Journal of Natural Gas Science and Engineering
Journal of Natural Gas Science and Engineering
Journal of Natural Gas Science and Engineering
A R T I C L E I N F O A B S T R A C T
Keywords: As a potential replacement for CH4 hydrates in the petroleum industry and as an environment-friendly secondary
Carbon dioxide refrigerant in the chemical industry, CO2 hydrates are proven for several industrial applications. Most of the
Kinetics studies on CO2 hydrates are mainly conducted in bench top facilities with very limited research work in the flow
Hydrate formation loop. A newly built high-pressure flow loop was used to investigate the effect of four parameters (initial pressure,
Flow loop
temperature, flow rate, and liquid loading) on CO2 hydrate formation. The process of hydrate formation and its
Gas consumption
morphological evolution in the flow loop were observed visually and analyzed. The experimental results re-
vealed that the gas consumption increased as the initial pressure increased; however, it decreased with the
increase of the temperature, flow rate, and liquid loading. The effect of the induction time on CO2 hydrate
formation was also analyzed in detail.
1. Introduction hazards (Fournaison et al., 2004; Marinhas et al., 2006; Jerbi et al.,
2010).
The transportation of unprocessed well streams has revealed critical For an elaborative understanding of hydrates, it is required to
issues with respect to flow assurance, such as wax deposition (Chi et al., characterize the hydrate forming elements and mechanisms on its for-
2016, 2017, Dubey et al.), hydrate formation, etc. Hydrate formation mation and dissociation, with which appropriate models could later be
has been considered as a serious economic and safety issue in the oil developed. Sun et al. (2003) studied the kinetic behavior of refrigerant
and gas production ever since blockages were discovered in the pipeline CCl2 F2 (R12 ) hydrates using a transparent flow loop. The pressure had
(Byk and Fomina, 1968). The coexistence of natural gas and water little effect on the particle size, however it increased the rate of hydrate
under appropriate pressure and temperature conditions leads to the formation. Moreover, the hydrate particle concentration increased with
formation of crystalline solids, and thermodynamically, these com- the increase of the liquid flow rate. Sarshar et al. (2010) investigated
pounds are solid solutions called as gas hydrates (Davy, 1811; Byk the kinetics of hydrate formation for a propane mixture using a circu-
et al., 1968; Englezos, 1992). These are formed by the hydrogen bonded lating flow reactor. A mathematical model was later developed for the
water molecules trapping the guest molecules (hydrocarbons and noble process of hydrate formation based on the crystallization, mass transfer,
gases) within a cage like structure. The unique properties of gas hy- and thermodynamic concepts. This model's prediction matched fairly
drates such as high latent heat of melting (374 kJ kg−1) and high gas well with the experimental gas consumption data. Talaghat (2013)
storage along with the industrial concerns led to extensive research measured the rate of hydrate formation with and without kinetic hy-
works on its development and handling (Jerbi et al., 2010). This pro- drate inhibitors in a circulating loop and concluded that the hydrate
blem becomes predominant in the offshore projects where the seabed growth rate increased as the pressure increased. Lv et al. (2015) studied
has much lower temperature and higher pressure (Li et al., 2013; Gao the hydrate induction time using a high-pressure flow loop. The results
et al. 2016a; Gao et al. 2016b; Gao and Gray, 2017). The oil and gas showed that the induction time of natural gas hydrate formation was
industry is mainly focusing on hydrate inhibition and prevention, while affected by various factors such as supercooling, supersaturation de-
the chemical industry is showing its potential industrial applications as gree, liquid loading, and anti-agglomerant dosage. It has to be noted
a two-phase secondary refrigerant to minimize the environmental that the induction time of hydrate formation has both microscopic and
∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: zsd@cczu.edu.cn (S. Zhou), yuandao-chi@utulsa.edu (Y. Chi).
https://doi.org/10.1016/j.jngse.2017.10.022
Received 10 June 2017; Received in revised form 26 October 2017; Accepted 31 October 2017
1875-5100/ © 2017 Elsevier B.V. All rights reserved.
S. Zhou et al. Journal of Natural Gas Science and Engineering 49 (2018) 385–392
macroscopic definitions (Kashchiev et al., 1991; Natarajan et al., 1994; and OD of outer pipe are 52.6 and 60.3 mm, respectively.
