ScienceDirect. The Experimental Study on a New Type Low Temperature Waterbased Composite Alcohol Drilling Fluid

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Available online at www.sciencedirect.com ScienceDirect Procedia Engineering 73 ( 2014 ) 276 282 Geological Engineering Drilling Technology Conference (IGEDTC), New International Convention Exposition Center Chengdu Century City on 23rd-25th May 2014 The Experimental Study on a New Type Low Temperature Waterbased Composite Alcohol Drilling Fluid Nikolaev N.I. a ; Liu Tianle b *; Wang Zhen b ; Jiang Guosheng b ; Sun Jiaxin b Zheng Mingming b ; Wang Yu c a Russia national mineral resources university b China University of Geosciences (WuHan), WuHan, 430074, China c China University of Geosciences (Beijing), Beijing, 430074, China Abstract Based on the characteristics of gas hydrate bearing permafrost in western China, and the application of alcohols drilling fluid, the performances of composite alcohol drilling fluid composed by polyethylene glycol and propylene glycol at low temperatures were comprehensively studied in this paper. The results show that the composite alcohol drilling fluid has a reasonable density, good low-temperature rheology, lubricity, shale hydration inhibition and hydrate formation inhibition, which can effectively inhibit shale expansion in a long time, and prevent hydrate formation from a small amount of free gas released from gas hydrate decomposition around the wellbore in the circulation of drilling fluid. Therefore, the composite alcohol drilling fluid has great significance for safe and high efficiency drilling in the permafrost gas hydrate bearing formation. 2014 The Published Authors. by Published Elsevier Ltd. by Elsevier Open access Ltd. under CC BY-NC-ND license. Selection and peer-review under responsibility of of Geological Engineering Drilling Technology. Key words: Permafrost; Nature Gas Hydrates; Composite Alcohol Drilling Fluid; Low Temperature Performance 1. Introduction With the traditional fossil fuels exhausting gradually, nature gas hydrate with massive reserves considered as a promising new energy has received more and more attention [6, 11]. The permafrost region is one of the two types of * Corresponding author. Tel.: +8615327185363. E-mail address: liutianle2008@163.com 1877-7058 2014 Published by Elsevier Ltd. Open access under CC BY-NC-ND license. Selection and peer-review under responsibility of Geological Engineering Drilling Technology doi: 10.1016/j.proeng.2014.06.199

N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 277 geological environment that could form nature gas hydrate. The area of permafrost in China is 2.15 106 km2, the third largest in the world [2]. Presently, the main nature gas hydrate accumulations discovered include eastern and western Siberia, Alaska of the U. S., and Mackenzie Delta of Canada, all of which are near the Arctic Circle [4]. While the permafrost in Qinghai-Tibet Plateau locates at Mid-latitude region, and it is quite different from the conditions of the Arctic regions [10, 13]. The activity zone of Qinghai-Tibet permafrost possesses special geological conditions for forming nature gas hydrates [2]. Firstly, the permafrost in Qinghai-Tibet Plateau is the largest in China with an area of 8.8 105 km2 and depth of 50~139 m. Secondly, the daily average temperature is lower than 0 C, and the annual average temperature is lower than -6 C. The low temperature condition is suitable for formation of nature gas hydrate and can prevent gas hydrate dissociation. The existence of good hydrocarbon source rock provides great potential for nature gas hydrate deposits. Additionally, the good trap boundary conditions in the area such as lithological trap, permafrost trap is preferable for forming gas hydrate reservoir [2]. From 2008 to 2009, under the organization of China Bureau of Geologic Survey, the nature gas hydrate scientific drilling project in permafrost region of Muli, Qilian Mountain, northern of Qinghai-Tibet Plateau was carried out by institute of mineral resource research, institute of exploration technology and the 105th coal geological exploration team in Qinghai of China Academy of Geological Exploration [13]. Four wells (DK-1, DK-2, DK-3 and DK-4) were drilled and several gas hydrate samples were obtained, which proved that gas hydrate reservoirs exist in the permafrost zone of Qilian Mountain, China, became the first country that discovered nature gas hydrate in permafrost of middle latitude region. When drilling in permafrost gas hydrate bearing formation, the disturbance of in situ formation caused by drilling can alter the geological conditions and make gas hydrates unstable. The dissociation of gas hydrates can lead to a series of problems about drilling safety. In case of an open hole, gas hydrate dissociation will cause the borehole unstable, and the gas released from gas hydrate will enter into the drilling pipe and the leak of permafrost formation. The gas circulated with drilling fluid may also reform as hydrate plug which could block the drilling pipe and terminate the fluid circulation. If the borehole is cased, the high pressure accompanied by gas hydrate dissociation may cause casing failure and borehole collapse. In addition, permafrost regions contain a large section of shale, whose