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Gas Dehydration

GAS DEHYDRATION
INTRODUCTION
y in contact with water in the p g Natural g gas is usually producing reservoir, and comes to the wellhead saturated with all the water vapor it can hold. It may either be dehydrated at the wellhead or brought into the plant as it is wet by using some means to prevent hydrate problems as heating , or injecting methanol. If an amine or other aqueous sweetening process is used in the plant, the sweetened gas will again be saturated with water.

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Removing most of the water vapor from the gas is required by most gas sales contracts. because it
1. Prevents hydrates from forming when the gas is cooled in the transmission and distribution systems . 2 prevents water vapor from 2. f condensing d i and d creating i a corrosion problem. 3. Dehydration also increases line capacity marginally. it means water will reduce the line capacity by creating a layer parallel to the line walls. 4 Important for downstream user viewpoint 4. 5. Water vapor Minimize Gas Heating Value ( Gross heating value , net heating value) see the next slide. 6. Water cause unsatisfactory instrument operation.

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The heating value of 1 kg of gas is nearly equal to the heating value of 1 kg of oil ( NOT 1m3 of gas and 1m3 of oil )
The heating value increase as the carbon atoms number increased.
Heating value in MJ

Component Methane n- heptanes Remarks

Heating value in MJ

kg
55.5 48.5 nearly the same

/ m3
37.69 205.4 about 6 times

DENISTY 0.68 4.24

1 Kg of Methane has about 62 carbon atoms 1000 gram / 16 gram = 62.5 Carbon atoms = 62.5 x 1 = 62.5 , Hydrogen atoms = 1 Kg of heptanes has about 70 carbon atoms 1000 gram / 100 gram = 10 Carbon atoms = 10 x 7 = 70

Most sales contracts call for reducing the water content in the gas: In the Southern United States to less than 7 lb/mmscf / f In colder climates, in the Northern United States sales gas water content is less than 4 Lb / mmscf In Canada requirements is 2 to 4 lb/mmscf are common. common In Egypt based on the agreement and the further treatment requirements LNG asking for water content less than 1 ppm.

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ppm & Lb / mmscf

If the water content is 147.5 ppm Convert it to Lb / mmscf 147.5 ppm = 147.5 ft3 / mmscf 18 Lb occupy 379.4 ft3 so 147.5 ft3 will weight ?

(147.5 x 18)

/ 379.4 = 7 Lb / mmscf

7 Lb = 3.17 Kg Lb / mmscf = 147.5 / 7 = 21.06 ppm

The molar heat of vaporization of water is 40.79 kJ at 100oC what is the heat of vaporization of 1 g of water?

well you have not mentioned the complete unit...it is 49.79 kJ/mole or also 2.766 kJ/gram just divide 49 KJ/Mole by 18 g / mole (which is the molar mass of water) and have your answer Each gram of water exist in the fuel will consume 2.76 KJ heat from the gross heating value of the fuel the remaining heat value is the net heating value

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The first problem of water in the gas stream is the hydrate

Basics of Hydrates
Basic Hydrates Definition :Natural gas hydrates are ice-like physical structures composed p of free water and light g end hydrocarbons molecules Under favorable conditions of pressure and temperature.

What are the light end hydrocarbons?

Water molecules form cages g which encapsulate p light end hydrocarbon molecules inside a hydrogen-bonded solid lattice. Host = water molecules Guest = gas molecules

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When Hydrates forms?

Hydrates form when these factors are present:A sufficient amount of water not too much, not too little. A hydrate former , Hydrate formers related to guest molecules , light ends hydrocarbons C1 , C2 , C3 ,iC4 ,Co2 ,H2S The right combination of temperature and pressure. Hydrate formation is favored by low temperature and high pressure, but it can happened at low pressure ( see the next slide chart )

Just Move the arrows up and down also right and left to check the right P & T combination

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some useful facts regarding hydrates

They can form in gas, gas condensate & oil systems. Hydrate formation temp depends on gas composition Richer gases will tend to form hydrates at higher temperatures. 1cubic foot of hydrate can contain 180 scf of gas. Hydrate blockages can occur very rapidly, due to hydrate particles ability and tendency to collide. Brines needs more sub cooling for hydrate formation. Water usually s all prod produced ced with ith nat natural ral gas , b but t also man many treatment process of the gas may cause the gas to be saturated with water as sweetening process, what is saturation means ??

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Start-up, shutdown & blow down can leads to hydrates, due to high pressure drop and so a temperature drop. Hydrate ice crystals are generally softer than normal ice and as such will not normally cause damage to tubing, flow line, or vessels. However, in some cases the crystals are harder and cause erosion or destroy sensitive parts in the production facilities. The size of the water lattice structure can vary vary, the final arrangement being dependant on the specific availability of guest molecules , where the water lattice surrounding the available guest molecules

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Other phenomena that enhance hydrate formation:Turbulence

1. High velocity:Hydrate formation is favored in regions where the fluid velocity is high. This makes choke valves particularly subject to hydrate formation. First, there is usually a significant temperature drop when natural gas is choked through a valve because of the Joule-Thomson effect. 2. Agitation and Mixing in a pipeline, process vessel, heat exchanger, and so on enhances hydrate formation.

proper sites ( locations) for hydrate accumulation include an imperfection in the pipeline, as a weld spot, a pipeline fitting (e.g., elbow, tee, valve), and so on. Silt, scale, dirt, and sand all make good nucleation sites.( a place for hydrate to accumulate ).

Water crystal formation sequence

At temperatures above 0oC, water molecules are moving freely from each other, called the Brownian movement of molecules.
Brownian motion ( (named after the Scottish botanist Robert Brown) ) is the seemingly random movement of particles suspended in a fluid (i.e. a liquid or gas)

When temperatures are approaching the normal freezing point of water, these movements are becoming slower and the water molecules tend to group themselves in a more stable structure structure. This is done via the so-called Hydrogen Bonding in which the Hydrogen atoms from the water molecules are forming a loose bond with the Oxygen atom of another water molecule.

