Energy 218 (2021) 119507

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Energy
journal homepage: www.elsevier.com/locate/energy

New insights into the evaluation of kinetic hydrate inhibitors and

energy consumption in rocking and stirred cells
Shima Foroutan a, b, Hanie Mohsenzade a, b, Ali Dashti a, b, *, Hadi Roosta a, b
a
Department of Chemical Engineering, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad, Iran
b
Research Laboratory of Polymer Testing (RPT Lab.), Research Institute of Oil & Gas, Ferdowsi University of Mashhad, Mashhad, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The present paper aims at identifying suitable apparatus to perform KHIs test. Therefore, for the first
Received 26 June 2020 time, the comparison of rocking and stirred cells was performed based on KHIs performance and energy
Received in revised form consumption during hydrate formation experiments. Growth rate of hydrate, induction time measure-
4 November 2020
ments, and calculation of the kinetic parameter of aK* were applied for evaluation of KHIs and synergists
Accepted 29 November 2020
Available online 3 December 2020
in the rocking and stirred cells. The rate of hydrate formation showed that the performance of the KHIs
and the synergists was more potent in the rocking cell compared to the stirred cell. Induction time
measurements also indicate that hydrate nucleation is more retarded in the rocking cell compared to the
Keywords:
Hydrate
stirred cell. However, new insights were revealed when energy measurements during hydrate formation
Energy experiments were applied. In the process of hydrate formation with weak inhibitors such as polyethylene
Kinetic inhibitors glycols the consumed energy was up to 30 times greater than that in the rocking cell, although it was 3
Synergists e8 times higher in the presences of Luvicap EG and synergists. In addition, analysis of energy con-
Rocking cell sumption based on growth rate of hydrate determined that the rocking cell is preferred compared to the
Stirred cell stirred cell for experimental development of KHIs.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Natural gas hydrates are crystalline compounds which due to
their widespread distribution in subsea, high energy density, and
their high potential for gas storage can be applied as a clean energy
source for future development [1,2]. However, despite this potential
advantage and other benefits such as gas separation [3,4], CO2
capture [5,6], and gas storage [7,8], it can cause problems in the
energy distribution through blockage of oil and gas pipelines.
Heating of pipelines can be used to hinder this problem, although
due to high energy consumption, the use of kinetic hydrate in-
hibitors (KHIs) is considered as a cost-effective method for hydrate
formation prevention [4,9e11]. KHIs are mostly polymeric com-
pounds often with added various synergists for boosting their
performance [12,13]. Poly-N-vinyl lactam polymers such as poly-
vinylpyrrolidone (PVP) and polyvinyl caprolactam (PVCap) are the
most common KHIs that inhibit hydrate formation by retarding the
nucleation and/or reducing the hydrate growth rate [14e17]. Amino
* Corresponding author. Department of Chemical Engineering, Faculty of Engi-
neering, Ferdowsi University of Mashhad, Mashhad, Iran.
E-mail address: dashti@um.ac.ir (A. Dashti).
acids (such as glycine), salts (such as MgCl2 and KCl), and quater-
nary salts also show inhibition effects on nucleation and growth of
hydrate [18e20]. On the other hand, the abundantly-studied clas-
ses of synergists are glycol ether compounds [21,22], quaternary
ammonium salts [23e27], ionic liquids [28] and polyethylene oxide
(PEO) [29e31].
Due to the importance of the study of KHIs, appropriate
equipment should be selected for testing of KHIs. The most
commonly used experimental devices for hydrate formation tests
are tabulated in Table 1. The benefits and applications of each of
these devices are summarized in this table. According to this, the
rocking and stirred cells are the most common apparatus to
conduct kinetic tests of KHIs. Therefore, a thorough understanding
of the suitability of this equipment for testing of KHIs is of
importance.
A key factor in choosing suitable setup is the amount of energy
consumed during the tests. Although limited studies have been
conducted to compare the rocking and stirred cells for kinetic tests
of hydrate formation, but there is no study for comparison of the
two setups in terms of energy consumption when KHIs are tested.
Study on energy in hydrate formation process can justify the
applicability of hydrate-based technologies. In this regard, Table 2

https://doi.org/10.1016/j.energy.2020.119507
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Table 1
The most commonly used equipment for hydrate formation experiments.

Setup Advantages/Applications Refs.

