Facilities Engineering

Gas Dehydration
Purpose of Dehydration
Dehydration is the removal of water vapour from the natural gas stream. There are two main reasons for carrying out dehydration, which are:1) 2) to prevent the formation of solid hydrates, which can cause obstruction and blockage in flow lines, chokes, valves, etc; to reduce the risk of corrosion to pipelines and other system components; this is particularly important when carbon dioxide and/or hydrogen sulphide are present in significant concentrations.

Hydrate Formation
Hydrates are crystalline solids (somewhat like dirty, sticky snow or ice in appearance) which can be formed by water molecules crystallising around guest molecules of certain other substances. This can occur at high pressures when the temperature is sufficiently low. The water molecules in hydrates are linked together by hydrogen bonds to form crystal lattices which contain cages (or voids) into which the guest molecules fit and stabilise the crystal lattice by their presence. It has long been known that the light hydrocarbon gases (e.g. methane, ethane, propane and the butanes) can act as guest molecules and form hydrates under suitable conditions, either individually or in combination. Some gaseous nonhydrocarbons which are often present in natural gases (such as carbon dioxide, hydrogen sulphide and nitrogen) can also act as guest molecules and form hydrates. Recent research has shown that some hydrocarbons with relatively large molecules can also form hydrates under suitable conditions; these include benzene, iso-pentane, neo-pentane, cyclopentane, cyclohexane and isopropanol. Hydrocarbons with more carbon atoms in the molecule than these are not hydrate formers, as their molecules are too large to fit in the cages of the crystal lattice. Although they are a particular source of danger at low temperatures, hydrates can form at temperatures well above the freezing point of water when the pressure is sufficiently high, and give rise to serious hazards in the production and transport of oil and gas. Hydrate formation tends to occur in flows just downstream of some partial obstruction such as a valve or choke, and once formation begins the quantity of hydrate can build up rapidly until the pipeline becomes completely blocked by a solid plug. This has been known to occur in pipelines over 1 m in diameter, and a case was reported from the Gulf of Mexico where a hydrate plug over 500 m in length formed in a riser. There have been many examples of hydrate formation in oil and gas production facilities causing major disruption to production operations. Frequently, serious hazards have resulted from the build-up of hydrate plugs which have obstructed flows in wells, Christmas trees, flowlines and other items of processing and production equipment, often stopping production for days or weeks. It is therefore essential to understand the conditions under which hydrates can form and the steps that can be taken to prevent this from occurring. Although rather similar in appearance to ice, hydrate crystal lattices differ from it in structure. Hydrates are solid solutions rather than true chemical compounds, and the guest 1

molecules occupying the cages in the crystal lattices are actually free to rotate inside them. They belong to the class of chemical complexes known as clathrates. The chemical composition of hydrates is not fixed (as with true chemical compounds), as they can be stable even when a considerable proportion of the cages are not occupied by guest molecules. Hydrate crystal lattice structures can exist in three different forms, called Type I, Type II and Type H. The existence of Types I and II has been known for many years, but Type H is a fairly recent discovery. Type I is the simplest structure, and contains two sizes of cage; a smaller one with 12 sides and a larger one with 14 sides. The unit cell for this structure is built from 46 water molecules and contains 2 small cages and 6 large cages. These cages can only accommodate the guest molecules which are smaller than propane; for example methane, ethane, carbon dioxide and hydrogen sulphide. Of these, ethane molecules can only occupy the larger cages, while the other hydrate formers mentioned can occupy both sizes of cage. The Type II crystal lattice is larger and more complex than the Type I lattice; it also contains two sizes of cage, a smaller cage with 12 sides and a larger cage with 16 sides. The unit cell of this structure is built from 136 water molecules, and contains 16 small cages and 8 large cages. The common hydrate formers acting as guest molecules for this hydrate structure include propane, iso-butane and nitrogen; of these, nitrogen can occupy both sizes of cage while propane and iso-butane occupy only the larger cages. The information given above refers to situations where only a single hydrate former is present in the system with the water (which need not be in the liquid phase for hydrate formation to occur). When two or more hydrate formers are present together in a system the situation becomes rather more complex. If only type I hydrate formers are present, the hydrate formed will always be Type I. If the system contains, for example, methane (Type I former) and propane (Type II former), it is found experimentally that the hydrate formed will nearly always be Type II unless the amount of propane present is very small. The most complex situation is one where several hydrate formers are present along with hydrate nonformers (as very commonly occurs in oil and gas production systems); in such a case it can be difficult to predict which type of hydrate will form as knowledge of this subject is still patchy and incomplete. However, it appears that in most oil and gas production systems the hydrates formed are likely to be of Type II. Note that n-butane does not form a hydrate on its own, but it can fit into the large cages of the Type II structure, and will do so in the presence of another Type II hydrate former. Until recently it was thought that molecules larger than n-butane do not form either Type I or Type II hydrates; however recent research has shown that benzene can form a Type II hydrate. The Type H hydrate crystal lattice contains three types of cage, and requires two types of guest molecule to be present before it can form. One of these must be a small molecule, such as methane, while the other must be a large molecule which is referred to as a Type H former or HHF (heavy hydrate former). Type H formers have been found to include such hydrocarbons as benzene, 2-methylbutane, 2,3-dimethylbutane, cycloheptane and cyclooctane. However, type H forming compounds occur only in quite small amounts in the well fluids from typical oil and gas reservoirs. It therefore seems unlikely that type H hydrates play any significant part in oil and gas production and transport systems and they

