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-7230 online DOI: 10.1080/009083190933988
A Review of Strategies for Solving Gas-Hydrate Problems in Subsea Pipelines
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 operation of oil and gas production systems. As production activities progress into deeper waters, ﬂow assurance challenges become more prevalent, and system design must address these issues from a fresh perspective. Hence, new management and remediation techniques have to be developed to reliably, efﬁciently, safely, and economically prevent 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 formation 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 questions 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 deepwater production operations. Keywords ﬂow assurance, gas hydrates, prevention techniques, subsea pipelines
Gas hydrates form in untreated multiphase ﬂows when water molecules crystallize around guest molecules at certain pressure and temperature conditions. The most common guest
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Typical gas hydrate envelope of Gulf of Mexico. multiple hydrate plugs can form. 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. Mokhatab et al. ethane. isobutane. At that condition. High pressures and low temperatures are common in deepwater oil and gas ﬁelds. normal butane. surface for crystal formation. In general. 1998). The hydrate curve represents the thermodynamic boundary between hydrate stability and dissociation. molecules are methane. Figures 1 and 2 show the hydrate envelope (HE) examples for oil and gas. of which methane occurs most abundantly in natural hydrates (GPSA. Operating under such conditions does not necessarily mean that hydrates will form. it becomes colder. Conditions to the left of the curve represent situations in which hydrates are stable and “can” form. While many factors inﬂuence hydrate formation. 2000). kinetics. and (2) the gas being at or below its water dew point. shut-in and startup are also primary times when hydrates form. nitrogen. 1998). propane. type of physical site. . which provide ideal conditions for the formation of hydrates. Hydrates are known to occur when natural gas and water coexist at elevated pressure and reduced temperature. 1996). the two major conditions that promote hydrate formations are (1) the gas being at the appropriate temperature and pressure. only that they are possible (Leontaritis. which means most subsea pipelines could experience hydrates at some point in their operating envelope. Moreover. when the multiphase ﬂuid produced at the wellhead ﬂows through the subsea pipelines. Figure 1.40 S. On shut-in. carbon dioxide and hydrogen sulﬁde.. agglomeration and the salinity of the system (Edmonds et al. Other factors that affect hydrate formation include mixing.
Typical oil hydrate envelope of Gulf of Mexico. Hydrate Prevention Techniques Gas hydrate formation can be prevented by several methods. they represent a severe operational problem as the hydrate crystals deposit on pipe walls and accumulate as large plugs. For this reason.. Possible Problems Although gas hydrates may be of potential beneﬁt both as an important source of hydrocarbon energy and as a means of storing and transmitting natural gas.g. 2002). the hydrate formation in subsea gas transmission pipelines should be prevented effectively and economically to guarantee the pipelines operate normally. single-sided depressurization after hydrate formation) can also cause considerable damage to production facilities. The primary practical means of avoiding hydrate formation rely on the idea of preventing the HE and P and T production facilities proﬁle from crossing each other during normal production (see oil and gas HE examples .Hydrate Management 41 Figure 2. The removal of hydrate plugs in subsea production/transmission systems poses safety concerns and can be time consuming and costly (Wilkens. The permanent solution is removal of water prior to pipeline transportation. which are not often the most cost effective solutions. and therefore create a severe safety and environmental hazard. over pressuring and eventually shut down of production facilities. Acceleration of these plugs when driven by a pressure gradient (e. resulting in blocked pipelines. such as using an offshore dehydration plant or subsea separation. Another way to prevent hydrate plugs is to maintain the pressure and temperature conditions outside the hydrate formation region.