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In this way clusters of water molecules are being formed where the hydrogen bonds move from one molecule to another. During these changes in hydrogen bonding, also l the th formation f ti of f ** unstable t bl crystal t l like lik lattices may occur. In the presence of certain Guest Molecules which have a size to nicely fit in the cavity of a lattice of water molecules, the total structure can thereby ** be stabilized such to form a hydrate crystal. As result hydrate ice crystals can be formed above the pure water freezing point.

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Two hydrate structures are often encountered in oil and gas production operations. Firstly, y, the simplest p of all crystalline y cavity y structures can be formed by a pentagonal dodecahedral of 20 water molecules linked together by hydrogen bonds
This structure has 12 regular pentagonal (five-ring) faces.

The almost spherical cavity inside this structure can accommodate small molecules such as Methane, Ethane and Hydrogen sulphide.

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As a result of minor deformations, other structures containing cavities can be formed besides the regular pentagonal-dodecahedron ones. Typical examples examples, like the fourteen and the sixteen face cavity structure are shown on the next figure to the left and right of the twelve faces structure. The larger the cavity the larger molecules that it can contain, including propane, propane iso-butane iso butane and carbon dioxide.

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is a hydrate test cell for research the effectively and efficiency of kinetic and thermodynamic gas hydrate inhibitors, as well as anti-agglomerates.

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Examination of Gas Hydrate Formation Characteristics

1. 2. 3. 4. Pressure range up to 700 bar Visual observation during test Take photos and videos Simulates pipeline conditions.

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Physical Properties of Hydrates

The estimation of the properties of hydrates is complicated by the fact that the properties depend on :(1)The type of the hydrate, I or II . (2) The guest molecule encaged in the hydrate. hydrate (3) The degree of saturation.

Table 8-1 summarizes the molar masses of a few hydrate formers. It is a little surprising that the molar masses of all six components are approximately equal (~20 g/mol).

This is because ::
The hydrate is composed mostly of water (18.015 g/mol). It is interesting that the molar masses of hydrates are a function of the temperature and the pressure, since the degree of saturation is a function of these variables.

We usually think of molar masses as being constants for a given substance.

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The densities of some pure hydrates at 0o C are given in Table 8-2. Note that the densities of the hydrates of the hydrocarbons are similar to ice. The hydrates of carbon dioxide and hydrogen sulfide are significantly more dense In fact, they are denser than water.

note 1 A =10 -10 meter

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Indicates the cavity occupied by the simple hydrate former. Indicates that the simple hydrate is only formed at very high pressure. a The structure has been confirmed by single crystal x-ray analysis (Udachin et al., 2002). b Molecular diameters obtained from von Stackelberg and Muller (1954), Davidson (1973), Davidson et al. (1984a, 1986a), or Hafemann and Miller (1969). c The cavity diameter is obtained from the cavity radius from Table 2.1 minus the diameter of water (2.8 ).

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Figure 1-3. Micro photographs of snowflakes.

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The hydrogen bonding structure of the hydrate is weak and will collapse unless it is supported by molecules occupying the cavities. This explains why propane and butane, which only l can fill the th larger l cavities iti , forms very unstable hydrates- as they do not fill enough cavities to support the weak lattice structure.
(C3 & C4 can't fill the small cavity and also they are smaller than the large cavities so they form unstable hydrate).

Molecules larger than butane are too big to form hydrates as they cannot fit into the cavities. In fact they tend to inhibit hydrate formation because the crystal tries to form around it.

The number of guest molecules that can enter the cavities is dependant upon temperature and pressure (pressure distorts the lattice, and so change the cavity shape). Not all the voids may be filled, and hence hydrate structure tend to be varied. The existence of single guest molecule stabilized hydrate crystals would not cause a problem in production facilities as their physical size is very small (+/ ( /_ 0.50 nm.) , However, like normal ice, the crystal particles tends to group themselves in typical three dimensional crystal shapes, As such their size increases to that extend that blockages of the flow system can occur.

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General conditions for hydrate formation

Hydrate formation in natural gas can, only be formed in the presence of water. Its formation temp is mainly dependant on pressure. hydrates can be formed both in the gas and liquid phase of the gas (any where to the left of the hydrate line in the picture below).

At lower pressures, the temperature has an effect on hydrate formation, but the temperature effect significantly decreases when pressure increases. increases o At 3000 psi hydrate may formed at 25 c
Hydrate formation area

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Hydrate forming conditions for pure Propane (C3H8).

The line in red indicates the hydrate curve while the blue line is the Propane vapor pressure curve. The Pink area can be formed.

indicates the total area where hydrates

Below the water freezing point of 0 oC, both ice and hydrate are present, while above this temperature only hydrate can be formed. At temperatures above 0oC, the pressures required for h d t f hydrates formation ti increases i steeply t l , above the vapor press. line, hydrate formation becomes virtually independent of pressure as appears in the chart the pressure line move nearly straight above the vapor pressure.

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Hydrate is f formed d while water not converted to ice

Note to convert from the pressure from Mpa to psi Mpa to bar

MPa = 145 psi MPa ~ 10 bar

Density of propane gas 1.83 kg/m3, Density of liquid propane 507.7 kg / m3, this leads to bbl = 507.7 / 6.28 = 80.84 kg Ton of Propane = 1000 / 80.84 = 12.4 bbls

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RVP Component MW psia

Gross heating value Btu / ft3 @ std cond. 1016 1769.6 2516 3251.9 3262 3 3262.3 4000.9 4008.9 4755.9

Critical Critical Pressure temperature o F psia 666.4 706.5 616 527.9 550 6 550.6 490.4 488.6 436.9 - 116.67 89.92 206.06 274.46 305 62 305.62 369.1 385.8 453.6

Methane Ethan Propane i-butane n-butane b t i-pentane n-pentane hexane

16 30 44 58 58 72 72 86

5000 800 188 72 51 20 15 5

( 25o C)

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When the water molecules line up, they form a hexagonal pattern ,from from elementary geometry ,it it is well known that the angle between the sides of a regular hexagon is 120 degrees, which is greater than the 105-degree angle in the water molecule ,So the volume increased.

