteria, the precision of the rocking cell net subcoolings should be
lower than the HP-ALTA net subcoolings because of the order of
magnitude fewer measurements, and the IQF method should have
the highest precision of the HP-ALTA analysis methods because it
is obtained by a double integration of the measured histogram.
 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12
Inspection of the PDDFs indicates that the statistical uncertainty of
a particular probability threshold is about 70.03. The slopes of the
quantile functions shown in Fig. 5 indicate that near the beginning of
the distribution (i.e. p-0) the net subcooling is most sensitive to
uncertainties in the probability. This contributes a statistical uncer-
tainty of about 1 to 2 K to the net subcoolings obtained by the SPT
method with pt ¼0.01, which decreases at larger formation probabil-
ities to a level approximately equal to that of the histogram bin size
(0.2 K). The statistical uncertainty of the expected net subcooling
calculated using the IQF method is estimated to be about 0.05 K given
the further averaging associated with the integration of the entire
distribution (which was constructed from about 100 formation
measurements).
Four of the six HP-ALTA estimates of net KHI subcoolings in
Table 3 have an average absolute difference (AAD) from the rocking
cell net KHI subcoolings of between 2 and 3 K: the IQF and SPT:
pt ¼0.5 methods for the NME experiments have AADs of 5.1 and
6.3 K, respectively, but these two measures are known to be affected
by ice formation because they are both strongly influenced by the
formation events that occurred at temperatures below 267 K. Com-
parison of the rocking cell results with the NME HP-ALTA results
indicates that certain inhibitors that are very effective in quiescent
systems are far less effective in systems with significant agitation (i.e.
KHI-4, KHI-5 and KHI-6). Interestingly, the impact of the ME on the
performance of those KHIs in the quiescent HP-ALTA system appears
to be like that of agitation. The IQF and SPT: pt ¼0.5 methods for the
ME experiments both had AADs from the rocking cell net subcoolings
of only 2.3 K, and maximum absolute deviations of 3.6 and 4.3 K.
Comparison of the subcoolings obtained by HP-ALTA experi-
ments for NME and ME experiments allows quantification of
memory effect under the quiescent conditions. Fig. 4(b) shows the
integrated loss of subcooling caused by the memory effect in pure
water. Table 4 lists the differences between the subcoolings deter-
mined by the IQF and SPT: pt ¼0.5 methods for water and each KHI
in the ME and NME experiments. The size of the numerical shifts
caused by the ME is similar for the IQF and SPT: pt ¼0.5 methods,
which reflect the similarities in the means and medians of each
distributions and also indicates that stochastic effects have been
minimised. The shift in the subcoolings achieved with pure water is
about 4 K, which provides a baseline for comparing the impact of
the memory effect on the performance of the KHIs. It has the least
impact on KHI-3 (0.4 K subcooling decrease) while KHI-1 and KHI-2
are affected less than pure water by about 2 K. The memory effect
has a significant impact on the three worst performing KHIs,
reducing the subcoolings achieved by between 2 and 3.5 times
the shift observed by pure water. As shown in Fig. 5(b), the 14 K
reduction in subcooling caused by the ME for KHI-6 causes it to no
longer have any inhibitive effect, with the data indicating that
hydrate formation with this KHI present may even be more likely to
occur than is the case for pure water.
The quantitative changes in the inhibition performance of the
different KHIs caused by the memory effect appear to support the
Table 4
Quantification of memory effect through the difference in subcoolings
ΔT ME  ΔT NME measured with the HP-ALTA using the integrated quantile function
(IQF) and subcooling probability threshold (SPT) methods.
Label IQF SPT: pt ¼0.5
Water  4.0  3.8
KHI-1  2.2  2.7
KHI-2  2.2  3.1
KHI-3  0.4  0.4
KHI-4  7.6  8.4
