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Experiences in the Operation of Dehydration and Mercury Removal Systems in LNG Trains

Jon Mock, Paul Hahn and Ram Ramani (ConocoPhillips Company) and David Messersmith (Bechtel Corporation)

The ConocoPhillips Optimized CascadeSM LNG process has emerged as an economical, proven alternative for the liquefaction of natural gasi. In addition to the original Cascade plant in Kenai, Alaska, built in 1969, eight plants have been constructed in the last ten years: four in Trinidad and Tobago, two in Egypt, one each in Australia and Equatorial Guinea. Each facility has met or exceeded design operating rates. An effective pretreatment system for moisture and mercury removal is key to the successful operation of any LNG plant. The start-up of so many facilities over such a short period presents a great opportunity to compare the performance of the pretreatment systems as designed and operated, evaluate economic impact on both operating costs and capital costs, and incorporate modifications into new designs that reduce operating and capital costs and improve operations. Successful functioning of the dehydration and mercury systems is critical to problem free operation of an LNG Plant. Sharing the lessons learned from the operation and the use of tools to troubleshoot the systems resulted in rapid ramp up to full production rates. Understanding and application of the troubleshooting tools will be important in long term operation at rates above design. Examples of key issues that arose during the start-up are shared. Tools for successful operation are also demonstrated. The importance of regeneration gas system performance, cycle time, valve performance, recovery from breakthrough, bed design constraints, and feed conditioning are discussed.

Overview of the Optimized CascadeSM LNG Process

The proper design and operation of the inlet treating units upstream of an LNG plant is critical to the success of the overall facility. For this paper, the LNG plants of concern all used the ConocoPhillips Optimized Cascade technology. However, the issues discussed apply broadly to any liquefaction technology. Design of the LNG plant is typically completed in major units including acid gas removal, dehydration and mercury removal, propane refrigeration, ethylene refrigeration, heavies removal and methane refrigeration. Additional units, for example LPG fractionation, can also be added to meet an owners objectives. If left in feed gas, water and carbon dioxide would freeze, making the plant ineffective. Likewise mercury could damage equipment used in the process. To eliminate these problems, the feed gas is first processed in the feed-treatment section of the plant. Feed treatment sections include the AGRU, dehydration and mercury removal. An amine-based gas sweetening process is typically used to reduce the H2S concentration to less than 4 ppm and the CO2 concentration to less than 100 ppm. Gas, saturated with water from the amine system, is cooled as much as possible, the limit being the hydrate formation temperature to reduce moisture content, and then fed to the molecular sieve dehydrators, where the remaining water vapor is removed and processed through activated carbon beds to remove any mercury. The treated gas is fed to the liquefaction unit where it is cooled and condensed in stages prior to entering the LNG tanks. A schematic of the ConocoPhillips Optimized Cascade process configuration is shown in Figure 1. In order to better illustrate the core process, LPG and condensate recovery are omitted from the figure. Key to any LNG plant is the refrigeration compressor/drivers. A typical plant will require

around 200 MW of power for about 3.8 million metric tones per annum of LNG production. Different driver configurations can be utilized for the LNG process depending on the plant capacity, owner preferences, and other requirements [1, 2]. The resulting process provides high thermal efficiency and process flexibility, while reducing capital cost [3]. The technology has provided cost competitive solutions that have been successfully licensed for multiple trains in several locations around the world including Point Fortin, Trinidad (four trains); Idku, Egypt (two trains); Darwin, Australia and Bioko Island, Equatorial Guinea [4-7]. Several other LNG projects utilizing versions of the process are at various stages of development.

Figure 1: Simplified Block Schematic of an LNG plant utilizing the ConocoPhillips Optimized Cascade LNG Process

Features of the process include that it is well proven, efficient, easy to operate, and has high plant availability. The Optimized Cascade process is licensed by ConocoPhillips through the ConocoPhillips-Bechtel Worldwide LNG Collaboration. The Collaboration jointly designs the liquefaction system, while Bechtel designs the remainder of the plant and constructs the entire facility from inlet metering to product loading. ConocoPhillips provides review of the design and construction. Together, ConocoPhillips and Bechtel commission and start up the plant. After initial running of the plant, a performance test is completed and the plant is turned over to the owner. This paper will focus on our experience with the dehydration and mercury removal systems in four plants completed between March 2005 and June 2006, namely Egypt Trains 1 and 2, Atlantic Train 4, and Darwin. Specifically, observations on the start-up and operation of the dehydration and mercury removal systems will be reported here.