hydration will also lead to the instability of borehole. As a result, the problems related to conventional oil or gas drilling in permafrost regions or marine hydrate reservoirs must be taken into consideration. Birchwood et al. [1] concluded that the influence of drilling through gas hydrate bearing sediments can be minimized by cooling drilling fluid and decreasing the circulation rate,. Therefore, it is important to take appropriate measures to minimize gas hydrate dissociation or inhibit the formation of gas hydrate within the drill string or annulus to ensure safe drilling operations. The choice of appropriate drilling fluid system could effectively relieve the problems mentioned above. In order to overcome the problems that might be encountered during drilling in gas hydrate bearing formation of permafrost region, a suitable drilling fluid system should have the following characteristics: (1)The density (p) of the drilling fluid must have an appropriate changing range. The drilling fluid can supply a definite pressure to balance the stratum and prevent hydrate around the borehole from decomposing to maintain the stability of the borehole. Results of previous experiments in our lab indicate that the optimum density is in the range of 1.1-1.2 g/cm3. (2)The drilling fluid should be able to effectively inhibit shale hydration and gas hydrate aggregation in the drilling pipe and blowout preventer. (3)The drilling fluid should have a low temperature that can effectively prevent the dissociation of hydrate around the borehole. (4)The drilling fluid should have good rheological properties and stability at low temperatures. (5)The drilling fluid must have sufficient lubrication and low filtration. At present, the typical drilling fluid system used in permafrost drilling is a polymer drilling fluid containing salts and organic agents which are known as thermodynamic hydrate inhibitors. Water-based composite alcohols drilling fluids with a low salt content and partially hydrolyzed polyacrylamide (PHPA) have been successfully used in several permafrost drilling activities. In most cases, the thermodynamic inhibitors are added into drilling fluids to prevent gas hydrate formation in deep water drilling, whereas the results of kinetic hydrate inhibitors (KHIs) are still under investigation [7, 8]. Compared with traditional thermodynamic inhibitors, kinetic inhibitors are effective at very low concentration (generally 0.01-1 wt. %), which can significantly reduce the drilling cost. At the same time, kinetic inhibitors are more environmentally friendly and could be applied under more and more restrictive

278 N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 regulations [8, 9]. In addition, for drilling in permafrost gas hydrate bearing formation, the use of thermodynamic inhibitors should be considered carefully because they prevent hydrate aggregation in the borehole, but can also cause the dissociation of hydrate around the borehole if their concentration is too high [5], which can then affect borehole stability. Therefore, KHIs or anti-agglomerates (AAs) should also be considered for preventing hydrate aggregation that may occur during the drilling operation. In this work, we develop a formulation of composite alcohols drilling fluid with KHI specially designed for drilling in permafrost gas hydrate bearing formations of the Qinghai-Tibet Plateau. We simulate the conditions encountered in permafrost drilling and evaluate the performance of the drilling fluid in the laboratory. The shale inhibition, low-temperature performance, and hydrate inhibition of the composite alcohols drilling fluid were tested with conventional drilling fluid test equipment and a gas hydrate integrated simulation experimental system was developed by the laboratory. 2. Experiment 2.1. Apparatus The conventional performance test equipment used for testing the drilling fluid includes a mud densimeter, a ZNN-D6 rotational viscosimeter, an API filter press and a ZNP swelling amount tester. The experimental gas hydrate integrated simulation system was used to test the inhibition of the drilling fluid. This system has also been used in our previous work [12]. It was developed to launch various simulation tests of hydrate formation and the inhibition of drilling fluid. A schematic of the experimental apparatus is shown in Fig.1. 2.2. Materials Fig. 1 Schematic Diagram of Experimental Gas-hydrate Integrated Simulation System The composite alcohol used in the experiments was a mixture of polyethylene glycol and propylene glycol. The polyethylene glycol and propylene glycol were produced by Shanghai Shiyi Chemical Reagent Co. Ltd. The average relative molecular weight of polyethylene glycol and propylene glycol is 4000 and 76, respectively. The kinetic inhibitor polyethylene pyrrolidone PVP K90 was made by Henan Boai Pharmaceuticals Co. Ltd. The methane was provided by Wuhan Huaxing Industrial Technology Co. Ltd., with a purity of 99.9%. The other reagents used in our drilling fluid were commonly used products manufactured by well-known companies. 2.3. Materials According to the laboratory research and practical drilling operations, the drilling fluid containing 10% composite alcohol (polyethylene glycol and propylene glycol) and 3%bentonite has a relatively comprehensive performance.

