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Hydrate Formation and Plugging Mechanisms in Different Gas-Liquid Flow

Patterns

Article  in  Industrial & Engineering Chemistry Research · March 2017

DOI: 10.1021/acs.iecr.6b02717

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Hydrate Formation and Plugging Mechanisms in Different Gas−

Liquid Flow Patterns
Lin Ding,† Bohui Shi,*,† Xiaofang Lv,†,‡ Yang Liu,† Haihao Wu,† Wei Wang,† and Jing Gong*,†
†
National Engineering Laboratory for Pipeline Safety/MOE Key Laboratory of Petroleum Engineering/Beijing Key Laboratory of
Urban Oil and Gas Distribution Technology, China University of Petroleum-Beijing, Beijing 102249, People’s Republic of China
‡
Jiangsu Key Laboratory of Oil and Gas Storage and Transportation Technology, Changzhou University, Changzhou, Jiangsu 213016,
People’s Republic of China

ABSTRACT: As oil/gas exploitation moves into deep water,

hydrate formation and plugging in flowline have been a main
concern of the flow assurance engineers. A series of experiments
were conducted in a gas-emulsion multiphase flow system using
a high pressure flow loop. The properties of hydrate
agglomeration and deposition in different flow patterns were
investigated. First, based on the hydrate chord length
distribution and the changes of slurry density, several methods
were proposed to quantitatively estimate the hydrate agglom-
eration degree and deposition degree. Second, typical results in
each flow pattern were analyzed, and the plug formation
mechanisms in each flow pattern were proposed. Then, after
comparing the results in each flow pattern, it was found that the
order of hydrate agglomeration degree from high to low is slug flow, stratified flow, bubble flow, and annular flow; and the order
of hydrate deposition degree from high to low is annular flow, slug flow, bubble flow, and stratified flow.

1. INTRODUCTION liquid multiphase flow, especially the plug mechanism in

Natural gas hydrates are complex crystalline, icelike solids
formed by natural gas molecules and water under low
temperature and high pressure.1 In recent years, as the
development tendency of petroleum industry moves to deep
water, hydrates have been a major hazard to the flow assurance
of subsea transportation systems.2 Hydrate formation in the
pipeline can increase the pressure loss, make the flow more
complex and unpredictable, and may even block the pipeline.3
Traditional ways of hydrate prevention, including pipeline
insulation, pressure reduction, and thermodynamic inhibitor
injection, have been used for decades in field production; but
the traditional ways are of great economic cost that may
become extremely unacceptable in future field production with
high water cut. Antiagglomerant is an alternative approach in
the hydrate management strategy, which allows hydrates to
form but prevents their agglomeration.4 In this condition, the
system forms a slurry flow in flowline. In this approach, the
hydrate slurry must have good fluidity and must not block the
flowline. Therefore, to promote a better application of the
hydrate risk management strategy, two key problems have been
widely investigated: hydrate formation kinetics5−12 and hydrate
slurry flow properties.13−20 At present, most of these studies
focus on the water or water/oil emulsion system, and very few
of them involve a gas−liquid two phase flow, which is the most
common system in subsea pipeline transportation. So, the
interaction effect between hydrate formation and the gas−
different flow patterns, is an important problem to be solved.
In the past few years, some studies have been done to
investigate the influence of hydrate formation on multiphase
flow property. In the experimental aspect, Joshi et al.21
observed in experiments for the first time that the formation
of a small quantity of hydrates may immediately lead to slug
flow onset in a system near the stratified/slug flow or bubble/
slug flow transition point. This is the first evidence that hydrate
can affect the flow pattern transition in multiphase flow
systems. Then, to further identify that whether hydrate
formation influences the flow pattern transition, Lv et al.22
studied the flow pattern of the gas-slurry flow with hydrate
particles on a high pressure flow loop with 1 in. internal
diameter. Their results revealed that the Mandhane flow
pattern map could not predict the gas-slurry flow pattern
efficiently, and this indicated that hydrate formation did affect
the flow pattern transition apparently. However, because the
Mandhane flow pattern map has a great dependence on the
experimental apparatus and materials, it is likely that the results
of Lv et al. may not reflect the influence of hydrate formation
accurately. Then, Ding et al.23 conducted a series of flow loop
experiments and made two flow patterns maps, one with
Received: July 18, 2016
Revised: March 8, 2017
Accepted: March 14, 2017
Published: March 14, 2017