KHI-5  9.6  10.6
KHI-6  14  15.6
9
retained structure theory of the underlying mechanism (Sloan
et al., 1998; Sefidroodi et al., 2013). However, this assumes that the
diffusion rate of dissolved gases that have formed upon dissocia-
tion of the gas hydrates remains unaffected by the presence of the
KHI. Future work to elucidate the underlying mechanism might
attempt to combine HP-ALTA measurements of the memory effect
with a method that could monitor the dissolved gas concentra-
tion; Raman spectroscopy as described by Subramanian and Sloan
(2002) may be suitable for this purpose.
6. Improving KHIs and inhibition strategies
The IQF-method of ranking of a KHI produces a performance
metric that is weighted to penalise failures (i.e. formation) at
lower subcoolings, even when the CPDF indicates that the KHI
can achieve higher subcoolings at greater formation probabilities.
The relative impact of the penalty for failures at low subcoolings
depends on the choice of integration limit. This understanding
can be used to obtain additional quantitative insight into the
performance of a KHI by integrating the QF over a sub-domain of
probability from 0 to pmax (i.e. changing the upper integration
bound in Eq. (3) from 1 to pmax). We distinguish performance
metrics calculated from the formation probability distribution
using a restricted domain 0 op ox using the notation IQF:
pmax ¼ x. To illustrate the aspect of inhibitor performance that
the restricted domain IQF method can quantify, it is useful to apply
and compare the methods SPT: pt ¼ 0.4 and IQF: pmax ¼ 0.4 to the
distributions obtained during the ME tests of KHI-1 and KHI-3,
with key results shown in Fig. 6.
Fig. 6(a) shows an expanded view of the data plotted in
Fig. 3(b), but represented as the quantile functions for formation
probabilities ranging from 0.1 to 0.5, that were obtained for the
three best inhibitors during the ME experiments. Upon application
of the SPT method, the performance of KHI-3 is determined to be
better than KHI-1 for threshold probabilities larger than 0.17
or, equivalently, subcooling thresholds of 20.2 K or greater.
Fig. 6(b) shows the functions produced using Eq. (3) from all the
distributions measured during the ME experiments if the upper
integration bound is set equal to p and varied from 0 to 1: the
maximum numerical values on the plot at p¼ 1 correspond to the
expected subcooling 〈ΔT〉 for each KHI and for pure water. These
integrated quantile functions are used to determine the numerical
values that will be obtained from the IQF method (which penalises
formation at low subcoolings more severely than the SPT method)
for any sub-domain of formation probability. Fig. 6(c) shows an
expanded view of the IQF functions for the three best inhibitors
over the range 0.4 op o0.5 in which, according to this metric, a
transition occurs between the relative ranking of KHI-1 and KHI-3.
For subcoolings of 20.2 K or less and formation probabilities of
0.17 or smaller, KHI-1 is the best inhibitor based on an analysis of
the formation probability distributions with either the SPT or IQF
methods. However, if pt and pmax are set equal to 0.4, the two
methods differ in the assessment of the ranking order of the two
best inhibitors. The SPT: pt ¼0.4 method leads to the ranking of
KHI-3 above KHI-1, as indicated by Fig. 6(a), whereas the IQF:
pmax ¼ 0.4 method produces a ranking of KHI-1 above KHI-3. There
is a difference in the physical meaning of pt ¼0.4 and pmax ¼0.4
with the former being the subcooling corresponding to a forma-
tion probability of 0.4 and the latter being the most likely
subcooling that the inhibitor will achieve if the system is allowed
to sample the first (or worst) 40% of the formation distribution.
Inspection of Fig. 6(c) indicates that the IQF metric ranks KHI-1
above KHI-3 until a formation probability of 0.42 (with a statistical
uncertainty bound of about 0.03). At this probability threshold, the
CPDF for KHI-3 has a subcooling about 2 K greater than that of
10 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12