N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 279 Therefore, the designed formulation of our composite alcohol drilling fluid for permafrost gas hydrate drilling is: water + 6% polyethylene glycol + 4% propylene glycol + 3%bentonite + 3%NaCl + 1% PVP (k90) + 5% Na-CMC + 2.5% SMP-2. The formulation and the concentration of each component were designed on the basis of our work. All of the concentrations are expressed in mass ratios. In this formula, sodium carboxymethyl cellulose (Na-CMC) and sulfomethylated phenolic resin (SMP-2) can reduce the filtration of drilling fluid, and PVP K90 is a kinetic hydrate inhibitor. Since 1990s, many types of KHIs have been developed [8]. The PVP was considered the first generation of KHIs. Although the subsequent KHIs such as PVCap and Gaffix VC-713 outperform PVP, the PVP is the basic one and has relatively easier acquisition and lower cost compared with these KHIs. So it is selected as the hydrate inhibitor in our study. The normal performance of composite alcohol drilling fluid was tested with the conventional equipment. The ZNP swelling amount tester was used to test the capability of shale inhibition of the drilling fluid. The mud densimeter, the ZNN-D6 rotational viscosimeter and the API filter press were used to test the density, rheology and filtration at low temperatures, respectively. In the low-temperature tests, the drilling fluid and the test equipment were put into a programmable cooler in the order of corresponding tests. The programmable cooler was set at a predefined temperature to cool the drilling fluid. When the cooler reached the predefined temperature, the drilling fluid was stirred every ten minutes in one hour, which can allow the drilling fluid to reach a uniform temperature. After that, the corresponding tests were performed. And then, the hydrate inhibition of drilling fluid was tested by the simulation experimental system as shown in Figure 1. About 2000 ml of drilling fluid and some methane were injected into an autoclave until the pressure in the autoclave reached 8MPa. The autoclave was kept in the programmable cooler which was set at -2 C for 20 hours. This temperature (-2 C) and pressure (8MPa) simulate the conditions in permafrost at a depth of 400 m. Because the formation of hydrate consumes gas and releases heat, the pressure inside the autoclave would decrease and the temperature would increase during the experiments. These changes could then be used to evaluate hydrate formation in the drilling fluid and the effectiveness of inhibitor used. 3. Results and Analysis 3.1. Materials There are two common methods for shale-inhibition evaluation: The dispersing inhibition test (rolling collection test) and the expansion inhibition test. Here, the shale expansion tests were conducted and compared with pure water. The results are shown in Fig.2. Fig. 2 The Shale Expansion in Pure Water and Drilling Fluid

280 N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 It is indicated that the polyethylene-glycol drilling fluid has a significant inhibition on shale expansion. After two hours, the linear expansivity of shale in drilling fluid is only 2.9%, a reduction of 59.72% compared with that in pure water. After 16 h, the linear expansivity of shale in drilling fluid is 12.3%, a reduction of 69.4% compared with that in pure water. Furthermore, we can find that the linear expansivity of shale in pure water has a significant growth trend throughout the whole test, while the linear expansivity of shale in the polyethylene-glycol drilling fluid increases very slowly. 