© 2017 American Chemical Society 4173 DOI: 10.1021/acs.iecr.6b02717

Ind. Eng. Chem. Res. 2017, 56, 4173−4184
Industrial & Engineering Chemistry Research
hydrate particles and the other one without hydrate particles.
Through the comparison between these two flow pattern maps,
they confirmed that the hydrate formation would cause three
main changes of the flow pattern map: (i) the area of the
stratified smooth flow decreases, and the stratified smooth flow
will transform into the slug flow or the stratified wave flow at
smaller gas/liquid velocities; (ii) the boundary of the annular
flow moves a little to the left, meaning that the slug flow and
the stratified wave flow will transform into the annular flow at
smaller gas velocities; (iii) the boundary between the slug flow
and the bubble flow slightly moves down, and it is easier for the
slug flow to transform into the bubble flow. Besides, in the
model research aspect, Zerpa et al.24 established a hydro-
dynamic slug model that considered the gas−liquid-hydrate
flow in the gas−water system. Their results indicated that the
hydrate formation would induce a flow regime transition from
the stratified flow to the slug flow, which was consistent with
the experimental observation of Joshi.21 Then, Hegde et al.25
used the model established by Zerpa et al.24 to predict the
effects of hydrates on the slug characteristics, such as the slug
length distribution, number of slugs, and slug frequency. Their
results showed that the liquid-hydrate slip, hydrate volume
fraction, and hydrate aggregation affected the slug character-
istics significantly. Then, Rao et al.26 used a hydrodynamic slug
model coupled with a transient hydrate formation model to
simulate the gas−liquid flow in subsea pipeline. This model can
predict the flow regime transition among the stratified flow, the
stratified wave flow, the slug flow, and the bubble flow, both
with and without hydrate particles.
The above studies have uncovered the mechanisms of how
hydrate formation influences the multiphase flow properties,
and effective models have been proposed to predict the flow
property variation. However, for the influence of different
multiphase flow factors on hydrate formation kinetics, there are
very few relevant studies.
Lv et al.22 studied the influence of gas/liquid flow rates on
gas-slurry flow pressure drop and found that the influence of
liquid superficial velocity on the pressure drop was more
obvious than that of the gas superficial velocity in the stratified
flow; but they did not clarify the influence of gas/liquid flow
rates on hydrate formation kinetics, which is very important in
modifying the hydrate growth model in multiphase flow
systems. Lorenzo et al.27,28 investigated the hydrate formation
process in annular flow systems; their results confirmed that the
hydrate growth rate in a gas dominant system was significantly
larger than that in the water or oil dominant systems. This
indicates that changing the gas/liquid flow rates (or gas/liquid
volume fractions) can influence the hydrate formation rate. In
addition, they also pointed out that, in the annular flow, the
plugging mechanism was dependent on the supercooling
degree of the experimental system. Then, Cassar et al.29
conducted hydrate formation experiments in both the annular
flow system and the stratified flow system. They found that in
both systems the line blockage was reached after three steps:
(1) rapid hydrate formation and growth, (2) hydrate formation
rate slowdown, and (3) the increase of the formation rate, and
they also found that the gas−water flow pattern affected the
hydrate formation rate and plugging time apparently.
The hydrate plug formation mechanism is different in
different flow systems, which has been studied by many
researchers. Davies and Boxall et al.30 improved the hydrate
formation and plugging mechanism proposed by Turner31 for
oil dominant systems. They pointed out that, in oil dominant
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systems, hydrate would first form at the oil−water interface as a
hydrate shell. Then, the hydrate plug formed mainly due to the
shell growth and the decrease of hydrate transportability, which
was dependent on the pump speed and water cut. In addition,
they simplified and improved the hydrate formation model and
found that the effective diffusivity and the hydrate−oil slip ratio
were the most sensitive parameters with respect to the plugging
tendency.32 For water dominant systems, Joshi et al.33 divided
the hydrate plug formation process into three stages based on
their experimental results: stage I consists of constant pump
ΔP, stage II consists of a sharp increase in the pump ΔP, and
stage III consists of large fluctuations in the pump ΔP. Then,
they pointed out that the hydrate plug formation in water
dominant systems was a consequence of the increase of hydrate
concentration, which would further lead to the formation of
hydrate bed and wall deposit. The mechanism of hydrate plug
formation in gas dominant systems has been studied by Rao et
al.34 They found that, in gas dominant systems, hydrate would
deposit on the pipe wall, starting from nucleation to dendritic
growth to annealing/hardening of the deposit. Also, they
proposed a model to predict the hydrate deposition process,
and results indicated that the hydrate thickness and the distance
of plug formation length were significantly affected by the water
saturation and fluids velocity. Hydrate plugging mechanisms in
these three systems are briefly shown in Figure 1.
Figure 1. Schematic diagram of the hydrate plugging mechanism in
different systems.
Based on the above studies, mechanisms of how hydrate
formation affect the multiphase flow properties have been well
addressed; however, in turn, the influence of different
multiphase flow parameters on hydrate formation kinetics is
still unclear, especially the influence of different flow patterns
on hydrate agglomeration and deposition properties. In the
present work, a series of experiments were conducted using a
high pressure flow loop. Hydrate agglomeration and deposition
properties were studied, and the plugging mechanisms in
different flow patterns were proposed.
2. EXPERIMENTAL SECTION
2.1. High Pressure Hydrate Flow Loop. The experiments
in this work were conducted using a high pressure flow loop,
which was constructed by the State Key Laboratory of Pipeline
Safety in China University of Petroleum (Beijing). The loop
consists of a centrifugal pump, a gas compressor, four test
sections, a data acquisition system, and several data sensors.
The test section is 30 m long in total, and the internal diameter
is 2.54 cm. It is made from carbon steel, and the design pressure
DOI: 10.1021/acs.iecr.6b02717
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Industrial & Engineering Chemistry Research Article

