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energies

Article
Investigation of the Flow Characteristics of Methane
Hydrate Slurries with Low Flow Rates
Cuiping Tang 1,2,3,4 , Xiangyong Zhao 1,2,3,4 , Dongliang Li 1,2,3,4 , Yong He 1,2,3,4 ,
Xiaodong Shen 1,2,3,4 and Deqing Liang 1,2,3,4, *
1 Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
tangcp@ms.giec.ac.cn (C.T.); zhaoxy@ms.giec.ac.cn (X.Z.); ldl@ms.giec.ac.cn (D.L.);
heyong@ms.giec.ac.cn (Y.H.); shenxd@ms.giec.ac.cn (X.S.)
2 CAS Key Laboratory of Gas Hydrate, Guangzhou 510640, China
3 Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development,
Guangzhou 510640, China
4 Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, China
* Correspondence: liangdq@ms.giec.ac.cn; Tel.: +86-20-8705-7657

Academic Editors: Enrico Sciubba and Alireza Bahadori


Received: 8 September 2016; Accepted: 11 January 2017; Published: 23 January 2017

Abstract: Gas hydrate blockage in pipelines during offshore production becomes a major problem
with increasing water depth. In this work, a series of experiments on gas hydrate formation in
a flow loop was performed with low flow rates of 0.33, 0.66, and 0.88 m/s; the effects of the initial
subcooling, flow rate, pressure, and morphology were investigated for methane hydrate formation
in the flow loop. The results indicate that the differential pressure drop (∆P) across two ends of the
horizontal straight pipe increases with increasing hydrate concentration at the early stage of gas
hydrate formation. When the flow rates of hydrate fluid are low, the higher the subcooling is, the faster
the transition of the hydrates macrostructures. Gas hydrates can agglomerate, and sludge hydrates
appear at subcoolings of 6.5 and 8.5 ◦ C. The difference between the ∆P values at different flow rates
is small, and there is no obvious influence of the flow rates on ∆P. Three hydrate macrostructures
were observed: slurry-like, sludge-like, and their transition. When the initial pressure is 8.0 MPa,
large methane hydrate blockages appear at the gas hydrate concentration of approximately 7%.
Based on the gas–liquid two-phase flow model, a correlation between the gas hydrate concentration
and the value of ∆P is also presented. These results can enrich the kinetic data of gas hydrate
formation and agglomeration and provide guidance for oil and gas transportation in pipelines.

Keywords: natural gas; hydrate; flow assurance; slurry; sludge; flow characteristics

1. Introduction
Gas hydrates are non-stoichiometric clathrate crystalline compounds and they form by water
and gas molecules such as methane, ethane, or propane at high-pressure and low-temperature
conditions [1]. Water molecules are hydrogen-bonded so as to form cage structures that are stabilized
by filling with gas molecules.
Gas hydrates, primarily those of methane, mainly exist in sea floor deposits and permafrost.
In order to overcome the problem posed by the shortage of onshore oil and gas resources, increasingly
more attention is being paid to marine gas hydrates as a potential energy source [2]. However,
their use can also cause some problems such as geological collapse of the seafloor owing to gas
hydrate dissociation and greenhouse effects caused by the release of methane to the atmosphere [3,4].
Most commonly, gas hydrates can form in the pipeline during oil and gas transportation and result in
security risks.

Energies 2017, 10, 145; doi:10.3390/en10010145 www.mdpi.com/journal/energies


Energies 2017, 10, 145 2 of 15

Hammerschmidt [5] first reported the formation of hydrates in gas pipelines. As the petroleum
industry is now moving towards deep water, gas hydrates easily form under such conditions and
aggregate in the pipe, eventually blocking the pipeline. Thus, the issue of pipeline blockage by gas
hydrates must be resolved. Several studies have also investigated this topic [6,7]. The use of gas
hydrate inhibitors is the most common method to prevent hydrate blockage [8].
Thermodynamic hydrate inhibitors have been widely used, such as methanol, glycol,
and electrolytes. These inhibitors are effective; however, they must be used in large concentrations,
which adversely affect the profits of a project [9]. The cost of using methanol per day for hydrate
inhibition is about US $740,000 worldwide [10]. In addition, some thermodynamic hydrate inhibitors
such as methanol are harmful to the environment.
A new type of gas hydrate inhibitor, low-dosage hydrate inhibitors (LDHIs), has been proposed
to prevent hydrate nucleation and growth [11]. There are two kinds of LDHIs: anti-agglomerants
(AAs) and kinetic hydrate inhibitors (KHIs). Although neither of these can change the thermodynamic
conditions required for gas hydrate formation, they can prevent and delay gas hydrate nucleation or
growth. These inhibitors are used at low concentrations, often less than 1 wt % [12–17], and have been
used in many fields [18].
Gas hydrates with effective LDHIs can flow in pipelines without blocking the pipe or
agglomerating together. This method is the so-called risk control method. Thus, the study of gas
hydrate formation is very important to solving the problem of hydrate blockage.
Some researchers have studied natural gas/water systems with flow assurance. However, most of
these studies were conducted using high-pressure autoclaves [19,20]. Joshi [10] presented an analysis
of hydrate formation experiments to discover the mechanism of gas hydrate blockage in a pipeline
with high water cut systems. In their work, methane hydrate slurries were investigated with flow
rates of 1 m/s or more. Gas hydrate formation was divided into three regions and the gas hydrate
concentration could be used as an indicator of hydrate plugging. Andersson and Gudmundsson [21]
reported a frictional pressure drop of water–methane and a gas mixture hydrate slurry in turbulent
flow, which was identical to the frictional pressure drop of pure water. However, the frictional pressure
drop increased with increasing gas hydrate concentration in the laminar region. Zerpa et al. [22]
proposed a three-phase flow model and compared the model results against the experimental data in
an industrial flow loop.
Some research focused on the gas/oil/water system in both a high-pressure autoclave and a flow
loop [23–25]. Webb et al. [26] investigated in situ methane hydrate formation from water-in-crude
oil emulsions in a high-pressure rheology apparatus. The viscosity of the hydrate slurry attained
the maximum value in 20 min, and then it began to decay. Sinquin et al. [27] pointed out that when
hydrates form in pipelines, the pressure drop is decided by the friction factor and apparent viscosity in
the turbulent and laminar flow regimes, respectively. Yan et al. [28] investigated the characteristics of
gas hydrate slurry with initial water cuts of 5–30 vol %. Their experimental results showed that the
hydrate slurry presented obvious shear-thinning behavior when the hydrate volume fraction increased.
Fidel-Dufour et al. [29] examined the crystallization process of the methane hydrate/water/dodecane
system and found that the viscosity of hydrates slurry increased before reaching a constant value and
again increased after achieving the contestant value; this behavior is dependent on the water content.
Moradpour et al. [30] predicted the viscosity of a water/oil/hydrate mixture using a bimodal model,
which considered the mixture’s viscosity as its binary components’ viscosity.
Few data are available on the flow assurance in pipelines for natural gas/water systems, especially
for low flow rate systems. Low flow rates sometimes appear in the oil and gas field because of the
terrain constraints or for unpredicted reasons. It is necessary to obtain more data on the flow properties
of hydrate particles so as to be able to control the flow assurance in pipelines. In this work, the flow
characteristics and rheological properties of methane gas hydrate slurries in a pipeline were examined
with the initial water cuts of 48 vol % at different flow rates (0.33, 0.66, and 0.88 m/s) and subcoolings
(4.5, 6.5, and 8.5 ◦ C). The pressure drop, hydrate concentrations, and morphologies of the hydrate
Energies 2017, 10, 145 3 of 15

slurry at different stages were investigated. Using the experimental data obtained, an empirical
rheological model based on the Lockhart–Martinelli gas–liquid two-phase flow equation was proposed
to describe the viscosity at different hydrate concentrations.

