Surface Production Operations ENPE 505 Lecture Notes #6 Gas Water System and Dehydration Processing

Hassan Hassanzadeh EN B204M hhassanz@ucalgary.ca

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Gas Water System and Dehydration Processing

Learning Objectives predict water content of natural gas, hydrate formation conditions, inhibitor requirement for hydrate prevention, and perform preliminary design and sizing calculations of absorption and adsorption dehydration units.

Gas water system and dehydration processing

Water vapours is the most common undesirable impurity found in natural gas. The water content of natural gas is usually in the range of 400-500 lbm/MMSCF of gas Reasons to remove water from natural gas: 1. Hydrate formation 2. Presence of liquid water and sour gases promote corrosion 3. Slugging and decreasing flow line efficiency 4. Reducing heating value of the gas Pipeline specification for natural gas restricts the water content to a value not grater than 6-8 lbm/MMSDF lbm/MMSDF Since most gas sweetening processes involve the use of aqueous solution, dehydration is often done after desulfurization. Partial dehydration, or hydrate inhibition are commonly done at wellsites.

Water content of natural gas

A reliable estimate of natural gas water content is necessary to design and operate dehydration process. Water content of natural gas depends on temperature, pressure, composition, and water salinity. 1. 2. 3. 4. Water content of natural gas increases with increasing temperature Water content of natural gas decreases with increasing pressure Salt content of the water decreases the water content of natural gas Higher gravity gases have lower water content

Dew point of natural gas: is defined as the temperature at which the gas is saturated with water at a given pressure. Dew point depression: is the difference between the dew point before and after dehydration

Water content of natural gas

Reservoir gas (5000 psig/250oF) ~ 500 lbm/MMSCF Pipeline ~ 6-8 lbm/MMSCF
Separation facility 100 oF and 500 psia Water content = 100 lb/MMSCF

Separation facility 100 oF and 500 psia Water content = 100 lb/MMSCF

Dehydration facility

Free water= 70lb/MMSCF

Pipeline conditions 500 psia 60 oF Water content =30 lb/MMSCF Free water =100-30 =70 lb/MMSCF

Pipeline conditions 500 psia 60 oF Water content =30 lb/MMSCF Free water =0 lb/MMSCF

In this example, the dehydration facility results in a dew point depression of 100-60=40, In practice, although a dew point depression of 40 is just sufficient, a 50 degree F depression my be desirable for operational safety.

Methods for water content calculation

1. Partial pressure approach, valid up to 60 psia. 2. Empirical plots 3. Equations of state Partial pressure approach assumes ideal gas behaviour. Where

Pw=Pyw

and

Pw=Pvxw

P is absolute total pressure yw is mole fraction of water in gas phase Pv is vapor pressure of water xw is mole fraction of water in aqueous phase Assuming xw1, yw=Pv/P

Empirical plots: McCarthy et al. (1950), McKetta and Wehe (1958), GPSA plot, Campbell (1984), Robinson et al., and others

Water content of natural gases (Guo and Ghalambor, 2005).

Water content of sweet natural gases, Campbell (1984)

Water content of H2S & CO2 in saturated natural gas, After Campbell (1984) CO2
H2S

Water content of natural gases, McKetta and Wehe (1958)

Example: Find the water content of 0.75 gravity gas at 1500 psia and 120 oF. Solution: From the McKetta and Wehe chart: chart W=78 lb/MMSCF gas Correcting for the gas gravity, W=0.99(78)=77.2 lb/MMSCF gas Using Campbells correlation correlation: W=77 lb/MMSCF gas

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Example
Find the water content of a gas at 1000 psia and 100 oF. Using Campbells correlation C1 = 80.0 % The gas composition is as follows: C2 = 5.0 % C3 = 1.5 % n-C4 = 0.5 % CO2 = 2.5 % N2 = 2.0 % H2S = 8.5 % Solution: yHC= 0.8 + 0.05 + 0.015 + 0.005 + 0.02 = 0.89 yCO2= 0.025 yH2S= 0.085 From Campbells chart WHC=59 lb/MMSCF gas From Campbells chart WCO2=67 lb/MMSCF gas From Campbells chart WH2S=150 lb/MMSCF gas W=(0.89)(59) + (0.025)(67) + (0.085)(150) =66.9 lb/MMSCF gas