will not be discussed further in these notes.

Hydrate Stability
The thermodynamic stability of hydrates is usually shown on a pressure-temperature diagram (or phase diagram) such as that shown in Fig 1, which shows equilibrium data for several common hydrate formers found in oil and gas systems. This is known as a hydrate locus diagram. Each locus (or line) plotted on the diagram refers to the simple system containing only the hydrate former named and water (or water vapour). For any of the hydrate formers shown, hydrate can form and will be thermodynamically stable in the area on the left-hand side of the locus, but it will be unstable and cannot form in the area on the right-hand side of the locus. (Note that on these diagrams the pressure is usually plotted on a logarithmic scale). If a mixture of methane and water (or water vapour), for example, is maintained at conditions of 10 MPa and 12C, Fig 1 shows that methane hydrate can start to form and will be stable under these conditions. If, however, the temperature of the system is raised to 14C while the pressure is kept constant the methane hydrate will become unstable and start to decompose as soon as the locus is crossed - the methane molecules will start to escape from the cages in the crystal lattice which will then gradually collapse and become liquid water (or water vapour). (In practice, this decomposition may be quite a slow process). If the temperature is again lowered to 12C and the pressure kept constant methane hydrate will once again start to form as soon as the locus is crossed, and hydrate formation may continue until either the water or the gas is all used up and only two phases are left - the hydrate plus the constituent (water or methane) that is present in excess. The temperature value lying on the hydrate locus for a given system pressure is often called the hydrate formation temperature, since it is the temperature at which hydrate formation can start as the gas is cooled. In the above example, for instance, at a pressure of 10 MPa the hydrate formation temperature for methane is 12.8C. As the pressure of the system is increased, the hydrate formation temperature increases. Systems of the simple kind just discussed very seldom occur in oil and gas industry practice, where in almost all cases any gas present will contain a mixture of hydrocarbons. Fig 2 shows hydrate locus data for various mixtures of methane with propane. The topmost locus in the figure refers to pure methane (i.e. 0% propane) and the lower lines show loci for mixtures containing increasing amounts of propane. It can be seen that the addition of quite small amounts of propane to the gas greatly increases the range of hydrate stability - the hydrate becomes stable at higher temperatures for any given pressure, i.e. the hydrate formation temperature increases. Hydrate locus diagrams can be obtained for the more complex gas mixtures common in the oil and gas industry; these are often called Katz charts after Donald L. Katz who, with his co-workers developed these in the 1940s. One form of a Katz chart is given in Fig 3, which shows the hydrate loci for pure methane and for several natural gases mixtures of different compositions expressed in terms of the gas specific gravity (0.6, 0.7, 0.8 etc). These curves are only approximate, since the exact composition of a gas of given gravity can vary somewhat, and this variation can significantly affect its hydrate forming behaviour. Although these charts are convenient to use, therefore, they can only be expected to give a rough estimate of the hydrate formation temperature. It is better to rely on the specialist software now available (e.g. CSMHYD from the Colorado School of Mines) for accurate prediction 3

