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Hydrate Formation Utility

14.12 Hydrate Formation Utility

To add the Hydrate Formation utility, refer to the section on Adding a Utility.

The Hydrate Formation utility calculates the incipient solid formation point for hydrates. The predictive models are based on fundamental thermodynamic principles and use equation-ofstate 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 PengRobinson 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 nbutane 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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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 VaporLiquid-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:
d ln f w MT - P = ln f w, o + --------------- dP T
MT

ln f w

MT

(14.20)

where: fw
MT

= 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:
MT ln f w, o = 14.269 5393 ----------T

(14.21)

d ln f w - = 0.00036 T 0.1025 --------------- dP T where: T = temperature in Kelvin

MT

(14.22)

For hydrates of Structure II, the fugacity relationships are found to be:
MT ln f w, o = 18.062 6512 ----------T

(14.23)

d ln f w - = 0.0001109 T 0.03192 --------------- dP T where: T = temperature in Kelvin

MT

(14.24)

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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 aqueouscontaining systems. All fluid properties including phase behavior, volumetric behavior, and fugacities are calculated with the selected equation of state (PengRobinson 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-LiquidAqueous) 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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Hydrate Formation Utility

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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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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The Hydrate Formation status at the current stream conditions are also shown on the Connections page.
Hydrate Formation Status Hydrate Formation Flag Description Displays the status of hydrate formation. There are two possibilities: Will Form Will NOT Form Displays the types of Hydrate formed (Type I, Type 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. Possibilities are Use 2-Phase Model, Use 3-Phase Model, Use SH Model, and Assume Free Water. Possibilities are Included and Not Included.

Hydrate Type Formed

Calculation Mode Inhibitor Calculation

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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, refer to Section 1.3.5 Notes Page/Tab.

The Notes page provides a text editor where you can record any comments or information regarding the utility or to your simulation case in general.

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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 calculation models are discussed in the Hydrate Calculation Models section.

The Formation Temperature at Stream Pressure group displays the formation temperature at which hydrates are formed at the stream pressure. The hydrate type formed at this formation 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-LH, 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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Hydrate Formation Utility

Formation Pressure at Stream Temperature Group

The hydrate types and calculation models are discussed in the Hydrate Calculation Models section.

The Formation Pressure at Stream Temperature group displays the formation pressure at which hydrates are formed at the stream temperature. Similar to the Formation Temperature at 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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Hydrate Formation Utility

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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