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Gas hydrates
Water molecules form cage-like structures in which gas molecules are enclosed as guest molecules. Such structures are called clathrate hydrates . Natural gas hydrates are formed when natural gas components such as C1, C2, C3, i-C4, H2S, CO2, and N2 enter the water lattice and occupy the vacant lattice position causing to water to solidify at temperature considerably higher than the freezing point of water. Different type of crystalline hydrate have been proposed for gas hydrates.

Low temperature, high pressure, natural gas at or below dew point in the presence of free water promote hydrate formation. No hydrate formation is possible if free water is not present
Secondary factors are : High velocities, agitation, pressure pulsation, presence of small seed crystal of hydrate, presence of CO2 and H2S.
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http://peer.tamu.edu/curriculum_modules/ecosystems/module_3/whatweknow2.htm

Prediction of hydrate formation

Approximate method for sweet gases
1. Hydrate formation due to decrease in temperature (or increase in pressure) with no sudden expansion (or compression) such as flow in well tubing and surface lines. Example: A 0.7 gravity gas is at 500 psia and 100 oF. To what value can the temperature be reduced without hydrate formation? ~ 55 oF
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Approximate method for sweet gases

2. Hydrate formation due to sudden expansion, such as orifices, chokes, backpressure regulators.

SG= 0.6

SG=0.8
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Approximate method for sweet gases

2. Hydrate formation due to sudden expansion, such as orifices, chokes, backpressure regulators.

SG=0.9

SG=1

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Approximate method for sweet gases

2. Hydrate formation due to sudden expansion, such as orifices, chokes, backpressure regulators. Example: How far can be pressure lowered without expecting hydrate formation for 0.7 gravity gas at (a) 1500 psia and 100 oF. (b) 1000 psia and 100 oF. a) Final pressure = 800 psia b) The 100 oF does not intersect p=1000 psia, therefore, the gas at this condition can be expanded to any pressure without hydrate formation

SG=0.7

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Preventing hydrate formation

In practice , hydrates are problem only when allowed to accumulate and grow to a size that restricts or stops the flow. Otherwise, they are of no consequence.
http://www.csiro.au/resources/Gas-Hydrates.html

At the wellsite, two techniques are applicable for hydrate prevention: 1. Heating the gas stream so that it becomes under-saturated 2. Inhibitor injection The permanent solution for hydrate problem is dehydration of the gas to sufficiently low dew point. 1. Absorption using a liquid dessicant 2. Adsorption using a solid dessicant 3. Simultaneous dehydration and gas-liquid separation by expansion

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Preventing hydrate formation by inhibitors

Inhibitor injection in gas gathering and transmission system 1. Methanol (less expensive, widely used, disperses well in gas stream, does not require recovery) However, it may cause contamination problem. It is very useful where low gas volumes prohibit dehydration processing. It is suitable for mild hydrate formation problem, infrequent, periodic, temporary injection during field development. 2. Ethylene glycol (EG) 3. Diethylene glycol (DEG) EG and DEG are used primarily at low-temperature processing plants for extracting NGL. The aqueous phase of the process liquid contains the EG and DEG, which can be recovered or regenerated.
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Prediction of inhibitor requirements

The weight % inhibitor concentration in the aqueous phase, w, required to lower the gas hydrate freezing point by T oF, is given by: Hammerschmidts equation:

MT (100 ) wK or T = w= K + MT 100 M + wM

Where M is the molecular weight of the inhibitor K= a constant 2335 for Methanol, 4000 for Glycols. Typically, this equation would predict injection requirement of 2-3 Gallons of methanol/MMSCF of gas. In practice, only about 1 to 1.25 G/MMSCF may be required in most cases. The process of chemical inhibition is economical if the minimum required amount of chemical is injected. Most predictive models are no better than a rule of thumb; it is advisable to determine the chemical requirements by field testing

