Process

Optimization
A. KATYAL, Independent Researcher/Inventor,
New Delhi, India

Accurate prediction of phase equilibrium

properties—Part 2
Phase equilibrium properties, such as bubble point, hydro-
carbon dewpoint, water dewpoint, phase envelope, two-phase
compositions, compressibility factor, hydrate equilibrium
properties, etc., for hydrocarbon mixtures have been calculated
accurately using the Peng-Robinson cubic equation of state by
implementing constant and temperature-dependent binary in-
teraction parameters in the Van der Waals mixing rule.
These phase equilibrium properties find usage in the design
and operation of all kinds of hydrocarbon equipment, such as
hydrocarbon pipelines, hydrocarbon pumps, pressure vessels,
hydrocarbon storages and distillation columns. Phase equilibri-
um properties are also required in upstream oil and gas activities
like well simulation and oil and natural gas production. Atmo-
spheres of various heavenly bodies are made of hydrocarbons,
such as methane (CH4), ethane (C2H6), propane (C3H8), etc.,
and inorganic gases like nitrogen (N), carbon dioxide (CO2)
and hydrogen sulfide (H2S). Simulation of these atmospheres
also requires knowledge of phase equilibrium properties.
A new vapor liquid equilibrium (VLE) softwarea has been
developed using basic calculation tools like MS Excel and Visual
Basic for Applications (VBA, macro programming) to accu-
rately calculate various phase equilibrium properties. The Peng-
Robinson cubic equation of state and Van der Waals mixing rule,
using a combination of temperature-dependent and constant bi-
nary interaction parameters, are used for these calculations.
Part 1 (October 2019) discussed how the proprietary phase
equilibrium softwarea is designed to give accurate phase equi-
librium properties for any mixture of nonpolar or mildly polar
hydrocarbons and inorganic gases up to a maximum number of
112 components in the hydrocarbon mixture.
Hydrate-forming components included in the phase equilib-
rium software are CH4, C2H6, C3H8, n-butane, i-butane, ethyl-
ene, propylene, cyclopropane, acetylene, N, H2S, CO2, carbon
monoxide (CO), argon and oxygen. Additionally, the effects of
hydrate inhibitors, such as salts (LiCl, NaCl, KCl, CsCl, CaCl2
and MgCl2); salt mixtures; organic liquids (methanol, ethyl-
ene glycol, ethanol, 1-propanol, 2-propanol, t-butyl alcohol
and glycerol); sugars (deoxyribose, ribose, fructose, sucrose,
glucose and maltose); urea; and formamide can be included in
the calculation of gas hydrate equilibrium properties, using the
phase equilibrium software.
Gas hydrate properties. Gas hydrate equilibrium properties
calculated using the phase equilibrium software include:
• Equilibrium temperature
• Hydrocarbon liquid and vapor phase compositions
• Aqueous phase composition in cases where aqueous
phase exists
• Hydrate phase composition
• Fraction of hydrocarbons in liquid phase
• Type of hydrates formed (S I or S II)
• Hydration number of hydrates formed
• Density of hydrates formed.
800
Bubble point
700 Dewpoint
Hydrate point
600
500
Pressure, bar