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or at least buried the pipe line

Anti-Freezes
Do Not React with gas hydrates but dilute the liquid water phase thereby shifting the hydrate curve to lower temperatures by 0.8 degrees per mole % of particles dissolved in the Water
Glycols, due to their higher boiling points compared to water, can more easily be recovered from the gas in gas dehydration systems, and is therefore the preferred preventative method. Methanol however, due to its lower viscosity, acts faster and is mostly used for remedial applications when hydrates already have been formed.

The methanol freezing temperature is ( 144o F )

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Methanol Formula Freezing point, F Molecular Wt Boiling point @ 760 mm Hg,F Specific gravity 20C/20C Flash point, F CH3OH 143.8 32.04 148.1 0.7917 58

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Polar compounds (alcohols, glycols) fight with hydrates for hydrogen bonding By using the glycol More Hydrogen Bonding Opportunity With Water Through One More Hydroxyl Group Than Alcohols
(TEG formula HOCH2CH2OCH2CH2OCH2CH2OH)

Glycols Generally Have Higher Molecular Weights Which Inhibit Volatility ( TEG MW 150.17) Alcohols & Glycols when dissolved in aqueous solutions form hydrogen bond with the water molecules and make it difficult for the water molecules to participate in the hydrate structure. MEG is preferred over DEG for applications If the temperature is expected to be 10 C or lower due to high viscosity at low temperatures

Other chemicals which depress the hydrate

freezing point are:salts such as common kitchen salt (NaCl) or Ammonium Chloride (NH4Cl). Regardless of being cheap products, their disadvantages are the relatively large quantities required and their corrosively to carbon steel. Heating is a third option to prevent hydrate formation. This option is often applied in gas sales systems where the lines around the pressure reduction system are insulated and electrically heated.

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Thermodynamic Hydrate inhibitors

Salts
NaCl Na KCl CaCl2 Na-Formate K-Formate NaBr Na r CaBr2 ZnBr2

Alcohol/diols
Methanol M thano Ethanol Glycerol Ethylene glycol Propylene glycol Polyalkylene o ya y n glycol g yco

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How salts prevent / delay the hydrate formation

Salt Ionizes In Solution And Interacts With The Dipoles Of The Water Molecules And Causes Clustering This Clustering Also Causes A Decrease In The Solubility Of Potential Hydrate Guest Molecules In The Water These These Combine Require More Sub-cooling Sub cooling To Form Hydrates.

The last option for hydrate formation prevention is by crystal growth prevention. This can be achieved in two ways namely: y shape p modification in which the The first is the Crystal crystal is reshaped into a more shapeless appearance. ( loose fitting , fluid appearance) The second type of growth preventers are the so-called crystal-crystal bond fighting , damaging products. As the word says it does interfere with the growth of crystals by positioning around the single crystal lattice, resulting in only very fine (and harmless) hydrate particles to be formed, An example of the chemical is the Shell developed product Armoblen 802.

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Delay the onset of formation Slow the rate of formation Prevent the agglomeration of hydrates Reduce the amount of hydrate that form

Kinetic Inhibitors

While kinetic inhibitors work by slowing down the kinetics of the nucleation, anti-agglomerants do not stop the nucleation, they rather stop the agglomeration (sticking together) of gas hydrate crystals.

Kinetic Inhibition Hydrate Hydrate

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Low dosage hydrate inhibitors (LDHIs) have been developed over the last 15 yr as a new gas hydrate control technology for the oil industry, which can be more cost-effective than traditional practices such as the use of thermodynamic inhibitors e.g. methanol and glycols. Two classes of LDHI called kinetic inhibitors (KHIs) and anti-agglomerants (AAs) are already being successfully used in the field This paper discusses new types of AAs, field. AAs which are based on surfactants with a high degree of propoxylation. High pressure tests in sapphire cells show that polyamine polypropoxylates and other branched polypropoxylates are able to disperse gas hydrates in a hydrocarbon fluid as long as there is good agitation in the fluids. Formation of an emulsion is not required for this AA effect. Linear, unbranched or low molecular weight polypropoxylates did not perform well under the same conditions, as well as many other surfactant classes including anionic and various polyethoxylated surfactants. Some polyamine polypropoxylates gave weak kinetic hydrate y inhibition effects. Addition of kinetic hydrate y inhibitors such as polyvinylcaprolactam reduces the performance of polyamine polypropoxylates as AAs.

Part of the mechanism for the AA effect of the surfactant polypropoxylates is proposed to rely on their low solubility in both the aqueous and hydrocarbon phases. The surfactant polypropoxylates form a separate layer between the two phases, which coat the dispersed water droplets as they are converted to gas hydrates, keeping them from agglomerating. After shutting in the cell by stopping the stirring for some hours the hydrates can be redispersed again have a high interfacial concentration, were tested as AAs. Some other demulsifiers showed the gg p properties p as the p polypropoxylates. yp p y One demulsifier, same anti-agglomeration Dowfax DM655, an alkylphenol formaldehyde resin alkoxylates, gave good AA performance at up to 16.5 C subcooling when dosed at 10,000 ppm in synthetic sea water. However, the performance decreased at low salinity ( 0.5 wt.%) and at water cuts of 35% or more.

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Interesting Properties of hydrate

Large amounts of methane hydrates exist in nature Capture large amounts of gas (up to 15 mole%) so it may be used to remove light components from oil. oil Form at temperatures well above 0 C Generally lighter than water , only pure Co2

and H2S hydrate is more dense than water.