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Absorption dehydration
Absorption involves the use of a liquid dessicant to remove water vapor from the gas. A commercial liquid dessicant for dehydration process should possess the following properties: 1. High absorption efficiency 2. Easy and economic regeneration 3. Non-corrosive and non-toxic 4. No operational problems when used in high concentrations 5. No interaction with the hydrocarbon portion of the gas and no contamination by acid gases The glycols particularly EG, DEG and Triethylene glycol (TEG) and Tetraethylene glycol satisfy these criteria to varying degrees. Glycols are preferred because: Offer superior dew-point depression Process reliability and lower initial capital and operation costs Less expensive than adsorption dehydration (57% more for 10 MMSCFD and 33% more for 50 MMSCFD as compared to TEG) 20 Simple operation and equipment

Absorption dehydration
Of all the glycols, TEG is more favourable because of lower vapour losses and better dew-point depression. It has been successfully dewdepression used for dehydration of sweet and sour natural gases to effect a dewpoint depression of 40 to 140 degree F, for operating conditions ranging from 25-2500 psig and 40-160 degree F. 2540F

Typical TEG dehydration process flow scheme

www.ogj.com

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Glycol dehydration sizing

The primary variables required for design include: 1. 2. 3. 4. 5. Gas flow rate Gas gravity Operating pressure and maximum working pressure Gas inlet temperature Outlet water content required in the gas

In addition two criteria must be selected for design: 1. Glycol to water circulation rate (2-6 gal TEG/lb water removed, usually 2.5-4 in field applications ) 2. Concentration of the lean TEG from regeneration system. (99.0% to 99.9%, usually 99.5%) The amount of water to be removed , Wr in lb/hr, can be calculated as follows: Wr = q(Wi-Wo)/24
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Inlet scrubber
Inlet scrubber: to remove any liquid water and hydrocarbons, sand, drilling mud, and other solid matter. These impurities must be thoroughly removed, because they may lead to foaming, flooding, poor efficiency, higher glycol losses and maintenance problems in the absorber. Two-phase inlet scrubbers are generally constructed with 7 -ft shell heights. The required minimum diameter of a vertical inlet scrubber can be determined based on the operating pressure and required gas capacity [Sivallss data ,1977], see next slides.
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Gas capacity of vertical inlet scrubbers based on 0.7specific gravity at 100 oF (Sivalls, 1977)

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Gas capacity of vertical inlet scrubbers based on 0.7specific gravity at 100 oF (Sivalls, 1977)

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Glycol contactors
Glycol contactors are generally constructed with a standard height of 7 ft. The minimum required diameter of the contactor can be determined based on the gas capacity of the contactor for reference gas of 0.7 specific gravity at standard temperature 100 oF. q

qref =

Packed Glycol Contactors

Ct C g

Trayed Glycol Contactors

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Gas capacity for trayed and packed glycol contactors based on 0.7-specific gravity at 100 oF (Sivalls, 1977). Trayed glycol contactors

Packed glycol contactors

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Gas capacity for trayed glycol contactors based on 0.7-specific gravity at 100 oF (Sivalls, 1977).

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Gas capacity for packed glycol contactors based on 0.7-specific gravity at 100 oF (Sivalls, 1977).

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Gas capacity for trayed and packed glycol contactors based on 0.7-specific gravity at 100 oF (Sivalls, 1977).

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The required approximate minimum height of packing of a packed contactor, or the minimum number of trays of a trayed contactor (Sivalls, 1977).