Stirred autoclaves (cells) Suitable for gas hydrate studies with agitation/Useful for studying KHIs [32e34]
Unstirred cells Reduction of capital costs and operating costs during hydrate formation process/ [35]
Suitable for studying kinetic hydrate promoters
Semi-batch autoclaves Suitable for adding components or taking samples [36]
Sapphire cells Used for observation of hydrate formation process/Investigation on hydrate [37]
morphology
Rocking cells Useful for studying of KHIs/Suitable for multiple tests in the same unit [38e41]
PVT cells Suitable for studying of thermodynamic of hydrate formation process [42]
Wheel loops Suitable for LDHIs evaluation under pilot scale/Used for testing AAs [42,43]
Flow loops Suitable for KHIs evaluation under simulated industrial conditions/Suitable for [44e46]
measuring the subcooling and induction times of KHIs
High pressure automated lag time apparatus (HP-ALTA) Used for studying of the statistics of hydrate formation/Useful to perform a large [47e49]
number of experiments
High pressure differential scanning calorimetery (HP-DSC) Used for studying of KHIs on hydrate formation in emulsions/Used for analysis [50]
of the KHIs in a short time period
Bubble column Suitable for the more contact of gas and liquid during hydrate formation process [51]
Fixed bed reactor Suitable for reduction of power required during hydrate formation process [3]
Cells equipped to magnetic stirrer bar Used to mix the contents in the cells without mechanical mixer [52e55]
Static mixer Helpful for continuous hydrate formation process/Reduction of energy [56]
consumption
Spraying reactor Useful for rapid production of gas hydrates/Helpful for the more contact of gas [57]
and liquid during hydrate formation process
Sandy cells Suitable for simulation of equipments with sandy sediments or sandy reservoirs [58,59]

Table 2
Studies on energy in various areas related to gas hydrates.

Field of study on energy description Refs.

Separation Estimation of energy consumption for greenhouse gas separation by hydrate formation in [60]
comparison with liquefaction separation process
CO2 capture Estimation of required energy for mechanical agitation in new hydrate formation apparatus [61]
CO2 capture Investigation on minimization of energy consumption during hydrate formation for CO2 [62]
recovery
Methane production Evaluation of the energy conversion efficiency during gas production process of hydrate [63]
deposits
Gas storage Calculation of required energy for methane storage by hydrate formation [64]
Desalination Evaluation of energy consumption during hydrate based desalination process [65]
Separation Evaluation of energy consumption during hydrate based biogas upgrading with CO2 valorization [66]
Methane production Investigation on energy consumption in the process of hydrate exploitation from flue gas by [67]
energy efficiency simulation
CO2 storage Estimation of energy consumption by the static mixer during CO2 hydrate formation [56]
CO2 storage Experimental investigation on optimum energy consumption during CO2 hydrate formation [68]
Hydrogen storage Evaluation of energy consumption for hydrogen storage by a binary hydrogen-THF hydrate [69]
Gas storage and transportation Energy consumption estimation for the transportation and storage processes of NGH [70]
Desalination Investigation on energy consumption in gas hydrate and reverse osmosis hybrid system for [71]
seawater desalination
Desalination Estimation of required energy for seawater desalination by hydrate formation process [72]
CO2 capture Estimation of required energy for reduction of CO2 emission by CO2 hydrate cooling system [73]
CO2 and H2S capture Energy evaluation for removal of CO2 and H2S by hydrate formation process [74]
CO2 capture Evaluation on energy consumption for CO2 emission reduction using hydrate-based gas [75]
separation
CO2 capture Simulation of hydrate-based CO2 capture from biogas and calculation and analysis of the energy [76]