Gas hydrate equilibrium properties for mixtures of nonpolar 400

or mildly polar hydrocarbons and inorganic gases existing with
water and including at least one hydrate former can be calcu- 300
lated using the phase equilibrium software. It uses temperature-
200
dependent binary interaction parameters, as per the Enhanced
Predictive Peng Robinson 78 (E-PPR78) equation, to calculate 100
component fugacity. These parameters are used in an accurate
0
and reliable statistical thermodynamic model for clathrates 0 50 100 150 200 250 300 350
developed by Van der Waals and Platteeuw in 1959 to predict Temperature, K
gas hydrate equilibrium curves and properties for any mixture
of non-polar or mildly polar hydrocarbons and inorganic gases FIG. 1. Phase envelope curve with hydrate equilibrium curve for a typical
natural gas composition, using proprietary phase equilibrium software.
existing with water and including at least one hydrate former.6
Hydrocarbon Processing | NOVEMBER 2019  53
 Process Optimization
Gas hydrate equilibrium properties are calculated at inter-
vals of 0.4 bar, beginning with 0.4 bar and ending at 800 bar
(FIG. 4 and TABLE 5). Apart from calculating hydrate equilib-
rium temperature values and gas hydrate properties through-
out the gas hydrate equilibrium curve, the phase equilibrium
software also calculates hydrate equilibrium temperature val-
ues and gas hydrate properties at any desired pressure value
below 800 bar.
The calculation of the fraction of hydrocarbon mixture
converted to gas hydrates, the composition of gas hydrates
formed, and other properties of formed gas hydrates at tem-
peratures below the gas hydrate equilibrium temperature at
the system pressure are desirable in the prediction of pipeline
blockage due to hydrate formation. These calculations are also
required in the use of the gas hydrate concept in the separation
of hydrocarbon mixtures. The phase equilibrium software can
calculate the fraction of gas hydrocarbon mixture present in
gas, liquid or two-phase form converted to gas hydrate at a
temperature value lower than the gas hydrate equilibrium
temperature at the system pressure. This applies to any mix-
ture of non-polar or mildly polar hydrocarbons or inorganic
gases containing at least one hydrate former. It also calculates
the final hydrate, liquid and vapor composition; the average
hydration number; the average hydrate density; and the total
fraction of initial mixture of water and hydrocarbons/inorgan-
ic gases converted to gas hydrates. Additionally, it calculates
the gas hydrate equilibrium curve and gas hydrate equilibrium
properties at the system pressure (< 800 bar).
If gas hydrates are formed from a hydrocarbon mixture
at a temperature slightly lower than the equilibrium hydrate
formation temperature at the system pressure, then a small
amount of hydrates will form and some hydrocarbon mixture
will convert to hydrates. The composition of hydrate formers
in the hydrate phase will be different from the composition of
hydrocarbon mixture in the gas or liquid phase, resulting in a
change in composition of the hydrocarbon mixture in the gas
or liquid phase after a small amount of hydrates form. This
results in the separation of the hydrocarbon mixture.
Therefore, the phase equilibrium software can be used for
hydrate-based gas separation (HBGS) calculations. This new
composition will require a lower hydrate equilibrium tempera-
TABLE 5. Phase envelope curve with hydrate equilibrium curve
for a typical natural gas composition, using proprietary phase
equilibrium software
Components Z mixtures, including a maximum of 112 components, can be
Methane (CH4) 0.7
Ethane (C2H6) 0.1
Propane (C3H8) 0.05
Iso-butane (C4H10) 0.02
n-butane (C4H10) 0.01
n-pentane (C5H12) 0.02
Nitrogen (N2) 0.03
Carbon dioxide (CO2) 0.02
Hydrogen sulfide (H2S) 0.05
Total 1 sitions, hydrate equilibrium curve and properties, and water
54 NOVEMBER 2019  | HydrocarbonProcessing.com
ture to form hydrates and will result in the formation of hy-
drates of different properties, such as type, density, hydration
number, composition, etc. The phase equilibrium software
continuously calculates hydrate properties at decreasing tem-
perature values, until the desired temperature is reached.
Additional calculations. Binary VLE curves, such as the
concentration diagram (x-y plot), temperature concentration
diagram (T-x-y plot) and enthalpy concentration diagram
(H-x-y plot) used in the McCabe Thiele and Ponchon Savarit
methods to design binary distillation columns, can be calcu-
lated using the phase equilibrium software. Binary VLE curves
for any binary mixture of non-polar or mildly polar hydrocar-
bons and inorganic gases at a column operating pressure value
of less than the lower critical pressure among the critical pres-
sures of the two pure components of the binary mixture can be
calculated using the phase equilibrium software.
Rigorous and more accurate, basic, stage-by-stage design
calculations for binary and multicomponent distillation col-
umns can be performed using the phase equilibrium software
to calculate minimum reflux ratio, number of equilibrium
stages in the rectification and stripping sections, equilibrium
temperature of various stages, and liquid and vapor composi-
tions at various stages. The phase equilibrium software calcu-
lates the minimum reflux ratio and attainable distillate compo-
sition using the Underwood correlation, as well as the overall
column efficiency, actual number of stages, column diameter
and column height for the distillation column being designed