especially in deepwater environments. heating-medium circulation. line-depressurization approach is not practical in long and high-pressure gas transmission pipelines. It may be possible to operate at a pressure less than the hydrate formation pressure. conventional insulation 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. 1999). at the wellsite. The effect is also an increase in production as there is no time lost by unnecessary depressurization. either for a pipe-in-pipe system or for a bundle.g. e. 1996). Thermal Methods Thermal methods use either the conservation or introduction of heat in order to maintain the ﬂowing mixture outside the hydrate formation range.. either regular. This method can be feasible for some subsea applications depending upon the ﬂuid being transported. However. Alternatively. Chemical inhibitors are injected at the wellhead and prevent the hydrate formation by depressing the hydrate temperature below that of the pipeline operating temperature. In general. The simplest is an external hot-water jacket. 1998). However.. 2004). 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. In addition.. 1995). the tie back distance. pigging. Typical gas ﬂowlines do not have insulation and require continuous chemical inhibition for hydrate inhibition..42 S. This is done by either pushing the HE to the left using thermodynamic inhibitors. In addition to its high capital expenditure level and the technical challenges. it will not also prevent entering the hydrate formation region during a long-term shutdown.. oil ﬂowlines are typically insulated but require hydrate inhibitors for start-up and shut-in restarts (Notz et al. recently utilized offshore in the Gulf of Mexico. the intended operability of the system. Heat conservation is common practice and is accomplished through insulation.. There is concern over the reliability of conductive systems. . Other methods use either conductive or inductive heat tracing (Lervik et al. it generally prevents hydrate formation during normal operation conditions. Such systems provide environmentally friendly ﬂuid temperature control without ﬂaring for pipeline depressurization. The design of such conservation systems typically seeks a balance between the high cost of the insulation. or removal of hydrate blockage. where available insulation is insufﬁcient. 2002). or for shut-in conditions (Oram. However. An economical thermal loss reduction method. is with pipeline burial. 2000). namely thermal and chemical (Mokhatab et al. 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. rapid gas decompression at the wellhead (e. Mokhatab et al. Wilkens. Both oil and gas ﬂowlines require some hydrate inhibition. An electrical resistance heating system may be desirable for long offset systems. two methods are applicable. 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 ability to heat during production depends on the speciﬁc electrical heating implementation.g. and topsides capabilities of host platform. 1996. and the acceptable risk level. above). A number of different concepts are available for introducing additional heat to a pipeline (Hansen et al. methanol or glycols.
cost-effective and environmentally acceptable hydrate inhibitors is a technological challenge for the oil and gas production industry (Lederhos et al.... new. regenerated and reinjected. producers are also reducing methanol content in gas because of severe penalties incurred for deviating from gas plants speciﬁcations. 1996). Since glycols are expensive inhibitors.Hydrate Management 43 This method is expensive if the water production is signiﬁcant. the most common practical approach to prevent hydrate formation in gas production systems has been the addition of massive amounts of methanol. 1995). costly and space consuming. form the basis of a technique that does not operate by changing the thermodynamic conditions of the system. Hydrate inhibition using chemical inhibitors is still the most widely used method. or triethylene glycol (at a high enough concentration) to the gas/water stream. For most oil production systems. In addition. called low dosage hydrate inhibitors (LDHIs). However. Thermodynamic Inhibitors Traditionally. methanol is used in a non-regenerable system because it is a relatively inexpensive inhibitor and therefore. there is a deﬁnite need for extra. 1998). since methanol is lower viscosity and its lower surface tension makes effective separation easy at cryogenic conditions (below −13◦ F). glycols must be added at rates of up to 100% of the weight of water. downstream problems can be caused by the methanol slug. there is a signiﬁcant push from reﬁneries to limit the allowable concentration of methanol in the produced oil or condensate. hydrate plug formation is prevented through the addition of glycols (usually ethylene glycol because of its lower cost. 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. ethylene glycol. But in order to be effective. In many cases. In addition. which causes the hydrate formation point to be displaced to a lower temperature and/or a high pressure. 1995. cost-effective. These new hydrate inhibitors. Upon re-start. However. These new hydrate inhibitors can lead to very substantial cost savings. High methanol concentration in the oil can cause problems in desalting operations and management of efﬂuent streams. These chemicals are called “thermodynamic inhibitors” and have the effect of shifting the hydrate formation loci to the left.. onshore or offshore plants for their regeneration. this cost is prohibitively expensive whereas it can be the least expensive alternative for gas systems. lower viscosity and lower solubility in liquid hydrocarbons) to depress the hydrate formation temperature. it is usually preferred (Esteban et al. where it is possible to redesign production facilities on a smaller scale (Goodwin and Hunt. a primary factor in the selection process is whether or not the spent chemical will be recovered. The thermodynamic inhibitor selection process often involves comparison of many factors including capital/operating cost. 2000). 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. gas dehydration capacity. etc. In fact. these materials are inconvenient and hazardous due to chemical toxicity and ﬂammability (Edmonds et al. Often when applying this inhibitor. Therefore. In practice. the economics of methanol recovery will not be favorable in most cases. pumping and storage facilities. and the development of alternative. not only for the reduced cost of the new inhibitor but also in the size of the injection. there is a signiﬁcant expense associated with the cost of “lost” methanol. safety. physical properties.. 2004). LDHIs act at the early stages of hydrate formation by modifying the rheological properties of the system (Sinquin et al. corrosion inhibition. Typically. 2000). .