of the locus using detailed gas composition data. Note that the presence of the higher hydrocarbons causes the locus to move downwards and to the right, so that for a given system pressure the hydrate formation temperature always increases as the gas gravity increases. Hand calculation methods (due to Katz) for predicting hydrate formation temperatures are also available (based on K factors), but these methods are again essentially approximate and the specialist software referred to above is more reliable. In flowing oil and gas production systems it is often found that hydrates tend to form just downstream of chokes, valves and other fittings which restrict the flow path. The reason for this is that as the gas flows through the restriction the resulting pressure drop brings about a substantial drop in temperature caused by the Joule-Thomson effect. This temperature drop is often sufficient to cool the gas well below the hydrate formation temperature and hydrate formation can then proceed rapidly in many cases. One common method of inhibiting this hydrate formation is to inject glycol into the stream upstream of the valve of other fitting causing the pressure drop.

Water Content of Natural Gas

The water content of sweet natural gas for various conditions of temperature and pressure can be obtained from the standard McKetta-Wehe chart (Fig. 4). The solid constant pressure lines on the chart show the maximum amount of water vapour that can be held in vapour form by the gas at the temperature and pressure specified - e.g. it can be seen that at a pressure of 14.7 psia and a temperature of 60F 1 MMSCF of gas can contain 780 lb of water vapour. The gas will be saturated with water vapour under these conditions, and any more water vapour added will condense to liquid water. Another way of expressing this is to say that the water dewpoint of gas containing 780 lb water/MMSCF at 14.7 psia is 60F. (Note:- MMSCF stands for million standard cubic feet - measured at 14.7 psia and 60F). The chart is plotted for sweet natural gas of specific gravity 0.6 - a small supplementary diagram on the chart allows for correction for gases of different gravity. Data from the McKetta-Wehe chart must not be used directly if the gas contains any appreciable amounts of hydrogen sulphide and/or carbon dioxide, since these two gases have a major effect on the water/gas equilibrium. Correlations are given in the literature which have been developed to make corrections for the presence of these acid gases. The water content of natural gas is often expressed in terms of the water dewpoint. The chart can be used to convert water dew-point to water content on a mass basis and vice versa. For example, the maximum allowable water content for pipeline gas is frequently specified in the southern US as 7 lb/MMSCF; the chart shows that at a typical pipeline pressure of 1000 psia this will correspond to a water dewpoint of 35F for 0.6 gravity gas. It can be seen from the chart that if a saturated gas is compressed while its temperature is kept constant liquid water will condense, since as pressure is increased at constant temperature the mass of water vapour held by the gas decreases. Free gas present in an oil, gas or gas-condensate reservoir will be saturated with water vapour under reservoir conditions, and the McKetta-Wehe chart shows that for typical reservoir pressures and temperatures the water vapour content of the gas will be quite high - of the order of 200 lb water/MMSCF or more. As the gas is produced and flows to the wellhead its pressure and temperature will both fall, and this typically causes large amounts of the water vapour to condense; the resulting free water will usually be removed from the produced gas in the

surface separators. If the gas velocity in the tubing is not sufficiently high to carry the condensed water droplets up to the surface water will accumulate at the bottom of the wellbore (liquid loading) and this can cause a serious reduction in well deliverability, particularly in the later life of the reservoir. The McKetta-Wehe chart includes a hydrate formation line which is the approximate hydrate locus for natural gas of 0.6 gravity, so hydrate formation is possible in the area to the left of this line. Note that at a pressure of 2000 psia, the hydrate formation temperature is 68F, and hydrate formation can begin as soon as the temperature falls below this value. An alternative form of the water content chart is sometimes used which is basically similar to the McKetta-Wehe chart but on which the lines of constant pressure are curved instead of (approximately) straight as in Fig 4. The change in the shape of these lines is due to the use of a modified scale on the vertical (water content) axis. On the McKetta-Wehe chart a nonlinear scale is used for the vertical axis to give straight constant pressure lines.

Hydrate Prevention Strategies

Two main strategies can be used to make sure that hydrates do not form plugs that can cause serious obstruction in production, processing and transmission systems; these can conveniently be classified as (1) thermodynamic methods, and (2) non-thermodynamic methods. Thermodynamic methods are based on hydrate stability and the hydrate locus diagram, and work by making sure that conditions in the system are always kept to the right of the appropriate locus, so that hydrates either cannot form in the first place, or if they are already present they will be unstable and begin to decompose. This can be done by:1) 2) 3) 4) removing the liquid water (free water) from the system; keeping up the temperature of the fluid flow so that it is above the hydrateformation temperature at the pressure concerned; reducing the system pressure until the temperature of the fluids lies above the hydrate formation temperature; moving the hydrate locus to the left on the phase diagram by the addition of a suitable inhibitor to the fluids.

