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Experimental Study On Natural Gas Hydrate Slurry Flow
Experimental Study On Natural Gas Hydrate Slurry Flow
This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, USA, 8-10 October 2012.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not
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Abstract
To better understand hydrate slurry flow, a series of experiments have been performed, including water, natural gas
and diesel oil, under 4MPa (system pressure), 40Hz (initial pump speed). The experiments have been conducted in a
high-pressure hydrate flow loop newly constructed in China University of Petroleum (Beijing), and dedicated to flow
assurance studies. A Focused Beam Reflectance Measurement (FBRM) is installed in this flow loop, which provides a
quantitative chord length distribution (CLD) of the particles/droplets in the system. Firstly, the influence of flow rate on
the hydrate slurry flow was discussed. Then we have studied the factors such as water-cut and additive dosage on the
hydrate induction period and the CLD before/after hydrate formation. Finally, we have fitted a new correlation between
the dimensionless rheological index, n´, and water-cut as well as additive dosage, according to these experimental results.
And a laminar flow pressure model of quasi-single phase hydrate slurry has been established in this paper.
Keyword:
Natural gas hydrate; slurry flow; water-cut; induction period; pressure drop model
1. Introduction
Nowadays, subsea multiphase pipeline have become the commonly used for the oil-gas gathering and transportation
of deepwater oil-gas field all over the world, along with the development of offshore resources exploitation. However,
the complex deepwater conditions, usually presenting as high pressure and low temperature, inevitably lead to the flow
accidents in the pipeline system. Major accidents include the solid precipitation, such as hydrate, asphaltene, wax, etc.
Therefore, the deep-water flow assurance has been becoming the focus of the international oil-gas field development
(Shi, 2012). Hydrate (Fig.1) is one of the critical precipitates which have to be controlled for the subsea flow assurance.
The controlling methods contain traditional inhibition and risk control technique (Sloan et al., 2007 and 2010). On the
traditional way, either we can inject Thermodynamic Hydrate Inhibitor (i.e. methanol or mono-ethylene glycol) or can
heat and/or insulate pipelines, to prevent the fluid falling into hydrate forming region in the pipeline (Fig.2). On the other
risk control technique way, Kinetics Hydrate Inhibitor and/or Anti-Agglomerant Additive (AA) (Sinquin et al., 2004;
Frostman, 2000) can be used, or we can adapt the Cold Flow technology (Gudmundsson, 2002; Turner and Talley, 2008).
That is, Hydrate formation is permitted, yet hydrate is carried by the fluid in the pipeline to form a hydrate slurry flow,
then to avoid the hydrate plugging.
The former traditional method is the main hydrate control technology at present. But as exploration and subsequent
production go to deeper water, hydrate formation avoidance can reach economic limits; insulation becomes too costly,
and thermodynamic inhibitor application becomes too expensive. The focus of flow assurance strategies thus is also
shifting from the traditional to the risk control technique. While at the same time, the formed hydrate slurry might change
the fluid’s property fundamentally (for example, fluid viscosity or yield stress); and may result in transportation problem
or in alteration of the system production capacity. Consequently, it is important to investigate the hydrate slurry flow
behavior for the slurry transportation. Yet there is few researches on hydrate slurry flow so far. For example, Andersson
and Gudmudsson (1999) performed experiments on the flow behavior of oil-based hydrate slurry flow, studied the
impact of hydrate fraction on pressure drop. Boxall et al. (2008) investigated the influencing factors i.e. water-cut and
flow rate experimentally, focused on their effects on the trend of hydrate blockage. Dellecase et al. (2008) analyzed more
factors such as water-cut, flow rate, fluid property and restart on the hydrate flow loop in Tulsa University. Later
Sjöblom et al. (2010) discussed the factors of hydrate blockage and recommended capillary attractive forces between
hydrate particles as the key cause of agglomeration and plugging. However, the experimental data is insufficient, and the
slurry flow law and various influencing factors are not clear and definite. In sum, it is necessary to carry out hydrate
slurry experimental research.
In this case, a high-pressure hydrate flow loop devoted to Flow Assurance studies has been newly constructed by
multi-phase flow research group in China University of Petroleum (Beijing). On this high-pressure hydrate flow loop, a
series of flow experiments have been performed with natural gas+diesel+water system under 4MPa(system pressure),
2 SPE 158597
40Hz(initial pump speed) to investigate the effects of influencing factors, i.e. flow rate, water-cut and AA dosage.