e. but keep the particles small and well dispersed so that ﬂuid viscosity remains low. and suggestion received from him for the article. In addition. 2000. V. A. 1998. and “anti-agglomerants” (AAs). which are effective at concentrations typically ten to one hundred times less than thermodynamic inhibitors concentrations. for the kind assistance. pilot plant and ﬁeld. poly[N-vinyl pyrrolidone] or poly[vinylmethylacetamide/vinylcaprolactam]). AAs appear to be effective at more extreme conditions than KHIs. KHIs may prevent crystal nucleation or growth during a sufﬁcient delay compared to the residence time in the pipeline. where they require a continuous oil phase and therefore only applicable at lower water cuts.. however.V. References Edmonds. These additives are currently applied in the Gulf of Mexico. Contrary to thermodynamic inhibitors and kinetic hydrate inhibitors. Moorwood. which are surface active chemicals (i.e. 2002). and Szczepanski.. AAs. Hydrate update. R. Proceedings of 79th GPA Annual Convention. S. GA. and the transferability among different plants. they have mainly limitations in terms of water cut. 2000). 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.. which make these products of interest to operators looking for cost effective hydrate control in deepwater ﬁelds (Frostman. UK. the shorter the time during which kinetic hydrate inhibitors can delay hydrate formation. Ulfert Klomp of Shell Global Solutions International B. This limitation is caused by the rheological properties of suspensions with high solid fraction and may depend on ﬂow regime conditions. A. Atlanta. GPA Europe Spring Meeting. Acknowledgment The authors would like to thank Dr. . Mokhatab et al. There are a few documented cases of commercial deployment of LDHIs (Frostman. Hernandez. K. The Netherlands. USA. However. and extensive laboratory testing will be required to support the use of LDHIs in deepwater operations. The maximum water cut is expected to be between 40 and 50%. LDHIs have been actively investigated for the last ten years in both academia and industry (Mehta et al. 2003). allowing the hydrates to be transported along with the produced ﬂuids. There are two types of LDHIs: the “kinetic hydrate inhibitors” (KHIs). 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. Most commercial kinetic inhibitors are high molecular weight polymeric chemicals (i. Esteban. County Durham. Amsterdam.. R. comments. the North Sea (Palermo et al.. May 1998. alkyl aromatic sulphonates or alkylphenylethoxylates) do not prevent the formation of hydrate crystals.. the industrial application of kinetic inhibitors depends on the repeatability of multiphase pipeline testing results among laboratory. AAs performance is relatively independent of time. B. they are essentially new technology. Darlington. However.44 Low Dosage Hydrate Inhibitors S. The deeper a system operates in the hydrate region. Exploit the Beneﬁts of Methanol.. 2000) and West Africa.. and Lunsford. Kinetic inhibitors are relatively insensitive to the hydrocarbon phase and may therefore turn out to be applicable to a wide range of hydrocarbon systems.
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