J. Ind, Eng. Chem., Vol. 8, No. 5, (2002) 493-498 Effect of Flow Velocity and Inhibitor on Formation of Methane Hydrates in High Pressure Pipeline Jeong-Hwan Lee’, Young-Soon Baek, and Won-Mo Sung* *R&D Division, Korea Gas Corporation, Incheon 406-130, Korea *Dept. of Geosystem & Environmental Eng., Hanyang University, Seoul 133-791, Korea Received July 22, 2002; Accepted September 10, 2002 Abstract: Hydrate blockages can occur in natural gas pipelines operated under high pressure and moderately low temperature conditions. Accordingly, the current study was carried out to understand the mechanism of hydrate plugging and examine inhibitors so as to prevent hydrate plugging in natural gas pipelines. The experiments were performed using a flow loop apparatus consisting of a 1.575 em inside diameter and 400 cm Jong tube with a 20 cm long transparent view pipe. Most experiments were conducted at 4.90 MPa, 5.90 MPa, and 6.87 MPa with various flow velocities ranging from 0.28 through 0.78 mis. The temperature in the loop was decreased at a rate of 2.2 K/h from initial temperature of 290.15 K until the pipe was plugged by hydrates. The hydrate equilibrium conditions under various flowing conditions with the methane were measured. And, the hydrate forming phenomena were observed when adding methanol as an inhibitor. ‘The results of both the plugging tendency and the effect of the methanol concentration are presented. Consequently, the current study provides methods for predicting hydrate plugging phenomena and hydrate control techniques using. an inhibitor for use in sub-sea pipeline s} Keywords: pipeline, flow loop, hydrate equilibrium condition, subcooling, plugging, inhibitor Introduction Hydrates, which contain a large amount of methane, are being considered as a future energy resource. However, the formation of hydrates in the oil and gas industries has been a serious problem for a long time [1,2]. The formation of hydrates in a pipeline is common in seasonally cold or sub-sea environments with low temperatures and high pressures. In particular, hydrate plug formation becomes a real menace to flow assurance in inadequately protected transmission lines. Hydrates can exist far above the freezing point of water, hence they can cause the plugging of pipelines and nozzles. In addition, they can also cause many difficulties in a deep-water drilling platform, as they can block the mud line, choke, and blow out preventer (BOP) [3,4]. For over 160 years, hydrates have remained a mere scientific curiosity. Their importance to the oil and gas industry was realized in the early 1930's when Hammerschmidt * To whom all correspondence should be addressed (email: jhwan@kogas.re kr) stems as well as PNG (pipelined natural gas) transmission systems, discovered that the solid compounds, which frequently plugged the gas transmission lines during cold weather, were not ice but hydrates [5]. It has been discovered under which conditions hydrates could form and how to prevent hydrate formation by the use of chemicals, During the past few years, the quest for the long-distance transport of untreated or partly treated pipelines has caused an increased interest in the area of hydrate formation, hydrate crystallization, and hydrate mitigation {6-8}. Recently published field experiments have shown that hydrate blockages form more readily in under- inhibited systems than in systems without any inhibitor {9]. As such, under-inhibited systems would appear to be more likely to experience hydrate problems than systems without any inhibitor. Consequently, the amount of inhibitor in the pipeline needs to be maintained at such a level that hydrate formation will not be encountered. In the current study, a visualized pipeline experimental apparatus, called a flow loop system was set up to determine the methane hydrate equilibrium conditions and formation conditions. And, methanol as an inhibitor was used to investigate the inhibitor performance,494 Jeong-Hwan Lee, Young-Soon Baek, and Won-Mo Sung Water bath Water pomp Figure 1. Schematic diagram of flow loop apparatus. Accordingly, this study experimentally demonstrates the phenomena related to the potential problems associated with hydrate formation and deposition in pipelines and how to prevent hydrate formation and remove a hydrate blockage. Experimental Experimental Apparatus and Procedure ‘The flow loop system was a lab-scale apparatus used to conduct hydrate plugging research in a pipeline environment. The system consisted of a main closed-loop pipeline and high pressure vane pump contained within @ water bath. The temperature of the loop was controlled using a water bath circulator. A simplified