2. Materials and
Energies 2017,Experimental
10, 145 Section 3 of 15

empirical Flow
2.1. Experimental rheological
Loop model based on the Lockhart–Martinelli gas–liquid two-phase flow equation
Description
was proposed to describe the viscosity at different hydrate concentrations.
All experiments were performed in a flow loop (Figure 1). The flow loop has three sections:
2. Materials
gas and liquid and Experimental
injection sections, and Section
the main loop. These sections are made of 316 stainless steel.
The main2.1.loop was 51.85 m long, with
Experimental Flow Loop Description
an internal pipe diameter of 2.54 cm, including a horizontal part
of 42.35 m and a connection part. There were three transparent visual windows, two of them located at
All experiments were performed in a flow loop (Figure 1). The flow loop has three sections: gas
the middle of the horizontal straight pipe and the other at the vertical section that was not used in
and liquid injection sections, and the main loop. These sections are made of 316 stainless steel. The
this experiment,
main loop and hence
was 51.85 not shown
m long, in Figure
with an internal pipe1. One ofofthe
diameter 2.54 visual windows
cm, including was equipped
a horizontal part of with
a digital 42.35
camera.m and The maximum
a connection designed
part. There werepressure that thevisual
three transparent flow windows,
loop could twobeof pressurized
them located atwith was
the middle
15 MPa. The of the horizontal
temperature straight
of the flow loop pipe
was and the other at
controlled inthe
thevertical
rangesection
from − that
20 was
to 50not◦ C
used in the help
with
this experiment, and hence not shown in Figure 1. One of the visual windows was equipped with a
of a refrigerating unit.
digital camera. The maximum designed pressure that the flow loop could be pressurized with was
Eight thermocouples (±0.15 ◦ C) were used to measure the temperature of the fluid in the different
15 MPa. The temperature of the flow loop was controlled in the range from −20 to 50 °C with the help
sections of
of athe flow loop;
refrigerating the temperature sensing elements of four of them were located at one-third
unit.
of the pipe cross section and (±0.15
Eight thermocouples the others
°C) wereatused
two-thirds
to measureofthethe cross section.
temperature Eight
of the fluid in thepressure
different sensors
sections of the flow loop; the temperature sensing elements of four of them were
(±0.25% full scale, FS) and a differential pressure transducers (±0.065% FS) were used to measure the located at one-third
of the pipe cross section and the others at two-thirds of the cross section. Eight pressure sensors
gas pressure in the loop and differential pressure across the inlet and outlet of the horizontal pipe.
(±0.25% full scale, FS) and a differential pressure transducers (±0.065% FS) were used to measure the
The flowgas rate was measured
pressure by adifferential
in the loop and C7B5D0B1AD1E1Z
pressure acrossmass flow
the inlet andmeter
outlet(Xian Dongfeng
of the horizontal Machinery
pipe.
& Electronic Co.,rate
The flow Ltd.wasXi’an,
measuredChina) with an accuracy
by a C7B5D0B1AD1E1Z mass ±0.065%
of flow FS. ADongfeng
meter (Xian 3DXP-2.2/10-30-T7
Machinery & piston
pump (Chongqing
Electronic Co.,Pump Industry
Ltd. Xi’an, China)Co.,
withLtd., Chongqing,
an accuracy China,
of ±0.065% FS. A this pump was custom-designed
3DXP-2.2/10-30-T7 piston pump to
(Chongqing Pump Industry Co., Ltd., Chongqing, China, this pump was
minimize shear effect on hydrate slurries and influence of operation mode) was used to recycle the custom-designed to
minimize shear effect on hydrate slurries and influence of operation mode) was used to recycle the
fluid with a maximum reciprocating time of 338 min−1−1 . The data of temperature, pressure, flow rate,
fluid with a maximum reciprocating time of 338 min . The data of temperature, pressure, flow rate,
and differential pressure
and differential throughout
pressure the the
throughout experiments
experimentswere collectedusing
were collected using a data-acquisition
a data-acquisition systemsystem at
an interval ofinterval
at an 10 s. of 10 s.

liquid injection
8

V7

P T
V1 A B
V5
V4 P T P T

V2 V6

2
T

DP C
1
D
P

3 T P
7
6
2
V3 P T
4 jacket
P

P T coolant
5 E pipe wall
T

gas injection experiemtnal space

connecting part horizontal part


main loop

Figure 1. Schematic of the hydrate flow loop system. 1: gas cylinder; 2: visual window; 3: camera;
4: mass flow meter; 5: gas-liquid separator; 6: piston pump; 7: gas compressor; 8: tank for liquid;
V1–V7: valve; P: pressure sensors; T: thermocouple; DP: differential pressure transducer.
Energies 2017, 10, 145 4 of 15

Figure 1. Schematic of the hydrate flow loop system. 1: gas cylinder; 2: visual window; 3: camera; 4:
mass flow meter; 5: gas-liquid separator; 6: piston pump; 7: gas compressor; 8: tank for liquid; V1–V7:
valve; 2017,
Energies P: pressure
10, 145 sensors; T: thermocouple; DP: differential pressure transducer. 4 of 15

Temperature profiles in the main loop are shown in Figure 2, derived from the reliability
Temperature profiles in the main loop are shown in Figure 2, derived from the reliability
experiments
experimentsconducted
conducted using
using this
thissetup.
setup. The
Thetemperatures
temperatures are aresimilar
similartoto each
each other
other in different
in different
sections of the
sections loop,
of the thethe
loop, temperature
temperaturedifferences are small,
differences are small,and
andthethe change
change is the
is the same. same.
The The
first first
increase in the
increase temperature
in the temperature occurs
occursatatabout
about500
500 ss and is attributed
and is attributedtotothe
the starting
starting of the
of the liquid
liquid pump.
pump.
For ease of understanding,
For ease of understanding, thethe
temperature
temperatureandand pressure atpoint
pressure at pointEEare
are chosen
chosen as the
as the representatives
representatives
for the
forfollowing analysis.
the following analysis.

25

A
20 B
C
D
15
E
T/ C
0

10

0 2000 4000 6000 8000


t/s

Figure
Figure 2. Temperature
2. Temperature profileininthe
profile theflow
flow loop
loop(A,
(A,B,B,C,C,
D,D,
E represent the different
E represent locations
the different shown shown
locations in
Figure 1).
in Figure 1).

2.2. Experimental Procedure and Materials


2.2. Experimental Procedure and Materials
Before conducting the experiments, the flow loop was cleaned by flushing with pure water and
Before conducting the experiments, the flow loop was cleaned by flushing with pure water and
was then drained by nitrogen gas. Thereafter, 15.0 L of distilled water (self-made in the lab) was
was charged
then drained by nitrogen gas. Thereafter, 15.0 L of distilled water (self-made in the lab) was
into the loop and the system was vacuumed for 15 min. The loop was pressurized for about
charged
3 min with methaneand
into the loop gas the system
(99.9% was
purity, vacuumed
Guangzhou for 15
Puyuan min.
Gas Co.,The loop wasChina)
Guangzhou, pressurized for about
to the desired
3 min with methane
pressure (6.3 MPa or gas (99.9%
8 MPa purity,
in this work).Guangzhou Puyuan Gas
Then, the temperature of theCo.,
loopGuangzhou,
was decreasedChina)to 9.2 ◦to
C the
desired
frompressure (6.3 MPaatorthe
room temperature 8 MPa
initialin this
gas work).ofThen,
pressure 6.3 MPa, ◦
theortemperature
to 11.6 C at 8.0 of MPa.
the loop
The was
fluidsdecreased
were
to 9.2recycled
°C from in room
the looptemperature
with a flow at the
rate ofinitial
0.18 m/sgasfor
pressure
about 1 hofto6.3 MPa, or
saturate theto 11.6 phases
liquid °C at 8.0 MPa.
with gas. The
fluidsAfter
were that, the loop
recycled in was repressurized
the loop with a flow to 6.3
rateMPa or 8.0
of 0.18 m/sMPa
forto compensate
about for the pressure
1 h to saturate the liquid dropphases
caused by temperature decrease. Then, the gas supply was cut off. The flow
with gas. After that, the loop was repressurized to 6.3 MPa or 8.0 MPa to compensate for the pressure loop was then cooled
droptocaused
the desired temperatures,decrease.
by temperature which wouldThen, bethe
mentioned in thewas
gas supply specific experimental
cut off. The flowruns. loopAt wasthethen
same time, the fluid was recycled at the experimental flow rates (0.33, 0.66, or 0.88 m/s). Gas hydrate
cooled to the desired temperatures, which would be mentioned in the specific experimental runs. At
formation could be observed by visual windows or inferred by an increase in temperature or abrupt
the same time, the fluid was recycled at the experimental flow rates (0.33, 0.66, or 0.88 m/s). Gas
decrease in pressure. Hydrate growth occurred until the time pressure became stable or gas hydrate
hydrate formation could be observed by visual windows or inferred by an increase in temperature
morphologies remained stable for more than 1 h. Finally, the flow loop temperature was increased to
or abrupt decrease intopressure.
room temperature dissociateHydrate growth
the hydrates, whichoccurred
marked until
the endtheof time pressure became stable or
the experiment.
gas hydrate Themorphologies remained
flow characteristics stable for more
and morphology of thethan 1 h. Finally,
hydrate slurry were the flow loop temperature
investigated at different was
increased to room
subcoolings, temperature
flow to dissociate
rates, and initial pressures.theInhydrates, which to
all experiments, marked
reducethe the end of the
impact experiment.
of accidental
The flow
factors, gascharacteristics and morphology
hydrate were formed and dissociated,of theandhydrate
then the slurry
experiment werewasinvestigated
repeated withat different
this
reacted solution
subcoolings, according
flow rates, to the experimental
and initial pressures. Inprocedure. The data
all experiments, tofrom
reduce the repeating
the impact experiment
of accidental
were collected (the secondary hydrate formation method).
factors, gas hydrate were formed and dissociated, and then the experiment was repeated with this
reacted solution according to the experimental procedure. The data from the repeating experiment
were collected (the secondary hydrate formation method).