Dehydration and Mercury Removal Systems

Prior to entering the LNG process, the feed gas flows through an acid gas removal system where CO2, H2S and other sulfur components are removed. The saturated, treated gas from the acid gas

removal system is then chilled to a temperature slightly above the hydrate point to condense most of the water, which is then removedgas stream by simple phase separation before entering the dehydration system. Hydrates are solids formed from the interaction of water molecules with hydrocarbons and other contaminants such as H2S and CO2. Hydrate formation potential as a function of process conditions and gas composition can be calculated using standard vapor-liquid equilibrium constants and equations of state [8]. Free water is separated in the Dryer Inlet Separator and filtered in the Filter Coalescer prior to entering the Dehydration Beds. The molesieve dehydrators consist of zeolite-based adsorbents that reduce the water content to a dew point of -100 C or less at atmospheric pressure. Typically three molecular sieve (mole-sieve) dehydration beds are used, with two in adsorption mode and one in regeneration or stand-by mode. The use of feed chilling removes as much as 90% of the free water from the feed gas, reducing the size of the molecular sieve system. Upstream upsets resulting in excess water or amine/hydrocarbon liquid carryover into the dehydration beds can cause longer regeneration times, downtime, and even ultimate failure and premature replacement of the mole-sieve beds. Various modes of mole-sieve bed failure are known and documented [9, 10] but yet not fully understood as individual plant operating conditions are unique and vary as a function of many variables. Regeneration of the saturated dehydration beds is a critical operation and involves flowing hot, dry gases at pressures slightly lower than that of the feed gas through the mole-sieve beds to vaporize and remove adsorbed moisture and other fluids. Over repeated adsorption and regeneration cycles, the adsorbent undergoes deterioration through particle breaking, binder separation and caking on the adsorbent surface. During a typical adsorption-regeneration operation sequence, the mole-sieve bed switches from adsorption to regeneration and then stand-by, based on a timed scheme developed as a function of the feed gas and regeneration gas flow rates or temperature and pressure. Some plants use a water breakthrough alarm or moisture detector to provide operations with warning about bed saturation, but the reliability level for these devices is not very high and require operator diligence. A dynamic calculation as a part of the monitoring strategy can provide additional operational information and be used to optimize the adsorption and regeneration cycles, and extend the mole-sieve bed life and improve its performance. The bone-dry feed gas exiting the dehydrator beds then flows through an activated carbon-based mercury removal system to reduce mercury concentration. Mercury can occur in various forms namely elemental or metallic, organic and inorganic forms [11]. In LNG plant operations, the presence of cryogenic conditions and brazed aluminum heat exchangers makes mercury removal critical [12]. Mercury removal becomes a critical operation in the LNG service and several vendors provide technologies to combat the problem. Most commonly used is one based on activated carbon impregnated with sulfur, whereby the mercury from the feed gas reacts with the sulfur to form mercuric sulfide, which remains on the carbon support. Regeneration is not done in situ and when the carbon bed is saturated with mercuric sulfide it is decommissioned and the bed is either sent to land fill or for mercury reclamation. It has been reported [12] that a five year life was typically quoted for the mercury removal beds. Shorter bed life is usually a result of high pressure drop or bed channeling. A sulfur-impregnated activated carbon system and a mixed sulfide absorbent system such as PURASPECTM offered by Johnson Matthey companyiv have been used upstream of the LNG process.

Case Studies:
Like all large plants, during start-up, some malfunctions were experienced in dehydrator and mercury removal systems in LNG operating plants. Effective and timely collaboration between the process, operations, and maintenance teams helped troubleshoot issues and develop solutions to mitigate or prevent problems from reoccurring. The solutions to these instances are discussed below.