consumption of this process
hydrate separation Study on reduction of the energy consumption of CO2 hydrate separation [77]
Hydrate production Energy cost for production of methane hydrate in a scaled-up system [57]
CO2 capture Simulation and analysis of CO2 separation by hydrate formation process and calculation of [78]
energy consumption

2
S. Foroutan, H. Mohsenzade, A. Dashti et al.
Table 3
The chemicals used for the experiments.
Component Chemical Structure Supplier
Ethylene Technical gas services
PEG300 Merck
PEG20000 Merck
PVP Merck
Luvicap EG BASF
Water Abtin
reviews studies on energy in various areas related to hydrates.
However, as mentioned, there is a research gap in comparing the
two setups for required energy and energy analysis during testing
of KHIs. Also, there are a few available investigations regarding the
comparison of KHIs performance in the rocking and stirred cells,
especially when synergists meet KHIs.
In this work, for the first time, the rocking and stirred cells are
compared based on the required energy during KHIs tests. Mea-
surements and analysis of energy consumption would give new
insights of the different abilities and capabilities of these two
setups. In this regard, first, the performance of KHIs (PVP and
Luvicap EG) and synergists (polyethylene glycols) in the rocking
and stirred cells are examined and compared. The comparisons
would be based on the growth rate of hydrate, induction time
measurements, and calculation of the kinetic parameter of aK*.
Then, energy consumption in the rocking cell and the stirred cell
during the KHIs tests are experimentally measured and subse-
quently the analysis of energy consumption is performed during
the progress of hydrate formation.
2. Experimental section
2.1. The applied materials
Ethylene with the purity of 99.9% was supplied from Technical
gas services. PEGs with the molecular weights of 300 and 20000 g/
mol and PVP with the molecular weight of 10000 g/mol were
purchased from Merck. Luvicap EG was obtained from BASF. The
deionized water was supplied from Abtin. Table 3 presents the
chemical structures of these materials.
2.2. Experimental apparatus
The KHI performance and the synergistic effect tests were car-
ried out in two different reactors. The first one is a stirred cell which
has been clarified in prior studies [79,80]. The second one is a high-
3
Energy 218 (2021) 119507
pressure rocking cell which is shown in Fig. 1. The apparatus con-
sisted of a pressure transmitter with the accuracy of ±0.1 bar, a
thermometer with a precision of ±0.1 K, and a data acquisition
system to record the pressure and temperature of the cell. The
volume of the cell is 100 mL which is equipped with a cooling bath
to keep the experimental temperature constant. Also, a speed
controller was applied to adjust the rocking rate in the 30 rocks per
minute. In addition, a wattmeter with an accuracy of ±0.01 W was
used to measure the energy consumption of the rocking cell and the
stirred cell during hydrate formation tests.
2.3. Experimental procedures
First, the rocking and stirred cells were rinsed 4 times with
distilled water and then were evacuated by a vacuum pump. The
cells were subsequently charged with aqueous solution of the KHIs.
Then the temperature of cells adjusted at 275 K by coolant system
because of the hydrate formation at a constant temperature. When
the temperature was reached, the cells slowly pressurized to the
initial pressure of 20 bar by ethylene. Subsequently, rocking or
mixing was initiated and when a sudden pressure drop was
occurred, ethylene hydrate was formed and pressure and temper-
ature data were recorded to equilibrium state (temperature of 2
C
and pressure of 6 bar). The amount of gas consumed during the
formation of hydrate was obtained by following equation which Z
was calculated by Peng Robinson equation of state [81]:
   