A more accurate procedure for calculating the number of trays (or the depth of packing) required is to use the McCabeThiele diagrams

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Glycol Re-concentrator
Sizing the various components of a glycol regenerator starts from calculating the required glycol circulation rate:

(GWR)Cwi q qG = 24
where qG = glycol circulation rate, gal/hr GWR = Gal TEG/lbm H2O Cwi = water content of inlet gas, lbm H2O/MMscf q = gas flow rate, MMscfd Reboiler: The required heat load for the reboiler can be approximately estimated from the following equation: Ht = 2,000qG Ht = total heat load on reboiler, Btu/hr
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The mentioned equation for reboiler heat load is accurate enough for most high-pressure glycol dehydrator sizing. A more detailed procedure for determination of the required reboiler heat load can be found from Ikoku (1984). The general overall size of the reboiler can be determined as follows:

A fb = H t / 7000
where Afb is the total firebox surface area in squared feet. Glycol circulating pump: The glycol circulating pump can be sized using the glycol circulation rate and the maximum operating pressure of the contactor (see next page for glycol pump specifications). Glycol Flash Separator: A glycol flash separator is usually installed downstream from the glycol pump to remove any entrained hydrocarbons from the rich glycol. A small 125-psi vertical two-phase separator is usually adequate for this purpose. The separator should be sized based on a liquid retention time in the vessel of at least 5 minutes. Vs =qGtr/60 Where Vs = required settling volume in separator, gal 33 qG = glycol circulation rate, Gph, tr = retention time approximately 5 minute

Glycol pump specification Glycol re-concentrator spec.

www.kimray.com

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Adsorption dehydration
Adsorption is defined as the ability of a substance to hold gases or liquids on its surface. In adsorption dehydration, the water vapor from the gas is concentrated and held at the surface of the solid desiccant. Solid desiccants have very large surface areas per unit weight (200-1000 m2/g) The most common solid adsorbents used today are silica, alumina, and certain silicates known as molecular sieves. 1. 2. 3. 4. 5. Chemically inert, cheap, non-corrosive Physically durable and mechanically strong Easily Regenerated Thermally Stable and low pressure drop Larger Surface Area for Adsorption and high mass transfer rate Dehydration plants can remove practically all water from natural gas using solid desiccants. Because of their great drying ability, solid desiccants are employed where higher efficiencies are required.
http://www.processystems.coml

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Types of adsorbents
1. Bauxite ore, consisting primarily of alumina (Al2O3.xH2O) (unsuitable for sure gas) 2. Alumina 3. Silica gel 4. Silica-Alumina gel 5. Molecular sieves 6. Activated carbon ( no capacity for water)

Alumina:
Results dew point depression up as low as -100oF Good resistance to liquid It requires much more heat for regeneration. It is alkaline and cannot be used in the presence of acid gases, or acidic chemicals. Tendency to adsorb heavy hydrocarbons is high http://www.processystems.coml making regeneration difficult. Little resistance to mechanical agitation by the flowing gas 36

Types of adsorbents
Silica gel and Silica-Alumina gel:
Gels manufactured from sulfuric acid and sodium silicate reactions are called silica gels. Can dehydrate gas to as low as 10 ppm Easy regeneration Adsorb heavy hydrocarbon but release more easily during regeneration Can handle sour gas Cannot handle alkaline material such as caustic or ammonia Good for H2S content less than 5-6%

Molecular sieves:

http://www.processystems.coml

Crystalline form of alkali metal (calcium or sodium) alumina-silicate, very similar to natural clays Are alkaline and subject to attack by acids (special acid resistance are available for very sour gases) Very high surface area Can produce water content less than 1 ppm Most expensive Subject to contamination by glycol Need high regeneration temperature Can be used for simultaneous dehydration and desulfurization
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Process flow scheme

1. Adsorption is downwards to lessen bed disturbance due to high gas velocity 2. Regeneration is upwards to ensure through regeneration of the bottom of the bed 3. Most contamination occurs at the top of the tower, and by sending the regenerated gas upwards, these contaminations can be removed without flushing them through the entire bed.
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The regeneration cycle