schematic diagram of the flow loop apparatus used in this experimental study is shown in Figure 1. The flow line was made of 316 grade stainless steel with a 1.575 em inside diameter and 400 em in length. The fluid inside the loop was observed using a 20 cm long transparent view pipe made from polycarbonate. A high pressure view pipe (up to limit 15 MPa) was located downstream of the pump. The flow was provided by a high pressure vane pump driven by a 1 hp motor with a variable speed drive. The pump could provide up to 12 liter'min. The loop was monitored with 6 temperature sensors and 6 pressure transmitters arrayed around the loop. 100 ohm platinum resistance temperature detectors were used to measure the temperature in the loop, and the accuracy of the temperature measurement was within -+0.1 K. The pressure of the system was controlled with a high sensitive pressure regulator (Tescom Co.). To measure the system pressure, calibrated pressure transmitters were used, and the accuracy of the measurements was within +20 KPa, To prevent the contents of the loop from drafting backward and remove any impurities contained in the gas, a check valve and a line filter were installed. To measure the gas consumption required for hydrate formation, a mass flow meter was installed in front of the gs inlet line, The methane gas used in the experiments was high purity grade (99.95%), and the water was distilled twice. The methanol was also high purity grade (99.8%) from DC Chemical Co. All the data was automatically recorded and monitored using a data acquisition system, called DaqBook ([Otech, Inc.). The pressure, temperature, and flow rate can be recorded and the loop can be operated in a constant pressure, constant volume, of constant temperature mode. Before starting the experiments, the entire system was evacuated to at least a 758 mmHg vacuum for several minutes to remove any foreign gases. Next, the required volume of distilled water was pumped into the flow loop, and the methane gas was charged into the loop. The pressure in the loop was raised above the expected equilibrium pressure to form hydrates and the contents of the loop then cooled at a constant rate until the pipe was plugged by hydrates. As soon as hydrates were formed, the loop pressure was reduced by the methane gas entrapped hydrates, When the formation of hydrates in the system was completed, the system temperature was inereased to decompose the hydrates. During this process, the system temperature was increased slowly, allowing sufficient time for the equilibrium to be achieved. It should be noted that the temperature was slowly increased to avoid the possibility of measuring the wrong equilibrium condition. In this experiment, the equilibrium point was taken as the point when the hydrates disappeared in the loop. To start an experiment for investigating the effect of the flow velocity, the loop was cooled at a constant pressure under the gas/liquid flow regime. During the coolingEffect of Flow Velocity and Inhibitor on Formation of Methane Hyérates in High Pressure Pipeline 495 process, the temperature at which the onset of hydrate formation occurred was determined and corresponded to the so-called temperature of formation. To observe the flow velocity effect, the subcooling temperature was ‘measured under a constant pressure. The pressure was set at 4.90 MPa, 5.90 MPa, and 6.87 MPa, respectively. The flow velocity was varied between 0.28 and 0.78 m/s, and the temperature in the loop was decreased at a rate of 2.2 K/h from an initial temperature of 290.15 K until the pipe was plugged by hydrates. To measure the inhibitor performance, methanol concentrations were varied within a range of 2, 4, and 6 wt%, The data was recorded ‘automatically at 10-second intervals. The recorded variables were the loop internal temperature, loop pressure, and ‘gas consumption rate, For the current tests, the quantity of water in the loop was 400 mL. Detection of Hydrate Formation ‘The onset of hydrate formation can be determined from the occurrence of several events. The following events are commonly used to detect the formation of hydrate plugging. 