Bishnoi et al., 1996, Kashchiev, 2000; Kashchiev and Firoozabadi, A magnetic centrifugal pump with a flow rate of 3 m3/h is installed
2003). The former refers to the period of time starting from the initial to circulate the mixture in the flow loop. The admission line is equipped
equilibrium state to the time of the nucleation being finished. The latter with a gas booster pump which delivers a maximum outlet pressure of
has been used in this work, which refers to the period of time starting 42 MPa. This pump is used to pressurize the gas when the operating
from the initial equilibrium state to the time when the system tem- pressure goes above the gas cylinder pressure. In addition, the auto-
perature is about to rise suddenly due to massive hydrate formation. matic control valve (TESCOM) is used to improve the accuracy of the
As discussed before, the kinetics of hydrate formation are affected gas pressure control. In order to maintain a constant wall temperature,
by several parameters, and elements forming hydrates have unique a coolant with a capacity of 500 L is installed outside the pipe, and the
properties of their own. Among several guest molecules, carbon dioxide temperature is controlled by a water chilling unit with an operating
(CO2 ) is well-known to form gas hydrates with water under positive range of -15 °C to 20 °C.
temperature and high pressure conditions (Sun et al., 2011). It has an The flow rate and density of the mixed fluids are measured by a
interesting application in the oil and gas industry as a swapping mo- Coriolis mass flowmeter (YKLK-S-025), which are obtained from Dalian
lecule for natural gas (CH4 ) and in the chemical industry for its appli- Youke Instruments and Apparatuses Development Center. The un-
cation as a secondary refrigerant (Fournaison et al., 2004) and CO2 certainty in flow rate measurement is 0.15–0.25% and in density
sequestration (Servio and Englezos, 2001; Park et al., 2006). Moreover, measurement is ± 0.002 g/ml. As shown in Fig. 1, two differential
CO2 hydrates are found to be more stable even under low pressure pressure transmitters (Honeywell STD720) are installed in upstream
conditions (Fournaison et al., 2004), and they are easily formed by and downstream of the test section. The pressure transmitters (Rose-
injecting into the cooled aqueous solution, thereby avoiding the usage mount 3051) and temperature transmitters (Rosemount Pt100) are in-
of mechanical process for refrigeration (Marinhas et al., 2006; Jerbi stalled in each segment of the test section. The data from all the
et al., 2010). equipment are collected and recorded in a Data Acquisition System.
Most of previous research works on CO2 hydrate formation were 1: gas cylinder; 2: gas booster pump; 3: buffer tank; 4: gas mass flow
conducted in high-pressure reactor vessels (Lv et al., 2015), while very meter; 5: liquid storage tank; 6: turbine flowmeter; 7: liquid booster
few studies have been reported using a flow loop. In fact, due to the pump; 8: liquid mass flow meter; 9,10 – viewport; 11: circulating pump;
geometry differences between the reaction vessel and flow loop, the 12: tank reactor; V1,V5: pressure regulating valve; V2-V4, V7, V9, V14-
results obtained from the reaction vessels were unable to be applied to V16,V18: needle valve; V6, V8, V10-check valve; V11-13, V18: high-
the flowing system directly. Until now, only Jerbi et al. (2010) studied pressure ball valve; V17: safety valve; PR1-5: pressure transducer; TR1-
CO2 hydrate formation and dissociation kinetics using a flow loop and 5: temperature sensor; PDR1, PDR2: differential pressure transducer.
concluded that the increase in gas injection rate facilitates hydrate
formation. 2.3. Experimental procedures
Since the kinetics of CO2 hydrate formation have not yet been
clearly understood, it is of critical importance to conduct research on Firstly, the tightness of the flow loop system was carefully checked
CO2 hydrate formation in the flow loop system. In this work, a high- and cleaned three times thoroughly using distilled water. The flow loop
pressure flow loop has been newly built to systematically and statisti- was then filled with the desired amount of water followed by evacua-
cally study the effects of the initial pressure, temperature, flow rate, and tion procedure using a vacuum pump until the pressure reaches
liquid loading on the kinetics of CO2 hydrate and to understand its -0.02 MPa CO2 was then injected gradually into the flow loop until the
hydrate formation process. Hence, understanding the mechanism of gas system pressure reaches the set value. In order to maintain fixed initial
hydrate formation and factors affecting the hydrate formation process conditions in all the tests during the gas injection process, the tem-
in a flowing system is of great importance to help not only in the pre- perature of the ambient (19 °C) was maintained above the hydrate
vention of hydrate formation but also in its industrial applications as formation temperature. The fluids were then circulated at the desired
refrigerants. flow rate for an hour to make sure that the gas gets saturated in the
liquid at the ambient temperature. As the flow rate and system pressure
2. Experimental program become stable, the cold glycol with the desired temperature was in-
troduced into the annular region, and the experiment was started. The
2.1. Materials hydrate formation process was monitored in a high-pressure visual
observation window. The conditions such as differential pressure ex-
The Changzhou City tap water was used as the liquid phase, which ceeding the maximum allowable range, pressure and temperature of the
was distilled and deionized before use, and CO2 was used as the gas system getting stabilized, and test duration reaching the set value, in-
phase [certified purity of 99.8 vol% (Changzhou Jinghua Industrial dicate the completion of the experiment.
