14-126 Hydrate Formation Utility

14.12 Hydrate Formation

Utility
To add the Hydrate The Hydrate Formation utility calculates the incipient solid
Formation utility, refer
to the section on
formation point for hydrates. The predictive models are based
Adding a Utility. on fundamental thermodynamic principles and use equation-of-
state generated properties in calculating the equilibrium
conditions. These predictive models can therefore be applied to
various compositions, and extreme operating conditions with a
greater degree of reliability than one may expect with empirical
expressions or charts.

Hydrate formation prediction is restricted to the Peng-

Robinson and Soave-Redlich-Kwong equations of state.
A hydrate curve can be plotted with the Envelope utility.

Hydrate Calculation Models

The only requirement for hydrate formation is that some water
must be present in either the vapour or condensed hydrocarbon
phase with hydrate forming components. Once favourable
pressure and temperature conditions are reached (high
pressures or low temperatures), the mixture of hydrate-forming
molecules and water molecules form a non-stoichiometric solid
phase.

These favourable conditions can be well above the freezing

point of water, or well before the point where free water or
ice would drop out.

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The three types of hydrates formed are known as Structure I,

Structure II, and Structure H. The hydrate formers are limited to
molecules that are small enough to fit into the cavities formed
by the host water lattice structure. A single hydrate former is
required for the Structures I and II. These hydrate formers
typically include:
low molecular weight paraffinic hydrocarbons up to n-
butane
some olefins
some of the smaller non-hydrocarbon components such
as carbon dioxide, nitrogen, oxygen, argon, and
hydrogen sulphide

In contrast to the Structures I and II, the Structure H hydrate

requires two kinds of molecules in its formation:
a small Structure H former
- methane
- nitrogen
- xenon
a large Structure H former
- isopentane
- neohexane
- 2,3-dimethylbutane
- 2,2,3-trimethylbutane
- 2,2-dimethylpentane
- 3,3-dimethylpentane
- 2,3-dimethyl-1-butene
- 3,3-dimethyl-1-butene
- cyclooctane
- cycloheptane
- methylcyclopentane
- ethylcyclopentane
- methylcyclohexane
- cis-1,2-dimethylcyclohexane
- 1,1-dimethylcyclohexane
- ethylcyclohexane
- cis-cyclooctene
- cycloheptene

Therefore, to obtain the Structure H prediction, the given

stream must consist of at least one small Structure H former
and at least one large Structure H former.

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14-128 Hydrate Formation Utility

Models used for predicting the incipient hydrate point are

generally based on the original hydrate equilibrium model
proposed by van der Waals and Platteeuw12, coupled with a
modification suggested by Parrish and Prausnitz8. These models
have been incorporated and enhanced by AspenTech for its
hydrate predictions. In addition, the equation of state is used to
predict properties of the hydrate-forming components that are
in equilibrium with the solid hydrate phase.

The hydrate prediction models implemented are reported in the

Calculation Mode field on the Design and Performance tabs in
the Hydrate Formation utility. The calculation modes reported
are set to Use 2-Phase Model, Use 3-Phase Model, Use SH
Model, and Assume Free Water. These four hydrate
calculation modes and the appropriate model treatment are
described as follows.
Use 2-Phase Model
For scenarios that result in the absence of a free aqueous
phase after an equilibrium flash (in other words, Vapor
only, Liquid only, Vapor-Liquid, Liquid-Liquid, and Vapor-
Liquid-Liquid, where Liquid refers to a hydrocarbon
liquid), the 2-Phase model is used for hydrate predictions
of the Structures I and II.
The 2-Phase model is based on the work of Ng and
Robinson6. The fugacity of water, as a function of
pressure and temperature in the empty lattice (MT), is
determined by data reduction. Plots of ln f w, o vs. 1 T and
of ( d ln f w ) ( dP ) vs. T show linear relationships.

where:

fw,o = fugacity of the water at zero pressure over the unfilled

structure II lattice

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The empty lattice water fugacity at any pressure is

represented by the following expression:

MT
MT MT d ln f w
ln f w = ln f w, o + ----------------- P (14.20)
dP T

where:
MT
fw = empty lattice fugacity at any pressure

fw,o = fugacity of the water at zero pressure

P = pressure.