Furthermore, a laminar flow pressure model of quasi-single phase hydrate slurry has been established in this paper,
according to these experimental results.
Figure.1 Two examples of pipeline blockages removed from slug catchers (Boxall et al., 2011): (a) a solid hydrate plug, (b) a
liquid hydrate sludge
Figure.2 Hydrate formation pressures and temperatures as a function of methanol concentration in free water for a given
natural gas (Sloan et al., 2010)
The test section is a stainless steel pipe, the internal diameter of which is 2.54 cm (1 inch) and the length 30 m.
Geometrically it is constituted of two rectilinear and horizontal parts, connectedly a circular one with a low curvature. It
is connected to a separator. The test section is surrounded by a 5.08 cm (2 inches) diameter jacket in which a calorific
SPE 158597 3
water/glycol blend circulates in counter-current. Process temperature can be controlled from -20 to 80 °C. The total
volume of liquid phase needed for running an experiment is 80 liters.
2.2 The Hydrate Experimental Loop Instrumentation
This experimental flow loop is equipped with several sensors. Thermocouples are regularly set along the pipe, inside
the separator, inside the water/glycol system and on the different gas utilities. A Coriolis flowmeter measures the density
of the liquid mixture and the flow rate. The mean density of the multiphase fluid can also be measured using two
FM1000 gamma ray densitometers. Differential pressure sensors are located along the loop to follow the evolution of the
linear pressure drop along the loop. A rapid data acquisition is used to detect rapid phenomena.
The evolution of objects (droplets, bubbles and solid particles) carried inside the flow can be followed thanks to a
FBRM (Focused Beam Reflectance Measurements) probe which was recently installed on the loop. This apparatus
comprises a low intensity rotating LASER beam (Fig.4) which is reflected when intercepting a particle. From the
reflection time a chord length is deduced. After every measurement duration which was chosen equal to 10 sec, a Chord
Length Distribution (CLD) and a mean chord length are given. This CLD gives an idea of the Particle Size Distribution
(PSD) of the objects carried by the flow. As recommended for a representative sampling of the particle size distribution,
this particle size analyzer was installed on the straight vertical pipe which is ahead of the inlet of the experimental loop .
The probe window of probe cuts the flow streamlines at an angle of 45° and reaches the centre of the pipe. The FBRM
probe was used to estimate the initial water droplet (Dp) size inside the fluid and to follow the hydrate particles
agglomeration with the time. The mean square-weighted chord length can give more weight to the longer chord length
and it is particularly well adapted to agglomeration phenomena.
(a)
(b)
Figure.4 Principle of the FBRM particle size analyser (a, b)
2.3 Fluids
To better simulate the practical situation, deionized water, civil natural gas and -20# diesel were employed for these
tests, shown as Table.1 and Table.2. The Anti-Agglomerants (AA) is combined Span20. The electronic balance is used to
weigh the AA’ quality (with measuring error ±0.01g). the quality ratio of AA/water-phase can be adjusted to 0 wt%, 1
wt%, 2 wt% and 3 wt%, through the high pressure measurement piston pump. The natural gas hydrate formation curve
(Fig. 5) can be defined by the Chen-Guo model with the natural gas composition.
4 SPE 158597
N2 1.5603 C3 3.1207
C2 3.1207 -- --
C11 C16
0.886328 6.830973
C12 C17
3.358613 7.989042
C13 C18
5.388601 7.461769
C14 C19
6.198984 6.375197
C15 C20+
6.778046 48.73252
25
20
15
Pressure(MPa)
10
0
0 2 4 6 8 10 12 14 16 18 20
Temperature(°C)
Figure.5 Hydrate formation curve of test natural gas
Figure.6 A schematic picture for hydrate formation and transportation (Turner, 2005).