Need N d relatively l ti l large l latent l t t heat h tt to d decompose. Result from physical combination of water and gas, both water & gas prosperities not changed when combined Reject salts and other impurities.(clean energy level )

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Hydrates have potential as a future energy resource each cubic feet of hydrate contain 180 ft3 of gases. Hydrates may be an alternative to pipeline transmission as a way to move natural gas from deep water to the terminals of existing offshore pipelines

A source of clean burning fuel?

For a given T Hydrate formation P increases as HC size decreases

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As the molecular weight of the gas increase the hydrate may be formed at higher temperature assume the pressure is constant

They are crystalline water based solids physically similar to ice, in which small non polar molecules (typically gases) are trapped inside "cages" of hydrogen bonded water molecules. Without With t the th support t of f the th trapped t d molecules, l l th the lattice structure of hydrate clathrates would collapse into conventional ice crystal structure or liquid water
Most low molecular weight gases (including O2, H2, N2, CO2, CH4, H2S, Ar, Kr, and Xe), as well as some higher h d hydrocarbons b and d freons f will ill form f hydrates h d t at t suitable it bl temperatures and pressures.

gas hydrates are not chemical compounds as the sequestered molecules are never bonded to the lattice.

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Around 6.4 trillion (i.e. 6.4x1012) tonnes of methane is trapped in deposits of methane clathrate on the deep ocean floor. Such deposits can be found on the Norwegian continental shelf These natural gas hydrates are seen as a potentially vast energy resource, but an economic extraction method has so far proven elusive. Hydrates have a strong tendency to agglomerate and to adhere to the pipe wall and thereby plug the pipeline. Once formed, they can be decomposed by increasing the temperature and/or decreasing the pressure. Even at these conditions, the clathrate dissociation is a slow process. The experiments indicates that methane hydrate will not be formed at temperature more than 30o C

Hydrate inhibitor Two options generally exist: Thermodynamic inhibitors Kinetic inhibitors/anti-agglomerants The most common thermodynamic inhibitors are, methanol, monoethylene glycol (MEG) and diethylene glycol (DEG) commonly referred to as glycol. All may be recovered and re-circulated, but the economics of methanol recovery will not be favorable in most cases. MEG is preferred over DEG for applications where the temperature is expected to be 10 C C or lower due to high viscosity at low temperatures. Tri-ethylene glycol (TEG) has too low vapor pressure to be suited as an inhibitor injected into a gas stream. More methanol is lost in the gas phase when compared to MEG or DEG.

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The use of Kinetic inhibitors/anti-agglomerants in actual field operations is a new and evolving technology, It requires extensive tests and optimization to the system. While kinetic inhibitors work by slowing down the kinetics of the nucleation, anti-agglomerants do not stop the nucleation, they rather stop the agglomeration (sticking together) of gas hydrate crystals. These two kinds of inhibitors are also known as Low-DosageHydrate-Inhibitors because they require much smaller concentrations than the conventional thermodynamic inhibitors. Kinetic inhibitors (which do not require water and hydrocarbon mixture to be effective) are usually polymers or copolymers and anti-agglomerants (requires water and hydrocarbon mixture) are polymers or zwitterionic (usually ammonium and COOH) surfactants being both attracted to hydrates and hydrocarbons.

No Hydrates Forming 45o line

Hydrates Forming

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Initial P =3000 psia Initial T = 170oF

Safe (no hydrate) final P = 350 psia and final T = 50oF

n-Butane
In the study of hydrates, n-butane is an interesting anomaly By itself, n-butane does not form a hydrate; however, its size is such that it can fit into the large g cages g of the Type yp II hydrate lattice. Thus, in the presence of another hydrate former, n-butane can enter the cages, Where n-butan usually linked with propane molecules Based on the observed behavior of n n-butane butane, is a transition component. Molecules smaller than n-butane are hydrate formers, whereas molecules larger than n-butane do not form Type I or Type II hydrates.

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Liquid Hydrate Formers

It is a commonly held belief that hydrates do not form in the presence of a Non-aqueous liquid phase (i.e., that hydrate will not form in the presence of condensate or oil). This is not true. Many experimental investigations demonstrate that liquid hydrocarbons can form hydrates. As discussed all that is required is the presence of a hydrate former, enough water present to form a hydrate, and the right combination of press. and Temp. No mention was made of the phase of the former. There is an unfortunate ( bad )habit among engineers of referring to these compounds as gas hydrates. This leaves the impression that they form only with gases.

Mixtures Although the behavior of pure formers is interesting, in industrial practice we usually deal with mixtures. What type of hydrate is formed in a mixture? What is the effect when a non-former is in the mixture? We have already encountered one interesting situation that arises with the behavior of nbutane. The hydrate formation conditions in mixtures of ethane, a Type I former, and propane, a Type II former. They developed a map (reproduced here as next Figure), showing which regions each type of hydrate would form. As an approximation of their results, if the mixture is greater than 80% ethane, then the hydrate is Type I; otherwise it is Type II. When the hydrate is Type I, the propane does not enter the crystal lattice; only the ethane does. On the other hand, mixtures of methane, a Type I former, and propane, a Type II former, almost always form a Type II.

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Volume of Gas in Hydrate

The purpose of this section is to demonstrate the volume of gas encaged in a hydrate. Therefore, we examine only the methane hydrate. The properties of the methane hydrate at 0oC: are the density is 913 kg/m3, the molar mass (molecular weight) is 17.74 kg / kmol, and methane concentration is 14.1 mole percent; this means there are 141 molecules of methane per 859 molecules of water in the methane hydrate. This i Thi information f ti can b be used dt to d determine t i th the volume l of f gas in the methane hydrate. From the density, I m3 of hydrate has a mass of 913 kg. Converting this to moles 913/17.74 = 51.45 kmol of hydrate, of which 7.257 kmol are methane as follow ( 51.45 * 14.1% = 7.257 k mole).

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The ideal gas law can be used to calculate the volume of gas when expanded to standard conditions (15C and 1 atm or 101.325kPa).