PV PV
nci ¼ no  ni ¼  (1)
ZRT o ZRT i
The slope of gas consumption versus time curve could reflect the
hydrate growth rate which could be also evaluated by the kinetic
parameter of aK* calculated from following equation [82,83].
 
dn
fg
 ¼ aK * mg  meq ¼ aK * RTln (2)
dt feq
3. Results and discussions
3.1. The inhibition potential of the KHIs and the synergists on
hydrate growth in the rocking cell and the stirred cell
In the present study, two different reactors were applied to
investigate the performance of KHIs and synergists. In this respect,
the inhibition effect of the previously mentioned component on
ethylene hydrate formation at 2
C was evaluated. First, the effect of
PVP in both reactors was assessed. The change of gas consumption
with time at the concentrations of 0.01, 0.1, 0.5, and 1 wt% are
illustrated in Fig. 2. The results demonstrated that PVP reduced the
rate of gas consumption which implies the reduction of the growth
rate in both reactors. According to the results of the tests carried out
in the rocking cell (Fig. 2a), increasing the concentration of PVP
from 0.01 to 1 wt% resulted in a decrease in growth rate. However,
the experimental results which were carried out in the stirred cell
were different from those of the rocking cell, and at the concen-
trations of 0.01 and 0.1 wt% stronger inhibition performance was
obtained, but when the concentration increased from 0.1 to 1 wt%,
the inhibition effect decreased. In other words, the KHI perfor-
mance of PVP was reduced. For quantitative and accurate analysis,
the kinetic parameter of aK* was calculated and compared in the
rocking and stirred cells. This parameter reflects the hydrate
growth rate and its low value indicates lower growth rate and more
inhibition effects. Table 4 presents obtained values of aK* for
ethylene hydrate formation in the presences of 0.01, 0.1, 0.5, and
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 1. Schematic of the high-pressure rocking cell apparatus.

4
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 3. The effect of Luvicap EG, based on aK* in the rocking cell and the stirred cell.

Table 5
The values of aK* in the presence of the PEGs during the hydrate formation in both
reactors.

Aqueous Concentration aK* (mol2/ Relative aK*

solution (wt%) (s.J))  108 (PEG/Pure
Water)

Rocking Cell
PEG20000 0.01 2.41 0.88
PEG20000 0.1 2.53 0.92
PEG20000 1 2.75 1.00
PEG300 0.1 2.42 0.88
PEG300 1 3.12 1.13
Fig. 2. The inhibition effect of PVP on the hydrate growth in the rocking cell and the Stirred Cell
stirred cell. PEG20000 0.01 2.41 1.11
PEG20000 0.1 3.32 1.52
PEG20000 1 3.72 1.70
Table 4 PEG300 0.01 2.19 1.01
The kinetic parameter of aK* in the presence of PVP in both reactors. PEG300 0.1 2.19 1.01
PEG300 1 2.22 1.02
Aqueous solution Concentration aK* Percentage reduction
(wt%) (mol2/(s.J))  108 of aK* compared to
pure water