Figure 2. Top - schematic diagram of the high pressure hydrate flow loop; bottom -photograph of the flow loop test section.

is 15 MPa. The working temperature of the flow loop ranges
from −20 to 100 °C, which is controlled by four Julabo water
baths with a precision of 0.01 °C. Besides, the loop is equipped
with 5 pressure sensors and 8 temperature sensors, with the
precision of 0.01 bar and 0.1 °C, respectively. It is also
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equipped with two flow meters, one for the liquid flow rate and
the other one for the gas flow rate. On the test section, a
focused beam reflectance measurement (FBRM) probe and a
particle video microscope (PVM) probe are quipped, which can
help to study the size and behaviors of hydrate particles from a
DOI: 10.1021/acs.iecr.6b02717
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Table 1. List of Experiments

exp. no. flow pattern Qg (kg/h) Ql (kg/h) P (MPa) exp. no. flow pattern Qg (kg/h) Ql (kg/h) P (MPa)
1 stratified 50 500 5 11 slug 100 1100 5
2 stratified 80 500 5 12 slug 100 1100 5
3 stratified 100 700 5 13 slug 100 1100 5
4 stratified 100 500 6 14 slug 100 1100 6
5 bubble 50 1200 5 15 slug 100 1250 6
6 bubble 50 1750 5 16 slug 150 1100 5
7 bubble 60 1100 5 17 annular 180 450 5
8 bubble 70 1800 6 18 annular 260 400 5
9 slug 120 1100 5 19 annular 260 500 6
10 slug 100 1100 5