3.2. Properties at Low Temperatur The temperature of circulating drilling fluid is normally about -2 C to 2.4 C when drilling in permafrost regions of the Qinghai-Tibet Plateau [8]. For our test, we expand the possible range of circulating drilling fluid temperatures to range from -4 C to 4 C. The density (ρ), rheology (plastic viscosity (PV), gel strength (Gel), and yield point (YP)) and filtration (FL) of the drilling fluid are tested and the results are shown in Fig.3. Fig. 3 The Change of Gel Strength and Yield Point of Polyethylene Glycol Drilling Fluid at Different Temperatures As can be seen from Fig. 3, the density, YP, PV and Gel value have increasing trends as the temperature decreases, but the changes are small and acceptable. Furthermore, the high ratios of yield point and plastic viscosity will help to carry cuttings and clean the borehole. Although filtration has an increasing trend, it shows very little change. In conclusion, the polyethylene glycol exhibits good performance on the basis of the rheological properties and stability at low temperature measured. 3.3. Hydrate Inhibition To test hydrate inhibition, the drilling fluid without PVP K-90 is injected into the autoclave and cooled to -2 C by the programmable cooler at the pressure of 8MPa. The whole cooling time is 20 h. During the experiment, the pressure and the temperature in the autoclave change significantly (Figure 4a). The pressure decreases significantly from 8MPa at the beginning to 4.5MPa at the end. The temperature has a sharp rise when the experiment lasted for 970 min, which could indicate that there is a great deal of hydrate formed. This also implies that the thermodynamic inhibitors (in this case, the drilling fluid contains 6% polyethylene glycol and 3%NaCl) cannot fully prevent hydrate formation and aggregation under this temperature and pressure. Under the same conditions, drilling fluid with 1wt% PVP K-90 is injected into the autoclave. The results showed no significant changes in temperature and pressure over 20 hours in the autoclave (Fig. 4b). It is obvious that the temperature in the autoclave shows almost no change. In other words, there is no hydrate forming in the autoclave. The experiment shows that a low dose of PVP K90 has

N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 281 excellent performance on hydrate formation inhibition, and the composite alcohol drilling fluid can effectively inhibit gas hydrate formation at low temperature and high pressure. The inhibition will be even more obvious when the addition of PVP K90 increases. However, since it is a macromolecule polymer, adding too much PVP K-90 will inevitably lead to excessive shear viscosity. Tab. 1 shows the effect of PVP K90 on the rheological properties of polyethylene-glycol drilling fluid. It can be found that the gel strength and yield point of drilling fluid are preferable when the concentration of PVP K90 increases to 1%, especially the plastic viscosity that reaches 19.5mPa s. Fig. 4 The Contrast of Temperature and Pressure Evolution of Composite Alcohol Drilling Fluid without and with Addition of PVP K-90 Table 1 The Rheological Properties of Polyethylene-glycol Drilling Fluid with Different Concentration of PVP K-90 PVP Content ρ (g/cm 3 ) Gel (Pa/Pa) PV (mpa s) YP (Pa) FL (ml) 0.4% 1.175 2.0/2.5 13.5 5.2 7.5 0.5% 1.175 2.5/3.0 14 5.25 7.2 0.6% 1.175 2.0/3.0 14 6.25 6.8 0.7% 1.177 2.5/3.0 16 6.78 6.2 0.8% 1.178 2.5/3.5 17.5 7.66 5.5 0.9% 1.178 3.0/3.5 18.5 8.82 5.3 1.0% 1.18 3.0/3.5 19.5 9.36 5 1.1% 1.18 3.0/4.0 22 8.86 5 1.2% 1.18 3.5/4.5 23.5 9.15 5 Besides, the yield point/plastic viscosity ratio approaches 0.48, which also shows that the drilling fluid has good rheological properties and is capable of suspending drilling cuttings and stabilizing boreholes. If the concentration of PVP K90 increases more than 1%, the rheological properties of drill fluid become worse, which will influence the circulation rate of drilling fluid and even cause pressure surges in the borehole. Therefore, the concentration of 1% PVP K-90 can achieve the balance of good hydrate inhibition and relatively suitable rheology behavior in the polyethylene-glycol drilling fluid over at least 20 h at 8MPa pressure and low temperature. 4. Results and Analysis (1) The designed composite alcohol drilling fluid system has good performance concerning shale and gas hydrate inhibition, rheological properties and stability in low temperature. Therefore, it is able to maintain borehole