Rocking Cell concentration to more than 0.1 wt% does not enhance the KHI
Pure Water 0 2.75 0 performance. The better performance of PVP in the rocking cell may
PVP 0.01 1.53 44 be due to better adsorption of PVP on hydrate crystals of hydrate.
PVP 0.1 1.53 44 The adsorption of PVP on hydrate surface leads to diffusion of gas
PVP 0.5 1.06 61
PVP 1 0.66 76
molecules to hydrate structure becomes harder and subsequently
Stirred Cell the hydrate growth rate is decreased.
Pure Water 0 2.18 0 The performance of Luvicap EG in both cells was also assessed.
PVP 0.01 1.15 47 As expected, it showed an inhibition effect on ethylene hydrate
PVP 0.1 0.87 60
growth in both reactors. Fig. 3 illustrates the inhibition potential of
PVP 0.5 1.67 23
PVP 1 1.67 23 Luvicap EG based on the values of the kinetic parameter of aK*at
different concentrations. The relative value of aK* (the ratio of aK*
obtained for hydrate formation in the presence of Luvicap EG to
1 wt% PVP. The value of aK* for ethylene hydrate formation with
pure water) in both reactors is less than one, which indicates
pure water was 2.75 (mol2/(s.J))  108. However, when a low
Luvicap EG has decreased the hydrate growth rate in both reactors.
dosage of PVP (0.01 wt%) was present in the cells, aK* was
However, the relative values of aK* in the rocking cell are less than
decreased, so that its values in the rocking cell and the stirred cell
that in the stirred cell. In fact, in the presence of Luvicap EG there is
was decreased 44 and 47%, respectively. The comparison of rocking
more reduction of hydrate growth rate compared to pure water in
and stirred cells performance shows that PVP has more inhibition
the rocking cell. This implies the more inhibition potential of
potential for hydrate formation in the rocking cell. In fact, PVP in
Luvicap EG in the rocking cell. It considers that the formed hydrate
the rocking cell can decrease aK* by 76% compared to pure water,
is more dispersed in the liquid phase of the rocking cell than that in
while in the stirred cell it is decreased by 60%. This indicates that
the stirred cell, therefore; it is more likely that Luvicap EG adsorbs
the rocking cell can show maximum potential of PVP for the
on hydrate surface and more inhibition effect on the hydrate
decrease of the hydrate growth rate. Also, the values of aK* reveal
growth is obtained in the rocking cell.
that in the rocking cell with the increase of PVP concentration, the
The inhibition effects of the polyethylene glycols with the mo-
inhibition effects is increased and at highest concentration,
lecular weight of 300 and 20000 g/mol are also investigated and
maximum inhibitory effect is obtained. But in the stirred cell the
the values of aK* are reported in Table 5. Based on the findings,
more effective concentration was 0.1 wt% and the increase of the

5
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 5. The synergistic effect of PEGs to Luvicap EG on reducing the hydrate growth
Fig. 4. The synergistic effect of PEGs to PVP in the rocking cell and the stirred cell.
rate in the rocking cell and the stirred cell.

Table 6
Table 7
The values of aK* in the presence of PEGs and PVP during the ethylene hydrate
The aK* values in the presence of mixtures of PEGs and Luvicap EG in the rocking cell
formation in the rocking and the stirred cells.
and the stirred cell.
Aqueous concentration aK* (mol2/ Relative aK*
Aqueous concentration aK* (mol2/ Relative aK*
solution (wt%) (s.J))  108 (PVP þ PEGs/PVP)
solution (wt%) (s.J))  108 (Luvicap EG þ
Rocking Cell PEG/Luvicap
PVP 0.5 1.06 1.00 EG)
PVP þ PEG300 0.01 0.87 0.82
Rocking Cell
PVP þ PEG20000 0.01 0.95 0.90
Luvicap EG 0.1 0.49 1.00
Stirred Cell
Luvicap EG þ PEG300 0.01 0.17 0.35
PVP 0.5 1.67 1.00
Luvicap EG þ PEG20000 0.01 0.16 0.33
PVP þ PEG300 0.01 1.62 0.97
Stirred Cell
PVP þ PEG20000 0.01 1.12 0.67
Luvicap EG 0.1 0.77 1.00
Luvicap EG þ PEG300 0.01 0.91 1.18
Luvicap EG þ PEG20000 0.01 1.01 1.31
unlike PVP and Luvicap EG, polyethylene glycols are poor inhibitors
of hydrate growth, and in some cases, they act as promoters when
used alone. The results also confirmed that when the concentration PVP in both reactors. When PVP is applied as KHIs, the value of aK*
increased, the aK* increased in both reactors. In other words, at the for ethylene hydrate formation in the rocking cell is 1.06 (mol2/
lowest concentration (0.01 wt%) they exhibit more inhibition ef- (s.J))  108, while when PEG300 and PEG20000 as synergist are
fects on the hydrate growth. In fact, it considers that the lack of applied with PVP, aK* is decreased 18 and 10%, respectively. The
effective functional groups (such as amide functional group) makes results in the stirred cell also indicated that the value of aK* in the
the PEGs weak inhibitors. However, since the hydrophilicity of presences of PEG300 and PEG20000 as synergist is decreased.
PEGs, they are expected to be synergists to kinetic inhibitors. The synergistic effects of PEG300 and PEG20000 on Luvicap EG
The synergistic effects of PEGs in both reactors are also scruti- were examined. Fig. 5a illustrates that both PEGs are found to be
nized at the concentration of 0.01 wt% because at this concentra- significant synergists to Luvicap EG in the rocking cell. In addition,
tion they acted more efficiently. Fig. 4a indicates that PEGs enhance based on Table 7, there is a considerable decrease in the aK* value
the performance of PVP in the rocking cell. Also, Fig. 4b demon- with the addition of PEGs to the solution of Luvicap EG. The pres-
strates that PEG20000 improves the KHI performance of PVP while ence of PEG300 and PEG20000 respectively reduce the aK* value of
PEG300 did not show a synergistic effect on PVP in the stirred cell. Luvicap EG by 65% and 67% compared to the case in which the
Table 6 shows the aK* in the presence of the mixture of PEG and Luvicap EG is only applied. The experiments have also been carried