400 F
Inlet gas temperature

375 F T3 240 F T2

T4

T5 125 oF T1 A B C D

100 F

Start of cycle

4 hrs Time

8 hrs End of cycle

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The regeneration cycle

Period A: The hot regeneration gas heats up the tower and desiccant from T1 to T2 (100240 oF) Period B: At above 240 oF, water beings to vaporize. The bed heats up at a slower rate because considerable portion of the heat input is used in vaporizing water from the desiccant, until T3 is reached. Period C: At point T3 all the water in the desiccant is desorbed. Heating is continued from T3 to T4 (375 oF) to drive off any heavier hydrocarbons and contaminants. When the temperature has reached T4 the regeneration gas has a higher water content contaminant. This ends the heating cycle and cooling begun. Period D: The cooling started at point T4 is terminated at T5 (125 oF).
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Design variables for adsorption process

Basic components 1. Adsorber tower 2. Regeneration and cooling equipment 3. Piping and equipment Design variables: 1. Cycle time 2. Allowable gas flow rate 3. Desiccant capacity 4. Required outlet water dew point 5. Total amount water to be removed 6. Refrigeration requirements 7. Allowable pressure drop

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Design variables for adsorption process

Cycle time: varies from less than 1 hr for a rapid cycle unit to grater than 8 hrs. It depends on desiccant capacity and bed geometry. Desiccant capacity:
Material Alumina Alumina Gel Silica Gel Molecular Sieves Bulk density (lb/ft3) 50-55 52-55 45 43-45 Surface Area m2/g 210 350 750-830 650-800 Capacity lb H2O/100 lb 4-7 7-9 7-9 9-12
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Adsorber bed design

Adsorber tower design is governed by:
1. 2. 3. 4. 5. Disiccant capacity Zone length Water loading (rate of water removal from the gas) Breakthrough time Allowable gas flow rate ad pressure drop

q 10 6 ZT 14.7 4 qZT vg = 2 = 1499.73 24 p 520 D pD 2 Where vg =superficial gas velocity ft/sec. Q=gas flow rate in MMSCFD Z = Gas compressibility factor D = Diameter of the adsorber bed, ft
Superficial gas velocity Allowable gas flow rate:

w=

139.77 M g D2
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Where w is allowable gas flow rate (lb/hr ft2) Mg is molecular weight of gas

Adsorber bed design (cont.)

For downward flow of gas, the maximum allowable gas mass flow velocity, w is given by:

w = 20428.22 where g = gas density in lb/ft3 d = bulk desiccant density in lb/ft3 Dp = average desiccant particle diameter, ft C = empirical constant in the range of 0.025 0.033
Water loading:

C g d D p

qw = 0.0531qWi D

where qw = water loading, lb H2O/hr ft2 Wi = water content of the inlet gas, lb H2O/MMSCF of gas Zone length Depends on gas comp., flow rate, relative water 0 saturation, and desiccant loading capacity. For silica gel 297.78qw.7895 (Simpson and Cummings, 1964) where hz = 0.5506 0.2646 hz = zone length, ft vg S r Sr = relative saturation of water in the inlet gas % For alumina and molecular sieve, the zone length determined is 44 multiplied by 0.8 and 0.6, respectively.

Adsorber bed design (cont.)

Desiccant capacity The dynamic desiccant capacity Xs is shown in the right. The temperature correction factor required for gels and alumina, but Xs not for molecular sieves is shown below. The useful desiccant capacity, x, is generally less than the dynamic capacity is given by:

x = xs C * xs (hz / ht )
where x = useful capacity of desiccant, lb H2O/100 lb desiccant Xs = dynamic capacity C* = (0.4 0.52) an imperial factor, a function of zone length, usually 0.45

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Adsorber bed design (cont.)