microscopic view. In front of the gas/liquid mixer there is a

density meter, which can measure the changes of the slurry
density. In addition, there are four glass windows equipped on
the test section, from which we can directly observe the flow
patterns and flow conditions in the pipeline. A photograph of
the test section and a process flow diagram are shown in Figure
2.
2.2. Materials and Procedures. The materials used in the
experiments include civil natural gas from Shanjing Natural Gas
Pipeline in China, deionized water, −20# diesel oil, and AAs.
For the composition of the gas and diesel oil, please refer to our
previous work.23 The AA is not an industrial AA, and it is
extracted from a saponins plant that was developed by the
Chemical Engineering Department in China University of
Petroleum-Beijing.35
The experiments were carried out with 10% water cut and
1% AAs dosage. The water cut was defined as the ratio of the
water volume to the whole liquid volume. The AA dosage is
defined as the volume fraction of AA additive in the water
phase. The setting temperature of the water bath was 0 °C. For
each experiment, the flow pattern was confirmed through the
observation from the glass window. The experiment list is
shown in Table 1.
The experimental procedure is briefly introduced as follows:
(i) Vacuum the loop to −1 bar using a vacuum pump to
eliminate the influence of air. (ii) Load the deionized water and
diesel oil at a specified water cut. (iii) Inject natural gas into the
loop to reach the experimental pressure. (iv) Circulate the
liquid and gas by the pump and compressor, respectively. The
gas/liquid flow rates can be adjusted to form different gas−
liquid flow patterns, in which the hydrates will form in the next
step. (v) When the monitored flow parameters reach a stable
state, cool down the loop to form hydrate crystals. In this
period, both the flow parameters and the hydrate particles
behaviors are recorded. (vi) When all the collected data keep
stable, increase the temperature to decompose the hydrates.
Then, start another set of experiments in another flow pattern
according to the above steps.
2.3. Methods of Quantitative Estimation for the
Hydrate Agglomeration and Deposition Degree. The
main objective of this work is to study the hydrate
agglomeration and deposition properties in different flow
patterns and then analyze the plugging mechanisms in each
flow pattern. In this section, several methods were proposed to
estimate the factor of hydrate agglomeration degree, fa, and the
factor of hydrate deposition degree fd.
The first method to estimate fa is based on the critical chord
length of hydrate agglomeration, Cc. Here we use the FBRM
results of Exp. 15 as an example, which is shown in Figure 3.
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Figure 3. Changes of chord length distribution in Exp. 15.
The three lines in Figure 3 stand for the particles/droplets
chord length distributions at three different time points in Exp.
15: just before hydrate formation (black line), 10 min after
hydrate formation (red line), and the final state of the
experiment (blue line). We can see that there is an intersection
point of the three lines at about 40 μm, and we define this point
as the critical chord length of hydrate agglomeration in Exp. 15.
After hydrate formation onset, due to the agglomeration
between hydrate particles and water droplets, the number of
particles/droplets smaller than Cc decreased apparently, while
the number of the particles/droplets larger than Cc increased
rapidly. Thus, we use the changes of the percentage of hydrate
particles larger than Cc to estimate the hydrate agglomeration
degree
fa = max φC c − φC0c
(1)where fa is the factor of hydrate agglomeration degree, φCc is
the number percentage of hydrate particles/water droplets
larger than Cc, and φ0Cc is the number percentage of water
droplets larger than Cc before hydrate formation.
However, this method is inapplicable for the annular flow
because no Cc occurred in annular flow experiments. FBRM
results of Exp. 19 in the annular flow are shown in Figure 4.
After hydrate formation onset, all particles decreased in
number, and there was no intersection point of the three
lines in Figure 4. This was because in the annular flow hydrate
formed mainly on the pipe wall surface in the form of a hydrate
layer, so hydrate agglomeration in the bulk phase was not
obvious. Therefore, another method is introduced to estimate
DOI: 10.1021/acs.iecr.6b02717
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Figure 4. Changes of chord length distribution in Exp. 19.
