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Unusual Phase Behavior of Hydrocarbon Mixtures

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Abstract

The phase behavior of quaternary mixtures of methane, propane, octane, and decane for the low concentration of heavy hydrocarbons (octane and decane) are qualitatively transformed compared to the customary concept. Each mixture splits into three phases, a macroscopic phase enriched by methane and propane and two microscopic phases enriched by octane or decane. Each microphase consists of one heavy component. The microphase phase behavior depends on the composition of the macrophase. If octane dissolves in the macrophase the line of formation of the decane-rich microphase shifts to the lower temperature. The heavy hydrocarbons provoke a split of the liquid part of the macrophase into two liquid phases. All phases are equilibrium phases. Based on the quasi-binary approximation the hydrocarbon mixtures for the low concentration of heavy components are prepared. The first quasi-component is a binary mixture with the constant methane/propane ratio. The second quasi-component is octane and decane.

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Abbreviations

P :

Pressure [MPa]

T :

Temperature [K]

U :

Internal energy [J]

Ω/V = − P :

Density of grand potential [MPa]

C V = (∂U/∂T)V :

Heat capacity at constant volume [kJ·kg−1·K−1]

(∂ P/∂T)V :

Temperature derivative of pressure at constant volume (the thermal pressure coefficient) [MPa·K−1]

(∂P/∂T)σ :

Temperature derivative of pressure along the equilibrium curve [MPa·K−1]

x :

Concentration [mole fraction]

m :

Mass [kg]

ρ :

Density [kg·m−3]

V:

Vapor phase

L:

Methane-propane liquid phase

L′:

Methane-propane-octane liquid phase

L1 :

Octane-, decane-lean liquid phase

L2 :

Octane-, decane-rich liquid phase

S1 :

Microphase enriched by octane

S2 :

Microphase enriched by decane

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Acknowledgement

This work was supported by the Russian Foundation for Fundamental Research under Grants № 19-08-00202.

Funding

Funding was provided by Российский Фонд Фундаментальных Исследований (РФФИ) (Grant Number 19-08-00202).

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Authors and Affiliations

  1. The Limited Liability Company “Scientific-Research Institute of Natural Gases and Gas Technologies” – Gazprom VNIIGAZ, Razvilka, Leninsky Dist., Moscow, Russia, 142717

    V. M. Buleiko

  2. Oil and Gas Research Institute (OGRI RAS), Gubkin Street, 3, Moscow, Russia

    D. V. Buleiko

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Correspondence to V. M. Buleiko.

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Buleiko, V.M., Buleiko, D.V. Unusual Phase Behavior of Hydrocarbon Mixtures. Int J Thermophys 43, 60 (2022). https://doi.org/10.1007/s10765-022-02988-0

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