3. Results and Discussion

3.1. Typical Experimental Run


Energies 2017, 10, 145 5 of 15

3. Results and Discussion


Energies 2017, 10,
3.1. Typical 145
Experimental Run 5 of 15

The typical
The typical changes
changes of of the
the temperature
temperature and and pressure
pressure during
during gasgas hydrate
hydrate formation
formation is is shown
shown in in
Figure 3.
Figure 3. Stage
StageA Awaswasthe
thepreparation
preparationstage,stage,which
whichincluded
included the the decrease
decrease in in temperature,
temperature, stabilizing
stabilizing
of the
of thetemperature,
temperature,and andrepressurization
repressurizationofofthe thegasgas
(to(to compensate
compensate forforthethe pressure
pressure dropdrop caused
caused by
by temperature drop). In stage B, temperature
the temperature ◦
temperature drop). In stage B, the was was
set atset
4.5at°C
4.5to C to promote
promote hydrate
hydrate formation.
formation. The
Thehydrate
gas gas hydrate formation
formation andand agglomeration
agglomeration occurred
occurred in in stage
stage C.C.
TheThe inflectionpoint
inflection pointononthe
thepressure
pressure
curveand
curve andthetheinstantaneous
instantaneoustemperature
temperaturefluctuation
fluctuationcan canindicate
indicatethetheonset
onsetof ofgas
gashydrate
hydrateformation.
formation.
Gas hydrate
Gas hydrate formation
formation ended
ended in instage
stageD.D.AtAt6.3
6.3MPa,
MPa,thetheequilibrium
equilibriumtemperature
temperaturewas wasapproximately
approximately
◦ C and the subcooling temperature was 4.5 ◦ C.
9.0 °C
9.0 and the subcooling temperature was 4.5 °C.
Gas hydrate
hydrateformed
formedatatstage
stageBBwhenwhenthe thetemperature
temperature approached ◦ C;
Gas approached thethe target
target value
value of 4.5
of 4.5 °C; at
at the
the same
same time,
time, therethere
werewere obvious
obvious fluctuations
fluctuations in temperature
in the the temperature and pressure
and pressure curvecurve (Figure
(Figure 3).
3). The
The temperature and pressure became steady after
temperature and pressure became steady after gas hydrate formation. gas hydrate formation.

7.0
22 A C D
B
20 6.5
18
T
16 P 6.0

P(MPa)
14
5.5
T(°C)

12

10 5.0
8

6 4.5

4
4.0
0 50 100 150 200 250 300
t(min)

Figure3.3.Temperature
Figure Temperatureand
andpressure
pressure change
change with
with elapsed
elapsed time
time from
from an
an initial
initial pressure
pressure of
of 6.3
6.3 MPa.
MPa.

The differential pressure (ΔP) was measured across the inlet and outlet of the horizontal pipe.
The differential pressure (∆P) was measured across the inlet and outlet of the horizontal pipe.
ΔP is an important parameter for the liquid flow system, which implies the resistance change.
∆P is an important parameter for the liquid flow system, which implies the resistance change.
In the following study, ΔP was connected with gas hydrate content, so in Figure 4, the change of ΔP
In the following study, ∆P was connected with gas hydrate content, so in Figure 4, the change of
with elapsed time was shown, which could supply an intuitive understanding. ΔP was constant
∆P with elapsed time was shown, which could supply an intuitive understanding. ∆P was constant
before gas hydrate formation. The fluctuation occurred 72 min after the beginning of the experiment
before gas hydrate formation. The fluctuation occurred 72 min after the beginning of the experiment
because of the change of the flow rate from 0.18 to 0.33 m/s. ΔP immediately increased upon hydrate
because of the change of the flow rate from 0.18 to 0.33 m/s. ∆P immediately increased upon hydrate
formation. After 190 min, the temperature and pressure became steady, and ΔP achieved the
formation. After 190 min, the temperature and pressure became steady, and ∆P achieved the maximum
maximum value. This tendency of ΔP with elapsed time is consistent with the results reported by
value. This tendency of ∆P with elapsed time is consistent with the results reported by Joshi et al. [10]
Joshi et al. [10] at low velocities. The up-and-down fluctuation in ΔP may be caused by the piston
at low velocities. The up-and-down fluctuation in ∆P may be caused by the piston pump, which
pump, which was designed to minimize shear on hydrate slurries and influence of the operation
was designed to minimize shear on hydrate slurries and influence of the operation mode. In the
mode. In the experiments, the up-and-down fluctuation of ΔP still exited but was small enough, and
experiments, the up-and-down fluctuation of ∆P still exited but was small enough, and the general
the general change tendency with time is very clear.
change tendency with time is very clear.
Energies 2017, 10, 145 6 of 15
Energies 2017, 10, 145 6 of 15

40

35

30

25

∆P(kPa)
20

15

10

0
0 25 50 75 100 125 150 175 200 225 250 275 300
t(min)

FigureFigure 4. Pressure
4. Pressure drop drop
acrossacross
the pipethewith
pipeelapsed
with elapsed time pressure,
time (initial (initial pressure,
6.3 MPa;6.3target
MPa;temperature,
target
temperature, 4.5 °C; and flow rate, 0.33 m/s).
4.5 ◦ C; and flow rate, 0.33 m/s).
After 190 min, ΔP began to decrease, and, within the next 100 min, the value of ΔP decreased by
9After
kPa 190
(24%min, ∆Pmaximum
of the began to decrease,
value). The and, within
hydrate the next
growth and100 min, the value
agglomeration ∆P decreased
wereofmore violent by
9 kPabecause
(24% ofofthe the presence value).
maximum of moreThe gas–liquid
hydrateinterfaces
growth and andagglomeration
gas–liquid–solid contact
were moreareas in the
violent because
of themultiphase
presence system,
of moreand pressure interfaces
gas–liquid decreased rapidly after hydrate formation
and gas–liquid–solid contact[31].
areasWebb
in theet al. [26]
multiphase
reported
system, the samedecreased
and pressure variation in the viscosity
rapidly using anformation
after hydrate autoclave,[31].
whileWebbJoshi et
et al.
al. [26]
[10] also observed
reported the same
similar results for ΔP in a flow loop. Through the visual window, the changes in the morphology of
variation in the viscosity using an autoclave, while Joshi et al. [10] also observed similar results for ∆P
the hydrate slurry could be seen, and the obvious agglomeration was observed. Thus, the drop in the
in a flow loop. Through the visual window, the changes in the morphology of the hydrate slurry could
ΔP value might indicate a change in the macrostructures of methane hydrate agglomeration. The
be seen,
mainand the obvious
characteristics of agglomeration was observed.
the hydrate macrostructures can beThus, the into
divided drop the ∆P slurry-like,
ingroups:
five value might indicate
slush-
a change
like, powder-like, and their transition zones [32]. Slurry-like hydrate is a liquid-like mixture ofof the
in the macrostructures of methane hydrate agglomeration. The main characteristics
hydrate macrostructures
particles and looks likecan beDuring
milk. divided theinto five groups:
transition slurry-like,
stage from slush-like,
slurry hydrate powder-like,
to slush, hydrate clustersand their
transition zones [32].
stick together. Slurry-like
In slush-like hydrate
hydrates, is aform
hydrates liquid-like mixture
larger clusters and of
lumpsparticles
and lookandlikelooks like milk.
wet snow.
DuringHydrate lumps break
the transition up from
stage during the transition
slurry hydratefrom slush-like
to slush, hydrates
hydrate to powder-like
clusters hydrates.
stick together. At
In slush-like
the powder-like stage, hydrates are powder-like and can be easily transported
hydrates, hydrates form larger clusters and lumps and look like wet snow. Hydrate lumps break up [32]. Slush-like
duringhydrates were also from
the transition observed when ΔPhydrates
slush-like approached the maximum hydrates.
to powder-like value. At the powder-like stage,
Methane hydrate concentration is an important parameter for a gas hydrate flow system. To
hydrates are powder-like and can be easily transported [32]. Slush-like hydrates were also observed
determine methane hydrate concentration in the fluid, the methane volume in the gas phase is
when ∆P approached the maximum value.
assumed to be constant (16.5 L in this work). Here, the hydrate volume concentration is expressed in
Methane
terms of thehydrate
conversionconcentration
percentage ofisgas,
an Φ,
important parameter
shown in Equation (1),for
andathegasamount
hydrate flow system.
of dissolved
To determine
methane inmethane
water is toohydrate
small toconcentration
be neglected: in the fluid, the methane volume in the gas phase
is assumed to be constant (16.5 L in this work). Here, the hydrate volume concentration is expressed
Vhydrate
= Φ, shown×in
in terms of the conversion percentage ofϕgas, 100%
Equation (1), and the amount of dissolved
(1)
Vhydrate + Vwater
methane in water is too small to be neglected:
Vhydrate = M hydrate ( n gi − n g ) / ρ hydrate (2)
Vhydrate
ϕ=
Vwater = (15000 − 6 M water ( n gi −×n g100%
)) / ρ water (3) (1)
Vhydrate + Vwater
Here, Vhydrate, Vwater, Mhydrate, Mwater, ngi, and ng represent the volumes of gas hydrate and water,
molecular weights of hydrateVand =M
water,
hydrate and (n gi −content
methane
hydrate n g )/ρhydrate
in the gas phase at the start of the (2)
experiment and at time t, respectively. Methane content in the gas phase was calculated by the Soave–
Vwater = (15000 − 6Mwater (n − n g ))/ρwater (3)
Redlich–Kwong equation of state using the P/T data. Thegihydration number of 6 is chosen and the
Here,gas hydrate
Vhydrate , Vformula
water , Mis considered as CH4·6H2O [10]. The densities of the gas hydrate and water here
hydrate , Mwater , ngi , and ng represent the volumes of gas hydrate and water,
are considered as 9.1
molecular weights of hydrate × 10 2 kg/m3 and 1.0 × 103 kg/m3, respectively. When hydrate dissolution in water
and water, and methane content in the gas phase at the start of the
is not taken into account, the value of Vhydrate + Vwater varies from 15.0 L to 15.4 L, as calculated by
experiment and at time t, respectively. Methane content in the gas phase was calculated by the
Equations (2) and (3), equation
Soave–Redlich–Kwong which implies a maximum
of state deviation
using the of 2.6%
P/T data. from
The the valuenumber
hydration of the constant
of 6 isgas
chosen
volume assumed for the experimental run shown in Figure 2. In fact, part of the hydrate would
and the gas hydrate formula is considered as CH4 ·6H2 O [10]. The densities of the gas hydrate and
water here are considered as 9.1 × 102 kg/m3 and 1.0 × 103 kg/m3 , respectively. When hydrate
dissolution in water is not taken into account, the value of Vhydrate + Vwater varies from 15.0 L to 15.4 L,
as calculated by Equations (2) and (3), which implies a maximum deviation of 2.6% from the value
Energies 2017, 10, 145 7 of 15