the hydrate agglomeration degree which is based on the square-
weighted mean chord length of hydrate particles, Cm. Changes
of the Cm of in Exp. 19 are shown in Figure 5. We can see that
Figure 5. Changes of the square-weighted mean chord length in Exp.
19.
the Cm increased rapidly after hydrate formation onset in the
annular flow. So we can use the increase of Cm to estimate the
hydrate agglomeration degree, which can be calculated by
max Cm − Cm0
f a′ =
Cm0 (2)
where fa′ is the factor of hydrate agglomeration degree
calculated by Cm, and C0m is the square-weighted mean chord
length before hydrate formation onset.
Both of the above two methods can be used to estimate the
hydrate agglomeration degree, and the results of these two
methods are compared in section 3.4.
The method to estimate hydrate deposition degree is based
on the changes of slurry density ρs. Here we also use the results
of Exp. 15 as an example, which is shown in Figure 6. We can
see from Figure 6, after the hydrate formation onset the total
number of hydrate particles/water droplets, Np, decreased
apparently, and the number of particles larger than 100 μm, Np
> 100, increased rapidly, which indicated that the hydrate
agglomeration occurred at this time. Then, Np >100 began to
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decrease gradually. This decrease of the large particles was not
caused by the agglomerates breaking, because the total number
of hydrate particles also decreased slightly instead of increasing
at this period. Therefore, this was likely caused by the hydrate
deposition on the pipe wall surface. In addition, it was worth
noting that the slurry density, ρs, also decreased apparently after
the hydrate formation. As we know, hydrate density is larger
than that of the oil phase (about 740 kg/m3), and the
unconverted water which is encapsulated in the hydrate
agglomerates may also deposit together with hydrate particles.
Therefore, hydrate deposition can lead to a significant
reduction of the slurry density. Thus, based on these two
phenomena, we concluded that hydrate deposition occurred in
this experiment. Here we use the level of the slurry density
reduction to estimate the factor of hydrate deposition degree,
fd, which is calculated by
(ρs − initial − ρs − final ) φH0
fd =
(ρs − initial − ρoil ) φH (3)
where ρs−initial is the slurry density just before hydrate formation
onset (kg/m3), ρs−final is the slurry density at the final state of
the experiment (kg/m3), ρoil is the density of the oil phase (kg/
m3), φH is the total volume fraction of hydrates formed, and φ0H
is the hydrate volume fraction under the condition that the
added water is totally converted into hydrates. The second item
at the right side of the equation is to eliminate the influence of
different hydrate formation amount on the hydrate deposition
process. The hydrate formation amount was obtained through
the gas consumption amount, which was calculated by
PV
1 PV
ng = − 2
z1RT1 z 2RT2 (4)
where ng is the mole number of gas consumption (mol), P1 is
the pressure before hydrate formation (Pa), P2 is the pressure
after hydrate complete formation (Pa), V is the gas volume in
the separator (m3), z is the compressibility factor in
experimental pressure, R is the gas constant (J/mol/K), T1 is
the temperature before hydrate formation (K), and T1 is the
temperature after hydrate complete formation (K).
Based on the gas consumption amount, the hydrate volume
fraction can be calculated by
ng Mg + N *ng M w
φH =
ρH VL (5)
where φH is the hydrate volume fraction, Mg is the hydrate
molar mass (g/mol), N is the hydration number (5.85 for
natural gas), Mw is the water molar mass (g/mol), ρH is the
hydrate density (kg/m3), and VL is the total volume of the
liquid phase (m3).
3. RESULTS AND DISCUSSION
During the experiments, the flow patterns were confirmed by
the visual observation through the glass windows, and the
following four flow patterns were studied in this work: the
stratified flow, the bubble flow, the slug flow, and the annular
flow. In this section, typical results of the experiments in
different flow patterns were presented and analyzed. Then,
based on the analysis of the typical results, plugging
mechanisms in different flow patterns were discussed. In
addition, degrees of hydrate agglomeration and hydrate
deposition in each flow pattern were compared.
DOI: 10.1021/acs.iecr.6b02717
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Figure 6. Changes of the slurry density and particle number in Exp. 15.

Figure 7. Results of Exp. 4 in stratified flow condition.

3.1. Results in Stratified Flow. Exp. 1−4 were carried out liquid phase as we can see the total number of particles
in stratified flow conditions, and the results of these four increased during this period; and finally, the loop was blocked,
experiments were similar. Here we use the results of Exp. 4 as which is shown in Figure 8 (b). We can notice that the slurry
an example to show the typical results in the stratified flow. density changed very little after hydrate formation, indicating
As shown in Figure 7, the relative DP is the pressure drop of
the flow loop divided by the liquid flow rate. When hydrate
began to form at about 1.7 h, the total number of hydrate
particles/water droplets decreased rapidly, indicating the
hydrate agglomeration occurred at this time. Due to the
hydrate formation and violent agglomeration, the liquid flow
rate decreased and the relative DP increased rapidly. After this
period, both the relative DP and the liquid flow rate kept
constant for about half an hour. Then again the liquid flow rate
began to decrease and the relative DP began to increase. This Figure 8. (a) Hydrate formation and (b) hydrate plugging in the
was caused by the hydrate growth and accumulation in the stratified flow.

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Industrial & Engineering Chemistry Research
that the hydrate deposition degree in the stratified flow was
very small. In addition, the total number of hydrate particles in
the liquid phase increased continuously after the initial
agglomeration, which also meant the hydrate particles tend to
grow in the liquid phase instead of depositing on the pipe wall
surface. So the plugging in this experiment was mainly caused
by the continuous growth and accumulation of hydrates in the
liquid phase, as shown in Figure 8 (b).
Based on the above analysis and the recorded picture, a plug
formation mechanism in the stratified flow is proposed, as
shown in Figure 9: (i) The system stays at the gas−liquid
Figure 9. Schematic diagram of plugging mechanism in the stratified
flow (adapted from the diagram proposed by Turner31).
stratified flow with the water dispersed in the oil phase as water
droplets; (ii) When the system runs into the hydrate stable
region, hydrate nucleation onset occurred; (iii) Hydrate
particles and water droplets begin to agglomerate with each
other; (iv) After the rapid agglomeration, the agglomerates
grow continuously; (v) Hydrates accumulate in the liquid phase
and then bedding on the pipe wall, and then the pipeline is
blocked.
3.2. Results in Bubble Flow. Exp. 5−8 were carried out
with very small gas flow rates in order to form bubble flow
conditions. Results in these experiments are similar, and here
we use the results of Exp. 5 as an example, which is shown in
Figure 10.
As shown in Figure 10, after the hydrate formation onset at
about 1.7 h, the total number of particles/droplets/bubbles
decreased rapidly, indicating that hydrate agglomeration
occurred at this period. Due to the hydrate formation and
agglomeration, the liquid flow rate decreased gradually and the
relative DP increased rapidly. Then the total number of
particles began to increase, which could be caused by several
Figure 10. Results of Exp. 5 in bubble flow condition.
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factors such as the breaking of hydrate-coated bubbles, the
breaking of hydrate agglomerates, or the hydrate continuous
growth in the liquid phase. Figure 11 shows the changes of the
Figure 11. Changes of mean chord length and number of particles in
Exp. 5.
square-weighted mean chord length of the particles, which
shows the similar trend with the change of total number of
particles. This indicates that the increase of particles number is
not caused by the agglomerate breaking or bubble breaking,
since this would cause reduction of the mean chord length. So
in this stage, hydrate grew continuously in the liquid phase.
Then, the total number of particles began to decrease, along
with the slurry density and the liquid flow rate. From the
reduction of the slurry density and particles number, we
deduced that this was caused by the hydrate deposition on pipe
wall surface. Then, the deposition process ceased, and the
system kept a stable state. No plug formed in this experiment.
Based on the above results, the hydrate formation and slurry
flow process in the bubble flow is proposed, as shown in Figure
12: (i) Water disperses in the oil phase as water droplets, and
the system maintains at a stable bubble flow; (ii) When the
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Figure 12. Schematic diagram of hydrate particles behaviors in the
bubble flow.
system runs into a hydrate stable region, hydrates begin to form
on the water/oil interface; (iii) Hydrate particles and water
droplets begin to agglomerate with each other, forming large
agglomerates; (iv) Hydrates and agglomerates grow in the
liquid phase; (v) Hydrates and agglomerates deposit on the
pipe wall surface, and then the system maintains a stable flow
condition.
3.3. Results in Slug Flow Condition. Exp. 9−16 were
carried out in slug flow conditions. Results of Exp. 10 are used
here to give an introduction of the typical results in the slug
flow, which is shown in Figure 13.
Results of the slug flow are similar to that of the bubble flow.
When hydrates began to form, the total number of particles/