By combining this expression with the linear regressed

plots, the fugacity of water over the unfilled hydrate
lattice as a function of temperature and pressure is
obtained. The relationships depend on hydrate structure
but are independent of the composition of the examined
mixture.
For hydrates of Structure I, the fugacity relationships are
found to be:

ln f w, o = 14.269 5393
MT
------------ (14.21)
T

MT
d ln f w
----------------- = 0.00036T 0.1025 (14.22)
dP T

where:

T = temperature in Kelvin

For hydrates of Structure II, the fugacity relationships

are found to be:

ln f w, o = 18.062 6512
MT
------------ (14.23)
T

MT
d ln f w
----------------- = 0.0001109T 0.03192 (14.24)
dP T

where:

T = temperature in Kelvin

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14-130 Hydrate Formation Utility

Use 3-Phase Model

For scenarios that result in the presence of a free
aqueous phase after an equilibrium flash (in other words,
Aqueous only, Vapor-Aqueous, Liquid-Aqueous, and
Vapor-Liquid-Aqueous, where Liquid refers to a
hydrocarbon liquid), the 3-Phase model is used for
hydrate predictions of the Structures I and II.
The 3-Phase model is based on the work of Ng and
Robinson3. The Parrish-Prausnitz algorithm is modified to
allow for the prediction of hydrates in aqueous-
containing systems. All fluid properties including phase
behavior, volumetric behavior, and fugacities are
calculated with the selected equation of state (Peng-
Robinson or Soave Redlich Kwong). The Kihara
parameters for each hydrate-forming component are
recalculated based on the work by Ng and Robinson.
Use SH Model
The SH model predicts the Structure H hydrate when two
conditions are fulfilled:
- The Structure H-forming condition as indicated by
available experimental data (namely Vapor-Liquid-
Aqueous) is obtained from an equilibrium flash
calculation.
- The given stream contains at least one small
Structure H former and at least one large Structure H
former.
Since the Structure I hydrate can also be formed at this
experimental condition, a comparison for the
thermodynamically-favored hydrate structure (either
Structure I, Structure H, or both) is performed at the end
of the calculation.
The SH model is based on the work of Mehta and Sloan
[E.D. Sloan, Clathrate hydrates of natural gases, 2nd
edition, 1998, 705pp]. The Parrish-Prausnitz algorithm
has been extended to include the determination of
Structure H phase equilibrium.
Assume Free Water
In the absence of water as a component in the simulation
or when the amount of water in the stream being
analysed equals zero, either the 3-Phase model or the SH
model is used for hydrate predictions.

By default, HYSYS automatically determines an appropriate

model (2-Phase, 3-Phase, SH, or Assume Free Water) to be
used based on the result of the equilibrium flash and the
presence of the appropriate hydrate formers. The default
calculation model is recommended for all the hydrate prediction
scenarios.

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If you want to have control over the hydrate calculation mode/

model selection, access the Model Override page, select the
Override Default Model checkbox, and select the appropriate
model from the Hydrate Calculation Model drop-down list.

The available calculation models in the Model Override page are:

Assume Free Water
Asymmetric Model
Symmetric Model
Vapour Only Model

Each of the calculation models is described in the following

sections and will be used only if you choose to override the
default model on the Model Override page.

Assume Free Water

The Assume Free Water model uses either the 3-Phase model or
the SH model and calculates the hydrate formation by assuming
the stream is at the saturation point of water at hydrate
conditions, neglecting the amount of water present in the
stream.

Hydrate results for a waterless stream that uses the Assume

Free Water in the default calculation model will be very similar
to the hydrate results for the same stream with water that has
had the calculation model manually changed to Assume Free
Water. The difference is due only to the composition difference
between the streams when water is removed.

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Asymmetric Model
The Asymmetric model is equivalent to the default calculation
model/method previously described; however, it does not
include the Structure H calculation. This Asymmetric model
automatically selects the 2-Phase model for scenarios that result
in the absence of free aqueous phase after an equilibrium flash,
the 3-Phase model for scenarios that result in the presence of
free aqueous phase after the equilibrium flash, and the Assume
Free Water model when water is not traceable in a given
stream.

Note: Using the Asymmetric model available in the current

Aspen HYSYS version is the same as using the default
method available in Aspen HYSYS 2006.5.

Symmetric Model
The Symmetric model is the 3-Phase model. (For more
information, refer to the Use 3-Phase Model section).

Vapour Only
The Vapour Only model is identical to the 2-Phase model (for
more information, refer to the Use 2-Phase Model section).
This model was originally developed for the Vapour only case.
With an extension proposed by Sloan11, the implemented model
can be applied for any scenarios that result in the absence of
free aqueous phase after an equilibrium flash (for example, the
Liquid only case).

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Most parameters used in the hydrate models in Aspen HYSYS

were fitted from experimental data obtained at the saturation
point of water at hydrate conditions. Therefore, the models will
provide reasonable hydrate predictions at the saturated water
condition. A saturated water condition can be obtained by: 1)
not incorporating water in a given stream (in other words,
forcing the Hydrate Formation utility to use the Assume Free
Water model), or 2) adding a sufficient amount of water in the
given stream so that a free aqueous phase appears at the
stream condition.

When Aspen HYSYS cases containing Hydrate Formation

utilities (without the override specification) are loaded from
previous versions, the default calculation method is
automatically selected and is used for hydrate predictions in
the current version. If you want to have control over the
model selection (namely Assume Free Water, Asymmetric
Model, Symmetric Model, or Vapour Only Model), you can
override the model by accessing the Model Override page
and then selecting the desired model.

Ice Formation
In the case of ice formation, HYSYS displays Ice Forms First in
the Hydrate Type Formed field, and the hydrate formation
temperature and/or pressure are set to <empty>. The
message Ice Forms First indicates that ice will form before the
formation of hydrates at that condition. Exceptions are for the
two equilibrium points, where ice and hydrates coexist:
the quadruple point (ice-aqueous-vapour-hydrate
equilibrium)
the quintuple point (ice-aqueous-vapour-liquid-hydrate
equilibrium)

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14-134 Hydrate Formation Utility

14.12.1 Design Tab

The Design tab contains the following pages:
Connections
Model Override
Notes

Connections Page
On the Connections page, you can connect a stream to the
Hydrate Formation utility and change the utilitys name.

Figure 14.77

Click the Select Stream button to open the Select Process

Stream property view. On the Select Process Stream property
view, you can select the stream you want to be connected to the
utility.

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 Utilities 14-135

The Hydrate Formation status at the current stream conditions

are also shown on the Connections page.

Hydrate
Description
Formation Status
Hydrate Displays the status of hydrate formation. There are
Formation Flag two possibilities:
Will Form
Will NOT Form
Hydrate Type Displays the types of Hydrate formed (Type I, Type
Formed II, Type I & II, Type H, Type I & H, Type II & H, or
Type I & II & H). It is possible that Ice forms first, in
which case HYSYS displays the message Ice Forms
First in this field. If the stream temperature is higher
than the formation temperature, then No Types is
displayed in this field.
Calculation Mode Possibilities are Use 2-Phase Model, Use 3-Phase
Model, Use SH Model, and Assume Free Water.
Inhibitor Possibilities are Included and Not Included.
Calculation

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14-136 Hydrate Formation Utility

Model Override Page

The Model Override page allows you to gain control over a
specific model for hydrate predictions. You can override the
default model by selecting the Override Default Model
checkbox and selecting an appropriate model for hydrate
calculations as shown in the following figure.

Figure 14.78

Notes Page
For more information, The Notes page provides a text editor where you can record any
refer to Section 1.3.5 -
Notes Page/Tab.
comments or information regarding the utility or to your
simulation case in general.

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 Utilities 14-137

14.12.2 Performance Tab

The Performance tab contains one page, Formation T/P. The
Formation T/P page contains two groups:
Formation Temperature at Stream Pressure
Formation Pressure at Stream Temperature

Figure 14.79

Formation Temperature at Stream Pressure

Group
The hydrate types and The Formation Temperature at Stream Pressure group displays
calculation models are
discussed in the Hydrate
the formation temperature at which hydrates are formed at the
Calculation Models stream pressure. The hydrate type formed at this formation
section. temperature and the calculation mode are also shown. In
addition, information on equilibrium phases that exist at the
predicted formation temperature and notification of the inhibitor
calculation are also displayed.

The Equilibrium Phases field can be V-H, Aq-H, L-H, V-Aq-H, V-L-
H, Aq-L-H, or V-Aq-L-H (where V, Aq, L, and H refer to vapour,
aqueous, non-aqueous liquid, and hydrate phases,
respectively). Refer to the Hydrate Inhibition section for a
detailed description of the inhibitor calculation information.

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Formation Pressure at Stream Temperature

Group
The hydrate types and The Formation Pressure at Stream Temperature group displays
calculation models are
discussed in the Hydrate
the formation pressure at which hydrates are formed at the
Calculation Models stream temperature. Similar to the Formation Temperature at
section. Stream Pressure Group, this group shows
the hydrate type formed
the equilibrium phases at the predicted formation
pressure
the calculation mode used
the notification of the inhibitor calculation

Unlike the Performance tab, information on the equilibrium

phases is not available in the Design tab. This is because the
actual phase equilibrium at the given stream condition (with
both stream pressure and temperature fixed) could be different
from the phase equilibrium predicted at the condition where
only the stream pressure or temperature is fixed. Information
on the actual phase equilibrium at the given stream condition
might be derived from the stream flash calculation.

Hydrate Inhibition
To avoid or inhibit the formation of hydrates, you can do one of
the following:
Set the operating conditions to be outside the predicted
equilibrium curve for hydrates (in other words, set the
operating temperature to be higher than the hydrate
formation temperature)
Inject inhibitors such as glycols (for example, EG, DEG,
TEG) or alcohols (for example, methanol) to suppress the
formation of hydrates. The inhibitors serve as antifreeze
agents and depress the freezing conditions of hydrates.

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To inhibit the formation of hydrates of a given stream in the

flowsheet, you must install a stream containing the inhibitors.
We recommend that you create an inhibitor stream which
contains the inhibitor solution (for example, 30 weight% of
methanol in water) and then use the Mixer operation to mix the
inhibitor stream with the process stream to create a new stream
which contains the desired amount of the inhibitor. You then can
access the Hydrate Formation utility to find the new solid
hydrate formation condition of the new stream. Due to the
limitation of the models used, a high concentration of inhibitors
is not recommended in the hydrate prediction (for example, the
methanol concentration should not exceed 50 weight% with
respect to water content when the given stream consists of
methane11).

The inhibitor model that Aspen HYSYS uses was developed using
available experimental data obtained at the saturated water
condition for the Structures I and II. At the saturated water
condition, a free-water (aqueous) phase must exist. Therefore,
Aspen HYSYS performs inhibition calculations only when there is
an aqueous phase after an equilibrium flash. You must ensure
that the stream of interest has sufficient amount of water to be
at a saturated water condition. This inhibitor model is also
applied to the Structure H hydrate. However, since there is no
experimental data available for the inhibition using alcohols and
glycols on the Structure H hydrate, the accuracy of this model
cannot be ascertained. Use it with care and only to provide a
rough estimate.

Using the Assume Free Water model is not applicable here

because the inhibitor calculation is not included in this
calculation mode/model. Additionally, due to the limitation of
the experimental data, the inhibitor calculation is not included
when the 2-Phase model is used (either as determined by the
Default model or specified using Model Override).

Since three phase thermodynamics are used to perform the

flash calculation, the phase distribution of the components,
including water and the inhibitors, can be calculated
rigorously. Therefore, inhibitor losses in the hydrocarbon
liquid and vapour phases are properly taken into account.

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The Peng-Robinson (PR) equation of state was not originally

designed for non-ideal components such as methanol and
glycols. You should ensure the resulting distribution of the
components in all phases is satisfactory, especially if three
phases exist. The solubility of methanol in the hydrocarbon and
aqueous phases is optimized with the PR equation of state for
the methanol-HC-water VLE. Make further adjustment to the PR
interaction parameters to meet your own specifications.

Overall, this approach should be more accurate than using

Hammerschmidt's equation which was developed specifically for
dilute solutions of antifreeze agents. The Hammerschmidt
equation applies only for typical natural gas mixtures and for
solute concentrations less than 20 mole per cent. Although it is
applied for cases beyond this region with reasonable success,
this is attributed to a number of compensating factors. For
validation of this model, refer to GPA Research Report RR-66.

14.12.3 Dynamics Tab

The Dynamics tab allows you control how often the utility gets
calculated when running in Dynamic mode.

Figure 14.80

The Control Period field is used to specify the frequency that the
utility is calculated. A value of 10 indicates that the utility is
recalculated every 10th pressure flow step. This helps speed up
your dynamic simulation since utilities could require some time
to calculate.

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The Use Default Periods checkbox lets you set the control
period of one utility to equal the control period of any other
utilities that you have in the simulation. For example, if you
have five utilities and require them all to have a control period
of 5 and currently the value is 8, with this checkbox selected if
you change the value in one utility all the other utilities change.
Alternatively, if you want all the utilities to have different
values, then clear this checkbox.

The Enable in Dynamics checkbox is used to activate this

feature for use in Dynamic mode.

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