1, Exothermic peak of temperature 2. Increased pressure drop in flow system 3. Rapid increase in gas consumption (beginning of water conversion into hydrates) 4, Decrease in liquid density 5. Variation in electrical load of pump driver In the current study, three methods were employed to detect the onset of hydrate formation in the pipeline. The first method relies on the fact that hydrate formation is an exothermic reaction [10]. As a result of hydrate formation, a temporary exothermic peak occurs in the pipeline temperature. The second method utilizes an increase in the pressure drop as an indication of the appearance of the first nuclei of hydrates [11]. Third method is @ rapid increase in the gas consumption as a symptom of the beginning of water conversion into hydrates. This gas consumption is due to both a decrease in the temperature and the formation of hydrate crystals. ‘The gas consumption was measured from the mass flow ‘meter installed in the gas inlet line. In the current tests, the pressure dropped by 25 KPa and exothermic temperature increased 0.2 K during hydrate formation. ‘These techniques were good indication in detecting, hydrate formation. In addition to being qualitative tools to detect hydrate formation, the measurements were also used to provide quantitative information on the amount, of hydrate formation. Results and Discussion To investigate hydrate formation in pipelines, the 0 Pa ™ ‘TEMPERATURE (K) Figure 2, Pressure-temperature trace of formation of methane hydrate. equilibrium conditions of methane hydrates were measured in the current study. Figure 2 shows a pressure- temperature trace that describes the hydrate formation! dissociation process. After pressurizing the system with gas, the experiment started at point A (8.27 MPa, 291.75 K). The A-B curve is the cooling curve, which indicated a slight decrease in gas pressure. This decrease is considered to be the result of the gas cooling and dissolving in water. This interval has been described as the nucleation region by Sloan and several other researchers [12-14]. The B-C curve represents the continuous and rapid growth that took place until the solid hydrate phase became massive enough to plug the pipe. The rapid hydrate growth was accompanied by a catastrophic pressure drop in the constant volume pipeline due to the encapsulation of gas molecules in the hydrate. The hydrate formation stopped at Point C. The CE curve represents the dissociation region, where the system was warmed up and the hydrates were decomposed into the liquid and vapor phases. Point E (7.93 MPa, 284.35 K) is the equilibrium point where all the hydrate particles disappeared. Beyond point E, no more hydrate particles were observed. These experiments measuring the equilibrium conditions were performed ‘under various pressures and temperatures. ‘The results were all consistent with those previously published by Sloan and calculated by the CSMHYD program, as seen in Figure 3 [12]. CSMHYD program is a computer program developed by Sloan at Cololado School of Mine in 1984 and widely used to estimate hydrate equilibrium conditions in oil and gas industry. The program used the method of van der Waals and Platteeuw for the hydrate phase, and Soave-Redlich-Kwong equation of state for496 Jeong-Hwan Lee, Young-Soon Back, and Won-Mo Sung, on 5 7 5 5 7 © | = § : 2 i a0 e j D i Py Ss zi so aaa r T T ea ee t 22a ‘TEMPERATURE (K) Figure 3. Validation of experimental data. ow os ‘VELOCITY (mvs) Figure 5. Subcooling vs. flow velocity ——T “ os ‘VELOCITY (mis) Figure 4. Formation temperature vs. low velocity the fluid phases. Ina high pressure pipeline consisting of gas and water, there are several factors that have not been clearly defined yet but are favorable to hydrate formation, such as the flow velocity, pipe diameter, and incline degree of the pipeline. In the current study, to investigate the effect of the flow velocity in the pipeline, the formation temperature was measured with the flow velocities ranging from 0.28 m/s to 0.78 m/s under a constant pressure. Based on all the data from the current experiments, hydrate formation occurred when the system was cooled at a constant temperature rate of 2.2 K/h Figure 4 shows the relationship between the hydrate Velocity increase No hydrate region Equilibrium curve 2 TT a m wae ‘TEMPERATURE (K) Figure 6. Effect of flow velocity m formation temperature and the flow velocity for three different pressures of 4.90 MPa, 5.90 MPa, and 6.87 MPa. It was remarkable to note that the formation temperature tended to increase with the flow velocity under the given conditions. Subcooling is defined as the difference between the equilibrium temperature and the measured hydrate formation temperature [15]. In the current experiments, the subcooling varied between 1.90 and 3.58 K. Figure 5 shows that an increase in the flow velocity caused a linear decrease in the subcooling temperature. Figure 6 shows a clearer presentation of the behavior of theEffect of Flow Velocity and Inhibitor on Formation of Methane Hydrates in High Pressure Pipeline 497 PRESSURE (MPa) 67 MPa, 044 ms 4 a4 T T T 2 T T a m aa Ey a Hi u 4 ‘ TEMPERATURE (K) METHANOL CONCENTRATION (wt %) Figure 7. Effect of methanol concentration. Figure 8, Subcooling vs, concentration. pressure and temperature according to the flow velocity. 