droplets decreased apparently in a very short time. This was
caused by both the hydrate agglomeration in the liquid phase
and the hydrate deposition on the pipe wall surface. Because we
can see from Figure 13 and Figure 14, at this time, the slurry
density decreased, and also the square-weighted mean chord
length increased rapidly. This indicated that the hydrate
agglomeration and deposition occurred at the same time,
which caused a large decrease of the liquid flow rate and a large
increase of the relative DP. The deposition process in the slug
flow occurred much earlier than that in the bubble flow and the
stratified flow. This was because the slug flow had large flow
fluctuations, and thus the hydrate particles could be carried and
contact with the pipe wall at high frequency. Therefore,
deposition occurred immediately after hydrate formation onset
in the slug flow. This process lasted about 40 min, and then the
deposition process ceased as the slurry density almost kept
constant. We can notice that, during this period, the mean
chord length decreased a little, and the total number of particles
increased slightly. This indicated that some of the hydrate
agglomerates broke up, which also led to a slight reduction of
Figure 13. Results of Exp. 10 in the slug flow.
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the relative DP. However, this phenomenon did not occur in
every slug flow experiment and may not be regarded as the
typical features of the slug flow. Then the system kept a stable
state until the end, and no plug formed at last.
Based on the above results, the hydrate formation and slurry
flow process in the slug flow is proposed as shown in Figure 15:
(i) The system maintains at the stable slug flow with water
droplets dispersed in the liquid phase; (ii) When the system
runs into a hydrate stable region, hydrates begin to nucleate on
the water/oil interface; (iii) Hydrates and water droplets begin
to agglomerate in the liquid phase and deposit on the pipe wall
surface at the same time; (iv) Some of the agglomerates are
broken up by the flow shear force (may not occur); (v) The
system maintains a stable flow state, and no plug formed in the
flow loop.
3.4. Results in Annular Flow Condition. Exp. 17−19
were carried out in annular flow conditions, in which the liquid
phase flows close to the pipe wall as annulus and the gas phase
flows continuously in the center of the pipe. Results of Exp. 17
are shown in Figure 16.
As shown in Figure 16, the hydrate formation onset occurred
at about 2.5 h. Then the slurry density and the number of
particles decreased immediately. This was not because of the
hydrate deposition on the pipe wall, but because hydrates
formed directly on the pipe wall surface. A thick hydrate layer
was observed on the inner surface of the pipe wall at this time,
as shown in Figure 17(a). Because of the formation of this
hydrate layer, the liquid flow rate decreased and the relative DP
increased. Then both the slurry density and the number of
particles began to increase, and at the same time we observed
that the formed hydrate layer began to slough, as shown in
Figure 17(b). Then the liquid flow rate decreased to 0, and the
loop was blocked in a very short time. Based on the changes of
the slurry density and particles number and the recorded
pictures in Figure 17, we deduced that the plugging was
because the sloughed-off hydrate fragments accumulated in the
pipe and were stuck somewhere in the flow loop like the elbows
or valves.
The plugging mechanism in the annular flow is shown in
Figure 18: (i) The system maintains at the annular flow before
hydrate formation. Some of the water disperses in the oil phase
DOI: 10.1021/acs.iecr.6b02717
Ind. Eng. Chem. Res. 2017, 56, 4173−4184
Industrial & Engineering Chemistry Research
Figure 14. Changes of mean chord length and number of particles in Exp. 5.
Figure 15. Schematic diagram of hydrate particles behaviors in the slug
flow.
as water droplets, and some distributes as water film covering
the pipe wall; (ii) Hydrates begin to form on the pipe wall or
on the water/oil interface, forming a thick hydrate layer
covering the pipe wall; (iii) The thick hydrate layer begins to
slough due to the intense flow shear force; (iv) The sloughed
hydrate fragments accumulate at some uneven section and
block the flow section.
3.5. Comparison of the Results in Each Flow Pattern.
In section 2.3, several methods were proposed to estimate the
hydrate agglomeration degree and deposition degree. In this
section, results in different flow patterns are compared,
Figure 16. Results of Exp. 17 in annular flow condition.
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Article
Figure 17. (a) Hydrate layer formed on the glass window and (b)
hydrate film sloughing.
including the factor of hydrate agglomeration degree fa and f′a,
the factor of hydrate deposition degree fd, and the hydrate
volume fraction φH. Detailed results are listed in Table 2.
The volume fraction of hydrates formed in each flow pattern
is shown in Figure 19. We can see that the hydrate volume
fraction (or hydrate formation amount) in the bubble flow and
the slug flow has the maximum value, both of which are about
4.4%; but the error range in the slug flow is larger. The hydrate
DOI: 10.1021/acs.iecr.6b02717
Ind. Eng. Chem. Res. 2017, 56, 4173−4184
Industrial & Engineering Chemistry Research Article