of theEnergies
constant gas
2017, 10, 145volume assumed for the experimental run shown in Figure 2. In fact, part 7 of 15of the
hydrate would dissolve
Energies 2017, 10, 145 in water, and the total gas volume was between 15.0 and 15.4 L. To7 simplify
of 15
dissolve in water, and the total gas volume
the calculation, Vhydrate + Vwater were considered as 15.0 L. was between 15.0 and 15.4 L. To simplify the calculation,
Vdissolve
The + Vwater
hydratezero inpointwere
water, considered
ofand
time the allasfigures
intotal 15.0
gas L.following
volume was between
Figure15.04 isand 15.4 L.asTo
defined simplify
3 min priorthetocalculation,
the beginning
Vhydrate
of stage BThe + VFigure
in zero were
water point3. considered
of time in allasfigures
15.0 L.following Figure 4 is defined as 3 min prior to the beginning
of stage
Figure TheB in
5 zero Figure
shows point 3.of time in
changes inallthe
figures following
calculated Figure 4volume
hydrate is defined as 3 min prior with
concentration to the respect
beginning to the
of Figure
stage B in5 shows
Figure 3.changes in the calculated hydrate volume
elapsed time during gas hydrate formation. After about 75 min, the slope of the Φ vs. elapsed concentration with respect to the time
time during
Figure 5 showsgas hydrateinformation.
changes the calculatedAfterhydrate
about 75volume
min, the slope of the with Φ vs. elapsedtotime
formation concentration
rate declined withrespect the
elapsed
curve decreased, which indicated that the gas hydrate the elapsed time.
curve
elapsed decreased,
time during which gasindicated that the gasAfter
hydrate formation. hydrate formation
about 75 min,ratethe declined
slope of with
the Φthe
vs.elapsed
elapsedtime.
time
This meant that the gas hydrate formation rate first increased, then decreased, and, finally, approached
This
curvemeantdecreased,that which
the gas hydratethat
indicated formation rate first
the gas hydrate increased,
formation then decreased,
rate declined with the and,
elapsedfinally,
time.
zero.approached
At the final stage,
zero. At the
the gas
finalhydrate
stage, concentration
the gas hydrate did not change
concentration
This meant that the gas hydrate formation rate first increased, then decreased, and, finally, did any
not further.
change Combined
any further. with
Figures 3 and with
Combined
approached 4, zero.
inFigures
theAtlastthe 110
3 and 4,min,
final in thetemperature
stage, last
the110 min,
gas t andconcentration
temperature
hydrate methane hydrate
t and methane
did not concentration
hydrate remained
changeconcentration
any further.
constant,
remained but the differential
constant, but thepressure
differentialbegan to drop,
pressure beganwhich
to also
drop, implied
which
Combined with Figures 3 and 4, in the last 110 min, temperature t and methane hydrate concentration alsomorphological
implied change
morphological in gas
hydrate
change aggregation.
remained in gas hydrate
constant, aggregation.
but the differential pressure began to drop, which also implied morphological
change in gas hydrate aggregation.
14

14
12

12
10

10
8
Φ (%)

8
Φ (%)

6
4

4
2

2
0
0 25 50 75 100 125 150 175 200 225 250
0
t (min)
0 25 50 75 100 125 150 175 200 225 250
t (min)
Figure
Figure 5. Calculated
5. Calculated hydratevolume
hydrate volume concentration
concentration during gas hydrate
during formation
gas hydrate (initial pressure,
formation 6.3
(initial pressure,
MPa;
6.3 MPa; target
Figure temperature,
5. Calculated
target 4.5
hydrate
temperature, °C;
◦ and
4.5volume flow
C; and rate, 0.33
concentration m/s).
during
flow rate, 0.33 gas hydrate formation (initial pressure, 6.3
m/s).
MPa; target temperature, 4.5 °C; and flow rate, 0.33 m/s).
3.2. Effect of Initial Subcooling
3.2. Effect of Initial Subcooling
3.2. Effect of Initial Subcooling
Figure 6 shows the evolution of P and T in the experimental process. For each subcooling
Figure 6 shows
experiment,
Figure the
6 showsthe pressure
initial evolution
the wasof
evolution ofPMPa
6.3 Pand
and TTin
and in the
the the experimental
flow process.
rate was 0.33 m/s.
experimental Three
process. For
initial
For eacheach subcooling
subcoolings
subcooling
experiment,
were the
examined:initial
4.5,pressure
6.5, and was
8.5 6.3
°C. MPa
With and
gas the
hydrateflow rate was
formation, 0.33 m/s.
subcoolings Three
were initial
changing
experiment, the initial pressure was 6.3 MPa and the flow rate was 0.33 m/s. Three initial subcoolings subcoolings
with
wereelapsed
examined: 4.5, ◦
time.
were examined: 4.5, 6.5, and 8.5 °C. With gas hydrate formation, subcoolings were changing withwith
6.5, and 8.5 C. With gas hydrate formation, subcoolings were changing
elapsed
elapsed time.time.
6.5

6.5
6.0

6.0
5.5

5.5
5.0
P (MPa)

5.0
4.5
P (MPa)

4.5
4.0 Initial subcooling 8.5 0C
4.0 Initial subcooling 6.5 0C
3.5 Initial subcooling 8.5 0C
Initial subcooling 4.5 0C
0
Initial subcooling
Equilibrium data 6.5 C
3.5 Initial subcooling 4.5 0C
3.0
Equilibrium data
3.0
2.5
0 1 2 3 4 5 6 7 8 9 10
2.5
0 1 2 3 4 T(°C)
5 6 7 8 9 10
T(°C)
Figure 6. Evolution of P and T in different experimental runs with 6.3 MPa of the initial pressure and
0.33
Figure 6.m/s
Figure 6.ofEvolution
the flow
Evolution rate.
of Pofand
P and T in
T in differentexperimental
different experimental runs
runswith
with6.3 MPa
6.3 of of
MPa thethe
initial pressure
initial and and
pressure
0.33 of
0.33 m/s m/stheof the
flowflow rate.
rate.
Energies 2017, 10, 145 8 of 15

The temperature
Energies 2017, 10, 145 and pressure changes were almost the same as those of three experimental 8 of 15 runs
with different initial subcoolings before gas hydrate formation; the temperature decreased at nearly
The
Energies temperature
2017, 10, 145 and pressure changes were almost the same as those of three experimental8 runs of 15
the same rate. After gas hydrate formation, the change in pressure with temperature became different
with different initial subcoolings before gas hydrate formation; the temperature decreased at nearly
but showed thetemperature
The
the same same
rate. tendency.
After and
gas pressure
hydrate changesthe
formation, were almost
change inthe same as
pressure those
with of three experimental
temperature became differentruns
Figure
with 7 shows the change
but showed the samesubcoolings
different initial tendency.inbefore
gas hydrate
gas hydrate concentration with elapsed
formation; the temperature time. atFor
decreased nearlythe initial
the same
subcoolingsFigure rate. After
of 6.57 shows gas
and 8.5 ◦
hydrate formation,
C, the in
the change gas the
gashydratechange in
hydrate formationpressure with
concentrationrate temperature
withwas almost
elapsed became
time. the
For samedifferent
the initialas that at
but showed the
subcoolings same
of 6.5 andtendency.
8.5 °C, the gas
the beginning stage. This indicated thathydrate
when formation
the driving rate force
was almost the same
was larger as that
than at the value,
a certain
Figure stage.
beginning 7 shows the change that
in gas hydratedriving
concentration with elapsed time. For the initial
the difference in the gasThis indicated
hydrate formation when
ratethewas smallforce if thewas larger
system wasthan a certain
cooled down value,at athefixed rate.
subcoolings
difference inof the6.5
gasand 8.5 °C,
hydrate the gas hydrate
formation rate was formation
small if therate was was
system almost the down
cooled same at
as athat
fixedatrate.
the
When gases were
beginning progressively
stage. consumed and the target temperature was approached, the the value
P/T
When gases were This indicatedconsumed
progressively that whenand thethe
driving
target force was larger
temperature than a certain
was approached, thevalue,
P/T value
was close to the
difference
was close to equilibrium
in the
the gas condition
hydrate formation
equilibrium and
condition rate the
and was driving force
small ifforce
the driving for
the system all
for all was cases
casescooled
became became
down smaller;
at a fixed
smaller; therefore,
rate.
therefore,
When
the hydrate gases were
concentration
the hydrate progressively
concentration increased consumed
increasedwith
withtheand the
thedriving target temperature
force(subcoolings
driving force was
(subcoolings approached,
here)here) the
increasing
increasing P/T value
at this stage.
at this stage.
was close to the equilibrium condition and the driving force for all cases became smaller; therefore,
the hydrate concentration increased
16 with the driving force (subcoolings here) increasing at this stage.

