Article pubs.acs.org/jced
Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Ternary Vapor−Liquid Equilibrium Measurements and Modeling of Ethylene Glycol (1) + Water (2) + Methane (3) Systems at 6 and 12.5 MPa Francois J. Kruger,‡ Marie V. Danielsen,† Georgios M. Kontogeorgis,‡ Even Solbraa,† and Nicolas von Solms*,‡ ‡
Department of Chemical and Biochemical Engineering, Center for Energy Resources Engineering (CERE), Technical University of Denmark, DK-2800 Lyngby, Denmark † Research and Development Center, Statoil ASA, N-7005 Trondheim, Norway S Supporting Information *
ABSTRACT: Novel technologies in the field of subsea gas processing include the development of natural gas dehydration facilities, which may operate at high pressure due to their proximity to reservoirs. For the qualification and design of these processing units, ternary vapor−liquid equilibrium data are required to validate the thermodynamic models used in the design process. For this purpose, 16 new ternary data points were measured for ethylene glycol (1) + water (2) + methane (3) at 6.0 and 12.5 MPa with temperatures ranging from 288 to 323 K and glycol content above 90 wt %. Glycol in gas (y1), water in gas (y2), and methane solubility (x3) were measured with relative experimental uncertainties (ur(x) = u(x)/|x|) below 12%, depending on the type of data. The Cubic-PlusAssociation (CPA) equation of state was used to model the data. Literature pure component and binary interaction parameters were used. It was found that the model provides a good qualitative description of the experimental data for y1 and y2, while a significant over-prediction occurs for x3. The modeling errors for CPA ranged between 5−40% average absolute relative deviation.
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INTRODUCTION
economics. Additionally, its lower viscosity aids direct injection applications, especially at lower temperatures.3 Very few glycol-related data sets are found in the open literature. Natural gas related binary data for MEG consists mainly of gas solubility measurements4−11 in mixtures with methane, ethane, nitrogen, and carbon dioxide. Most literature sources for modeling applications advocate the use of data from the research groups of Jou4,7 or Zheng.5 Due to the difficulties in quantifying vapor-phase glycol content, only a few sources8,12 present this type of data. Furthermore, only two sources6,8 provide ternary gas−water−glycol data, and only Folas et al.8 present data for both phases. A few more data sets appear in sources not within the open literature, such as the Gas Processors Association (GPA). Data for CH4 + C3H8 + MEG + H2O and CH4 + CO2 + MEG + H2O measured by Ng and Chen13 are shown in Boesen et al.14 Given this relative dearth of available data, we aim to generate new experimental data for ternary systems (MEG + H2O + CH4) relevant to subsea natural gas dehydration
Monoethylene glycol (MEG) (IUPAC: 1,2-ethanediol) is used in the oil and gas industry as both a hydrate inhibitor in gas transport lines and dehydrating agent for gas processing applications. The use of MEG has been considered for highpressure subsea natural gas dehydration,1 and process designs for such applications require phase equilibria measurements for gas−water−glycol mixtures. This is crucial for the design of separation equipment, where the critical product specifications are the water and glycol content of the vapor phase. Sales gas specifications vary from region to region, but are generally in line with those specified by GASSCO:2 water dew point −18 °C at 6.9 MPag and maximum daily average glycol content 8 L·MSm−3. These stringent specifications are in place to prevent corrosion and ensure asset integrity in downstream transport networks but present a significant challenge in terms of process design. Triethylene glycol (TEG) is typically preferred for industrial dehydration applications as it can reach a lower water dew point and is less volatile. This results in lower glycol carryover into the product stream. MEG, however, offers dual purpose capability (inhibition and dehydration) and improved © XXXX American Chemical Society
Received: February 5, 2018 Accepted: April 10, 2018
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DOI: 10.1021/acs.jced.8b00115 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Figure 1. Experimental apparatus for high-pressure vapor−liquid equilibrium measurements of systems containing glycol, water, and natural gas.
from the incorporation of the improved GC−MS method of Miguens et al.12 for the analysis of MEG in the vapor phase. Vapor−liquid equilibrium was established inside a 450 mL nickel-alloy cell. The cell was located inside a climate chamber which has a range of T = (223.15−473.15) K with temperature control to within ±0.05 K. The pressure and volume were manipulated by hydraulic pistons, and a magnetic stirrer ensured sufficient contact between the phases. The apparatus was designed and built by Sanchez Technologies (now Core Laboratories) and is shown in Figure 1. The climate chamber, equilibrium cell, and control systems appear on the right side. The vapor−liquid interface was observed through a sight glass, and the apparatus was equipped with a camera for remote visual observation. The pressure inside the cell was measured using a Keller Pax 33X digital pressure transmitter [range: p = (0.000−100.000) MPa (abs), accuracy:
