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Energy Sources, Part A, 29:39–45, 2007

Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190933988

A Review of Strategies for Solving Gas-Hydrate
Problems in Subsea Pipelines

S. MOKHATAB
Lead Process Engineer
Tehran Raymand Consulting Engineers Ltd
Tehran, Iran

R. J. WILKENS
Chemical and Materials Engineering Department
University of Dayton
Dayton, Ohio, USA

K. J. LEONTARITIS
AsphWax, Inc.
Houston, Texas, USA

Abstract Flow assurance management is critical to successful and economic oper-
ation of oil and gas production systems. As production activities progress into deeper
waters, flow assurance challenges become more prevalent, and system design must ad-
dress these issues from a fresh perspective. Hence, new management and remediation
techniques have to be developed to reliably, efficiently, safely, and economically pre-
vent or handle these problems for the range of expected conditions including startup,
shutdown, and turndown scenarios.
An inherent problem with natural gas production or transmission is the forma-
tion of gas hydrates, which can lead to safety hazards to production/transportation
systems and to substantial economic risks. Therefore, an understanding of how, when,
and where hydrates form is necessary to overcoming hydrate problems. These ques-
tions have become all the more crucial since deepwater fields have been discovered or
brought in production, where these fields are perfect candidate to encounter hydrate
forming conditions. This article answers these crucial questions as well as provides
significant information on the best method to prevent and remediate hydrates in deep-
water production operations.

Keywords flow assurance, gas hydrates, prevention techniques, subsea pipelines

Gas Hydrates
Gas hydrates form in untreated multiphase flows when water molecules crystallize around
guest molecules at certain pressure and temperature conditions. The most common guest

Address correspondence to Saeid Mokhatab, Lead Process Engineer, Tehran Raymand Con-
sulting Engineers Ltd, No. 10, Ahmad Ghassir Street, Dr. Beheshti Avenue, Tehran, P.O. Box
15136, Iran. E-mail: s.mokhatab@tehranraymand.com

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only that they are possible (Leontaritis..40 S. Mokhatab et al. . Figures 1 and 2 show the hydrate envelope (HE) examples for oil and gas. Moreover. 1998). propane. shut-in and startup are also primary times when hydrates form. normal butane. ethane. 2000). isobutane. type of physical site. On shut-in. Other factors that affect hydrate formation include mixing. Operating under such conditions does not necessarily mean that hydrates will form. it becomes colder. when the multiphase fluid produced at the wellhead flows through the subsea pipelines. carbon diox- ide and hydrogen sulfide. At that condition. Typical gas hydrate envelope of Gulf of Mexico. multiple hydrate plugs can form. sur- face for crystal formation. and (2) the gas being at or below its water dew point. 1996). which provide ideal conditions for the formation of hydrates. nitrogen. molecules are methane. Figure 1. kinetics. the line temperature cools to that of the ocean floor so that the system is almost always in the hydrate region if the line is not depressurized (Hunt. of which methane occurs most abundantly in natural hydrates (GPSA. High pressures and low temperatures are common in deepwa- ter oil and gas fields. The hydrate curve represents the thermodynamic boundary between hydrate stability and dissociation. Hydrates are known to occur when natural gas and water coexist at elevated pressure and reduced temperature. agglomeration and the salinity of the system (Edmonds et al. In general. While many factors influence hydrate formation. Con- ditions to the left of the curve represent situations in which hydrates are stable and “can” form. which means most subsea pipelines could experience hy- drates at some point in their operating envelope. 1998). the two major con- ditions that promote hydrate formations are (1) the gas being at the appropriate tem- perature and pressure.

2002). Possible Problems Although gas hydrates may be of potential benefit both as an important source of hydro- carbon energy and as a means of storing and transmitting natural gas. they represent a severe operational problem as the hydrate crystals deposit on pipe walls and accumulate as large plugs.. single-sided depressurization after hydrate formation) can also cause considerable damage to production facilities. and therefore create a severe safety and environmental hazard.g. Hydrate Prevention Techniques Gas hydrate formation can be prevented by several methods. which are not often the most cost effective solutions. resulting in blocked pipelines. Another way to prevent hydrate plugs is to maintain the pressure and temperature conditions outside the hydrate formation region. Acceleration of these plugs when driven by a pressure gradient (e. The primary practical means of avoiding hydrate formation rely on the idea of preventing the HE and P and T production facilities pro- file from crossing each other during normal production (see oil and gas HE examples . the hydrate formation in subsea gas transmission pipelines should be prevented effectively and economically to guarantee the pipelines operate normally. Hydrate Management 41 Figure 2. The permanent solution is removal of water prior to pipeline transportation. over pressuring and eventually shut down of production facilities. The removal of hydrate plugs in subsea production/transmission systems poses safety concerns and can be time consuming and costly (Wilkens. Typical oil hydrate envelope of Gulf of Mexico. For this reason. such as using an offshore dehydration plant or subsea separation.

A number of different concepts are available for introducing additional heat to a pipeline (Hansen et al. 2004). Thermal Methods Thermal methods use either the conservation or introduction of heat in order to maintain the flowing mixture outside the hydrate formation range. An electrical resistance heating system may be desirable for long offset systems.. The design of such conservation systems typically seeks a balance between the high cost of the insulation. through flow-controlling sub-sea chokes in satellite wells producing to distant host platforms) results in lowering the temperature and could create favorable conditions for hydrate formation (Hunt. Chemical inhibitors are injected at the wellhead and prevent the hydrate formation by depressing the hydrate temperature below that of the pipeline operating temperature. line-depressurization approach is not practical in long and high-pressure gas transmission pipelines. especially in deep- water environments. and topsides capabilities of host platform. Typical gas flowlines do not have insulation and require continuous chemical inhibition for hydrate inhibition. is with pipeline burial. An economical thermal loss reduction method. 2000). recently utilized offshore in the Gulf of Mexico. The ability to heat during production depends on the specific electrical heating implementation. Both oil and gas flowlines require some hydrate inhibition. However.g. the intended operability of the system. it generally prevents hydrate formation during normal operation conditions. Wilkens. Heat conservation is common practice and is accomplished through insulation.. above). This is done by either pushing the HE to the left using thermodynamic inhibitors. heating-medium circulation. Alternatively. In addition to its high capital expenditure level and the technical challenges. where available insulation is insufficient. 1999). conventional insula- tion on the outer surface of the pipe and more effective pipe-in-pipe insulation methods are still preferred around the world because their performance can be predicted with engineering accuracy. 2002). Other methods use either conductive or inductive heat tracing (Lervik et al. at the wellsite.42 S. pigging.. oil flowlines are typically insu- lated but require hydrate inhibitors for start-up and shut-in restarts (Notz et al. It may be possible to operate at a pressure less than the hydrate formation pressure. or more exotic low dosage or by shrinking the P and T production facilities profile to the right by insulating and/or heating the flow line (Leontaritis. Chemical Inhibition Keeping operating pressures and temperatures out of the hydrate formation region can also be achieved by adding chemical compounds that change the behavior of the new mixture. The simplest is an external hot-water jacket. either for a pipe-in-pipe system or for a bundle. 1995). . 1996). Mokhatab et al. two methods are applicable. However. In general.. either regular. This method can be feasible for some subsea applications depending upon the fluid being transported. However. the tie back distance..g. 1998).. rapid gas decompression at the wellhead (e. e. 1996. There is concern over the reliability of conductive systems. it will not also prevent entering the hydrate formation region during a long-term shutdown. namely thermal and chemical (Mokhatab et al. methanol or glycols. and the acceptable risk level. or removal of hydrate blockage. In addition. The effect is also an increase in production as there is no time lost by unnecessary depressurization. Such systems provide environmentally friendly fluid temperature control without flaring for pipeline depressurization. or for shut-in conditions (Oram.

. since methanol is lower viscosity and its lower surface tension makes effective separation easy at cryogenic conditions (below −13◦ F). called low dosage hydrate inhibitors (LDHIs). These new hydrate inhibitors can lead to very substantial cost savings. glycols must be added at rates of up to 100% of the weight of water. it is usually preferred (Esteban et al. Therefore. . Upon re-start. Thermodynamic Inhibitors Traditionally. Typically. 2000). the economics of methanol recovery will not be favorable in most cases. However. lower viscosity and lower solubility in liquid hydrocarbons) to depress the hydrate formation temperature. which causes the hydrate formation point to be displaced to a lower temperature and/or a high pressure. Since glycols are expensive inhibitors. and the development of alternative. Hydrate inhibition using chemical inhibitors is still the most widely used method. a primary factor in the selection process is whether or not the spent chemical will be recovered. 1995). 1995. there is a significant push from refineries to limit the allowable concentration of methanol in the produced oil or condensate. In addition. the most common practical approach to prevent hydrate formation in gas production systems has been the addition of massive amounts of methanol. In many cases. regenerated and reinjected. cost-effective. For most oil production systems.. cost-effective and environmentally ac- ceptable hydrate inhibitors is a technological challenge for the oil and gas production industry (Lederhos et al. Often when applying this inhibitor. 2000). there is a significant expense associated with the cost of “lost” methanol. safety.. These chemicals are called “thermodynamic inhibitors” and have the effect of shifting the hydrate formation loci to the left. But in order to be effective. 2004). where it is possible to redesign production facilities on a smaller scale (Goodwin and Hunt. pumping and storage facilities. In addition. methanol is used in a non-regenerable system because it is a relatively inexpensive inhibitor and therefore. gas dehydration capacity. In practice. Methanol problems become more acute during events such as a hurricane shut-in when operators bullhead in several barrels of methanol into the tubing of oil wells. not only for the reduced cost of the new inhibitor but also in the size of the injection. or triethylene glycol (at a high enough concentration) to the gas/water stream. In fact. new. and environmentally acceptable hydrate inhibitors that allow multiphase fluids to be transported untreated over long distances have been under increasing investigation by the oil and gas industry (Kelland et al. These new hydrate inhibitors. 1996). The thermodynamic inhibitor selection process often involves comparison of many factors including capital/operating cost. 1998). etc. downstream problems can be caused by the methanol slug. form the basis of a technique that does not operate by changing the thermodynamic conditions of the system. High methanol concentration in the oil can cause problems in desalting operations and management of effluent streams. LDHIs act at the early stages of hydrate formation by modifying the rheological properties of the system (Sinquin et al. there is a definite need for extra.. ethylene glycol. costly and space consuming. corrosion inhibition. physical properties.. onshore or offshore plants for their regeneration. hydrate plug formation is prevented through the addition of glycols (usually ethylene glycol because of its lower cost. this cost is prohibitively expensive whereas it can be the least expensive alterna- tive for gas systems. However. these materials are inconvenient and hazardous due to chemical toxicity and flammability (Edmonds et al. producers are also reducing methanol content in gas because of severe penalties incurred for deviating from gas plants specifications. Hydrate Management 43 This method is expensive if the water production is significant.

e. and “anti-agglomerants” (AAs). they have mainly limitations in terms of water cut.e. Darlington. Most commercial kinetic inhibitors are high molecular weight polymeric chemicals (i. S. Deployment of LDHIs is a complex operation that must be carefully prepared in order to prevent any side effects that could compromise normal production operations or the efficiency of additional chemical treatments. and Lunsford. and the transferability among different plants. and Szczepanski. which are surface active chemicals (i. KHIs may prevent crystal nucleation or growth during a sufficient delay compared to the residence time in the pipeline. the shorter the time during which kinetic hydrate inhibitors can delay hydrate formation. A. . References Edmonds. which are effective at concentrations typically ten to one hundred times less than thermodynamic inhibitors concentrations. R. Esteban. GA. K. R. Amsterdam. poly[N-vinyl pyrrolidone] or poly[vinyl- methylacetamide/vinylcaprolactam]). This limitation is caused by the rheological properties of suspensions with high solid fraction and may depend on flow regime conditions. Low Dosage Hydrate Inhibitors LDHIs have been actively investigated for the last ten years in both academia and industry (Mehta et al. pilot plant and field. B. V. 2002). AAs.. The achievable delays range between weeks if the pipeline operates less than 42◦ F in the hydrate region to hours if the pipeline operates 50◦ F in the hydrate region. Proceedings of 79th GPA Annual Convention. UK.. however.. and suggestion received from him for the article. and extensive laboratory testing will be required to support the use of LDHIs in deepwater operations. comments. alkyl aromatic sulphonates or alkylphenylethoxylates) do not prevent the formation of hydrate crystals. The deeper a system operates in the hydrate region. Kinetic inhibitors are relatively insensitive to the hydrocarbon phase and may therefore turn out to be applicable to a wide range of hydrocarbon systems.V. These additives are currently applied in the Gulf of Mexico.44 S. Moorwood. where they require a continuous oil phase and therefore only applicable at lower water cuts.. The Netherlands.. The maximum water cut is expected to be between 40 and 50%... Hydrate update. In addition. Acknowledgment The authors would like to thank Dr. for the kind assistance. AAs performance is relatively independent of time. Mokhatab et al. which make these products of interest to operators looking for cost effective hydrate control in deepwater fields (Frostman. Ulfert Klomp of Shell Global Solutions International B. 2000. allowing the hydrates to be transported along with the produced fluids. There are two types of LDHIs: the “kinetic hydrate inhibitors” (KHIs). Hernandez. A. However. 1998. 2000) and West Africa. Contrary to thermodynamic inhibitors and kinetic hydrate inhibitors. GPA Europe Spring Meeting. Exploit the Benefits of Methanol. There are a few documented cases of commercial deployment of LDHIs (Frostman. AAs appear to be effective at more extreme conditions than KHIs. County Durham. they are essentially new technology.. May 1998. 2003). However. but keep the particles small and well dispersed so that fluid viscosity remains low. USA. 2000). Atlanta. the industrial application of kinetic inhibitors depends on the repeatability of multiphase pipeline testing results among laboratory. the North Sea (Palermo et al.

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