Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90356

EXPERIMENTAL STUDY ON BLOCKAGE OF GAS HYDRATE SLURRY IN A FLOW LOOP

Lv Xiaofang Beijing key laboratory of Urban Oil and Gas Distribution Technology, China University of Petroleum (Beijing) Beijing 102249 Yu Da Beijing key laboratory of Urban Oil and Gas Distribution Technology, China University of Petroleum (Beijing) Beijing 102249

Li Wenqing Beijing key laboratory of Urban Oil and Gas Distribution Technology, China University of Petroleum (Beijing) Beijing 102249

Shi Bohui Beijing key laboratory of Urban Oil and Gas Distribution Technology, China University of Petroleum (Beijing) Beijing 102249

Gong Jing* Beijing key laboratory of Urban Oil and Gas Distribution Technology, China University of Petroleum (Beijing) Beijing 102249

ABSTRACT Hydrate formation and blockage in long deepwater pipelines has long been a trouble for offshore petroleum production. Consequently, understandings of the procedures as well as influencing factors of hydrate blockage are key points to make reasonable flow assurance strategies. Thus two series of experiments have been conducted in a high-pressure hydrate flow loop newly constructed by multi-phase flow research group in China University of Petroleum (Beijing). One of the systems consists of water and CO2, while the other one includes water, diesel oil and natural gas. The relative time of hydrate blockage has been studied by varying pressure and flow rate for both two systems. The dimensions of hydrate particles in fluid during plugging are also investigated. The results indicate that the influencing factor exerts a similar effect on the relative time for the different systems. Besides, the sizes of particles in the fluid would change significantly due to hydrate formation. KEYWORDS: gas hydrate; relative time; hydrate

blockage; flow assurance

1. INTRODUCTION After the first discovery of hydrate in the natural gas transmission lines in the 1930s [1], hydrate formation and blockage in long deep-water pipelines has long been a trouble for offshore petroleum production. As oil and gas production moves towards the deeper water, the low temperature and high pressure conditions necessary for hydrate formation between

natural gas and water are frequently satisfied in petroleum pipelines. Upon formation, hydrate accumulation and agglomeration ultimately forms a plug, blocking the flow through the pipeline. These plugs can be costly and dangerous to remove and can lead to a significant loss in production [2,3]. Therefore, how to prevent hydrate blockage has been becoming a focal point in the hydrate research field all over the world. Nowadays, there are many remarkable achievements in this blockage prevention area. For example, Andersson et al. [4,5] and Kleehamme et al. [6] performed experiments on the flow behavior of water-based, oil-based and THF hydrates in crude oil, respectively. The results showed that low hydrate fraction had little impact on pressure drop, but the particles agglomeration could block the pipe. Wang et al. [7] defined a critical value of hydrate volume concentration in the waterTHF experiment; it was safe to operate under the value, yet when it exceeded the critical point, pipeline pressure would increase sharply leading to blockage. Boxall et al. [8] 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. [9] analyzed more factors such as water-cut, flow rate, fluid property and restart on the hydrate flow loop in Tulsa University. Later Sjblom et al. [10] discussed the factors of hydrate blockage with three different oils under three experimental conditions, and recommended capillary attractive forces between hydrate particles as the key cause of agglomeration and plugging. However, among these published literatures, little attention has been paid to the relative time of hydrate blockage, as well