These methods are collectively referred to as thermodynamic inhibition, since they all operate by ensuring that hydrates will be thermodynamically unstable or cannot form under the conditions existing in the system. Strictly speaking it is thermodynamically possible for hydrates to form in the absence of liquid water if water vapour is present in the system and the temperature is below the hydrate formation temperature for the system pressure (i.e. conditions are to the left of the hydrate locus). However, experience shows that if no liquid water is present in the system the amounts of hydrate formed under these conditions are too small to present any obstruction to the flow. (This is the basis for the statement often seen in the literature that hydrate formation cannot take place in the absence of liquid water - a statement that is thermodynamically inaccurate). Keeping up the fluid temperature in the system is a useful technique for hydrate inhibition. 5

This may be done by insulating the pipeline carrying the fluids, using external insulation applied to the outside of the pipe, or insulation occupying the annular space between the inner pipe carrying the produced fluids and an outer carrier pipe (so-called pipe-in-pipe). In some cases active heating of the line is used together with insulation; the heat may be supplied by circulating hot water or hot oil, or by electrical heating. These techniques are frequently used for subsea flowlines in deep water, where seabed temperatures may be close to or below 0C. Reducing the pressure in the system (depressuring) is a standard technique to deal with a hydrate plug that has formed; this will shift conditions to the right of the hydrate locus and allow the plug to melt. Other steps may be taken at the same time, such a local heating and addition of an inhibitor such as methanol, which has the effect of moving the hydrate locus to the left, i.e. lowering the hydrate formation temperature for a given pressure. In the case of flowlines from subsea wellheads, there is always the possibility that both liquid water and gas will be present (for both gas and oil wells), pressures will be high and hydrate formation is prevented by injecting liquid inhibitors into the flowline at the wellhead. Suitable inhibitors are methanol or glycols, which mix with any liquid water present and lower the hydrate formation temperature, i.e. move the hydrate locus to left on the phase diagram. The flowlines are usually insulated and may also may be provided with active heating to keep up the temperature of the produced fluids and so reduce the quantity of inhibitor required. Polar solvents (which mix with water) and ionic salts act as hydrate inhibitors; sodium chloride has a slight inhibiting effect but the most useful inhibitors are methanol and glycols. Fig. 5 shows how addition of various percentages of methanol to the liquid water in the system shifts the hydrate locus to the left. Methanol is a more effective inhibitor than glycol in lowering the hydrate formation temperature, but glycols may be preferred as they are less volatile and therefore are less liable to be vaporised and carried away by any gas present. The amounts of inhibitor required are estimated from correlations or proprietary software for the line operating conditions. If the produced fluids have a high water cut large amounts of methanol may be required, since it is often necessary to achieve a methanol content in the water in the range of 20% to 50% to make sure that hydrates cannot form. Handling such large amounts of methanol - which is toxic and flammable - adds considerably to the operating expenditure. Another disadvantage of using methanol is that substantial amounts of it get into any crude oil produced, and this causes problems to the refinery processing the crude. Several glycols are used for hydrate inhibition and gas dehydration, as they have a strong affinity for water. These compounds have the general formula HO(C2H4O)nH , where n has the following values for the glycols shown:n=1 n=2 n=3 n=4 MEG DEG TEG TREG - ethylene glycol (or mono-ethylene glycol) - diethylene glycol - triethylene glycol - tetraethylene glycol

An alternative form of thermodynamic inhibition which is very widely used for gas export lines from offshore fields and for long-distance gas transmission lines is to dry (dehydrate) the gas before it is fed to the line so that its water dewpoint is below the lowest expected temperature (LET) in the line. There will then be no risk of liquid water condensing out in

the system, and no risk of significant hydrate formation. (Although it is thermodynamically possible for hydrates to form in the absence of liquid water when the gas temperature falls below the hydrate formation temperature, the amounts formed will be so small that they cannot cause any problems in operation). Gas dehydration is the standard approach used for gas export lines from offshore fields and for long-distance gas transmission pipelines. The specification for the maximum permitted water content of gas entering such lines will depend on the LET assumed; in the southern US it has long been standard practice to dry the gas until its water vapour content is less than 7.0 lb per MMSCF; in more northerly regions where lower temperatures may be expected to occur, water contents of less than 4 lb or less than 3 lb per MMSCF may be adopted. In North Sea practice still lower water contents may be specified; e.g. for the gas export line from the Miller field, a maximum water vapour content of 1.0 lb per MMSCF was selected in view of the high carbon dioxide content of the gas, which would lead to severe corrosion of the carbon steel line in the event of any liquid water condensing in the line. In some cases alloy steels are used for pipelines transporting gas with high carbon dioxide contents. The processes used for dehydration are discussed below. In the case of offshore fields, the gas dehydration approach obviously requires the provision of dehydration facilities on the offshore installation so that the water content of the gas can be reduced to the required low level before the gas is fed to the gas export line. Some offshore gas fields have adopted the alternative wet gas export strategy, by carrying out only minimal processing offshore to remove free water, or carrying out no offshore processing at all. In such systems it can be expected that liquid water will condense in the gas export line, which will therefore require hydrate inhibition and may also require corrosion inhibition if acid gases are present. Examples of this wet gas export approach are the Troll A platform, the Ormen Lange field (both in Norway) and the North Morecambe field (UK); these all require hydrate inhibition and corrosion inhibition to protect the carbon steel pipelines used since the gas transported has a significant carbon dioxide content. In the case of Troll A, MEG (ethylene glycol or monoethylene glycol) is injected into the pipeline at the offshore platform end to act both as a hydrate inhibitor and also as a corrosion inhibitor. The glycol is separated in the slug catchers at the landward end of the pipeline and recirculated. After the first year of operation the pH in the water phase in the line was increased to 7.4 by adding sodium hydroxide to the MEG, and this was found to further reduce the corrosion rate. (This is known as the pH stabilisation technique). On the North Morecambe field a similar approach is used but with methanol injected into the gas export line to act as the combined hydrate and corrosion inhibitor instead of MEG. The Ormen Lange field now under development in Norway will also use wet gas export with MEG injection. Another example of the wet gas export approach is the Goldeneye gas condensate field (UK) recently developed by Shell, which has an unmanned wellhead platform on the field but no offshore processing, and MEG injection to provide hydrate inhibition in the 105 km long flowline which delivers the well fluids to shore at St Fergus. Increasing attention is being paid to the wet gas export option for offshore gas or gascondensate fields since it has been shown to lead to major reductions in capital cost for such 7

fields, and it is the only option available for all-subsea fields such as Ormen Lange which have no surface facilities on the field itself. As an alternative to the thermodynamic inhibition methods just discussed, recent research has focused on the development of the non-thermodynamic approach which makes use of low-dosage hydrate inhibitors (LDHIs). When these are added to the system, it becomes possible to operate under conditions at which hydrates can form (i.e. to the left of the hydrate locus), since these inhibitors act to slow down the growth of the hydrate crystals or to prevent them from agglomerating to build up plugs. The small hydrate crystals which do form in the line are carried along as a slurry by the flowing fluids and do not obstruct the flow. Some very promising LDHI inhibitors have been developed which are effective at very modest concentrations of the order of 1%; this is much less than the concentrations of methanol or glycol that would be required to achieve similar results by using the thermodynamic inhibition approach. Two main types of LDHI have been developed; these are (1) kinetic inhibitors (KI), also called threshold hydrate inhibitors (THI), which delay crystal growth, and (2) antiagglomerants (AA), which minimise agglomeration of the crystals and so prevent the formation of plugs. Examples of KI inhibitors are polymeric materials such as saccharides, n-vinyl pyrrolidone and n-vinyl caprolactam; examples of AA inhibitors are alkyl glycosides, quaternary ammonium salts and alkyl aromatic sulphonates. Some of these LDHIs also have a useful corrosion inhibitor action. The technical literature has recently contained reports of a number of promising trials using KI and AA inhibitors either alone or in combination, but so far they have found full-scale application in only a few cases - one example is the Mungo field in the North Sea which forms part of the BP-operated ETAP scheme.