6
S. Foroutan, H. Mohsenzade, A. Dashti et al.
Fig. 6. Adsorption of the KHIs and the synergists on hydrate surface in the rocking cell and the stirred cell.
out in the stirred cell at the same conditions, and the related data
are summarized graphically in Fig. 5b which confirms that despite
the fact that PEGs were proved to be effective synergists for Luvicap
EG in the rocking cell, but in the high-pressure stirred cell they
were ineffective. In fact, it considers that the inhibition effect of the
KHIs, the PEGs, and their binary mixture is more potent in the
rocking cell.
According to the experimental results, the kinetic hydrate in-
hibitors and the synergists showed more inhibition potential on
hydrate growth in the rocking cell compared to the stirred cell. In
fact, the stirred cell and the rocking cell are different in the type of
agitating systems, such that the particles are more dispersed in the
rocking cell. Therefore, as shown in Fig. 6, the chance of the in-
hibitors and the synergists to reach and adsorb on the hydrate
surface is more in the rocking cell compared to the stirred cell
which leads to more adsorption of the KHIs and the synergists on
scattered hydrate particles and more inhibition effect.
3.2. The inhibition effects of the KHIs and the synergists on the
nucleation of hydrate in the rocking cell and the stirred cell
Initially, the inhibition effect of PEG300 on the nucleation of the
hydrate was measured. Fig. 7a exhibits the ratio of induction time in
the presence of PEG300 to the induction time of pure water. The
ratios higher than 1 imply the inhibition influence of PEG300 on
retarding the nucleation. The results reveal that PEG300 can pro-
long the nucleation time at all concentrations in the rocking cell. In
this regard, PEG300 at the concentration of 0.01, 0.1, and 1 wt%
extended the induction time to 6.8, 2.5, and 1.2 times that of the
pure water nucleation time, respectively. The induction time ob-
tained from the solution of 0.01 and 0.1 wt% of PEG300 in the
stirred cell was 2.1 and 2 times that of the pure water nucleation
time, respectively, although, it was not effective at the
7
Energy 218 (2021) 119507
concentration of 1 wt%. The results confirm that in both reactors, an
increase in the concentration of PEG300 leads to a decrease in the
induction times which means the inhibition performance gets
weaker. Furthermore, PEG300 exhibit stronger performance in the
rocking cell in comparison with its performance in the stirred cell.
The effect of PEG20000 on hydrate nucleation time was also
assessed. Fig. 7b illustrates that in the presence of these poly-
ethylene glycols at all tested concentrations and in both reactors,
the induction time ratio was higher than 1. In other words,
PEG20000 retards the nucleation time effectively in comparison
with pure water at all the tested concentrations. In the rocking cell,
the nucleation time obtained from the 0.01, 0.1, and 1 wt%
PEG20000 solution was 7.2, 3.9, and 4.2 times that of pure water,
respectively, and in the stirred cell it was 2, 1.6, and 1.2 times that of
pure water, respectively.
In the present study, the synergistic effect of the polyethylene
glycols on PVP and Luvicap EG to retard the hydrate nucleation time
was also investigated. Fig. 8a shows the effect of PEG300 and
PEG20000 on PVP. Based on the experimental results the poly-
ethylene glycols cause more inhibition effect on nucleation
compared with when the PVP was applied alone. Besides, the KHI
performance of the inhibitors and the synergists was more efficient
in the rocking cell. The addition of PEG300 and PEG20000 as syn-
ergists to Luvicap EG also leads to increasing the nucleation time to
16.7 and 4.4 times that of Luvicap EG alone in the rocking cell. In the
stirred cell, they also show the synergistic effect but not as effective
as their performance in the rocking cell (Fig. 8b).
3.3. Comparison of the energy consumption in the rocking cell and
the stirred cell when the inhibitors are only used
It should be noted that in the studies of hydrate growth inhi-
bition, it is usually better to use equipment that can measure the
S. Foroutan, H. Mohsenzade, A. Dashti et al.
Fig. 7. The inhibition effect of the polyethylene glycols on induction time in the rocking and stirred cells.
performance of KHIs and synergists in a shorter period of time so
that less energy can be consumed by the apparatuses. In fact,
shorter test time can reduce energy consumption. In the present
study, the consumed energy by both the rocking cell and the stirred
cell during hydrate formation was measured. Initially, the energy
consumption during the hydrate formation in the presence of the
polyethylene glycols was investigated. Fig. 9a illustrates that the
consumed energy during evaluating PEG300 inhibition perfor-
mance in the stirred cell is much higher than the consumed energy
in the rocking cell such that at the concentration of 0.01, 0.1, and
1 wt% the consumed energy was 23, 25, and 30 times greater than
that in the rocking cell, respectively. The results in Fig. 9b also
demonstrate that the consumed energy during the testing of
PEG20000 at the concentration of 0.01, 0.1, and 1 wt% in the stirred
cell was considerably higher than that in the rocking cell. These
findings revealed that in terms of energy-saving the rocking cell
outperforms the stirred cell during hydrate formation in the pres-
ence of the polyethylene glycols.
The measurements of consumed energy during hydrate forma-
tion in the presence of PVP and Luvicap EG lead to observing
interesting results. Fig. 10a shows the ratio of energy consumption
in the stirred cell to the rocking cell during the hydrate formation
8
Energy 218 (2021) 119507
process with PVP. According to the results at the tested concen-
trations, this ratio is greater than one, which confirms the better
performance of the rocking cell in relation to less energy con-
sumption. Accordingly, at the lower concentrations (0.01 and 0.1 wt
%) the consumed energy in the stirred cell during the hydrate for-
mation was about 24 times greater than that in the rocking cell.
However, when the concentration increases to 0.5 and 1 wt% the
consumed energy in the stirred cell was 8.5 and 6 times greater
than that in the rocking cell, respectively. It seems that at higher
concentrations the greater potential of PVP to inhibit hydrate for-
mation even in the rocking cell causes considerable energy con-
sumption during the hydrate formation process though the rocking
cell is superior even in these concentrations. According to Fig. 10b,
the results also indicated that the consumed energy in the presence
of Luvicap EG in the rocking cell is lower than that in the stirred cell
(3e8 times lower), although the difference between energy con-
sumption values is not as much as that with the PVP and poly-
ethylene glycols. The greatest inhibition performance of Luvicap EG
at the concentration of 0.5 wt % in the rocking cell leads to
consuming much energy which is although lower than that in the
stirred cell.
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 8. The synergistic effect of polyethylene glycols to PVP and Luvicap EG on induction time in the rocking and stirred cells.