ConocoPhillips and Bechtel maintain a best practices system to track improvements developed during engineering, procurement, construction, commissioning, startup, and operations. When applicable, these improvements are applied to future plants and shared with other licensees of the Optimized Cascade process. 1. Dehydration bed failure from support buckling: a) A 304 SS support screen with an expansion rope material around the perimeter was used in the dehydration bed vessel made of carbon steel. After several regeneration cycles of the mole-sieve bed, it was discovered that molecular sieve particles were present in the process downstream. Upon examination of the system, it was determined that the expansion rope was improperly installed and the support screen had buckled, causing loss of the mole-sieve from the dehydration bed. . Subsequent installation procedures have included allowing for expansion room and limiting the ability of sieve material to get in the expansion area. b) A related failure was that of the basket installed to contain any mole-sieve lost from the dehydration beds. The basket downstream of the dehydration bed could not contain the mole-sieve, resulting in the mole-sieve leaking into the process downstream. When the fabricated basket was replaced with a JOHNSONSCREENS screen basketv or equivalent, supportbasket was attained with adequate mechanical strength. 2. Dehydration bed failure from increased pressure drop: Typical mole-sieve designs from the vendors call for a pressure drop across the bed of approximately 0.5 bar. In the ConocoPhillips-Bechtel LNG plants employing similar dehydration bed design, additional margin for the pressure drop is allowed. However, it was noticed in two cases that this was not sufficient. One of the plants had the option to increase mole-sieve bed height and thus increase cycle time. But the resulting weight and pressure drop increase was not included in the design margin. In another instance, an aging mole-sieve bed with adsorbed content resulted in a bed support failure from exceeding the design conditions due to high pressure drop from fines. This caused loss of mole-sieve from the dehydration bed, which subsequently ended up in the mercury removal bed causing that bed support to collapse as well. Based on these findings, we have included larger pressure drop differential in the bed support design, accounting for dead weight of the mole-sieve, support balls, maximum moisture content plus comfortable design margin (with owner input) to avoid issues in the future. 3. Thermal Pulsing in the dehydration bed: Typical mole-sieve bed regeneration consists of a heating flow to vaporize and desorb the water and hydrocarbons from the bed, followed by a cooling flow to restore the bed to adsorption conditions. The heating regeneration gas flow is upward through the bed and it is recommended to maintain the cooling gas flow also in the same upward direction to take advantage of thermal pulsing in the bed and minimize regeneration heat requirement, therefore reducing the energy consumption. With up flow heating and cooling, the bottom of the bed sees the hottest and coolest regeneration gas respectively which leaves it in the best condition after regeneration. 4. Water breakthrough in mole-sieve bed as a result of incomplete regeneration:

Mole sieve switching valves and communication protocols need to be thoroughly tested during commissioning. If switching valves do not seal off completely, incomplete regeneration or gas bypass can occur, which can result in premature saturation of the beds and water breakthrough. 5. Regeneration surge drum and valve sizing: The amount of water driven off the mole-sieve bed during regeneration is reasonably well understood. However, the amount of time and the rates of water removal from the beds can vary significantly over the regeneration cycle. The water knockout and level control valve need to be properly sized to match the peak rate of water rates driven from the mole sieve bed. 6. Dryer inlet separator sizing: When amine carryover is combined with condensed water from gas cooling, the resulting liquids can overwhelm the dryer inlet separator. This can result in liquid carryover to the mole-sieve bed, resulting in bed caking, binder dissolution and overall structural degradation. A key design parameter for sizing the dryer inlet separator is the high-pressure derating factor, which can affect the vessel size by as much as 25%. Amine performance, the potential for methanol in the gas, and other factors need to be considered in selecting the vessel size. 7. Moisture in the mercury removal system: LNG plants typically use activated carbon mercury removal technology, except in one plant where the PURASPEC mixed oxide adsorbent technology is used. The use of PURASPEC was to reduce pressure drop in the mercury removal bed. Another major advantage of this technology is the ability to operate in wet gas service compared to the activated carbon that must operate in a dry atmosphere. As is common practice, the mercury removal bed was located downstream of the molesieve bed. During startup the bed became wet and later water evolved from the bed and moved downstream into the cold section of the plant. Attempts to dry the PURASPEC bed took much longer than in activated carbon beds. Locating the PURASPEC bed upstream of the dehydration bed has significant operational advantages. This learning was shared with the vendor, who has updated their recommendation to now include locating this bed upstream of the dehydration bed. 8. Handling exothermic heat release in mercury bed: The reaction between mercury and sulfide present in the activated carbon bed is exothermic and releases heat from when initial contact of natural gas is made. This poses a heat build-up and material/adsorbent degradation risk over time. To overcome this, during startup of the mercury removal bed, feed gas should be slowly fed into the unit to control the temperature increase in the bed and the bed outlet temperature monitored. 9. Risk of fire from incorrect insulation: During construction, inspection of insulation installation is needed to ensure the specified insulation is correctly applied. Not all insulation materials can withstand the high temperatures experienced during regeneration of the mole sieve system. 10. Balanced piping layout: To maintain equal adsorption efficiency in the mole-sieve dehydration beds and to manage the adsorbent bed life and effectiveness, it is essential to install hydraulically balanced piping at the inlet (and outlet) to the dehydration beds. This eliminates the possibility of a preferential flow path of the feed gas through one of the dehydration beds and reduces troubleshooting time should a problem be noticed in one of the beds.