Dehydration Equipment
Dehydration is part of the normal gas conditioning process carried out on the offshore production platform or at the gas gathering station before the gas is fed to an export line or gas transmission line. In addition to dehydration, gas conditioning may also include (1) removal of some of the heavier hydrocarbons from the gas stream (to ensure that these do not condense out in the line and form liquid slugs) and (2) removal of acid gases (carbon dioxide and hydrogen sulphide) if these are present in significant amounts. The heavier hydrocarbons (propane, butanes, pentanes etc together with some of the ethane) are referred to as natural gas liquids (NGL), and their removal is called NGL extraction. Note that a natural gas has two dewpoints - a water dewpoint (i.e. the temperature at which liquid water will begin to condense out) and a hydrocarbon dewpoint (the temperature at which a liquid hydrocarbon phase will begin to separate out). Since water is not miscible with liquid hydrocarbons, these dewpoints are independent of one another and will frequently have quite different values. The gas conditioning facilities must be designed to ensure that both these dewpoints will be well below the lowest temperatures the gas will encounter as it travels through the pipeline. In some cases, gas export pipelines are designed to operate at high pressures in the dense phase (or supercritical) region of the pressuretemperature diagram, so that only a single hydrocarbon phase can be present; examples are the Miller, Frigg and Beryl gas export lines in the UK sector of the North Sea. This avoids the need to remove the heavier hydrocarbons before feeding the gas to the line, and simplifies the design of offshore processing facilities. The following processes are available for gas dehydration:-

1)

Refrigeration of the gas stream. As the temperature of the stream is reduced, liquid water will condense out and can be separated from the gas. Some liquid hydrocarbons will condense out at the same time and can also be separated. Refrigeration will therefore reduce both the water dewpoint and the hydrocarbon dewpoint of the gas stream. This method, however, is of limited application for dehydration, since it is difficult to achieve low water contents. Adsorption - i.e. contacting the gas with a suitable molecular sieve. The gas is passed through a tower packed with a suitable molecular sieve (a granular aluminosilicate) with adsorbs the water vapour. When the molecular sieve begins to lose its effectiveness the tower is taken off stream and the sieve is regenerated by passing high temperature gas through it. A minimum of two towers will therefore be required so that one tower can be on stream while the other is being regenerated. In practice, three or more towers may be used to give optimum performance. Adsorption is used on the Miller (BP) production platform in the North Sea for dehydrating the associated gas produced before it is exported to shore at St Fergus. A simplified flow diagram of an adsorption plant with two towers is given in Fig. 6. Membrane separation of water vapour is a promising new method for gas dehydration. This makes use of a semipermeable membrane which allows water vapour to pass through it while holding back most of the methane and other hydrocarbon gases. Membrane separation has been in use, for example, at the BP Easington terminal on the east coast of England since the early 1990s. Glycol dehydration in which the gas is contacted with one of the glycols; these are liquid chemicals having a strong affinity for water. This is an example of an absorption process. Triethylene glycol (TEG) is the glycol most widely used in current practice, although di-ethylene glycol was favoured in the earlier installations. Glycol dehydration is the most widely used dehydration method in both onshore and offshore applications. The major advantages of this process are that the plant has a smaller footprint and a lower capital cost than the other alternatives. However, it is not capable of achieving very low water contents; when these are required adsorption dehydration must be used, as in the case of LNG plants where the feed gas must be dehydrated to a very low water content approaching 1ppm.

2)

3)

4)

Glycol Dehydration Plant Design and Operation

Fig. 7 shows a schematic diagram of a basic glycol dehydration plant. The feed gas to be dehydrated flows up an absorber (or contactor) tower in countercurrent flow with glycol flowing downwards, and the glycol (normally TEG) absorbs water vapour from the gas. The gas pressure in the contactor should be in the range 500 psia to 1200 psia for optimum performance. The temperature of the gas stream remains fairly constant as it passes up the contactor, and will usually fall within the range 60F to 120F. Gas temperatures lower than 60F will cause the glycol viscosity to be undesirably high, and temperatures higher than 120F will tend to give high losses of glycol due to vaporisation. If gas temperatures above 120F are to be used, these losses may be reduced by using tetraethylene glycol (TREG); this has a lower vapour pressure than TEG, but it considerably more expensive and is also more viscous. As the gas temperature is increased, the dewpoint of the gas leaving the unit will increase (assuming that the concentration of the lean glycol entering the tower is kept 9