9
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 9. Comparison the consumed energy in the rocking cell and the stirred cell during the hydrate formation process in the presence of polyethylene glycols.

10
S. Foroutan, H. Mohsenzade, A. Dashti et al.
Fig. 10. The ratio of consumed energy in the stirred cell to that in the rocking cell during the hydrate formation process in the presence of PVP and Luvicap EG.
Fig. 11. Comparison the consumed energy during the test of evaluating the synergistic
effect of the polyethylene glycols on PVP and Luvicap EG.
3.4. Comparison of energy consumption in the rocking cell and the
stirred cell when the inhibitors meet the synergists
As previously was demonstrated when the kinetic hydrate in-
hibitors meet the synergists (PEG300 and PEG20000) the inhibition
effects were more significant. However, due to the evaluation of the
11
Energy 218 (2021) 119507
energy consumption during hydrate formation when the KHIs meet
the PEGs, the energy measurements were also performed. Fig. 11
presents the values of consumed energy during the hydrate for-
mation when the polyethylene glycols and the kinetic inhibitors are
applied simultaneously. The measurements of the energy during
the hydrate formation process to investigate the performance of
polyethylene glycols as synergisms to PVP and Luvicap EG also
indicate that more energy is spent for hydrate formation in the
stirred cell compared with the rocking cell. The consumed energy
by the stirred cell during evaluation of PEG300 and PEG20000 as
synergist to PVP was 6.3 and 7.7 times greater than that in the
rocking cell, respectively. Also, when PEG300 and PEG20000 were
applied with Luvicap EG in the stirred cell, the consumed energy
was 3 and 3.4 times greater compared to the rocking cell, respec-
tively. In fact, it seems that the simultaneous presence of PEGs and
Luvicap EG has led to less difference in energy consumption in the
rocking and stirred cells, although the rocking cell is still more
suitable in term of energy saving.
3.5. Analysis of energy consumption based on the hydrate growth
rate at different steps of hydrate formation in the rocking and stirred
cells
The analysis of the energy consumption during hydrate forma-
tion progress also indicates interesting and notable results. In this
S. Foroutan, H. Mohsenzade, A. Dashti et al.
Fig. 12. Comparison of the average growth rate and the consumed energy in the presence of PEG20000 in the rocking cell and the stirred cell during the hydrate formation progress.
regard, the average hydrate growth rate and consumed energy
during different intervals of hydrate formation process when the
25, 50, 75, and 100% of total moles of gas was consumed (at nci/
ncf ¼ 0.25, 0.5, 0.75, and 1), is calculated. For example, the results of
the analysis in the presence of PEG20000 as a weak inhibitor and
Luvicap EG as a strong inhibitor in the stirred cell and the rocking
cell are investigated. Initially, the average growth rate and analysis
of consumed energy during hydrate formation progress in the
presence of PEG20000 are evaluated. Based on the obtained results
(Fig. 12a and b), in the rocking cell at nci/ncf of 0.25, 0.5, 0.75, and 1,
the average hydrate growth rates are 20.6, 19.2, 17, and 9.8 mmol
per minute, respectively. However, in the stirred cell at the
mentioned nci/ncf, the average growth rate is 2.3, 1.5, 0.73,
0.21 mmol per minute. The noticeable point is that the average
hydrate growth rate in the rocking cell is higher than that in the
stirred cell, this leads to consuming more energy in the stirred cell
which confirms the previous results. Another point from Fig. 12b
which should be demonstrated is the drastic decrease in hydrate
growth rate in the stirred cell during hydrate formation progress. In
fact, in the stirred cell there is a greater difference between average
hydrate growth rate at the first moments of hydrate formation
(when nci/ncf is between 0 and 25) and at the last moments of
hydrate formation (when nci/ncf is between 0.75 and 1) than that in
the rocking cell. In other words, in the stirred cell when the larger
amount of hydrate is formed, the average growth rate is decreased
significantly which can lead to consuming much more energy
especially in the last moments of hydrate formation. The analysis of
energy consumption also confirms this issue. In this regard, Fig. 12c
12
Energy 218 (2021) 119507
and d shows in the stirred cell the majority of energy is utilized in
the last moments of hydrate formation (when the nci/ncf is between
0.75 and 1), such that 60% of the total used energy is consumed at
this interval, whereas it was 33% for the rocking cell.
In the presence of Luvicap EG as an effective kinetic inhibitor,
the average hydrate growth rate is compared and analyzed in
different intervals of nci/ncf for both reactors (Fig. 13a and b). Based
on the obtained results, Luvicap EG reduces the hydrate growth rate
remarkably. Also, the average growth rate is lower in the stirred cell
compared to the rocking cell so that in the final quarter of hydrate
formation, energy consumption is 53% while in the rocking cell is
39%. According to this, it could be concluded that performing of
hydrate formation test in the presence of the inhibitors would be
more suitable in the rocking cell compared with the stirred cell due
to the less energy consumption.
The significant decrease of hydrate growth rate in the last mo-
ments of hydrate formation in the stirred cell compared to the
rocking cell which leads to a remarkable increase of the consumed
energy in this cell may be in relation to agglomeration of hydrate
particle in the interface of gas-water. In fact in the stirred cell and
the rocking cell with the progress of hydrate formation the driving
force for hydrate formation is decreased which leads to the
reduction of the growth rate of hydrate and subsequently the en-
ergy consumption is also increased. However, the reduction of the
hydrate growth rate and the increase of energy consumption in the
final quarter of hydrate formation are more significant due to the
agglomeration of hydrate particles. In fact, when the agglomerated
hydrate particles are increased, the diffusion of gas molecules to the
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 13. Comparison of the average hydrate growth rate and the consumed energy in the presence of Luvicap EG in the rocking cell and the stirred cell during the hydrate formation
progress.

Table 8
The comparison of energy consumption of equipment in different fields of hydrate.

Process Energy (kWh) Refs.

Performance evaluation of KHIs 0.024e1.156 This work

Required energy for methane hydrate production in a reactor based on the best conditions 1.47e1.91 [57]
Energy consumption for separation of 1 Kg HFC-134a by hydrate formation process 0.144 [60]
Energy consumption for separation of 1 Kg SF6 by hydrate formation process 0.108 [60]
Energy consumption for capturing of 1 mol CO2 by hydrate formation process 0.541 [61]
Required Energy for hydrate-based biogas upgrading 0.182 [66]
Required Energy for production 1 Kg CH4 by hydrate exploitation process from flue gas 1.05e2.15 [67]
Energy consumption for hydrate-based CO2 capture with tetrahydrofuran and tetra-n-butylammonium bromide 2.44e2.92 [75]
Energy consumption for desalination of water by gas hydrate technology 1.58 [84]