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as its influencing factors. Here the relative time of hydrate blockage is defined as: the temporal distance from a certain initial temperature point to the hydrate blockage, which reflects the time needed for the plugging under different conditions. Hence, research on the relative time of hydrate blockage is helpful to make reasonable flow assurance strategies, and is significant with respect to the crucial field guidance. This work aims at the relative time, has conducted two series of hydrate plugging experiments. One of the systems consists of water and CO2 (water+ CO2 system), while the other one includes water, diesel oil and natural gas (water+diesel+natural gas system). Moreover this work has investigated the influence that two variables, pressure and flow rate, exerted on the relative time in different systems, as well as the particle size distribution in the plugging process. 2. EXPERIMENTAL APPARATUS AND PROCEDURE 2.1 HIGH PRESSURE HYDRATE EXPERIMENTAL LOOP Experimental tests have been performed with the high pressure hydrate experimental loop devoted to Flow Assurance studies (Fig.1).The loop, in which gas and liquid are separately injected by a plunger compressor (2200 Nm3/h) and a custommade magnetic centrifugal pump(flow rate up to 12 m3/h), is constituted of a test section. Two sight glasses are set in the test sections. The gas injection point is considered as the inlet of the test section. At the outlet of the test section, gas and liquid are collected in an insulated separator and re-directed to the test section towards the compressor and the pump. Several gas tanks allow maintenance of loop and/or separator pressure as hydrate is forming.

5.08 cm (2 inches) diameter jacket in which a calorific 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 and permits 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.2) 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 (Fig.3). The probe window of probe cuts the flow streamlines at an angle of 45 and reaches the centre of the pipe. The RBRM 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. 2.3 FLUIDS The first series of hydrate blockage experiments of water+ CO2 system were conducted with Beijing city water and industrial grade CO2 (Beijing, Purity 99.5%); the other water+diesel+natural gas system employed the city water, -20# diesel and Civil natural gas.

Figure 1. Schematic of the high pressure hydrate experimental loop

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

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Figure 2. Principle of the FBRM particle size analyser

the pipe wall section reacted with CO2 firstly and generated a thin layer of hydrate. (b)The water near the hydrate layer continued to react with the dissolved CO2 and the hydrate continuously adhered to the hydrate layer. The hydrate layer was getting thicker gradually and finally blocked the pipe. (c) When the pump restarted, the fluid could wash away the hydrate stemming. Some hydrates were washed away, while some might accumulate at the back of the blockage and increase the contact area. (d) Hydrate formed near the increscent contact area and adhered on it continuously, and finally blocked the pipe again. The generated amounts of hydrates in the second blockage are less than the first one. Furthermore, it can no longer make the fluid flow again after the second hydrate blockage by raising the pump frequency.

Figure 3. Positioning the FBRM probe in the loop

Figure

4. Procedures of blockage by CO2 hydrate formation in the loop

2.4 EXPERIMENT PROCEDURE (1). After the loading of liquid phase, the magnetic pump is turned on to circulate the diesel and water fluids, so as to mix the fluids to form w/o emulsion. In the meantime, the temperature control device is opened, and the loop temperature is regulated to the setting experimental initial temperature T0. (2). When the temperature drops to T0, data collecting begins. And another period of time is needed till the CLD of particles in fluids keeps stable under the monitoring of FBRM. (3). Through pressure reducing valve gas is injected into the separator until the pressure reaches the setting experimental pressure P. The setting value of the temperature control device is lowered to the experimental final target TC, so that to cool down the loop as well as the fluids. The pressure is kept constant while the temperature downward gradually. (4). When a set of the experiment is finished, the setting value of the temperature control device is turned up again, from TC to T0. Repeat steps (1-4) for the next set after hydrate dissociation. 3. RESULTS AND DISCUSSION 3.1 WATER+ CO2 SYSTEM Through the experimental observation from the sight glass in our loop, the block process of water+ CO2 system might be divided into four periods, as shown in a-d Figure4. (a)Water in