to separate binary and multicomponent mixtures. Distillation
column design calculations for the separation of multicom-
ponent mixtures of any number of non-polar or mildly polar
hydrocarbons and inorganic gases (up to a maximum limit of
112 components at an operating pressure lower than the low-
est critical pressure among the critical pressures of the pure
components included in the binary or multicomponent mix-
ture for suitably chosen light-key and heavy-key components)
can be performed using the phase equilibrium software.
Various thermodynamic properties (enthalpy change from
standard conditions, entropy change from standard condi-
tions, Gibbs free energy change from standard conditions,
specific heat at constant pressure, specific heat at constant
volume, specific heat ratio, sonic speed, isobaric thermal ex-
pansivity and the Joule-Thomson coefficient) throughout the
phase envelope curve at intervals of 0.4 bar for pure non-polar
or mildly polar hydrocarbons and inorganic gases and their
calculated using the phase equilibrium software.
Heavier components in oil and natural gas samples are
sometimes characterized as pseudo components. Critical
properties of these pseudo components are not documented
like normal components, but are instead calculated theoreti-
cally based on experimentally determined properties of these
fractions (e.g., density, boiling point). These critical proper-
ties, such as critical pressure, temperature and volume, and
acentric factor, enable the pseudo components to be consid-
ered as normal components in phase equilibrium calculations.
The proprietary software can include up to 40 pseudo com-
ponents and can calculate phase envelope, two-phase compo-
 Process Optimization
Put the Solution
dewpoint curve for hydrocarbon mixtures, including these
pseudo components.
Ammonia (NH3) is being widely used as a refrigerant be-
Before the Problem
cause of its excellent thermos-physical properties and ozone-
friendly characteristic. VLE properties of mixtures contain-
ing NH3 are desirable in numerous design calculations. The When you’re measuring pressure,
Peng-Robinson cubic equation of state being used in various inaccuracies or instrument failures will
calculation modules of the phase equilibrium software gives
accurate results of VLE properties only for mixtures of non- compromise production and safety.
polar or mildly polar compounds, whereas NH3 is highly po-
lar in nature. Therefore, the Peng-Robinson equation in its
You can avoid these problems by
usual form cannot be used to find VLE properties of mixtures designing-in our expert solutions.
containing NH3.
However, temperature-dependent binary interaction pa-
rameters can be calculated for pairs containing NH3 with few
non-polar compounds or water, and used in the Peng-Rob- Gauges with
inson equation to calculate VLE properties of mixtures con- the PLUS! ™
taining NH3. As temperature-dependent binary interaction performance
parameters can be calculated for pairs containing NH3 with option dampen
CH4, nitrogen (N2), argon (Ar), hydrogen (H2) and water
pulse & vibration
(H2O), VLE properties can be calculated for binary or multi-
component mixtures of CH4, N2, Ar, H2, NH3 and H2O. The for easier reading
various calculation modules of the phase equilibrium software and longer life.
that can be used for binary or multi-component mixtures of
NH3 with CH4, N2, Ar, H2 and H2O include:
• Bubble point temperature calculator
• Dewpoint temperature calculator
• Bubble point pressure calculator
• Dewpoint pressure calculator
• Two-phase composition calculator The 2198 MicroTube™
• Phase envelope calculator siphon dissipates
• Thermodynamic properties calculator. heat to avoid damage.
As the phase equilibrium software is made using basic cal-
culation tools, such as MS Excel and VBA (macro program-
ming), and is executed on a laptop computer of standard
configuration, it can be slow in its execution. However, the
emphasis of the phase equilibrium software is not on giving
instant results, but rather on providing extremely extensive Diaphragm seals isolate
and accurate results. and protect your valuable
Graphical results of the phase equilibrium software are also assets from corrosive
provided in Part 1 of this article, which appeared in the Octo-
media.
ber issue.

NOTES
a
EQ-COMP vapor liquid equilibrium (VLE) software

LITERATURE CITED
6
Sloan, Jr., E. D. and C. Koh, Clathrate Hydrates of Natural Gases, 3rd Ed., CRC
Press, September, 2007.

AMIT KATYAL is an independent inventor and researcher based in New Delhi, We’d like to help you.
India. He has designed and developed the EQ-COMP VLE software, which is
the result of more than 15 yr of continuous research in the field of vapor-liquid
Please contact us at (203) 385-0635 or
equilibrium of hydrocarbon/oil and natural gas mixtures and involves extensive visit our website at www.ashcroft.com
software development work to automate the calculations. Mr. Katyal earned a
BS degree in chemical engineering from the Indian Institute of Technology in
Delhi. He has 25 yr of experience in the hydrocarbon sector in diverse segments
such as research, operations and technical services. In addition to EQ-COMP,
Mr. Katyal has developed other software for the hydrocarbon sector, including
HYD-PREDIC, LIQ-PROP, BUBBLE-SIM and MIX-CP. He has also invented four
technologies for water treatment and the hydrocarbon sector. The author can
be contacted at amit@eq-comp.com.

Hydrocarbon Processing | NOVEMBER 2019 55

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