14
16

12
14

10
12
Φ (%) Φ (%)

subcooling 8.5 °C
8 subcooling 6.5 °C
10 subcooling 4.5 °C
subcooling 8.5 °C
6
8 subcooling 6.5 °C
subcooling 4.5 °C
4
6

2
4

0
2 0 25 50 75 100 125 150 175 200

0 t (min)
0 25 50 75 100 125 150 175 200
Figure 7. Change in hydrate concentration with elapsed
t (min) time with 6.3 MPa of the initial pressure and
Figure 7. Change in hydrate concentration with elapsed time with 6.3 MPa of the initial pressure and
0.33 m/s of the flow rate.
0.33 m/s of the
Figure flow rate.
7. Change in hydrate concentration with elapsed time with 6.3 MPa of the initial pressure and
0.33
In Figure the
m/s of 8, flow
ΔP rate.
almost increased with the increase of hydrate volume concentration at a
subcooling
In Figure of 4.5
8, ∆P °C within
almost the total
increased experimental
with the increasetime,
of except
hydrateforvolume
a small fluctuation of 9.5%
concentration at in the
a subcooling
valueInofFigure
Φ. 8,
However,ΔP almost
for increased
subcoolings of with
6.5 andthe
8.5 increase
°C, two of hydrate
turning volume
points were concentration
observed in the at
curvea
of 4.5 ◦ C within the4.5
subcooling total experimental time, except forexcept
a smallforfluctuation of 9.5% in the in value of Φ.
of ΔP with ofΦ. °C within the total experimental

time, a small fluctuation of 9.5% the
However, for
value subcoolings
of Φ. However, forofsubcoolings
6.5 and 8.5 of 6.5C, two
and 8.5 turning points
°C, two turning were
points observed
were observedinin the curve of ∆P
the curve
with Φ.of ΔP with Φ.
120
subcooling 8.5 °C
subcooling 6.5 °C
100
120 subcooling 4.5 °C
subcooling 8.5 °C
subcooling 6.5 °C
80
100 subcooling 4.5 °C
△P (kPa)

60
80
△P (kPa)

40
60

20
40

200
0 1 2 3 4 5 6 7 8 9 10 11 12
Φ (%)
0
0 1 2 3 4 5 6 7 8 9 10 11 12
Figure 8. Effect of subcoolings on ΔP during hydrate formation with 6.3 MPa of the initial pressure
Φ (%)
and 0.33 m/s of the flow rate.
Figure 8. Effect of subcoolings on ΔP during hydrate formation with 6.3 MPa of the initial pressure
Figure 8. Effect of subcoolings on ∆P during hydrate formation with 6.3 MPa of the initial pressure
and
For 0.33 m/s
all of theof experiments
the flow rate. were stopped at the time that pressure became stable and there was
and 0.33 m/s of the flow rate.
no change of gas hydrates morphologies. No obvious large agglomerates were observed for the
For all of the experiments were stopped at the time that pressure became stable and there was
For all of theofexperiments
no change gas hydrates morphologies.
were stoppedNo atobvious
the timelarge
thatagglomerates were observed
pressure became for the
stable and there was
no change of gas hydrates morphologies. No obvious large agglomerates were observed for the
subcooling of 4.5 ◦ C during the experiments. With increasing subcooling, the sludge hydrates could
Energies 2017, 10, 145 9 of 15

be observed through the visual window, and, therefore, the sudden change in ∆P could be owing to
changes in the hydrate macrostructures. Generally, ∆P increases with increasing Φ because the fluid
macrostructure changed to a solid–liquid–gas mixture from the liquid–gas system during gas hydrate
formation; as a result, the viscosity of the mixture also increased. The fluid viscosity and the friction
between the pipe wall and the fluid increased with increasing hydrate concentration. When solid
hydrates appeared, they attached to the pipe wall or flowed with liquid. The resistance between the
Energies 2017, 10, 145 9 of 15
pipe wall and internal friction of fluids both increased the viscosity. If the amount of gas hydrates was
up to a certain extent,
subcooling of the
4.5 °Cfluid
during would lose mobility
the experiments. and plug
With increasing the pipeline.
subcooling, the sludge hydrates could
be observed
Progressive gas through
hydrate theformation
visual window, and, therefore,
is beneficial to the
thesudden change in of
aggregation ΔP hydrates,
could be owingbuttothe flow of
changes in the hydrate macrostructures. Generally, ΔP increases with increasing Φ because the fluid
liquid is notmacrostructure
conducive changed to the formation of hydrate clusters. Therefore, if the formation rate is slow,
to a solid–liquid–gas mixture from the liquid–gas system during gas hydrate
the existingformation;
hydrateasclustersa result, thecan be broken
viscosity up, which
of the mixture may reduce
also increased. The fluid ∆P value.
theviscosity and theConversely,
friction if the
formation rate
betweenis high
the pipe wall and∆P
enough, thewill
fluid increase. Theincreasing
increased with visual window observation
hydrate concentration. Whenshowed
solid that gas
hydrates appeared, they attached to the pipe wall or flowed with liquid. The resistance between the
hydrate particles became small and the fluid became highly viscous; however, no hydrate clusters
pipe wall and internal friction of fluids both increased the viscosity. If the amount of gas hydrates
were seen atwasthe
upfinal stageextent,
to a certain for all theexperiments.
fluid would loseAs a result,
mobility ∆P the
and plug had the maximum value and a small
pipeline.
fluctuation of 9.5% was observed
Progressive in the Φisvalue
gas hydrate formation fortothe
beneficial the experiments with the
aggregation of hydrates, butinitial
the flow subcooling
of of
◦ liquid is not conducive to the formation of hydrate clusters. Therefore, if the
4.5 C. In Figure 8, the higher the subcooling, the faster the transition of the hydrate macrostructures, formation rate is slow,
the existing hydrate clusters can be broken up, which may reduce the ΔP value. Conversely, if the
which implied that there was no obvious difference in the gas hydrate formation rate at the early
formation rate is high enough, ΔP will increase. The visual window observation showed that gas
stage if thehydrate
subcoolingparticleswasbecame high enough,
small but became
and the fluid the total gasviscous;
highly hydrate formation
however, rateclusters
no hydrate increased with
increasing subcooling.
were seen at the final stage for all experiments. As a result, ΔP had the maximum value and a small
fluctuation of 9.5% was observed in the Φ value for the experiments with the initial subcooling of 4.5
3.3. Effect of°C.
FlowIn Figure
Rate 8, the higher the subcooling, the faster the transition of the hydrate macrostructures,
which implied that there was no obvious difference in the gas hydrate formation rate at the early
For eachstage if the subcooling
experimental runwas high section,
in this enough, butthethe total pressure
initial gas hydratewas
formation rate and
6.3 MPa increased with
the subcooling was
◦ increasing subcooling.
4.5 C. The following flow rates were considered: 0.33, 0.66, and 0.88 m/s.
Figure3.3.
9 shows effect of the three different flow rates on the value of ∆P. At different flow
the Rate
Effect of Flow
of ∆P
rates, the value For eachincreases
experimental with
runincreasing
in this section,hydrate concentration,
the initial pressure was 6.3and,MPa except for 0.33 m/s, a little
and the subcooling
∆P 4.5
drop in the was value was
°C. The observed
following flowat Φ were
rates of 9.5%; however,
considered: the ∆P
0.33, 0.66, and value
0.88 m/s.increased very quickly, which
was discussed Figure
above. 9 shows the effect of the
The difference three different
between flow rates
the values ∆Ptheatvalue
of on eachof flow
ΔP. Atrate
different
wasflowsmall. At the
rates, the value of ΔP increases with increasing hydrate concentration, and, except for 0.33 m/s, a little
same hydrate concentration, the flow rate did not appear to be an obvious influence on the value of ∆P.
drop in the ΔP value was observed at Φ of 9.5%; however, the ΔP value increased very quickly, which
The rate of temperature
was discussed above.decrease was the between
The difference same for thethe same
values of ΔPtarget temperature
at each flow rate was at different
small. At the flow rates.
When all conditions
same hydrate were the same,
concentration, theexcept for
flow rate didthe
notflow
appear to be∆P
rate, increased
an obvious abruptly
influence on the when
value ofthe hydrate
ΔP. The rate of temperature decrease was the same for the same target temperature at different flow
concentration, Φ, was about 11% for all experimental runs. Thus, the hydrate aggregation degree
rates. When all conditions were the same, except for the flow rate, ΔP increased abruptly when the
might change.
hydrate the
In previousΦ,analysis,
concentration, was aboutthe11%drop ∆P was thought
for allinexperimental runs. Thus,to the
result from
hydrate the breaking up of
aggregation
hydrate clusters, which
degree might madeInthe
change. transport
the previous of fluid
analysis, easy.
the drop However,
in ΔP was thought ∆Ptodid
resultnot
fromachieve the maximum
the breaking
up ofno
value and had hydrate
turning clusters,
pointwhich made the
in Figure 9, transport of fluid easy.
which indicated However,
that large ΔP did notclusters
hydrate achieve the
did not exist
maximum value and had no turning point in Figure 9, which indicated that large hydrate clusters
when the flow rate was higher. This may mean that the high flow rate was advantageous for fluid
did not exist when the flow rate was higher. This may mean that the high flow rate was advantageous
transportation with
for fluid hydrate particles.
transportation with hydrate particles.