Therefore Im3 of hydrate contains about 170 Sm3 of methane gas. American Engineering Units, this converts to l ft3 of hydrate contains 170 SCF of gas To look at this another way, to store 25,000 Sm3 (0.88 mmscf) of methane requires about 150 m3 (5,300 ft3) of hydrates So these days it is under studies to use the hydrate for gas transportation

From this table it can be seen that water has a fairly large enthalpy of vaporization, even in comparison to other polar substances. It takes significantly more energy to boil 1 kg of water than it does to boil any of the hydrocarbons listed in the table about 5 times

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GAS HYDRATES AND HYDRATE CONTROL

Gas hydrates are rather complicated compounds of hydrocarbons, water and other substances such as hydrogen sulfide or carbon dioxide which form granular solids, very similar to ice, under certain conditions of f temperature and pressure. There is some doubt whether hydrates can form if the water is mixed with liquid hydrocarbons, however, it should be realized that :If Water Is Present in the liquids, it very probably will also be present in the gaseous phase through the equilibrium conditions which will be reached in any stage of pipeline system.

Individual components alone, or mixtures of the lighter components of natural gas, will form hydrates over a wide range of temperatures, depending upon the system pressure. These temperatures are considerably above the normal freezing point of water and may go higher. The effect of heavier components is to increase the temperature at which hydrates will form for any given pressure, Normal-ly, hydrates of components heavier than butane are not considered to occur. In all cases, free water in the system is required to form hydrates. The presence of hydrogen sulphide greatly increases the temperature at which hydrates will form. Sour gases may have hydrate temperatures into the 90F temperature range under high pressures.

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End of hydrate

WATER DEW POINT

If it is said that the gas is water saturated at specific pressure and temperature, that means it hold the max carrying capacity and so any additional water added at the saturation point will not vaporize , but will fall out as f free liquid. li id Also at this point , if the pressure is increased and / or the temperature decreased the capacity of the gas to hold water will decrease and some water vapor will condense (drop out). This point is known as the water dew point which may be defined as the temperature at which the natural gas is saturated with water vapor at a given pressure. At the dew point, natural gas is in equilibrium with liquid water.

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DEW POINT DEPRESSION

The difference between the dew point temperature of water in saturated gas stream and the stream after it has been dehydrated is known as the dew point depression . To illustrate the concept of dew point depression, suppose that the natural gas at 500 psia, and 60 F , at the saturation point contains 30 Ibm of water per million cubic feet. The dew point of this gas is 60F. Suppose this natural gas is going to be transported in pipeline at 20 20 F. F The saturation point will then be 7 Ibm of water / scf The original 30 Ibm of water, if left in the gas, will exist in the from of 7 Ibm of water vapor and 23 Ibm of free water per mmscf, if the pressure remains the same.

This free water is a potential source of hydrates to form and plug the line . Suppose the natural gas is processed in a dehydration unit point is depressed p 50 F . and the dew p This means that no free water will exist in the gas until the temperature goes to 10 F or lower. Gas at 500 psia and 10 F contains about 5 Ibm of water vapor / mmscf. f The dehydration unit must remove 25 Ibm of water from each 1 million scf of gas in order to achieve the 50 F dew point depression.

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Gas dehydration techniques

Techniques for dehydrating natural gas include: Absorption using liquid desiccants. Adsorption using solid desiccants. Mechanical Refrigeration. Expansion Refrigeration.

Water can removed from gas by:Compression. C li Cooling.

But removing the water with these two methods will leave the gas stream saturated with water vapor so extra drop in temp. or increase in pressure will cause water condensation.

Absorption Process
The more common liquids in use for gas dehydrating are Monoethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Monoethylene and Diethylene glycol usually used in glycol injection system. Most glycol dehydrators use triethylene glycol, which can be heated to about 400 F. Tetraethylene glycol is more expensive, but it can handle hotter gas near 50o C without high losses and it can be heated up to 460F.

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Choice of Glycol

GLYCOL:
CHEMICAL NAME EHYLENE GLYCOL (MEG). DIETHYLENE GLYCOL (DEG). TRIETHYLENE GLYCOL (TEG). ( ) TETRAEHYLENE GLYCOL(TREG).

B.P

Thermal decomposition >165 C > 165 C > 206 C > 250 C

197.6 C 246.0 C 278.0 C 300.0 C

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TEG has gained almost universal acceptance as the most cost effective choice because:
TEG is more easily y regenerated. g TEG has a higher decomposition temperature of 460 F Vaporization losses are lower than EG or DEG TEG is not too viscous above 70 F. TEG dew point depressions range from 40 150o F As the lean Glycol temperature decreased its absorption capacity increased & also its tendency to flash decreased normal operating temp. of TEG is between 25 & 48o C

TEG
Triethylene glycol (TEG) is a member of a homologous series of di-hydroxy alcohols. It is a colorless, odorless ,stable liquid with low viscosities i iti and d high hi h b boiling ili points. i t

Properties
Molecular formula Molar mass li id D liquid Density it Boiling point C6H14O4 150.17 g mol1 1 119 kg/lit 1.119 k /lit o 285 C -58o C

pour point

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Absorption process

WATER NATURAL GAS GLYCOL

NATURAL GAS GLYCOL

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Dehydration basic process

difference in boiling point? DRY GAS DRY GLYCOL Water boils at 212o F. TEG boils at 546o F. F WATER VAPOUR

DEHYDRATION REGENERATION
WET GAS
WET GLYCOL

HEAT

Basic components of a glycol unit

Contactor tower . Glycol pumps. Reflux condenser ( still column ). Glycol / glycol low temp. Exchanger. Flash drum. Sock filter. Charcoal filter. filter Glycol / glycol high temp. Exchanger Re-boiler & surge vessel. Gas / lean glycol exchanger.