liquid bulk becomes difficult especially in the rocking cell, because
in this cell agglomerated particles may cover most of the gas-water
interface.
3.6. Comparative analysis on the energy consumption and hydrate
growth rate in different apparatus
In this work, for the first time, the measurement and analysis of
energy consumption for conducting KHIs tests in apparatus was
focused. However a comparative analysis can be performed for
better understanding of energy consumption in hydrate equip-
ment. According to this, first a comparison was made based on the
energy consumption for KHIs field (this work) with other fields of
hydrate (other literatures) and then analysis on the energy con-
sumption and hydrate growth rate of this work and our previous
13
work would be performed. Table 8 presents the comparison of
energy consumption of equipment in different fields of hydrate.
The consumed energy for the test of KHIs in this work was in the
range of 0.024e1.156 kWh, while in other fields of hydrate studies
such as CO2 capture, separation, hydrate production, hydrate
exploitation, and desalination, it varied in the range of
0.108e2.92 kWh.
Hydrate growth rate is one of the factors that affect energy
consumption. Based on this, the energy consumption and its rela-
tionship with the hydrate growth rate in this work (test of KHIs)
was compared with our previous work (hydrate formation in the
presences promoters) [68]. In the previous work, the tests were
performed in the stirred cell and kinetic hydrate promoters were
tested for promotion of hydrate formation. Fig. 14 shows the energy
consumption for each experiment of hydrate formation in the
S. Foroutan, H. Mohsenzade, A. Dashti et al. Energy 218 (2021) 119507

Fig. 14. The energy consumption for each experiment of hydrate formation in the rocking and stirred cells.

rocking and stirred cells. The results indicated that in each hydrate hydrate growth rate, so that the test of KHIs in the rocking cell is
experiment (test of KHIs or promoters) with the increase of average preferred compared to the stirred cell due to higher growth rate of
growth rate of hydrate, energy consumption was decreased. In this hydrate and consequently less energy consumption.
regard, when test of KHIs is carried out in the rocking and stirred
cells and promoters in the stirred cell, with the increase of the Credit author statement
growth rate of hydrate from 0.07 to 1.35, 0.32 to 0.87, and
1.46e4.85 mmol/min, the energy consumption was decreased from Shima Foroutan: Conceptualization, Methodology, Software,
0.379 to 0.024, 1.156 to 0.629, and 0.181 to 0.057 kWh, respectively. Validation, Formal analysis, Investigation, Writing e original draft,
The analysis of the results also revealed that, unlike the rocking cell, Writing e review & editing; Hanie Mohsenzade: Software, Vali-
the energy consumption changes versus growth rate were almost dation, Investigation, Writing e review & editing; Ali Dashti: Su-
linear in the stirred cell (for test of KHIs and promoters). In fact, for pervision, Conceptualization, Methodology, Resources, Data
the test of KHIs in the rocking cell, experiments with higher growth curation, Writing e review & editing, Project administration; Hadi
rate can lead to more significant decrease of energy consumption. Roosta: Conceptualization, Methodology, Supervision, Writing e
Also, while the growth rate of hydrate for the test of promoters was review & editing
more in the stirred cell, but some experiments for the test of KHIs in
the rocking cell required less energy compared to promoters. This
Declaration of competing interest
shows the high capability of the rocking cell for hydrate experi-
ments, which consumes low energy even at low growth rate of
The authors declare that they have no known competing
hydrate.
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
4. Conclusions
Nomenclatures
According to the experimental results, the KHIs and the syner-
gists could act better in the rocking cell compared to the stirred cell
so that PVP in the rocking cell decreased the aK* by 76% while in the Abbreviation
stirred cell it was reduced by 60%. Furthermore, the inhibition t Time, s
performance of Luvicap EG and the synergists was more potent in n Moles of gas in the cell, mol
the rocking cell. On the other hand, the addition of PEG300 and ti Time required to reach state i, s
PEG20000 as synergists to Luvicap EG increased the induction time nci Moles of gas consumed up to time ti, mol
to 16.7 and 4.4 times that of Luvicap EG was applied alone in the ncf Total moles of consumed gas, mol
rocking cell, while in the stirred cell, they also show the synergistic no Initial moles of gas in the cell, mol
effect but not as effective as their performance in the rocking cell. ni Moles of gas at time ti in the cell, mol
The experimental results also indicated that the consumed energy P Pressure, MPa
by the stirred cell during hydrate formation tests with PEG300 at V Volume of the gas phase in the cell, m3
the concentration of 0.01, 0.1, and 1 wt% was 23, 25, and 30 times R Universal gas constant, MPa m3/mol K
greater than that in the rocking cell, respectively. In addition, at the T Temperature, K
low concentration of PVP and Luvicap EG, the ratios of consumed Z Compressibility factor
energy in the stirred cell to that in the rocking cell were 24 and 8 a Interfacial area per unit of liquid volume, m2/m3
while the ratios at the high concentration were 6 and 3, respec- K* Overall kinetic constant, mol/m2 MPa s
tively. The analysis of results also indicated that the energy con- mg Chemical potentials of the guest molecule in the gas
sumption during hydrate formation process is related to the phase, J/mol
14
S. Foroutan, H. Mohsenzade, A. Dashti et al.
meq Chemical potentials of the guest molecule under
equilibrium, J/mol
fg Fugacity of the guest molecules in the gas phase, MPa
feq Fugacity of the guest molecules under equilibrium, MPa
Subscript
o Initial value
i State i
ci Gas consumed up to state i
cf Final consumed gas
eq Three-phase equilibrium condition
g Gas phase
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