11. Moisture Analyzer probes: An optimum location for the moisture analyzer probes or sample connection point is needed in the dehydration beds. The online moisture analyzers frequently get fouled due to contact with contaminants and hence are prone to failure. Locating the sampling point just above the bottom support bed or close to the bottom of the molesieve bed is useful for trouble-shooting and for breakthrough tests. A permanent sampling point a few feet downstream of each dehydration bed also helps to cancel out local flow fluctuations and provides reasonable average moisture content. A common sample point in the main feed line downstream is a useful secondary measurement. 12. Inlet distributors in the dehydration bed: Even distribution across the bed is critical to effective water removal and long bed life. Proper design of the inlet distributors is important to achieve uniform adsorption and efficient utilization of the mole-sieve beds. The use of a shelf ring or other device on top of the mole-sieve beds greatly helps the mixing and re-directing of flow away from the vessel walls, thus reducing the potential for channeling or short circuit flow. 13. Mercury bed drying options: Although downstream of mole sieve units, occasionally mercury beds can become laden with moisture. A simple but effective improvement to on-line mercury removal bed performance is the provision of options to dry out the beds while they are being bypassed after verifying absence of mercury in the gas stream and the plant is online. Often overlooked during design, this saves a lot of time with either the activated carbon bed or more importantly with the PURASPEC bed. It is important to evaluate the risk of mercury in the process during bypass operation. Applying the lessons learned during subsequent plant operations has resulted in significant improvements in terms of both the start-up schedule and demonstrated capacity as summarized in Table 1. Table 1: Performance improvements Facility A B C D Start-up time 160 days 131 days 66 days 50 days Demonstrated throughput as %Design 104.2% 104.5% 107.6% 109.5%

Every operating plant encounters a unique set of conditions that impact the feed pretreatment systems in a different way. Collection and presentation of the knowledge gained based on a standard set of design conditions is useful in diagnostics and trouble-shooting. We have attempted to share our findings in relation to the dehydration and mercury removal systems in natural gas liquefaction facilities built by Bechtel and employing the ConocoPhillips Optimized Cascade technology. In each instance, a viable solution was arrived at through effective collaboration amongst the client, EPC contractor and technology licensor. Several of these developments resulted in new and improved designs for the gas pretreatment section in facilities employing the ConocoPhillips Optimized CascadeSM LNG technology.

1) Ransbarger, W., A Fresh Look at LNG Process Efficiency, LNG Industry, Spring 2007.

2) Andress, D., The Phillips Optimized Cascade LNG Process: A Quarter Century of Improvements, GASTECH 2000 3) Houser, C. and Krusen, L., The Phillips Optimized Cascade Process, GASTECH 1996 4) Richardson, F., Hunter, P., Diocee, T. and Fisher, J., Passing the Baton Cleanly, GASTECH 2000 5) Hunter, P. and Andress, D., Trinidad LNG The Second Wave, GASTECH 2002 6) Redding, P., Hernandez, R., Qualls, W., and Avidan, A., Egyptian LNG The Value of Standardization, GASTECH 2005. 7) Diocee, T., Hunter, P., Eaton, A. and Avidan, A., Atlantic LNG Train 4 The Worlds Largest LNG Train, LNG 14 2004. 8) Gas Processors Suppliers Association Engineering Data Book, Chapter 20, 12th edition, 2004. 9) Rastelli, H. and Shadden, J., Extending Molecular Sieve Life in Natural Gas Dehydration Units, Gas Processors Association 86th Annual Convention Proceedings, 2007. 10) Huffmaster, M., Gas Dehydration Fundamentals Introduction, Laurance Reid gas Conditioning Conference 2004. 11) Ruddy, T., and Pennybaker, K., State of Mercury Removal Technology, Gas Processors Association 86th Annual Convention Proceedings, 2007. 12) Bourke, M., and Mazzoni, A., The Roles of Activated Carbon in Gas Conditioning, Gas Processors Association 68th Annual Convention Proceedings, 1989.

Optimized Cascade services are provided by ConocoPhillips Company, Phillips LNG Technology Services Company and Bechtel Corporation via a collaborative relationship with ConocoPhillips Company. Optimized Cascade, the Optimized Cascade logo, ConocoPhillips and its logo are trademarks of ConocoPhillips Company. Bechtel and its logos are trademarks of Bechtel Group Inc.

aMDEA is a registered trademark of BASF Aktiengesellschaft Corporation, Fed Rep Germany, Carl-Bosch-Strasse, 38 Ludwigshafen am Rhein, Fed Rep. Germany.

DIGLYCOLAMINE is a registered trademark of Huntsman Petrochemical Corporation, Corporation Delaware, 500 Huntsman Way, Salt Lake City, Utah 84108.

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JOHNSONSCREENS is a registered trademark of Weatherford/Lamb, Inc., Corporation Delaware, 515 Post Oak Blvd, Suite 600 Houston, Texas 77027. Copyright 2008 ConocoPhillips Company