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Flow Diagram for Glycol System

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Contactor towers: As it is appears from the name lean glycol contact the wet gas at the contactors towers.
Towers usually contains internal or external scrubber and mist extractor at the top. p Towers may be packed tower or trays , the trayed towers have many models of trays bubble cap , valve trays or molecular sieve the most common used is the bubble cap trays. Dry gas lean glycol heat exchanger

Bubble cap cap.

It is the most widely used because it is not weep at low gas rate, and dont drain the tray even during the unit shut down.

See the video describing different trays operations

Inlet scrubber is an essential part of the glycol: Free water will increase glycol flow rate, increase re-boiler heat duty, overload the unit Heavy hydrocarbons tends to form emulsion with glycol, it can plug the absorber trays, it may Coked on the heat transfer surfaces which decrease the heat transfer efficiency and cause hot spots With the fire tube At the well pore down hole additives, additives corrosion inhibitor ,acidizing, fluids could cause foaming. Solids may cause corrosion, plug the pump, trays, packing, and enhance the foaming formation.

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Gas / glycol heat exchanger, or glycol air cooler up

stream the contactor must working properly where if the glycol entering the contact with high temp., this will leads to High water vapor pressure which decrease the drying efficiency also High lean glycol temperature will leads to switching the top tray to act as heat exchanger and Cause high glycol loss. loss

Cooling of the glycol stream before entering the contactor will Increase its absorption capacity, where its capacity decrease as its temperature close to 120 o F

DRY GAS
MIST EXTRACTOR AT THE TOP
DRY GLYCOL

WEAR

DOWN COMER

WET GAS

WET GLYCOL

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Glycol mist extractor

DRY GAS

MIST EXTRACTOR

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Flash separator: Usually glycol absorb 1 scf gas / gal circulation rate at 1000 psig &100o F Glycol must be heated before enter the flash drum to reduce the glycol viscosity and improve the separation. Flash drum pressure should be adjusted to minimum 3 bars to achieve the following:1-Insure sufficient pressure for glycol circulation. 2-Prevent BTEX evaporation from glycol.
BTEX is an acronym for benzene, toluene, ethylbenzene, and xylene.

3-It is a suitable gas pressure if the gas used as a fuel.

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Flash tank
GAS VAPOUR Types of flash tanks. 3phase vessel. What is flashing? What is the pressure change? What is the effect of temperature temperature. Inter phase level control. Process problems.

GLYCOL FROM HEAT EXCHANGER

HYDROCARBON GLYCOL

Filters set
Purposes:Prevent pump wear, plugging of heat exchangers, foaming, g, fouling g of contactor trays, y , cell corrosion and hot spots on the fire tubes. Operating Parameters: Keep solids below 100 ppm Sock filter designed to remove 5 micron and larger particles Sock filters are designed for an initial pressure loss of 3 to 6 psi and change out at 15 to 25 psi. Activated charcoal filters used to remove condensate, surfactants and treating chemicals.

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Glycol Pump
Purpose:Returns Low pressure lean glycol to high pressure contact tower. tower

Operating Parameters: Contains the only moving parts in unit A spare pump should be provided since dehydration stops when glycol circulation stops. stops Typically a positive displacement (PD) pump , can be electric motor driven , or HP liquid driven pump (KIMARY PUMP ). Max recommended operating temp 250o F

Surge Tank
Purpose:It is the lean glycol reservoir its capacity must be design to handle a complete drain-down of TEG from th absorber-tower the b b t trays, t point i tf for quality lit checks h k as measuring of PH , glycol purity . Operating Parameters: Should be designed to operate at half full under normal operation. operation A gas blanket is recommended to prevent oxygen contamination (degradation ) Glycol will
oxidize in presence of oxygen to give corrosive organic acids, may be prevented by adding of oxidation inhibitors (such as oxygen scavenger) like hydrazine.

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degradation
1. A TEG tested by expose for air for 1 week 2. In less than a week in dry air at 70oC ONLY 30 % of the TEG remains 3. The degradation products found to some degree toxic 4. It found that TEG is stable in the nitrogen environment

Re-boiler
Purpose:Provides heat necessary to boil the water out of the rich or wet glycol.

Operating Parameters: Direct fired heaters often used onshore. Indirect heating often used offshore. TEG does not undergo thermal decomposition if temperature is kept below 400 F. U-shaped U shaped fire tube should be sized for 7000 Btu/hr Btu/hr-ft2. ft2. Water comes off as steam.

To check the hot spots of the fire tube, it must be checked during the night, and then you must shut off The Flame, so the hot spot will stay bright ,Hot spot may be due to deposits accumulation around the fire tube as heavy hydrocarbon, salt, solids coked off

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Glycol re-boiler
Reflux condenser by pass
REFLUX COIL Reflux condenser Water Vapour And Stripping gas

Still column packing INLET

GLYCOL

REGENERATED GLYCOL FUEL GAS

RE-BOILER Stripping Gas

GLYCOL RE-BOILER.

STEAM STILL COLUMN

REFLUX COIL Glycol inlet REGENERATED GLYCOL FUEL GAS FIRE TUBE RE-BOILER

Good flam specifications: - Laminar, long, rolling, with yellow tip

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Table4.2FlameColorsandTemperature(F)Ranges
FlameColor Lightred Darkred Darkcherry Mediumcherry Light Lightcherry Brightred Temperature FlameColor Temperature
900 1000 10001100 11001200 12001300 13001400 14001500

Salmon Orange Lemon yellow White Bright white

16001700 17001800 18001900 19002100 21502250 2500andover

Note: Overall the lighter the color of the flame, the higher the temperature. The significance of the color of smoke and flames in a fire should be considered with the time at which they were observed.

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Fire Suppression
Combustion ends when one of the four faces of the fire tetrahedron (fuel , oxygen, heat, chemical chain reaction) is removed. 1. Fuel Combustion ends either when the fuel is consumed or when the source of fuel is removed . 2. Oxygen Combustion ends when the oxygen level drops below that needed to maintain it (normally 15%). The foams used in certain suppression operations extinguish (smother) the fire by cutting off the oxygen supply. Remember that oxygen is not a fuel, and neither burns nor explodes. It merely supports oxidative combustion.