3.1.1 PRESSURE Experiments have been carried on at the same flow rate, but different pressure (2.8 MPa and 4 MPa), as shown in Fig.5a and Fig.5b. It could be seen that temperature and flow rate changed as functions of time during CO2 hydrate formation. In Fig.5a, as the relative time proceeded, temperature dropped from its initial value slowly to a nadir point (Tn) 3.5, then increased suddenly and eventually leveled off at a stable point (Ts) 5. On the other side, flow rate holds steady around 450 kg/h from beginning, then reduced sharply to 0 kg/h as soon as the first hydrate blockage took place. After restarted, the mass flow rate experienced a momentary recovery but fell to 0 quickly for the second hydrate blockage. The relative time of appreciable hydrates formation (t0) is about 11500s, of the first hydrate blockage (t1) is about 12200s, and the time interval between the first and second (tp) is about 2000s. Similar results are exhibited in Fig.5b, differ from Fig.5a in that Tn=5, Ts=8; and t0=5800s, t1=6200s, tp=1000s. In the experimental process above, the suddenly increased temperature as well as the soon-declined flow rate could be attributed to substantial hydrates formation which releases heat, leads to hydrate agglomeration and finally the loop plugging. By contrast between Fig.5a and Fig.5b, it is found that the relative time of hydrate blockage is pressure dependent. In detail, as pressure elevates, the plugging temperature rises

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while the relative time decreases, namely, it is more prone to hydrate blockage at higher pressure. In addition, as pressure elevates, the time interval between the first and second (tp) shortens.

Figure 6a. Temperature and flow rate as functions of time during CO2 hydrate formation (20Hz, 4 MPa) Figure 5a. Temperature and flow rate as functions of time during CO2 hydrate formation (10Hz, 2.8 MPa)

Figure 6b. Temperature and flow rate as functions of time during CO2 hydrate formation (30Hz, 4 MPa) Figure 5b. Temperature and flow rate as functions of time during CO2 hydrate formation (10Hz, 4 MPa)

3.1.2 FLOW RATE Experiments have been conducted at the same pressure, different frequency of 20 Hz and 30 Hz, results are shown in Fig.6a and Fig.6b, respectively. It could be concluded that temperature and flow rate varied with relative time in an identical way as in Fig.5. In other words, temperature decreased at first and then increased, yet flow rate holds steady at first and declined to 0 as a result of blockage. In Fig.6a, t0=5900st1=6200stp=800s; while in Fig.6b, t0=10000st1=10400stp=600s. By contrast between Fig.6a and Fig.6b, it seems that the relative time of hydrate blockage is affected by flow rate in the loop. Specifically, the relative time needed for blockage increases with flow rate, it is less possible to form plugging at higher flow rate. But it should be noticed that the time interval between the first and second (tp) shortens as flow rate rises.

3.1.3 THE DIMENSIONS OF HYDRATE PARTICLES It is shown in Fig.7a the statistical distribution of hydrate particles in different chord length ranges during the water+ CO2 experiment with a frequency of 15Hz (4MPa). Obviously it could be found that as the experiment proceeded, square-weighted chord length of particles increased in fluid. The population of particles whose chord lengths under 30m declined distinctly, numbers between 30~60m ascended slightly, and numbers between 60~120m increased significantly. It follows that numbers of particles in every chord length region have changed along with the hydrate formation and agglomeration. The majority of hydrate particles are between 10~60m (see Table.1). On the other hand, when experimental time exceeds 2 hours, square-weighted chord lengths of particles as well as numbers between 60~120m descend clearly. This phenomenon is contributed to the restart step, that is to say, hydrate particles are broken down under stronger shear stress. It evidences from microcosmic viewpoint that the dimensions of particles in the fluid has been altering throughout the hydrate formation process. The un-weighted CLD curves of three specific time points are compared in Fig.7b. It could be informed that the mean chord lengths of most particles increased gradually over the

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experiment, which demonstrated the formation and agglomeration of hydrate. Statistical numbers of particles in divided chord length regions at those specific time points (Fig.7b) are presented in Table.1.

phase, then form a thin hydrate shell on the surfaces of the droplets. Along with the continuous reaction, the surface shell becomes thick and the hydrate quantity keeps growing, and these finally lead to hydrate accumulation, agglomeration till blockage.
Step 1
H2O entrainment

Step 2 hydrate shell growth

Step 3 agglomeration

Step 4 plugging

Figure 8. A conceptual picture for hydrate formation and Figure 7a. Statistical distribution of different chord length ranges for the experiment (15Hz, 4MPa) plugging process [11].