282 N.I. Nikolaev et al. / Procedia Engineering 73 ( 2014 ) 276 282 stability, suspend drilling cuttings, and clean the bottom of the borehole while drilling in permafrost regions of the Qinghai-Tibet Plateau. (2) If permafrost depth exceeds a certain value, only relying on the thermodynamic inhibitors (in this case, the drilling fluid contains 3%NaCl and 6% polyethylene glycol) can't fully prevent hydrate formation in the designed drilling fluid. Adding a small amount of the kinetic hydrate inhibitor PVP K90 into the composite alcohol drilling fluid can effectively inhibit hydrate nucleation and aggregation; it can also prevent the gas dissociated from hydrates around the borehole from reforming as hydrates later in the circulating pipeline. (3) While drilling in permafrost gas hydrate bearing formations, it is suggested that the drilling fluid have a high circulating rate to inhibit gas hydrate decomposition and reformation. Because the heat produced by aiguilles cutting stratum can be rapidly dissipated by the drilling fluid, the drilling fluid can be renovated rapidly. This process is helpful for cooling the drilling fluid by the cold permafrost stratum around drill pipes, which can help control dissociation of the hydrates around the borehole and maintain wellbore stability. References [1] Birchwood, R.A., Noeth, S., Tjengdrawira, M.A., Kisra, S.M., Elisabeth, F.L., Sayers, C.M., Singh, R., Hooyman, P.J., Plumb, R.A., Jones, E., Bloys, J.B. Modeling the Mechanical and Phase Change Stability of Wellbores Drilled in Gas Hydrates-, Technical Report for Joint Industry Participation Program (JIPP) Gas Hydrates Project, Phase II: Anaheim, CA, USA, November 2007. [2] Cao, D.Y., Liu, T.J., Wang, D., Wang, T., Wen, H.J., Pan, Y.L. Analysis of Formation Conditions of Natural Gas Hydrate in Muli Coalfield, Qinghai Province. Coal geology of China, 2009, 21(9): 3-6. [3] Cohen, J.H., Williams, Т.Е., Kadaster, A.G., Liddell, B.V. Hydrate Core Drilling Tests. Available online:http://www.netl.doe.gov/technologies/oil-gas/publications/hydrates/pdf/hyd-core-drill-maurer.pdf (accessed on January 7, 2011). [4] Dallimore, S.R., Collett, T.S. Summary and implication of the Mallik 2002 gas hydrate production research well program[m]//dallimore S R, Collett T S. Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program, Mackenzie Delta, Northwest Territories, Canada. Geological Survey of Canada, Bulletin, 2005, 585: 1-36. [5] Fan, S.S., Zhang, Y.Z., Tian, G.L., Liang, D.Q., Li, D.L. Natural gas hydrate dissociation by presence of ethylene glycol. Energy Fuels 2006, 20, 324-326. [6] Jiang, G.; Wang, D.; Tang, F.; Ye, J.; Zou, H.; Ni, X. Natural Gas Hydrates Exploration and Development, 1st ed.; China University of Geoscience Press: Wuhan, China, 2002. [7] Kelland, M.A., Monig, K., Iversen, J.E., Lekvam K. Feasibility study for the use of kinetic hydrate inhibitors in deep-water drilling fluids. Energy Fuels 2008, 22, 2405-2410. [8] Kelland, M.A., Iversen, J.E. Kinetic hydrate inhibition at pressures up to 760 bar in deep water drilling fluids. Energy Fuels 2010, 24, 3003-3013. [9] Liu, Т.L., Jiang, G.S., Ning, F.L., Zhang, L., Tu, Y.Z. Inhibition of polyethylene glycol drilling fluid with kinetic inhibitor for marine gas hydrates formation. Geol. Sci. Tech. Inf. 2010, 29, 116-120. [10] Ma, G.D., Zhang, L. Features and their constraints on exploitation of gas hydrates in Qinghai province. The Journal of Chinese mining. 2011, 02, 16-20. [11] Makogon, Y.F. Natural gas hydrates a promising source of energy. J. Nat. Gas Sci. Eng. 2010, 2, 49-59. [12] Ning, F.L., Zhang, L., Tu, Y.Z., Jiang, G.S., Shi, M.Y. Gas-hydrate formation, agglomeration and inhibition in oil-based drilling fluids for deep-water drilling. J. Nat. Gas Chem. 2010, 19, 234-240. [13] Wang, P.K., Zhu, Y.H., Lu, Z.Q., Guo, X.W., Huang, X. Gas hydrate in the Qilian Mountain permafrost and its distribution characteristics. Geological Bulletin of China, 2011, 30(12):1839-1850.