Figure.7 Temperature, flow rate, friction coefficient, pressure drop and hydrate fraction as functions of time during natural
hydrate formation (40Hz, 4.1MPa, 1wt% AA, 15% water-cut)
Figure.8 The induction period under various Water-cut and AA dosage (initial pump speed 40Hz)
In Fig.8, the induction period was compacted at first then prolonged slowly with the increase of water-cut under the
same initial pump speed 40Hz. The induction period with higher water-cut (20%~30%) were significantly less than that
with 15% water-cut. Because in the W/O emulsion with higher water-cut, the larger contact area between water-oil
phases enhanced the mass transfer of hydrate guest molecules. There were more nucleation sites in favor of hydrate
formation on the water droplet surface, which could shorten hydrate induction period. Nonetheless, along with the further
larger water-cut, the shear stress that flow rate exerted on the dispersed water phase got stronger, so as to hinder the
critical nucleation on the water surface, then to prolong the induction period. As a result, the induction period exhibited
SPE 158597 7
the trend of slowly rise-up. It also can be seen from Fig.8 that hydrate induction period ascended with the AA dosage.
The probable reason is that the AA molecule adsorbed on water surface could inhibit the hydrate formation. In addition,
the randomness of induction period and the memory effect of hydrate particles might also affect the above phenomena.
3.3 The Influence of Water-cut, AA dosage on Particle Chord Length Distribution
According to Turner (2005) and Taylor et al. (2007), the chord length distribution (CLD) of hydrate particles
resembles that of dispersed droplets. The water droplets converted into hydrate particles directly without changing its
distribution at the hydrate formation. There are many influencing factors of W/O emulsion CLD, for example, the fluid
viscosity, pressure, flow rate, water-cut and AA dosage. This paper focuses on the water-cut as well as AA dosage to
investigate the CLD of water droplets, thus the CLD of hydrate particles. The results were shown in Fig.9 to Fig.13.
It can be known from Fig.9 to Fig.11 that at the same AA dosage, initial pump speed and system pressure, the CLD
range of major particles shrunk from 3~10 μm (15% water-cut) to 4~8 μm(25%). On the other part, when the water-cut,
initial pump speed and system pressure were fixed, the droplets also dispersed better in oil phase with gradually
increased dosages. The CLD range of major particles shrunk from 4~8 μm (1wt% AA) to 3~6 μm(3wt%), as shown in
Fig.11 to Fig.13.
Therefore, either high water-cut or AA dosage would facilitate altering the dispersed phase to a smaller size and
more uniform distribution, which promote the hydrate slurry formation. This also reinforces the influences of water-cut
and AA dosage on the pressure drop and hydrate volume fraction from microcosmic angle. From these Figures, it can be
found that the CLD of dispersed phase stayed pretty consistent before/after the hydrate formation in one set of
experiments. This confirms the contention that hydrate particles derived directly from water droplets before its
agglomeration in the W/O emulsion.
Gainville and Sinquin (2011) has chosen the mean diameter as 5μm in their viscosity model of hydrate slurry,
however it can be known from our study that the hydrate mean diameter varies with different water-cut and AA dosage.
In sum, the appropriate mean diameter under diverse conditions is significant to promote the accuracy of related
predicting models. Thus how to correlate the mean diameter with the viscosity model, even the slurry pressure
calculation can be considered in further researches, which are not in the discussion scope of this paper.
Figure.13 3D diagram of un-weighted chord length distribution of hydrate particles during the experiment
(25%, 40Hz, 4MPa, 3wt%)
3.4 Quasi-single Phase Laminar Flow Pressure Drop Model of Hydrate Slurry
Andersson and Gudmundsson (1999; 2000) and Peysson et al. (2003) have studied hydrate slurry rheology with
light hydrocarbon-brine-oil system, using experimental loop and autoclave cell respectively. They concluded that the
slurry showed the characteristics of non-Newtonian fluid even under a very low hydrate concentration (<6%). The
prevalent methods investigating the slurry rheology can be divided into two types: one takes hydrate slurry as a power-
law fluid; the other uses yielding pseudoplastic fluid with Herschel-Bulkley model. Based on the full pipe flow
experiment conducted in this paper, the hydrate slurry is found to present more power-law. Thus we regarded the hydrate
slurry as a time independent power-law fluid in the experimental process. By combining its flow behavior at laminar
state in round pipe, the laminar flow pressure drop model of quasi-single phase hydrate slurry has been established, with
the following expression:
n n
4 Lk ⎛ 1 + 3n ⎞ ⎛ 8uav ⎞
ΔP = ⎜ ⎟
D ⎝ 4n ⎠ ⎜⎝ D ⎟⎠
⎛ 1 + 3n ⎞
n
⎡⎛ 1 + 3n ⎞ n ⎛ 8uav ⎞ n ⎤
Where: n = n ;
'
k '
= k ⎜ ⎟ ; k = τ w ⎢⎜ ⎟ ⎜ ⎟ ⎥;
⎝ 4n ⎠ ⎣⎢ ⎝ 4 n ⎠ ⎝ D ⎠ ⎦⎥
And the dimensionless rheological index, n’, was fitted by the experimental data, which is the function of water-cut,
α, and AA dosage, ω. The correlation is expressed as:
n ' = − 11.557α • ω +0.26895ω − 0.49838α +1.08906 ;
The flow behaviors of hydrate slurry at various water-cut and AA dosage were shown in Table.3.