constant), and it is therefore desirable to keep the gas temperature down to about 60F if possible. In older units the absorbers were of the tray type, usually with 6 or 8 trays of the bubble-cap design. More recently, packed absorbers have been favoured, since modern designs of structured packing permit a higher gas throughput for a given diameter of contactor than the trays. In some plants, the original bubble cap contactors have been retrofitted with structured packing, permitting a considerable increase of gas throughput. The water-rich glycol leaving the base of the absorber is regenerated by heating it to a high temperature (around 400F) at atmospheric pressure in the reboiler, where most of the water boils off, leaving regenerated lean glycol with a glycol content of about 98.5% which is returned to the top of the absorber tower after cooling to a temperature which should be about 10F above the temperature of the gas stream leaving the absorber. (A higher temperature would increase the dewpoint of the exit gas, and a temperature below the gas temperature might cause condensation of heavier hydrocarbons present, which can promote foaming). The concentration of the regenerated lean glycol stream may be further increased by using a stripping column in conjunction with the reboiler. A small amount of dehydrated gas product is bled off to provide the stripping gas, or alternatively some of the plant fuel gas may be used for stripping. In older glycol dehydration units the water vapour boiled off in the regenerator was vented to atmosphere as steam. In many cases, however, this steam is found to contain significant quantities of aromatic hydrocarbons such as benzene and toluene which have been absorbed from the inlet gas stream, since aromatics (unlike alkanes) are fairly soluble in glycols. Any stripping gas used was also vented along with the steam. This release of hydrocarbons to the atmosphere is undesirable from an environmental protection point of view, especially in the case of the aromatics, and various modifications have been introduced in modern plants to deal with this problem. One widely-used modification is the Drizo process, in which a mixture of hydrocarbons (roughly approximating to heptanes and octanes in composition) is circulated in a closed loop to remove further water from the glycol after it leaves the reboiler. This can increase the lean glycol concentration to 99.99%, and overcomes the problem of aromatics discharges to atmosphere; however, its use results in major increases to the capital cost and footprint of the basic glycol plant. A simpler, more compact and less costly alternative is the use of the Cold Finger modification; this has been installed by Mobil in a number of its gas processing facilities, including the St Fergus plant handling gas exported from the Beryl field. Operational problems frequently result from contamination or degradation of the glycol. Continuous filtration of the glycol stream is essential, and is carried out using cartridge filters to remove particulate degradation products, and also an activated carbon filter to remove soluble contaminants. Accumulation of degradation products in the circulating glycol tends to cause foaming in the contactor, and encourages the build-up of deposits ('gunk') in bends in the pipework; rapid corrosion can then take place beneath these deposits. Long-radius ells should be used in the pipework instead of standard ells in order to minimise the formation of such deposits. The use of a corrosion inhibitor and maintenance of the pH value above 6.0 is effective in reducing corrosion problems. In some cases the absorber may be provided with corrosion resistant cladding to minimise the corrosive effects of any acid gases present.

Carryover of hydrocarbon liquid droplets in the gas entering the contactor is also a frequent source of foaming and other operational difficulties, and it is therefore essential that a liquid knockout is installed in the gas line upstream of the contactor. This will also prevent any water droplets present in the feed gas entering the absorber; these will always contain some salt which is slightly soluble in TEG and can lead to serious corrosion in the reboiler. Foaming in the contactor can be controlled by addition of a suitable anti-foaming agent to the glycol; tri-octyl phosphate at about 500 ppm concentration is one common choice. Trial and error is usually needed to find the optimum concentration of the agent in the glycol, since this is found to depend on the gas composition and on other process variables. Reboilers in glycol plants for onshore fields are commonly heated by direct firing using gas. For offshore installations this presents safety problems, and in such applications the reboiler is normally heated using a heat transfer fluid which recovers heat from the exhaust stream of the gas turbine used for power generation.

References
1) 2) 3) J J Carroll, Natural Gas Hydrates (Gulf Professional Publishing, Amsterdam, 2003) J M Campbell, Gas Conditioning and Processing, Vol. 2, The Equipment Modules (7th Edition), (Campbell Petroleum Series, Norman, OK, 1992) E Dendy Sloan Jr, Hydrate Engineering, (SPE, Richardson TX, 2000)

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