60
0.88 m/s
0.66 m/s
50 0.33 m/s

40
△P (kPa)

30

20

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12
Φ (%)

Figure 9. Effect of the flow rate on the value of ∆P during gas hydrate formation with 6.3 MPa of the
initial pressure and 4.5 ◦ C of the target temperature.
Energies 2017, 10, 145 10 of 15

Figure 9. Effect of the flow rate on the value of ΔP during gas hydrate formation with 6.3 MPa of the10 of 15
Energies 2017, 10, 145
initial pressure and 4.5 °C of the target temperature.

Induction
Induction times
times for
for gas
gas hydrate
hydrate formation
formation atat different
different flow
flow rates
rates are
are shown
shown inin Table
Table 1.
1. Although
Although
the
the secondary
secondary hydrate
hydrate formation
formation method
method waswas used,
used, the
the gas
gas hydrate
hydrate formation
formation induction
induction time
time is
is
arbitrary but close for the flow rates of 0.88 and 0.66 m/s; however, it was lower at
arbitrary but close for the flow rates of 0.88 and 0.66 m/s; however, it was lower at 0.33 m/s.0.33 m/s. At 0.33
m/s, them/s,
At 0.33 induction time for gas
the induction timehydrate
for gasformation was longerwas
hydrate formation thanlonger
that atthan
the other rates
that at thebecause the
other rates
disturbance
because the and mixing of
disturbance andthemixing
fluids of
were
the not sufficiently
fluids were not intense.
sufficiently intense.

Table 1. Gas hydrate


Table hydrate formation
formationtimes
timeswith
withdifferent
differentflow
flowrates atat
rates thethe
initial pressure
initial of 6.3
pressure MPa
of 6.3 andand
MPa the
subcooling of 4.5 ◦ C. °C.
the subcooling of 4.5

No. No. Flow


Flow Rate (m/s)
Rate (m/s) Induction
Induction Time
Time (min)(min)
1 0.88 22.5
1 0.88 22.5
2 2 0.66
0.66 21.021.0
3 3 0.33
0.33 33.833.8

3.4.
3.4. Effect
Effect of
of Pressure
Pressure
A
A subcooling
subcooling of of 4.5
4.5 °C
◦ C and
and aa flow
flow rate
rate of
of 0.33
0.33 m/s
m/swere
wereused
usedtoto examine
examine the
the effect
effect of
of the
the initial
initial
pressure. At 8.0 MPa, hydrate blockages occurred in the pipe; thus, no additional
pressure. At 8.0 MPa, hydrate blockages occurred in the pipe; thus, no additional higher pressureshigher pressures
were
were examined
examined except
except for
for the
the initial
initial pressures
pressures of of 6.3
6.3 and
and 8.0
8.0 MPa.
MPa.
At
At an
an initial
initialpressure
pressureofof8.0
8.0MPa
MPa(Figure
(Figure 10), thethe
10), maximum
maximum value of ΔP
value waswas
of ∆P 66.166.1
kPakPa
when the
when
gas hydrate concentration was approximately 7%, and 12% methane was
the gas hydrate concentration was approximately 7%, and 12% methane was consumed in theconsumed in the gas phase,
after which after
gas phase, the value
whichof the
ΔP value
began ofto ∆P
drop. Large
began to methane hydrate
drop. Large blockages
methane wereblockages
hydrate observed,were
and
they moved
observed, andslowly in the
they moved pipe inwhen
slowly ΔPwhen
the pipe approached the maximum
∆P approached value.value.
the maximum However,
However,the
macrostructure
the macrostructure of the hydrates was still slush-like, more hydrates agglomerated together, and no
of the hydrates was still slush-like, more hydrates agglomerated together, and no
powder-like
powder-like hydrates
hydrates appeared.
appeared.

70

60 8.0 MPa
6.3MPa
50

40
△P (kPa)

30

20

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12
Φ (%)

Figure
Figure 10.
10. Effect
Effectofof the
the initial
initial pressure
pressure on
on the
the ΔP
∆P values
values during
during gasgas hydrate
hydrate formation
formation (target
(target
temperature
temperature for
for the
theinitial
initialpressure
pressureofof6.3
6.3MPa,
MPa,4.5
4.5°C◦ Cand
andthat forfor
that 8.08.0
MPa, 7.07.0
MPa, °C,◦ C,
at aatflow raterate
a flow of
0.33 m/s).
of 0.33 m/s).

3.5.
3.5. Morphologies
Morphologies of
of Gas
Gas Hydrates
Hydrates in
in the
the Pipe
Pipe
Figure 11shows
Figure 11 showsthe the morphologies
morphologies of hydrates
of gas gas hydrates at different
at different formation
formation timesthe
times before before the
blockage
blockage
occurred. occurred. For the experiment
For the experiment shown11,inthe
shown in Figure Figure
initial11, the initial
pressure pressure
was 8.0 was 8.0 MPa,
MPa, subcooling was
subcooling
◦ was 4.5 °C, and flow rate was 0.33 m/s. The fluid in the pipe was clear and
4.5 C, and flow rate was 0.33 m/s. The fluid in the pipe was clear and transparent before hydrate transparent
before hydrate
formation formation
(Figure (Figure
11a). Gas 11a). Gas
hydrates hydrates
formed at theformed at the
gas–liquid gas–liquid
interface interface
during during the
the temperature
temperature
decrease, weredecrease,
flushedwere
to flushed
the pipetowall
the pipe wall11b),
(Figure (Figure
and11b),
thenand then agglomerated
agglomerated on theonpipe
the pipe
wall
(Figure 11c). The formed hydrates were slurry-like. Subsequently, more hydrates agglomerated and
Energies 2017, 10, 145 11 of 15
Energies 2017, 10, 145 11 of 15
wall (Figure 11c). The formed hydrates were slurry-like. Subsequently, more hydrates agglomerated
and attached to the wall (Figure 11d). Hydrate lumps appeared on the wall after 25 min and became
attached(Figure
bigger to the wall
11e).(Figure
As the11d). Hydrate
reaction lumps appeared
progressed, on the
slush-like wall after
hydrates 25 min (Figure
appeared and became bigger
11f,g) and
(Figure 11e). As the reaction progressed, slush-like hydrates appeared (Figure 11f,g) and
agglomerated together but could flow when ΔP approached the maximum value (Figure 11g). After agglomerated
together
the slushbut could flowed
hydrate flow when
away,∆Pnoapproached
liquid wasthe maximum
found at the value
window(Figure
glass11g). After
(Figure theIn
11h). slush
the
hydrate flowed away, no liquid was found at the window glass (Figure 11h). In the
experimental time employed, no powder-like and transition macrostructure from slush-like experimental time
to
employed, no powder-like
powder-like appeared. and transition macrostructure from slush-like to powder-like appeared.

(a) 0 min (b) 18 min

(c) 19 min (d) 20 min

(e) 25 min (f) 27 min

(g) 56 min (h) 57 min


Figure 11. Morphologies of gas hydrates during gas hydrate formation at different times.
Figure 11. Morphologies of gas hydrates during gas hydrate formation at different times.

The reaction could be summarized as follows: gas hydrates formed at the gas–liquid interface
and The reaction
attached to could be summarized
the pipe as follows:
wall, or were gas hydrates
suspended formed
in a liquid. at the
Then, thegas–liquid
hydrates interface and
on the wall
attached to the pipe wall, or were suspended in a liquid. Then, the hydrates on the wall agglomerated
Energies 2017, 10, 145 12 of 15
Energies 2017, 10, 145 12 of 15

and became lumps,


agglomerated and and the fluid
became became
lumps, slurry-like.
and the fluidFinally,
becameall hydrates agglomerated
slurry-like. together
Finally, all and
hydrates
formed slush-like agglomerates.
agglomerated together and formed slush-like agglomerates.

3.6. Pressure
3.6. Pressure Drop
Drop Model
Model
Here, the
Here, the gas
gasand
andliquid
liquidphases
phaseswere
wereassumed
assumed to to
be be
homogenous.
homogenous.TheThe
separated fluidfluid
separated model was
model
used to simplify the simulation (Figure 12). Gas filled the upper space of the pipe, and the bottom
was used to simplify the simulation (Figure 12). Gas filled the upper space of the pipe, and the bottom of
thethe
of pipe contained
pipe thethe
contained liquid.
liquid.

Figure 12. Schematic of the flow model (g, l represent gas and liquid phase respectively)
Figure 12. Schematic of the flow model (g, l represent gas and liquid phase respectively).