1 laminar flow
15 2 laminar flow
3 laminar flow
1 turbulent flow
20 2 turbulent flow
3 laminar flow
1 laminar flow
25 2 laminar flow
3 laminar flow
1 laminar flow
30 2 laminar flow
3 laminar flow
SPE 158597 9
Subsequently, the pressure drop at the laminar flow has been calculated using the new model mentioned above, the
comparison results between experimental data and predictive values were shown in Table.4.
Table 4 Comparison between pressure drop predictive results and experimental data under various
water-cut and AA concentrations (initial pump frequency 40Hz)
Water-cut(%) AA dosage(wt%) n´ ΔPe(Pa) ΔPp(Pa) relative deviation (%)
1 0.999657 1850.0 1898.7 -2.6
15 2 0.985011 4109.3 3921.1 4.6
3 0.970365 3456.9 3304.1 4.4
1 0.96896 -- -- --
20 2 0.948535 -- -- --
3 0.928111 7456.3 7266.0 2.6
1 0.938262 3347.9 3415.1 -2.0
25 2 0.912059 3683.2 3683.7 -0.01
3 0.885856 3172.3 3233.0 -1.9
1 0.907565 5194.3 5309.0 -2.2
30 2 0.875583 5382.4 5455.1 -1.4
3 0.843602 5996.3 6145.5 -2.5
It can be concluded from Table.4 that the maximum relative deviation of this laminar flow pressure model is 4.6%,
the minimum is -0.014%, all less than the permitted threshold 5%. Thus this model could well predict the pressure drop
of hydrate slurry at laminar flow state.
4. Conclusion
1. In the course of hydrate slurry experiments in this paper, the flow rate could be divided into four periods: the stable
stage before hydrate formation, the rapid hydrate formation stage, the meta-stable stage and contrived slow down stage.
And it is demonstrated from the analysis that: at the rapid hydrate formation stage, the drastic change/decline of flow rate
stems from the collision, coalescence and blockage of the hydrate particles formed in considerable amounts; At the meta-
stable stage, the notable variance of slurry pressure drop results from the Shear Thinning Behavior of non-Newtonian
fluid. In addition, a critical minimum flow rate is proposed for the hydrate slurry safe flow assurance.
2. At the same initial pump speed, the induction period is compacted at first then prolonged slowly with the increase of
water-cut; While the induction period extends a little with the augment of AA dosage.
3. The increase of water-cut or AA dosage would promote the alteration of dispersed phase in the W/O emulsion to some
extent, that is, the smaller size as well as more uniform distribution. This benefits the hydrate slurry formation.
Moreover, it can be found that the CLD of dispersed phase stayed pretty consistent before/after the hydrate formation in
one set of experiments.
4. Based on the hydrate slurry flow experimental data, a laminar flow pressure model of power-law fluid in round pipe
has been proposed, which could well predict the pressure drop of hydrate slurry at laminar flow state.
Nomenclature
FBRM Focused Beam Reflectance Measurements
CLD Chord Length Distribution
PSD Particle Size Distribution
n´ dimensionless rheological index
ΔPe experimental pressure drop(Pa)
ΔPp predictive pressure drop(Pa)
α water-cut(%)
ω AA dosage(%)
L length of flow loop (m)
D Internal diameter of the pipe (m)
uaυ Mean velocity(m.s-1)
τω Shear stress(Pa)
k´ Parameters empirically determined
k Parameters empirically determined
Acknowledgments
This paper was sponsored by National Science & Technology Specific Project (2011ZX05026-004) and National
Natural Science Foundation of China (51104167).
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