26
KHI-1
KHI-2
KHI-3

24

T/K
Subcooling,
22

20

18

0.1 0.2 0.3 0.4 0.5

Formation Probability

25
10.0 KHI-1
KHI-2
KHI-3

Subcooling integrated from p = 0 / K

20

9.5

15

9.0
10

8.5 5

Water KHI-1 KHI-2

KHI-4 KHI-5 KHI-6
0
0.40 0.42 0.44 0.46 0.48 0.50 0.0 0.2 0.4 0.6 0.8 1.0
Formation Probability

Fig. 6. Illustration of the difference in performance metrics obtained by the SPT : pt ¼0.4 and IQF: pmax ¼ 0.4 methods using distributions from the ME experiments.
(a) Expanded view of the data in Fig. 3(b) (axes swapped) for the three best performing KHIs over the range 0.1 o po 0.5, which can be used for the SPT method. (b) Integrals
of the quantile functions over a restricted domain (i.e. Eq. (3) with varying upper integration bound) for all measured distributions (KHI and pure water). (c) Expanded view
of integrated quantile functions for the three best performing KHIs over the range 0.4 o p o 0.5.

KHI-1. However, KHI-3 failed to completely inhibit hydrate forma- conventional techniques produce measures of performance that
tion for subcoolings greater than about 13 K whereas KHI-1 do not encapsulate much of the complex, stochastic information
completely supressed hydrate formation for subcoolings up to pertinent to the kinetic inhibition of hydrate formation. A first step
18 K. Effectively, the IQF method weights KHI-1's 2 K lower in being able to do so is the acquisition of sufficient data to allow
subcooling at a formation probability of 0.42 as equivalent to the the construction of a statistically meaningful representation of the
larger number of failures that occurred for KHI-3 at subcoolings formation probability distribution. Automated lag time apparatus
between 13 and 18 K. are ideal measurement tools for this task, and in this work an HP-
The IQF: pmax method provides additional insights on the ALTA was used to test the performance of six KHIs that had
measured hydrate formation distributions that could lead to more previously been screened using a conventional rocking cell appa-
effective/advanced inhibition strategies or improved KHI develop- ratus. The next challenge is to interpret the measured probability
ment. More effective inhibition strategies could be based on the distributions so that the entire suite of newly available information
selection of a KHI that has an expected subcooling slightly below can be used in the most effective way. The two key questions are
that of other KHIs but is far less likely to fail at low subcoolings. (1) how does one compare multiple formation probability dis-
Potentially, blends of KHIs that perform well according to different tributions that may overlap one another to determine which
metrics may be tested in a second phase of screening, although it performs “best”, and (2) how does one define “best”.
would be fortunate if the inhibitive effects turned out to be additive. In this work a new approach to the analysis of HP-ALTA data
Alternatively, the IQF: pmax may help researchers identify which was developed that has significant advantages over previous
attributes of two KHIs that have different IQF: pmax scores give rise approaches because it allows operations such as integration and
to this difference, so that an improved KHI which achieves high- subtraction to be applied directly to the numerical data represent-
subcoolings but does not fail at low ones might be developed. ing the PDDF for hydrate formation. This allows the impact of
apparatus effects to be subtracted from the data measured for a
KHI, the CPDF to be calculated by integration of the PDDF
7. Conclusions histogram, and the expected net subcooling for the KHI to be
calculated by integration of the quantile function. Geometrically,
While inhibitors can be ranked qualitatively or in general terms this second integration is a calculation of the area between the
through several different approaches, even the most quantitative inhibitor's CPDF and that of pure water and physically it represents
 E.F. May et al. / Chemical Engineering Science 107 (2014) 1–12
the most probable subcooling, beyond that achieved in tests with
pure water, which the KHI sample will achieve when subjected to
a linear cooling ramp in a quiescent system.
Once the CPDF and integrated quantile function are constructed
for a KHI, two methods are available for interpreting the full extent
of the information about the formation distribution. A threshold
subcooling can be chosen and the corresponding formation prob-
ability can be determined (or vice versa) to quantify the efficacy of
the KHI. The threshold chosen might reflect, for example, a
criterion based on an acceptable level of risk. Alternatively, the
IQF method can be used to determine more than just the most
probable subcooling; by integrating over a reduced probability
domain, performance metrics which give a penalty weighting to
formation at low subcoolings and can thus be used to assess worst
case scenarios can be calculated. The IQF method could potentially
help identify which functional groups of a KHI molecule are
responsible for failures at low subcoolings. These methods may
also help develop improved inhibition strategies, for example, by
trading-off higher expected subcoolings with fewer failures at low
subcoolings
or even through the development of KHI blends in which the
performance of each is additive.
The rankings and net subcoolings of the six KHIs determined
using the rocking cell were in reasonable agreement with those
determined from the HP-ALTA using several different methods of
quantifying KHI performance. It was possible to use the SPT
method with a plausible subcooling threshold to extract a ranking
from HP-ALTA measurements that exactly matched that of the
rocking cell. Holistically, however, the HP-ALTA measurements
indicate that the rocking cell's first and third ranked KHIs were
effectively equal best, with both being superior to the rocking cell's
second ranked KHI. The performance metrics determined for the
three worst KHIs from the HP-ALTA data always produced the
same ordering as the rocking cell, although in the quiescent HP-
ALTA these three KHIs achieved subcoolings only slightly smaller
than the three best KHIs unless the memory effect was allowed to
influence the experiments.
The HP-ALTA technique, when coupled with the new analysis
method, also allowed the impact of the memory effect on the
formation distributions of pure water and on each of the six KHIs
to be quantified. The expected subcooling of pure water in the
quiescent system was reduced by 4 K when the samples were held
for 300 s at a superheating of 6 K instead of 16 K. In the presence
of this memory effect, the expected subcoolings of the three best
KHIs were reduced by less than 2.2 K, while those of the three
worst ones decreased by between 7 K and 14 K. Interestingly, the
net subcoolings achieved in the HP-ALTA experiments with the
memory effect were similar to those measured using the rocking
cell with significant agitation. The significant difference between
the performance of some KHIs measured with and without the
memory effect provides some support for the retained structure
theory as the underlying mechanism, although further measure-
ments would be necessary to establish this conclusively. The HP-
ALTA method may prove to be a valuable tool in future efforts to
quantify and understand the memory effect.
This work has also helped identify some limitations that
can potentially afflict HP-ALTA measurements and which can be
avoided or even improved upon in future work. At very high sub-
coolings, the measured hydrate formation distributions became
clearly affected by ice formation. A means of establishing this ice
formation boundary unambiguously was demonstrated using
high pressure N2. Assessment of the asymptotic behaviour of the
distribution functions constructed with the new data analysis
method can identify whether the entire formation distribution
has in fact been sampled, and allow further experiments to be
conducted if necessary and not precluded by the ice formation
11
boundary. Ultimately the quiescent nature of the current HP-ALTA
experiments gives rise to this ice formation problem and places a
limit on the extent to which its measurements of KHI net
subcooling can be translated to turbulent systems. To address this
it would be desirable to incorporate a means of agitation into a
future HP-ALTA system. Although implementation would be far
from straightforward, one possibility for achieving adequate mix-
ing in the HP-ALTA may be through the integration of a bubble
supply into the liquid.
Acknowledgement
This work was supported by NM’s Australian Research Council
Future Fellowship (FT0991892) and CSIRO’s Petroleum and
Geothermal Research Portfolio.
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