Gases Co. Ltd.China)].
2.4. Test matrix
2.2. Experimental facility
In this work, all the experiments were conducted at constant volume
The schematic experimental setup is shown in Fig. 1. The newly (the initial operating pressure was maintained constant) as shown in
built flow loop is capable of conducting high-pressure (maximum of Table 1. Totally, four initial operating pressures (4.5, 5, 5.5, and
15 MPa) and two-phase (gas-liquid) flow experiments with two view- 6.5 MPa), four coolant temperatures (274.2, 275.2, 276.2, and
ports for visual observation of the process of hydrate formation. The 277.2 K), four flow rates (16, 24, 30, 40 and 48 L/min), and three liquid
total capacity of the flow loop is about 7.5 L. The test section consists of loadings (66.7, 73.3, and 80 vol%) were conducted. All experiments
six different sections. Along the flowing direction, three straight sec- were repeated and showed a reasonable consistency within 10% error.
tions of length 0.5, 1, and 2.5 m are followed by a semicircle section of Appendix A shows an example of a repeated experiment.
radius 0.63 m. It is then connected to another two straight sections with
the length of 3 and 1.5 m. In order to increase the contact surface be- 2.5. Calculation of the amount of gas consumed during hydrate formation
tween gas and liquid phases, a helical twisted stripe is installed inside
the first two sections of the pipe. The test section is a pipe-in-pipe heat Gas consumption is an important parameter in the process of CO2
exchanger made of stainless steel based on ANSI Schedule 40 Type S. hydrate formation. The moles of CO2 consumed is calculated from the
The ID and OD of inner pipe are 26.7 and 33.4 mm, respectively. The ID molar balance as shown in Equation (1). In this work, the mole of CO2
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Table 1
Test matrix of this study.
Test number Initial pressure Coolant temperature Flow rate Liquid loading
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flow stage (Fig. 3 (a)). In this initial stage, the water and CO2 are mixed
well in the flow loop, and the gas temperature is still higher than the
equilibrium temperature. Thus, there is no hydrate formation in the
flow loop yet. As the time progresses, the temperature of the flow loop
system starts dropping below the equilibrium temperature, thus, hy-
drates start forming, which leads to the second stage - the initial hy-
drate formation stage (Fig. 3 (b)). Compared to the first stage, the gas-
water mixture gradually becomes turbid due to hydrate formation.
However, there is no hydrate deposition observed at the inner wall of
the pipe. As the temperature further drops, the degree of supercooling
increases significantly, thus hydrates start forming rapidly in the bulk
fluid. This leads to the third stage - hydrate rapid growth stage, where it
can been seen clearly that the whole pipe becomes blurred, and an
initial deposition layer starts forming at the top of the pipe (Fig. 3 (c)).
With the progression of the time, it moves into the fourth stage - de-
Fig. 4. The influence of pressure on the gas consumption (24 L/min flow rate, control position growth stage (Fig. 3 (d)). The hydrate deposition layer starts to
temperature 276.15 K, 73.3 vol% liquid loadings). grow steadily which ultimately plugs a local position in the flow loop
due to the thickening of the deposited layer.