Fire Suppression
3. Heat Water is the most commonly used extinguishing agent. It is used because of its great heat-absorbing ability. This cools the surface temperature of the burning fuel to a point below its ignition temperature. 4. Chemical chain reaction When the oxidation reaction is chemically inhibited, the fire is extinguished. Certain extinguishing agents (Halon, carbon tetrachloride, potassium bicarbonate bicarbonate, etc etc.) ) combine with the radicals freed during the process of combustion to form new molecules. This chemical action prevents transfer of heat energy, and the fire is extinguished.

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Flow Diagram for TEG Dehydration

Design Factor Affecting The Glycol Performance

Inlet gas temperature must be between 80o F to110o F & not excess 120o F, reduce the gas temperature as possible to recover max water & heavy components Lean glycol temperature exceed gas temperature with about ( 7 10o F ). Contactor pressure has a little effect on the performance as the pressure remains less than 3000 psig. (preferred to operate at pressure between 500 to 1500 psig). psig) Contact time which is determined by the No. of trays, or height of packing. Glycol concentration preferred to be max as possible.

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Design Factor Affecting The Glycol Performance

Glycol concentration has an effect more than the glycol circulation rate (Pump & re-boiler load). Glycol re-boiler temp. Between 370o F & 390o F to minimize glycol degradation. Glycol re-boiler pressure must be atmosphere or less ( vacuum ) if required. Glycol circulation rate @ fixed no of trays & glycol concentration as the circulation rate increased the dew point depression also increased ( 2 4 gal glycol / lb water removed ). Glycol Ph must be kept between 6.8 up to 7.5 where as the PH of the glycol decreased the absorption efficiency of the glycol decreased & as the PH increase the glycol tendency to foaming increased.

Glycol unit design considerations details:Most TEG units are designed to operate between 80o F to 110o F.

1- Inlet gas temp.

Must be as minimum as possible where at high pressures (above 1000 psi) only 20o F could duplicate the water content , using the water content chart. Max temp < 120 o F (48 o C) Min. temp. Must be > 70o F Where from 60o F to 70o F glycol can form a stable emulsion with liquid hydrocarbon & cause foaming in the contactor and also below 60o F glycol become very viscous & could not be pumped.

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2-Contactor pressure: Contactor pressure has a little affect on absorption process as long as the pressure is below 3000 psig Usually typical dehydration pressures range is from f 500 to 1200 psig.

3-Number of contactor tray

As the number of trays increased the dew point depression increase and also the effect of the No. of trays is greater than the glycol circulation rate. Usually from 6 to 8 trays are common designed for 7 lb /mmscf water content (may be 10 -12 trays).

4- Lean glycol temp: Must be hotter than the gas inlet temperature with about 10o F to 15o F.

5 Glycol Concentration:5-Glycol Concentration:

The glycol concentration has a great effect in the dew point depression, as the concentration increased the water content decreased usually glycol & gas may reaches to equilibrium temp. Inside the contactor this based on:Contact temperature. Glycol concentration.

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6-Glycol re-boiler temperature:Typical re-boiler temp. between 370o F to 390o F if still extra glycol concentration required and could not achieved by all the operational control factors the stripping gas must be used. It is not preferred exceed the re-boiler temperature over 400 o F avoid the glycol degradation.

7-Reboiler pressure:As the pressure decreased below atmosphere the higher glycol concentration may be achieved so in some cases (rarely) reboiler operated at vacuum , the main reason of the rarely usage of the vacuum pump is that any minor air leak will cause glycol degradation (oxidation of glycol)

8-Stripping gas:Improve the glycol concentration instead of increasing the reboiler temperature or glycol flow rate.

9-Glycol circulation rate:Usually 2-4 gal. glycol / lb water removed excessive glycol flow rate may over load the re-boiler, so the high glycol rate may decrease the re-boiler temp , which will leads to a drop in the glycol concentration, concentration and consequently decrease the amount of water removed , and increase the dry gas dew point Only when the re-boiler temperature is constant the increase in glycol circulation rate will decrease the dew point.

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10- Still column temp:Must be adjusted to max 212O F where at 250O F or above some glycol will be carried out with the water vapor , and so glycol loss will occurred, Heat transfer factor U can be near to 100 BTU/hr.ft BTU/hr ft2.oF for reflux condenser coil. Also the Heat transfer factor U can be near to 10 - 12 BTU/hr.ft2.oF for lean glycol / rich glycol exchanger, and 45 BTU/hr.ft2.oF for dry gas / lean glycol.

Foaming may be mechanical or chemical foam:Mechanical foam, caused by high gas flow rate in the absorber where chemical foam, may caused by any contaminates such as salt, solid corrosion inhibitor and / or condensate.

Inlet scrubber is an essential part of the glycol: Free water will increase glycol flow rate, increase reboiler heat duty, overload the unit Heavy hydrocarbons tends to form emulsion with glycol, it can plug the absorber trays, it may Coked on the heat transfer surfaces which decrease the heat transfer efficiency and cause hot spots on the fire tube. At the well head down hole additives, corrosion inhibitor ,acidizing, fluids could cause foaming. Solids may cause corrosion, plug the pump, trays, packing, and enhance the foaming formation.