The model was based on the Lockhart–Martinelli gas–liquid two-phase flow Equations (4)–(6)
[33]: The model was based on the Lockhart–Martinelli gas–liquid two-phase flow Equations (4)–(6) [33]:
dp
dp= ϕ22 (dpdp
= ϕll ( ))l (4)
(4)
dzdz dz l
dz
ϕ2l ϕ=
2
1 + CX −
l = 1+
−11
++XX−2−2 (5)
(5)
dp
(dp
dz ))l
X 2 = ( dp l (6)
X 2 = ( dz ) (6)
dp
dz g
( )g
where (dp/dz)l represents the pressure drop when there dz is 100% liquid flow in the pipe at respective
superficial velocities, and (dp/dz) for 100% gas; ϕ 2 and X2 represents the liquid conversion coefficient
where (dp/dz)1 represents the pressure g drop whenl there is 100% liquid flow in the pipe at respective
and the Lockhart–Martinelli parameter, respectively. 2The laminar flow formulas (for the gas) and
superficial velocities, and (dp/dz)g for 100% gas; ϕl and X2 represents the liquid conversion
the turbulent flow formulas (for the liquid) were adopted according to the Reynolds number. Here,
coefficient and the Lockhart–Martinelli parameter, respectively. The laminar flow formulas (for the
c was 10.
gas) and the turbulent flow formulas (for the liquid) were adopted according to the Reynolds number.
For the gas phase, (dp/dz)g could be obtained from Equations (7) and (8) [33]:
Here, c was 10.
For the gas phase, (dp/dz)g could be obtained λfrom 2Equations (7) and (8) [33]:
dp g vg 1
( ) = 2
x2 (7)
dp g λdg vg2 2 ρ1g
dz
( )g = x (7)
dz d 2 ρg
64
λg = (8)
Re
64g
λg = (8)
Re g
where λg , vg , x, ρg , and Reg represent the friction coefficient, mass flow rate, mass concentration, density,
and Reynolds number for the gas, respectively, and d is the inner diameter of the pipe.
where λg, vg, x, ρg, and Reg represent the friction coefficient, mass flow rate, mass concentration,
For the liquid phase, (dp/dz)l could be obtained from Equations (9) and (10) [33,34]:
density, and Reynolds number for the gas, respectively, and d is the inner diameter of the pipe.
For the liquid phase, (dp/dz)l coulddp be obtained
λ v 2 from Equations 1 (9) and (10) [33,34]:
( ) = l l (1 − x )2 (9)
dz l d 2 ρl
dp λ l vl 2 2 1
( )l = (1 − x) (9)
dz d 2 64 ρl
λl = (10)
Rel
64
λl =
where λl , vl , ρl , and Rel represent the friction coefficient, (10)
Re l mass flow rate, density, and Reynolds number
for the liquid, respectively.
where λl, vl,empirical
Many ρl, and Relmodels
represent
arethe frictionfor
available coefficient,
the friction mass flow rate,[35].
coefficient density, and Reynolds
Equation number
(10) was used for
for the liquid, respectively.
the liquid in this work to simplify the calculations because the flow rate was low and the viscosity
would Many empirical
increase modelsthe
only when aregas
available
hydratefor theformed.
was friction In coefficient [35].
the actual Equationthe
operation, (10) was used
viscosity for
of the
the
gas liquid
hydrate inslurry,
this work to simplify
an important the calculations
parameter, could bebecause
used to the flow rate
determine thewas low and
properties of the
the viscosity
flow and
would increase only when the gas hydrate was formed. In the actual operation, the viscosity of the
gas hydrate slurry, an important parameter, could be used to determine the properties of the flow
Energies 2017, 10, 145 13 of 15

and pressure drop. The Thomas model [36] was used for the viscosity, and a regression equation
pressure
could drop. The Thomas model [36] was used for the viscosity, and a regression equation could
be obtained:
be obtained:
30.6φ
ηh η= (η1L +
ηh = (1 +265.75φ
265.75φ++ 10.05
10.05φφ22++0.368e
0.368e30.6φ ) ) (11)
(11)
L

where η
ηhh and η
ηll represent
represent the viscosities of the hydrate slurry and water, respectively.
respectively.
The pressure drop before
before gas
gas hydrate
hydrate formation
formation was
was deducted.
deducted. Figure
Figure 13
13 shows
shows that the
experimental data
datamatched
matchedwell
wellwith
withthe
thepredicted
predictedvalue for the pressure drop, ∆P. However, when
value for the pressure drop, ΔP. However, when
the
the hydrate concentration reached the turning point, the experimental values began to
hydrate concentration reached the turning point, the experimental values began to deviate fromdeviate from
the
the predicted
predicted ones.ones. The increasing
The increasing of ∆P of
valuevalue ΔP be
might might be affected
affected by the agglomeration
by the agglomeration of gas
of gas hydrates.
hydrates. Thus, Equation (11) could only be used before gas hydrate
Thus, Equation (11) could only be used before gas hydrate agglomeration. agglomeration.

140

120

100
∆P (kPa)

80

60

40

20

0
0 1 2 3 4 5 6 7 8
Φ (%)

Figure 13. Experimental


Figure 13. Experimental and predicted ∆P
and predicted ΔP values
values asas aa function
function of
of Φ.
Φ. The
The line/squares
line/squares indicate
indicate the
the
experimental
experimental values and the lines show the value calculated by the model. The conditions for
values and the lines show the value calculated by the model. The conditions for green
green
ones
ones are:
are: pressure:
pressure: 6.3
6.3 MPa,
MPa, subcooling:
subcooling: 8.5
8.5 °C;
◦ C; for
for blue
blue ones:
ones: pressure:
pressure: 8.0
8.0 MPa,
MPa, subcooling:
subcooling: 4.5
4.5 °C;
◦ C;
and
and for
for red
red ones:
ones: pressure:
pressure: 6.3
6.3 MPa,
MPa, subcooling:
subcooling: 4.5
4.5 °C,
◦ C, all
all with
with the
the flow
flow rate
rate of
of 0.33
0.33 m/s.).
m/s.).

Equation (11) was modified as a general form of ηh = ηL (1 + Aφ + Bφ2 + Ce2Kφ ) , where A, B, C, and
Equation (11) was modified as a general form of ηh = ηL (1 + Aφ + Bφ + CeKφ ), where A, B,
K
C,were
and constant. The experimental
K were constant. data withdata
The experimental different
withinitial conditions
different were used to
initial conditions testused
were this model;
to test
and
this model; and the results are shown in Table 2. However, if gas hydrate aggregation changes the
the results are shown in Table 2. However, if gas hydrate aggregation changes the
macrostructures, the model could not be used to simulate gas hydrate flow in the pipe. When
macrostructures, the model could not be used to simulate gas hydrate flow in the pipe. When the gas the gas
hydrate
hydrate macrostructures change, the
macrostructures change, the viscosity
viscosity of
of the
the fluid
fluid shows
shows very
very large
large change
change and
and Equation
Equation (11)
(11)
cannot be suitable, resulting in an unsuitable model for new macrostructures.
cannot be suitable, resulting in an unsuitable model for new macrostructures.

Table
Table 2.
2. Coefficients
Coefficients of
of the model with
the model with different
different conditions.
conditions.

Initial Condition
Initial Condition A B C K
Pressure (MPa) Subcoolings◦ (°C) Flow Rate (m/s) A B C K
Pressure (MPa) Subcoolings ( C) Flow Rate (m/s)
6.3 4.5 0.33 265.75 10.05 0.368 30.6
6.3 4.5 0.33 265.75 10.05 0.368 30.6
8.0
8.0 4.5
4.5 0.330.33 165.25 10.05
165.25 10.05 3.05
3.05 35.6
35.6
6.3
6.3 8.5
8.5 0.330.33 875.25 10.05 3.88
875.25 10.05 3.88 40.6
40.6

4.
4. Conclusions
Conclusions
A 51.85 m
A 51.85 m flow
flowloop
loopwith
withananinternal
internalpipe
pipe diameter
diameter of of
2.542.54
cmcmmademade
fromfrom
316 316 L stainless
L stainless steelsteel
was
was
adopted to investigate the flow characteristics of methane hydrate slurries at low flow ratesrates
adopted to investigate the flow characteristics of methane hydrate slurries at low flow of
of 0.33,
0.33,
0.66, 0.66, and m/s.
and 0.88 0.88 m/s. The experimental
The experimental results
results demonstrated
demonstrated that,that, at high
at high initial
initial subcoolings
subcoolings (6.5
(6.5 and
and ◦8.5 °C), the gas hydrates could agglomerate and change the gas hydrate cluster’s
8.5 C), the gas hydrates could agglomerate and change the gas hydrate cluster’s macrostructure. macrostructure.
High subcooling was conducive to the transition of the gas hydrate cluster’s macrostructure. The high
Energies 2017, 10, 145 14 of 15

High subcooling was conducive to the transition of the gas hydrate cluster’s macrostructure. The high
flow rate could promote gas hydrate formation, but it exerted little influence on the pressure drop
for the same hydrate concentration with different flow rates. In addition, for the initial pressure of
8.0 MPa, gas hydrate blockages appear when the gas hydrate concentration was approximately 7%;
slurry-like or slush-like hydrates and their transition states could also be observed. Based on the
two-phase gas-liquid flow model, a correlation between the gas hydrate concentration and ∆P was
presented. The experimental data were well matched to the predicted value for the pressure drop, ∆P.
However, when the hydrate concentration reached the turning point, the experimental values began to
deviate from the predicted ones. The increasing value of ∆P may be affected by the agglomeration of
gas hydrates. Through this research, the kinetic data of gas hydrate formation and agglomeration in
pipeline can be enriched, which provide the theoretical basis and technical guidance for gas hydrate
inhibition during oil and gas transportation.