00 Consequently, all the experiments exhibited the lowest Hetnne| Concenaton subcooling at the highest flow velocity. The effect of Seis increasing the flow velocity produced turbulence causing woo] o Aut ‘a more intense physical contact between the gas and the Aon water. This increase in turbulence led to an enhanced ‘mass transfer from the gas into the water phase through the gas-water interface, and an enhanced transport towards the hydrate particle interface due to the mixing. Methanol addition has been used effectively to prevent the formation of hydrates and release hydrate plugs restricting or stopping the gas flow [16,17]. When the gas is to be sent considerably long distances, methanol is used as a means of preventing hydrate plugging or freezing in the pipeline system. The current experiments were carried out to investigate the effects of the concentration of methanol on the hydrate formation and inhibition processes. All the tests were performed at 6.87 MPa and 0.44 m/s. Figure 7 shows the experimental data for the hydrate formation point and the predicted equilibrium curve with different amounts of methanol, The equilibrium curve was predicted using methanol, as calculated by CSMHYD. Figure 7 shows that the formation point shifted toward a low temperature with an increased methanol concentration under a 6.87 MPa set pressure. Figure 8 shows the subcooling temperature and ‘methanol concentration at the onset of hydrate formation. As the methanol concentration increased, the subcooling temperature also increased. However, in the cases of 2 wt % and 4 wt %, there was no significant difference in the subcooling temperature. Figure 9 shows the gas con- sumption after the onset of hydrate formation. Aqueous solutions of 2, 4 wt% of methanol showed considerably CUMULATIVE GAS CONSUMPTION (mi) tot 00 ‘TIME (eee) Figure 9. Cumulative gas consumption. higher rates and more amount of hydrate formation than that obtained with pure water. This means that aqueous solutions of 2, 4 wt% of methanol had a subcooling from 1.9 K to 24 K but actually they were used as promoter after the onset of hydrate formation. Therefore these results show that, although the addition of methanol inhibits hydrate formation by increasing the subcooling temperature, methanol enhances the rate and amount of hhydrate formation when added at low concentrations to the water,498, Jeong-Hwan Lee, Young-Soon Baek, and Won-Mo Sung Conclusion To investigate the plugging phenomena of hydrates in a pipeline, the current study conducted experiments to measure the equilibrium conditions of hydrates, the forming temperature with various flow velocities, and the effect of the methanol concentration as an inhibitor. As such, the following conclusions were drawn: 1) AS regards the measurements of the methane hydrate equilibrium conditions, the current experimental results were validated with previously published experimental results, and found to be a good match, 2) The flow velocity identified as the most significant factor leading to an increase in the subcooling temperature, The reason for this was that an increase in the flow velocity produced turbulence, thereby causing more intensive physical contact between the gas and the water. 3) When adding methanol, the subcooling increased from 1.9 K to 4.1 K. However, aqueous solutions of 2, 4.w1% of methanol showed considerably higher rates and ‘more amount of hydrate formation than that obtained with pure water and hydrate plugs were found in all experiments. These results indicate that, although ‘methanol is used as an inhibitor to prevent hydrate plugs in a pipeline, it tends to enhance the rate and amount of hydrate formation when present in low concentration. Therefore, the amount of the inhibitor in the pipeline needs to be added in such sufficient quantities that hydrate formation will not be encountered. 4) The current study provides methods for predicting techniques of the hydrate plugging phenomena and hydrate control techniques using an inhibitor for use in sub-sea pipeline systems as well as PNG transmissi systems. However, for more definite conclusions regarding the inhibition process, more work with various inhibitors is needed. References 1. D. Lysne and R. Larsen, in Proc. 5th Intern. Offshore and Polar Eng. Conference, pp. 257-262, Hague, Netherlands (1995). 2. A. Hunt, Oil, Gas. J., 94, 62 (1996). 3.4. W. Barker, etal, Pet. Tech, 32, 297 (1989). 4, 0. K. Kwon, S. S. Ryou, and W. M. Sung, Korean J. of Chem. 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