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Contact temperature.
usually the actual dry gas dew point be 5 to 10 o F higher than the equilibrium Common rule dew point depression is 60o F for the first four trays plus 7o F for each additional tray For 10 trays = 60 + (7x 6) =102o F dew point depression If the inlet dew point is 110o F so the outlet dew point is 8o F The dew point depression will depend on the number of achieved equilibrium stages with the glycol circulation rate and concentration; it usually assumed that each tray may achieve 25 % from each equilibrium stage. ( 25% of glycol mixes with gas ) each 4 trays gives only one equilibrium stage

Design considerations Glycol flash drum:1-Vertical Height (ft) = 3.4 +0.4 GPM ( gallon glycol per minute) Min height = 4 ft Max height = 10 ft Min diameter = 1.5 ft

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Design considerations Glycol flash drum:2H i 2-Horizontal t l separator t Length to diameter ratio = 3 Min length = 3 ft Min diameter = 2 ft f

Still column:Diameter (inch) = 9 x (glycol circulation rate gpm) 0.5 And typical packing height at least 4 ft may be increased to 8 g duty y units. ft for high Re-boiler :Re-boiler duty can be estimated as: Q = 900 + 966 m Q : BTU/ lb water removed m :- gal l glycol l l for f each h lb water t removed. d Re-boiler (length / diameter) ratio = 5 Min diameter = 1.5 ft Min length = 3.5 ft

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PH control, must be add slowly and as 1 lb Amine for each 400 gallon glycol The Injection dose must be calibrated at each case where the source of the PH drop may be different from place to place and the corrective action of the Amine will different based on the PH drop root causes if it is CO2 , H2S , glycol oxidization , etc .

Recommended glycol unit operating temperature

Inlet gas 80 100o F Glycol inlet contactor 10 15 o F warmer Glycol to flash drum 100 -150 (preferred to be 150o F) Glycol into filters 100 150 (preferred to be 150o F) Glycol to still column 300 -350o F Top of the still column max 212o F Re-boiler 380 400 ( preferred to be 380o F) Glycol to pumps < 250o F (preferred to be 180o F)

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Question: Find the moisture content of a gas at 20,000 kPa and 70 deg. C. if it is made up of 35 mole % H2S and 10 mole % CO2. 1) Find moisture content of sweet gas in Fig. 15-14 = _____ mg/m3 (note: psia conversion from kPa) (Psia = 0.145 kPa) 2) Find moisture content of CO2 in Fig. 15-21 3) Find moisture content of H2S in Fig. 15-22 = _____ mg/m3 = _____ mg/m3

4) Find total moisture content in gas: Total moisture content = sum of ( individual moisture content times mole frac). Therefore moisture content = 0.55 ( ______) + 0.10 ( ______ ) + 0.35 ( ______ ) = ________ mg/m3 water at standard conditions

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GLYCOL INJECTION WET GAS HEAT EXCHANGER

FLUSHING VALVE

DRY GAS & WET GLYCOL

DELTA PRESSURE GAUGE

GLYCOL

PH
Controlling pH is very important in most of the processes the following is offered to assist in understanding electrolyte solutions and PH. An electrolyte is a substance or material that will provide ionic conductivity when dissolved in water. Both bases and acids, if they ionize in water, can be electrolytes. In water, acids ionize or split, into H+ and the cation The H+ combines with a water molecule to form H3O+ which is usually written as H+ and is referred to as a hydrogen ion, or proton.

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Water soluble bases, on the other hand, ionize in water to produce hydroxyl or OH ions and an anion. Pure water ionizes such that the concentration of H + (and OH ) in the solution is 10 7 gram ions / liter. The method used for measuring hydrogen and hydroxyl ion concentrations uses pH (from the French pouvoir hydrogene), where the pH of a solution is the g (base ( 10) ) of the reciprocal p of the hydrogen y g logarithm ion concentration (gram mole / liter).

For pure water, then, the pH would be: PH = log (1/ [H+]) = 7 A strong acid (or strong base) is one which ionizes completely in water solution. Typical are HCl or NaOH. At an acid concentration of 0.1 mole / liter, the pH of a strong acid will be 1 as follows PH = log (1/ [H+]) = log ( 1 / 0.1 ) = log ( 1 / 10 -1) # PH = log10 10
1

= 1 ( very strong acid )

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pH Control

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pH AcidSide (ExcessH+)
1 2 3 4 5 6

Concentration, mole/liter H+ OH1.0*10-1 1.0*10-2 1.0*10-3 1.0*10-4 1.0*10-5 1.0*10-6 1.0*10-7 1.0*10-8 1.0*10-9 1.0*10-10 1.0*10-11 1.0*10-12 1.0*10-13 1.0*10-13 1.0*10-12 1.0*10-11 1.0*10-10 1.0*10-9 1.0*10-8 1.0*10-7 1.0*10-6 1.0*10-5 1.0*10-4 1.0*10-3 1.0*10-2 1.0*10-1

NeutralSolution

7 8 9 10 11

BasicSide

12 13

Examinationofthetableleadsonetotheconclusionthatweak electrolytes(thesetowhichtheconceptofpHcanbeusefullyapplied) rangeoverstrongacid(base)concentrationsupto0.1grammole/liter

First, consider the exposure of iron to aerated water at room temperature (aerated water will contain dissolved oxygen). The corrosion rate for iron as a function of pH is illustrated in Figure 7. In the range of pH 4 to pH 10 the corrosion rate of iron is relatively independent of the pH of the solution. In this pH range, the corrosion rate is governed largely by The rate at which oxygen reacts with absorbed atomic hydrogen thereby depolarizing the surface and allowing the reduction reaction to continue. For pH values below 4.0, ferrous oxide (FeO) is soluble., Thus, the oxide dissolves as it is formed rather than depositing on the metal surface to form a film.

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In the absence of the protective oxide film, the metal surface is in direct contact with the acid solution, and the corrosion reaction proceeds at a greater rate than it does at higher pH values. It is also observed that hydrogen is produced in acid solutions below a pH of 4, indicating that the corrosion rate no longer depends entirely on depolarization by oxygen, but on a combination of the two factors (hydrogen evolution and depolarization). For pH values above about pH 10, the corrosion rate is observed to fall as pH is increased. This is believed to be due to an increase in the rate of the reaction of oxygen with Fe(OH) (hydrated Fe O) in the oxide layer to form the more protective Fe O

Effect of Ph on the corrosion of iron exposed to aerated water at room temperature

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A plot of the relative corrosion rate for Iron at various pH values in 59o F

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