Following the nucleation and crystallization, the hydrate growth 3.2. Effects of initial pressure
process starts when the stable hydrate nuclei develop and grow as hy-
drate solids. The slope of the gas consumption curve indicates the hy- The deviation of the experimental pressure from the equilibrium
drate growth rate. Thus, it can be observed that the hydrate growth rate pressure is the driving force for hydrate formation (Bishnoi et al., 1996,
increased drastically up to the maximum, and then dropped rapidly Linga et al., 2007). In order to investigate the effect of the driving force
with the time progression. The peak value observed in the gas con- on hydrate formation, experiments were conducted with four different
sumption plot is possibly due to the high concentration of hydrate initial pressures (4.5 MPa, 5 MPa, 5.5 MPa, and 6 MPa) at constant
nuclei in the solution (Mohammadi et al., 2014). In addition, it can be liquid loading (73 vol%) and coolant temperature (276.2 K). The
observed that there is oscillatory gas consumption between 1500 and amount of gas consumed increases by almost 330% at 6.0 MPa when
3750 s. The increase of the gas consumption could be due to the settling compared with 4.5 MPa (Fig. 4). This clearly illustrates that, when the
of hydrate particles from the gas-liquid interface towards the inner pressure of the system increases, the rate of hydrate formation in-
wall, which increases the contact interface between gas and liquid creases. This increase is mainly due to the higher degree of super-
phases, facilitating hydrate formation. In addition, certain local tem- saturation triggered by the increase of the pressure as reported by
peratures (such as in the pump or smaller diameter locations) might be Bishnoi et al. (1996). For these four different initial pressures of
higher than the equilibrium temperature due to the friction, which 4.5 MPa, 5 MPa, 5.5 MPa, and 6 MPa, the supersaturation values are
causes the dissociation of hydrates, resulting in the decrease of the gas 1.24, 1.25, 1.56, and 1.59, respectively. Correspondingly, the tem-
consumption. The pressure and temperature recorded by PR6 and TR6 perature increases at the end point of induction time are 0.2 K, 0.4 K,
(Fig. 1) together with the gas consumption and equilibrium tempera- 0.6 K, and 0.9 K respectively. This reveals the formation of more stable
ture profile are plotted as shown in Fig. 2. nuclei, thereby leading to the formation of more hydrate crystals.
The morphological evolution of hydrates during hydrate formation In general, the induction time is shorter with the increase in driving
is visually observed at Location 10 (Fig. 1) and investigated as shown in force (Linga et al., 2007). However, from Fig. 5, it can be observed that
Fig. 3. According to the trend of gas consumption curve (Fig. 2) and the the induction time increased from 685 s to 2055 s as the initial pressure
morphological evolution pictures (Fig. 3), the CO2 process of hydrate increases from 4.5 MPa to 6 MPa. It can be rationalized that the equi-
formation can be divided into four stages. The first stage is the steady librium temperature is higher at the higher initial pressure condition,
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Fig. 5. Induction time versus the initial pressure. Fig. 7. Induction time versus temperature.
thus, the start point of the nucleation process is earlier for the higher
initial pressure condition. However, it is speculated that the nucleation
rate is slow due to the low supercooling rate available during the nu-
cleation process. The sudden rise in temperature could also be not ob-
served macroscopically, even though the heat is released during this
process. It has to be noted that the end point of induction time is re-
ferred to here as the moment when the system temperature is about to
rise suddenly due to massive hydrate formation. Under a constant
cooling temperature the higher and lower initial pressure conditions
have almost the same end points. Therefore, the induction time in-
creases as the initial pressure increases.
Fig. 6 shows the gas consumption versus temperature plot for four Fig. 8. The influence of flow rate on the gas consumption (control temperature 276.15 K,
4.5 MPa, 80 vol% liquid loading).
different coolant temperatures (274.15 K, 275.15 K, 276.15 K, and
277.15 K). These experiments were conducted at the constant pressure
(4.5 MPa), liquid loading (80 vol %) and flow rate (30 L/min). It can be
seen that the hydrate growth rate and amount of gas consumed in-
creases as the temperature decreases. This is because that the higher
degree of supercooling required for the hydrate nucleation and growth
is available at a relatively low temperature, which results in a higher
driving force and a higher rate of hydrate formation (Aifaa et al., 2015).
Similar results were also reported in the natural gas hydrates case (Kang
et al., 2014). In addition, the induction time of CO2 hydrate formation
increases from 395 s to 1150 s as the temperature increases from
274.2 K to 277.2 K (Fig. 7). This proves that the nucleation of gas
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Fig. 10. Pressure drop data versus flow rate. Fig. 12. Induction time versus liquid loading.
the induction time reduces as the flow rate increases (Fig. 9). One of the
possible reasons could be that under same coolant temperature condi- the gas and liquid is reduced at higher liquid loading, which is not
tions, the average cooling rate in the flow loop slows down as the flow conducive to the process of mass transfer at the gas-liquid interface.
rate increases, resulting in the decrease of the supercooling degree. Secondly, the increased liquid loading leads to the reduction of gas
Consequently, the hydrate growth is inhibited (weakening effect). solubility per unit volume of water.