Breakthrough time The breakthrough time for the water zone formed, tb in hours, can be estimated by:

tb = 0.01x d ht / qw

Minimum bed length The amount of water that can be removed per cycle by desiccant, Wc (lb) is given by:

Wc = ( x / 100) d ht D 2 / 4

On rearranging this equation, the minimum length of desiccant bed required can be written as:

(ht )min

127.3Wc = x d D 2

Note that (ht)min is the distance from the inlet to the front of the water zone. So, if the ht is less than the total length of the bed, it means that not all of the bed is being used.
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Removal of acid gases

Natural gases containing H2S are classified as sour, and those that are H2S free are called sweet in processing practice. Produced gas from reservoirs usually contain H2S in concentrations ranging from barely detectable quantities to more than 0.3% (3000 ppm) Other sulfur derivatives, besides H2S, are usually completely insignificant or present only in the trace proportions. Most contracts for the sale of natural gas requires less than 4 ppm (0.25 gr/100 ft3 of gas) in the gas. A characteristic of all H2S bearing natural gases is the presence of CO2, the concentrations which are generally in the range of 1-4%. H2S and CO2 are commonly referred to as acid gases because form acids or acidic solutions in the presence of water.
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Reasons for removal of H2S and CO2

1. Foul odor 2. Deadly poisonous, at concentration above 600 ppm it can be fatal in just three to five minutes 3. Corrosive to all metals normally associated with gas production and processing operations 4. In combustion it produces SO2 which is also highly toxic and corrosive. 5. H2S and other sulphur compounds can cause catalyst poisoning in refinery process. 6. CO2 has no heating value and may be removed to increase the energy content of the gas per unit volume 7. CO2 is corrosive in the presence of water 8. H2S and CO2 promote hydrate formation
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Removal processes
Iron sponge sweetening:
Sour gas is passed through a bed of wood chips that have been impregnated with a special hydrated form of ferric oxide that has a high affinity for H2S at 120oF. The chemical reaction is as follows: Fe2O3+3H2S Fe2S3+3H2O Iron oxide is regenerated by passing oxygen/air over the bed: Fe2S3+3O2 2Fe2O3+6S Advantages: 1. Simple process 2. Selective 3. Relatively inexpensive Disadvantages: 1. Difficult and expensive regeneration 2. Excessive pressure loss 3. Inability to remove large amount of sulfur 4. Sulfur disposal problem
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Removal processes (cont.)

Molecular Sieves
Synthetically manufactured forms of crystalline sodium-calcium alumino silicates, molecular sieves are porous in structure and have a very large surface area. The molecular sieves remove components through a combination of a sieving sieving and physical adsorption. Because of their narrow pore sizes, they discriminate adsorption among the adsorbates on the basis of their molecular sizes. The sieves possess highly localized polar charges on their surface that act as a adsorption site for polar materials. The flow process is similar to the iron sponge process. It is a cyclic operation with a cycle time on the order of 2 hours. The bed is regenerated by passing a portion of the sweetened gas (1-2%) preheated to about 400-600 oF or more, for about 4001.5 hrs to heat bed. 1. Very prone to poisoning by glycol 2. Requires a through gas cleaning method prior to adsorption 3. Regeneration is expensive and needs a lot of heat

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Removal processes (cont.)

Water wash (Aqua-sorption) process
In this process sour gas is sent upward through a contactor, countercurrent to the water. This process is effective for high pressure gas, with high acid gas content and high H2S to CO2 ratio. A wash process followed by an amine process is 12-15% lower in capital investment and about 50% lower in operating expenses as compared to single unit for amine an equivalent job. For gas with a high H2S to CO2 ratio, the saving can be as much as 40% in investment, and 60 to 70% in operating costs. Since H2S is more soluble in water than CO2, this process shows a quite good selectivity.
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Removal processes (cont.)

Alkanol-Amine processes
Amin processes are the most prominent and widely used processes for H2S and CO2. They offer good reactivity at low cost and good flexibility in design and operation. Some of the commonly used amines are: 1. Monoethanolamine (15% wt.) 2. Diethanolamine (20-30 % wt.) 3. Triethanolamine 4. Diglycolamine (40-70% wt.) 5. Di-isopropanolamine (30-50% wt.) 6. Methyldiethanolamine (30-50% wt.)
SWEET GAS ABSORBER H2S & CO2

STRIPPER

SOUR GAS

STEAM LEAN SOLVENT

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