Figure 7b. Comparison of un-weighted CLDs measured at different instants (15Hz, 4MPa) Table 1 Statistical numbers of particles in different chord length ranges

Trend Mean Sqr Wt counts No Wt <10 counts No Wt 10-30 counts No Wt 30-60 counts No Wt 60-200

00:19:36 (Fine) 26.38 34253.05 15306.31 1649.73 59.66

01:20:01 (Fine) 28.16 36127.36 14932.59 1561.54 139.52

01:58:06 (Fine) 26.81 35492.9 14564 1891.35 27.25

3.2.1 PRESSURE Experiments have been carried on at the same flow rate, but different pressure (3.2 MPa and 4.1 MPa), as shown in Fig.9a and Fig.9b. It could be seen that temperature, density and flow rate changed as functions of time during CO2 hydrate formation. In Fig.9a, as the relative time proceeded, temperature decreased slowly to the nadir point (Tn) 3, then increased suddenly and remained around a stable point (Ts) 4; And flow rate reduced slightly at first then rushed down to 0 at hydrate plugging. The relative time of the plugging (t1) is about 41000s in Fig.9a. Identical results are exhibited in Fig.9b, differ from Fig.9a in that Tn=4, Ts=6, and t1=22000s. In this experimental process, the suddenly raised temperature could be attributed to the considerable exothermic hydrates formation; gas dissolution caused density decrease and the slight reduction of flow rate; and the plummeting flow rate was a result of hydrate generation, accumulation, agglomeration and finally plugging. By contrast between Fig.9a and Fig.9b, it is found that the relative time of hydrate blockage is related to pressure. In detail, the plugging temperature rises with pressure, but the relative time decreases with pressure, so it is easier to hydrate blockage under higher pressure.

3.2 WATER+DIESEL+NATURAL GAS SYSTEM In this 10% water-cut system, the hydrate plugging process schematic picture is shown as Fig.8. When the conditions necessary for hydrate formation are satisfied, natural gas dissolved in diesel would react with the water droplets in oil

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Figure 9a. Density, temperature and flow rate as functions of time during natural hydrate formation20Hz, 3.2MPa, 10% water-cut

Figure 10. Density, temperature and flow rate as functions of time during natural hydrate formation15Hz, 4.1MPa, 10% water-cut

Figure 9b. Density, temperature and flow rate as functions of time during natural hydrate formation20Hz, 4.1MPa, 10% water-cut

3.2.2 FLOW RATE Experiments have been conducted at the same pressure, different frequency of 15Hz and 20Hz, results are shown in Fig.10 and Fig.9b, respectively. The trends of temperature, density and flow rate varying with relative time in Fig.9b have been stated above. Phenomena in Fig.10 resemble that in Fig.9b. The major difference is that Tn=4.5, Ts=5 in Fig.10. In Fig.10, t1=19500s. By contrast between Fig.10 and Fig.9b, it suggests that the relative time of hydrate blockage is affected by flow rate in the loop. Specifically, the relative time needed for blockage increases with flow rate, so it is less possible to form plugging at higher flow rate.

3.2.3 THE DIMENSIONS OF HYDRATE PARTICLES It is shown in Fig.11a the statistical distribution of hydrate particles in different chord length ranges during the water+diesel+natural gas experiment with a frequency of 15Hz (4.1MPa). It implied that as the experiment proceeded, squareweighted chord length of particles increased in the fluid. The amounts of particles whose chord lengths under 10m almost remained the same, numbers between 10~60m ascended slightly, and numbers between 60~200m firstly decreased and then increased. It can be inferred that numbers of particles in every chord length range have changing along with the hydrate formation and agglomeration, and the main sizes are between 10~60m (see Table.2). The un-weighted CLD curves of three specific time points are compared in Fig.11b. It could be known that the mean chord lengths of most particles increased gradually, which illustrated the formation and agglomeration of hydrate. Statistical numbers of particles in different chord length ranges at those specific time points (Fig.11b) are presented in Table.2

Figure 11a. Statistical distribution of different chord length ranges for the experiment (15Hz, 4.1MPa)