However, the turbulence facilitates the mass transfer across gas-liquid
interface theoretically (Yousif, 1994). The higher flow rate is supposed 4. Conclusions
to make the gas and liquid mix better compared to the lower flow rate
case, thus promoting hydrate formation (promotion effect). Thus, it is The kinetics of CO2 hydrate formation were investigated experi-
plausible that the weakening effect is more predominant compared to mentally in a newly built flow loop system with four different para-
the promotion effect. Besides, the pressure drop data (Fig. 10) also meters such as initial operating pressure (4.5, 5, 5.5, and 6.5 MPa),
shows that the ΔP increases more significantly with the higher flow temperature (274.2, 275.2, 276.2, and 277.2 K), flow rate (16, 24, 30,
rate. This might lead to the formation of larger-size hydrate particles, 40 and 48 L/min), and liquid loading (66.7, 73.3, and 80 vol%). The
which blocks the mass transfer between gas and liquid phases, further process of CO2 hydrate formation is studied in detail, and the visual
inhibiting hydrate formation. observation of the morphological evolution aids the classification of
different stages of CO2 hydrate formation. The four stages of hydrate
3.5. Effect of liquid loading formation process, starting from the initial formation of hydrates to the
final deposition stage in which the hydrates plug the flow loop at a local
The liquid loading reflects the volume ratio between the gas and point, are observed clearly. In addition, the effect of four parameters is
liquid. The variation in liquid loadings affects several parameters such quantified by analyzing the gas consumption and induction time re-
as the contact area of the gas and liquid, hydrate formation and dis- sults. Firstly, the high degree of supersaturation triggered by the in-
tribution (Chen et al., 2015; Song et al., 2017). In these experiments, crease of the initial pressure has a positive effect on hydrate growth,
temperature and pressure were maintained at 276.2 K and 4.5 MPa, because the amount of gas consumed increases significantly by almost
respectively. It can be observed that the gas consumption increases and 330% at 6.0 MPa compared to that at 4.5 MPa. However, the induction
the induction time decreases with the decrease of the liquid loading time is found to increase as the initial pressure increases. The amount of
(Figs. 11 and 12). The amount of gas consumed by the 66.7 vol% liquid gas consumed is relatively higher at low temperature with the induction
loading case is highest among all three liquid loading cases. The fol- time being shortened due to the high degree of supercooling available
lowing two reasons may explain the results. Firstly, the contact area of at lower temperatures. The gas consumption and induction time de-
crease as the flow rate increases. It is plausible that the weakening ef-
fect (reduction of the supercooling degree) is more predominant com-
pared to the promotion effect (enhancement of the mass transfer across
the gas-liquid interface). Moreover, combined with the pressure drop
data, it can be observed that the ΔP increases significantly with higher
flow rates. This might cause the formation of the larger-size hydrate
particles, which blocks the mass transfer between the gas and liquid,
further inhibiting hydrate formation. As the liquid loading increases,
the contact area between gas and liquid phases and the gas solubility
per unit volume of water might decrease, which lead to the decrease of
the gas consumption and the increase of the induction time.
Acknowledgments
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Appendix A
As the induction time is a stochastic variable depending on multiple factors, the experiments were repeated for consistent results. An example of a
repeated test condition with the pressure of 4.5 MPa, coolant temperature of 275.15 K, flow rate of 30 L/min, and liquid loading of 80 vol% is shown
here. As mentioned, the induction time defined in this study is that the period of time starting from the initial equilibrium state to the time when the
system temperature is about to rise suddenly due to massive hydrate formation. Therefore, the change of temperatures during hydrate formation
(Fig. A.1) and induction time results (Fig. A.2) are given. It can be seen that the uncertainty of the induction time measurement is within 2%.
Appendix B
Several trail runs were conducted by measuring the temperature and pressure with fixed operating conditions (Pressure: 4.5 MPa, Coolant
temperature: 275.15 K, Flow rate: 30 L/min, Liquid loading: 80 vol %) as shown in Figs. B.1 and B.2. It can be seen that the temperature and pressure
profiles in five different locations (PR2, PR3, PR4, PR5, and PR6) in the test section follow the same trend. Therefore, location No. 6 (Fig. 1) is chosen
as the investigation point, since it is easier to form hydrates.
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S. Zhou et al. Journal of Natural Gas Science and Engineering 49 (2018) 385–392
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