Acknowledgments: This work was supported by the National Natural Science Foundation of China
(Grant No. 50906087).
Author Contributions: Cuiping Tang and Deqing Liang conceived and designed the experiments; Cuiping Tang
and Xiongyong Zhao performed the experiments; Cuiping Tang and Deqing Liang analyzed the data; Dongliang Li,
Yong He and Xiaodong Shen contributed materials and analysis tools; Cuiping Tang wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Sloan, E.D. Clathrate Hydrates of Natural Gases, 2nd ed.; Marcel Dekker Inc.: New York, NY, USA, 1998;
pp. 27–49.
2. Wang, Y.; Feng, J.C.; Li, X.S.; Zhang, Y.; Li, G. Evaluation of Gas Production from Marine Hydrate Deposits
at the GMGS2-Site 8, Pearl River Mouth Basin, South China Sea. Energies 2016, 9, 22. [CrossRef]
3. Warzinski, R.P.; Lynn, R.; Haljasmaa, I.; Leifer, I.; Shaffer, F.; Anderson, B.J.; Levine, J.S. Dynamic morphology
of gas hydrate on a methane bubble in water: Observations and new insights for hydrate film models.
Geophys. Res. Lett. 2014, 41, 6841–6847. [CrossRef]
4. Wang, B.; Socolofsky, S.A.; Breier, J.A.; Seewald, J.S. Observations of bubbles in natural seep flares at MC 118
and GC 600 using in situ quantitative imaging. J. Geophys. Res. Oceans 2016, 121, 2203–2230. [CrossRef]
5. Hammerschmidt, E.G. Formation of gas hydrates in natural gas transmission lines. Ind. Eng. Chem. 1934, 26,
851–855. [CrossRef]
6. Sun, M.; Firoozabadi, A. Natural gas hydrate particles in oil-free systems with kinetic inhibition and slurry
viscosity reduction. Energy Fuels 2014, 28, 1890–1895. [CrossRef]
7. Kakati, H.; Kar, S.; Mandal, A.; Laik, S. Methane hydrate formation and dissociation in oil-in-water emulsion.
Energy Fuels 2014, 28, 4440–4446. [CrossRef]
8. Sohn, Y.H.; Kim, J.; Shin, K.; Chang, D.; Seo, Y.; Aman, Z.M.; May, E.F. Hydrate plug formation risk with
varying watercut and inhibitor concentrations. Chem. Eng. Sci. 2015, 126, 711–718. [CrossRef]
9. Lovell, D.; Pakulski, M. Hydrate inhibition in gas wells treated with two low dosage hydrate inhibitors
(SPE 75668). In Proceedings of the SPE International Symposium on Gas Technology, Calgary, AB, Canada,
30 April–2 May 2002.
10. Joshi, S.V.; Grasso, G.A.; Lafond, P.G.; Rao, I.; Webb, E.; Zerpa, L.E.; Sloan, E.D.; Koh, C.A.; Sum, A.K.
Experimental flowloop investigations of gas hydrate formation in high water cut systems. Chem. Eng. Sci.
2013, 97, 198–209. [CrossRef]
11. Kelland, M.A.; Svartaas, T.M.; Dybvik, L. Studies on gas hydrate inhibitors (SPE 30420). In Proceedings of
the SPE Offshore Europe Conference, Aberdeen, UK, 5–8 September 1995.
12. Seo, Y.; Kang, S.P. Inhibition of methane hydrate re-formation in offshore pipelines with a kinetic hydrate
inhibitor. J. Pet. Sci. Eng. 2012, 88–89, 61–66. [CrossRef]
13. Naeiji, P.; Arjomandi, A.; Varaminian, F. Amino acids as kinetic inhibitors for tetrahydrofuran hydrate
formation: Experimental study and kinetic modeling. J. Nat. Gas Sci. Eng. 2014, 21, 64–70. [CrossRef]
14. Villano, L.D.; Kelland, M.A. An investigation into the kinetic hydrate inhibitor properties of two
imidazolium-based ionic liquids on Structure II gas hydrate. Chem. Eng. Sci. 2010, 65, 5366–5372. [CrossRef]
Energies 2017, 10, 145 15 of 15

15. Nakarit, C.; Kelland, M.A.; Liu, D.J.; Chen, E.Y.-X. Cationic kinetic hydrate inhibitors and the effect on
performance of incorporating cationic monomers into N-vinyl lactam copolymers. Chem. Eng. Sci. 2013, 102,
424–431. [CrossRef]
16. Mohammad, R.T. Experimental investigation of gas consumption for simple gas hydrate formation in
a recirculation flow mini-loop apparatus in the presence of modified starch as a kinetic inhibitor. J. Nat. Gas
Sci. Eng. 2013, 14, 42–48.
17. Zhao, H.; Sun, M.; Firoozabadi, A. Anti-agglomeration of natural gas hydrates in liquid condensate and
crude oil at constant pressure conditions. Fuel 2016, 180, 187–193. [CrossRef]
18. Kelland, M.A. History of the development of low dosage hydrate inhibitors. Energy Fuels 2006, 20, 825–847.
[CrossRef]
19. Akhfash, M.; Boxall, J.A.; Aman, Z.M.; Johns, M.L.; May, E.F. Hydrate formation and particle distributions in
gas-water systems. Chem. Eng. Sci. 2013, 104, 177–188. [CrossRef]
20. Kang, S.P.; Shin, J.Y.; Lim, J.S.; Lee, S. Experimental measurement of the induction time of natural gas hydrate
and its prediction with polymeric kinetic inhibitor. Chem. Eng. Sci. 2014, 116, 817–823. [CrossRef]
21. Andersson, V.; Gudmundsson, J.S. Flow properties of hydrate-in-water slurries. Ann. N. Y. Acad. Sci. 2000,
912, 322–329. [CrossRef]
22. Zerpa, L.E.; Rao, I.; Aman, Z.M.; Danielson, T.J.; Koh, C.A.; Sloan, E.D.; Sum, A.K. Multiphase flow modeling
of gas hydrates with a simple hydrodynamic slug flow model. Chem. Eng. Sci. 2013, 99, 298–304. [CrossRef]
23. Greaves, D.; Boxall, J.; Mulligan, J.; Sloan, E.D.; Koh, C.A. Hydrate formation from high water content-crude
oil emulsions. Chem. Eng. Sci. 2008, 63, 4570–4579. [CrossRef]
24. Rao, I.; Koh, C.A.; Sloan, E.D.; Sum, A.K. Gas hydrate deposition on a cold surface in water-saturated gas
systems. Ind. Eng. Chem. Res. 2013, 52, 6262–6269. [CrossRef]
25. Daraboina, N.; Pachitsas, S.; Solms, N.V. Natural gas hydrate formation and inhibition in gas/crude
oil/aqueous systems. Fuel 2015, 148, 186–190. [CrossRef]
26. Webb, E.B.; Rensing, P.J.; Koh, C.A.; Sloan, E.D.; Sum, A.K.; Liberatore, M.W. High-pressure rheology of
hydrate slurries formed from water-in-oil emulsions. Energy Fuels 2012, 26, 3504–3509. [CrossRef]
27. Sinquin, A.; Palermo, T.; Peysson, Y. Rheological and flow properties of gas hydrate suspensions. Oil Gas
Sci. Technol. 2004, 59, 41–57. [CrossRef]
28. Yan, K.L.; Sun, C.Y.; Chen, J.; Chen, L.T.; Shen, D.J.; Liu, B.; Jia, M.L.; Niu, M.; Lv, Y.N.; Li, N.; et al.
Flow characteristics and rheological properties of natural gas hydrate slurry in the presence of
anti-agglomerant in a flow loop apparatus. Chem. Eng. Sci. 2014, 106, 99–108. [CrossRef]
29. Fidel-Dufour, A.; Gruy, F.; Herri, J.M. Rheology of methane hydrate slurries during their crystallization in
a water in dodecane emulsion under flowing. Chem. Eng. Sci. 2006, 61, 505–515. [CrossRef]
30. Moradpour, H.; Chapoy, A.; Tohidi, B. Bimodal model for predicting the emulsion-hydrate mixture viscosity
in high water cut systems. Fuel 2011, 90, 3343–3351. [CrossRef]
31. Ding, L.; Shi, B.H.; Lv, X.F.; Liu, Y.; Wu, H.H.; Wang, W.; Gong, J. Investigation of natural gas hydrate slurry
flow properties and flow patterns using a high pressure flow loop. Chem. Eng. Sci. 2016, 146, 199–206.
[CrossRef]
32. Lund, A. Comments to some preliminary results from the Exxon Hydrate Flow Loop. Ann. N. Y. Acad. Sci.
1994, 715, 447–449. [CrossRef]
33. Yan, C.Q. Gas-Liquid Two Phase Flow, 2nd ed.; Harbin Engineering University Press: Harbin, China, 2007;
pp. 114–128.
34. Monteiro, A.C.S.; Bansal, P.K. Pressure drop characteristics and rheological modeling of ice slurry flow in
pipes. Int. J. Refrig. 2010, 33, 1523–1532. [CrossRef]
35. Kitanocski, A.; Vuarnoz, D.; Ata-Caesar, D.; Egolf, P.W.; Hansen, T.M.; Doetsch, C. The fluid dynamics of ice
slurry. Int. J. Refrig. 2005, 28, 37–50. [CrossRef]
36. Kitanovski, A.; Poredoš, A. Concentration distribution and viscosity of ice-slurry in heterogeneous flow.
Int. J. Refrig. 2002, 25, 827–835. [CrossRef]

© 2017 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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