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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
Heating value in MJ
kg
55.5 48.5 nearly the same
/ m3
37.69 205.4 about 6 times
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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(147.5 x 18)
/ 379.4 = 7 Lb / mmscf
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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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.
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Just Move the arrows up and down also right and left to check the right P & T combination
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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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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 ).
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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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.
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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.
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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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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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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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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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Note to convert from the pressure from Mpa to psi Mpa to 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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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
16 30 44 58 58 72 72 86
( 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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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.
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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
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Alcohol/diols
Methanol M thano Ethanol Glycerol Ethylene glycol Propylene glycol Polyalkylene o ya y n glycol g yco
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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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