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T0 TC Ts t0 t1 tp

the experimental initial temperature, the experimental final target temperature, a stable temperature point, the relative time of considerable hydrates formation, s the relative time of first hydrate blockage, s the time interval between the first and second hydrate blockage, s

ACKNOWLEDGMENTS This paper was sponsored by National Science & Technology Specific Project (2011ZX05026-004) and National Natural Science Foundation of China (51104167).
Figure 11b. Comparison of un-weighted CLDs measured at different instants (15Hz, 4.1MPa) Table 2 Statistical numbers of particles in different chord length ranges

Trend Mean Sqr Wt counts No Wt <10 counts No Wt 10-60 counts No Wt 60-200

02:00:01 (Fine) 39.59 20493.41 6607.25 183.65

04:00:01 (Fine) 41.56 20580.04 6228.81 137.06

05:49:21 (Fine) 127.19 20185.59 6525.72 136.43

4. CONCLUSIONS It could be summarized from hydrate blockage experiments of water + CO2 system and water+diesel+natural gas system, that relative time is needed to form enough hydrates then to plug the loop. In other words, plenty of hydrates would not occur immediately even when the conditions necessary for hydrate are satisfied. Also, the dimensions of particles in the fluid have been changing throughout the hydrate formation process. It may be inferred that the occurrence of hydrate blockage is time dependent, and its relative time is affected by pressure as well as flow rate in the system. Moreover, for the two different experimental systems in this work, the same influencing factor (i.e. pressure, flow rate) exerts similar effect on the relative time: less relative time for hydrate blockage is needed with higher pressure or lower flow rate. For those two systems, distribution trends of particles in the fluid are generally consistent. NOMENCLATURE FBRM Focused Beam Reflectance Measurements CLD Chord Length Distribution PSD Particle Size Distribution Dp initial water droplet size, m Tn a nadir temperature point,

REFERENCES [1] Sloan, E. D., 2005, A Changing Hydrate Paradigm-from Apprehension to Avoidance to Risk Management, Fluid Phase Equilib, 228-229, pp. 67-74. [2] Sloan, E.D., 2000, Hydrate Engineering, Society of Petroleum Engineers Inc., Richardson, TX, Chap.1. [3] Sloan, E.D., and Koh, C.A., 2008, Clathrate Hydrates of Natural Gas(third ed.), CRC Press, Taylor & Francis Group, Boca Raton, FL. [4]Andersson, V., and Gudmudsson, J. S., 1999, Flow Experiments on Concentrated Hydrate Slurries, SPE56567, SPE Annual Technical Conference and Exhibition, Houston, TX, October 3-6. [5]Andersson, V., and Gudmudsson, J. S., 1999, Flow Properties of Hydrate-in-water slurries, Proceedings of the 3rd International Conference on Gas Hydrate, Salt Lake City, Utah, USA, July 18-22.pp. 322-329. [6]Kleehammer, D. M., 2005, Rheology of Hydrate Slurries: Transferability between a Laboratory Viscometer and a Pilot Scale Flow Loop, Ph.D. thesis, Colorado School of Mines, Golden, Colorado. [7]Wang, W. C. et al., 2008, Flow Assurance of Hydrate Slurry in Pipeline, Journal of Chemical Industry and Engineering, 59(6), pp. 1545-1550. [8] Boxall, J. A., et al., 2008, Hydrate blockage potential in an oil-dominated system studied using a four inch flow loop, Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, British Columbia, CANADA, July 6-10. [9]Dellecase, E., et al., 2008, Hydrate plugging or slurry flow, Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, British Columbia, CANADA, July 6-10. [10] Sjblom, J., et al., 2010, Investigation of the Hydrate Plugging and Non-Plugging Properties of Oils, Journal of Dispersion Science and Technology, 31(8), pp. 1100-1119. [11] Turner, D.J., 2005, Clathrate hydrate formation in waterin-oil dispersions, Ph.D. thesis, Colorado School of Mines, Colorado.

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