Figure 18. Schematic diagram of the plugging mechanism in the annular flow (adapted from the diagram proposed by Sum et al.36).

Table 2. Detailed Results for Each Experiment

exp. no. flow pattern φH fa fa′ fd exp. no. flow pattern φH fa fa′ fd
1 stratified 0.034 0.3 0.86 0.29 11 slug 0.037 0.58 1.37 1.85
2 stratified 0.036 0.46 1.31 0.30 12 slug 0.051 0.62 1.37 1.26
3 stratified 0.046 0.56 1.79 0.31 13 slug 0.046 0.58 1.30 1.03
4 stratified 0.036 0.33 0.98 0.36 14 slug 0.048 0.59 1.54 1.10
5 bubble 0.043 0.4 1.09 0.81 15 slug 0.048 0.64 1.77 1.40
6 bubble 0.044 0.15 0.38 1.47 16 slug 0.038 0.72 2.86 2.21
7 bubble 0.046 0.34 1.16 0.53 17 annular 0.014 0.49 1.90
8 bubble 0.043 0.19 0.48 1.55 18 annular 0.018 0.27 1.92
9 slug 0.039 0.66 2.89 2.33 19 annular 0.016 0.63 2.33
10 slug 0.047 0.75 2.79 2.18

The factors of hydrate agglomeration degree and deposition

degree in each flow pattern are shown in Figure 20. fa is

Figure 19. Hydrate volume fraction in each flow pattern.

volume fraction in stratified flow is about 3.8%, and the hydrate
volume fraction in the annular flow is only about 1.6%. We
should mention here that all the experiments in stratified flow
and annular flow conditions were blocked at last. The plugging
process in the annular flow was very rapid, while the plugging
process in the stratified flow occurred gradually. Because of the
plugging, the length of the hydrate growth period is different in
different flow patterns. Thus, the blockage is likely to be the
reason for the difference of the hydrate formation amount. As
we know, the hydrate formation amount is mainly affected by
the experimental pressure, temperature, and the water cut. So as
long as the flow system keeps a good flow stability, the hydrate
formation amount in each flow pattern should be very close to
each other.
4182
Figure 20. Factors in different flow patterns.
calculated based on the critical chord length, and f′a is calculated
based on the square-weighted mean chord length. We can see
that, for each flow pattern, the ratio of fa′/fa is almost a constant
of 3, which demonstrates that both of the above two methods
are valid for estimating the agglomeration degree. The results
show that these two factors have the same change tendency: the
slug flow > the stratified flow > the bubble flow > the annular
flow. This indicates that hydrates in the slug flow have the
largest agglomeration degree, which may be due to the unstable
flow condition. Because the slug flow has violent flow
fluctuations, hydrate particles in the slug flow can contact and
DOI: 10.1021/acs.iecr.6b02717
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Industrial & Engineering Chemistry Research
collide with each other more frequently. Thus, the agglomer-
ation degree is higher in the slug flow. In the annular flow,
however, hydrates tend to form and grow directly on the pipe
wall surface (Figure 17), so the agglomeration in the liquid
phase is not obvious. Therefore, the agglomeration degree in
the annular flow is the smallest.
Also, Figure 20 shows that the change tendency of the
hydrate deposition degree is the annular flow > the slug flow >
the bubble flow > the stratified flow. As discussed above, in
annular flow hydrates tend to form and grow directly on the
pipe wall surface, which can lead to a higher deposition degree.
For the stratified flow, because hydrate deposition mainly
occurs at the liquid−solid interphase, the liquid−solid interface
in the stratified flow is the smallest compared with other flow
patterns. That is likely to be the reason why the stratified flow
has the smallest hydrate deposition degree.
4. CONCLUSIONS
Experiments were carried out using a high pressure flow loop to
investigate the hydrate behaviors and the slurry plugging
mechanism in different flow patterns. Based on the changes of
slurry density and the particle chord length distribution, new
methods were proposed to estimate the degree of hydrate
agglomeration and deposition in different flow patterns. Results
showed that the agglomeration degree in order from high to
low is the slug flow > the stratified flow > the bubble flow > the
annular flow; the deposition degree in order from high to low is
the annular flow > the slug flow > the bubble flow > the
stratified flow. In addition, typical results of the experiments in
different flow pattern conditions were presented. It was found
that the slurry flow in the stratified flow and annular flow
conditions was easily blocked. The plugging in the stratified
flow was mainly due to the hydrate accumulation and bedding
in the liquid phase, while the plugging in the annular flow was
mainly caused by the hydrate layer sloughing.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: ydgj@cup.edu.cn.
*E-mail: bh.shi@cup.edu.cn.
ORCID
Jing Gong: 0000-0002-3722-5778
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
for Young Scientists of China (Grant 51306208), National
Natural Science Foundation of China (Grant 51274218 &
51534007), National Science and Technology Major Project
(No. 2016ZX05028004-001), and Science Foundation of China
University of Petroleum-Beijing (No. 2462014YJRC006, No.
2462015YQ0404, and No. C201602), which are gratefully
acknowledged.
■
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