Phase diagrams, hydrocarbon

The example of a binary mixture is used to demonstrate the increased complexity of the phase diagram through the introduction of a second component in the system. Typical reservoir fluids contain hundreds of components, which makes the laboratory measurement or mathematical prediction of the phase behaviour more complex still. However, the principles established above will be useful in understanding the differences in phase behaviour for the main types of hydrocarbon identified. 

One can effectively reduce the tliree components to two with quasibinary mixtures in which the second component is a mixture of very similar higher hydrocarbons. Figure A2.5.31 shows a phase diagram [40] calculated from a generalized van der Waals equation for mixtures of ethane n = 2) with nomial hydrocarbons of different carbon number n.2 (treated as continuous). It is evident that, for some values of the parameter n, those to the left of the tricritical point at = 16.48, all that will be observed with increasing... 

Figure A2.5.31. Calculated TIT, 0 2 phase diagram in the vicmity of the tricritical point for binary mixtures of ethane n = 2) witii a higher hydrocarbon of contmuous n. The system is in a sealed tube at fixed tricritical density and composition. The tricritical point is at the confluence of the four lines. Because of the fixing of the density and the composition, the system does not pass tiirough critical end points if the critical end-point lines were shown, the three-phase region would be larger. An experiment increasing the temperature in a closed tube would be represented by a vertical line on this diagram. Reproduced from [40], figure 8, by pennission of the American Institute of Physics.

Carbon disulfide is completely miscible with many hydrocarbons, alcohols, and chlorinated hydrocarbons (9,13). Phosphoms (14) and sulfur are very soluble in carbon disulfide. Sulfur reaches a maximum solubiUty of 63% S at the 60°C atmospheric boiling point of the solution (15). SolubiUty data for carbon disulfide in Hquid sulfur at a CS2 partial pressure of 101 kPa (1 atm) and a phase diagram for the sulfur—carbon disulfide system have been published (16). Vapor—Hquid equiHbrium and freezing point data ate available for several binary mixtures containing carbon disulfide (9). 

The physical chemical behavior of betaine esters of long-chain alcohols shows strong similarities to the common, closely related alkyltrimethylam-monium surfactants both in dilute and concentrated aqueous systems, hi consistence with the findings about CMC s of surfactants containing normal ester bonds (see above) it has been found that the CMC for a betaine ester with a hydrocarbon chain of n carbons is very close to the value for an alkyltrimethylammonium chloride surfactant with a hydrocarbon chain of n + 2 carbons [32], The binary phase diagram of dodecyl betainate-water has an appearance very similar to that of an alkyltrimethylammonium surfactant with a hydrophobic tail of a similar size [30]. 

SLE of quaternary ammonium ILs in alcohols, hydrocarbons, and water have been measured for many salts. Systematic studies of SLE phase diagrams for quaternary ammonium salts [(Cj)2C2HOC2N]Br, [(Ci)2C3HOC2N]Br, [(Cj)2C4HOC2N]Br, and [(Ci)2CgHOC2N]Br in water and alcohols have been published [52,79]. Other anions including [BFJ, [PFg], [dca] , and [TfjN] have also been investigated [53]. 

Since the petroleum engineer is rarely concerned with solid hydrocarbons, in the following discussion we will consider only the vapor-pressure line and the liquid and gas portions of the phase diagram. 

The phase diagram of a retrograde gas is somewhat smaller than that for oils, and the critical point is further down the left side of the envelope. These changes are a result of retrograde gases containing fewer of the heavy hydrocarbons than do the oils. 

The entire phase diagram of a hydrocarbon mixture of predominately smaller molecules will lie below reservoir temperature. An example of the phase diagram of a wet gas is given in Figure 5-4. 

Fig. 17-2. Hydrate portion of the phase diagram of a typical mixture of water and a light hydrocarbon.

The line of major interest on this phase diagram is the line Q]QZ, which represents the equilibrium between hydrocarbon gas, liquid water, and hydrate. 

Phase diagrams of water, hydrocarbon, and nonionic surfactants (polyoxyethylene alkyl ethers) are presented, and their general features are related to the PIT value or HLB temperature. The pronounced solubilization changes in the isotropic liquid phases which have been observed in the HLB temperature range were limited to the association of the surfactant into micelles. The solubility of water in a liquid surfactant and the regions of liquid crystals obtained from water-surfactant interaction varied only slightly in the HLB temperature range. 

These compounds differ from other surfactants in the pronounced sensitivity of their association structural organization to temperature. This characteristic feature was noted very early by Shinoda (3) with regard to their micellar association and solubilization. A corresponding sensitivity may also be observed in the strong dependence of the liquid crystalline regions in phase diagrams of the system water, surfactant, and hydrocarbon (4). 

The phase behavior of a synthetic lecithin, dipalmitoyllecithin, as analyzed by Chapman and co-workers (5), is diagrammed in Figure 3. The main features are the same as in the phase diagram of egg lecithin a mixture of numerous homologs. As a consequence of the variation in fatty acid chain length, the chain melting point is lowered which means that the critical temperature for formation of liquid crystalline phases is reduced. This temperature is about 42 °C for dipalmitoyllecithin, and, if the lamellar liquid crystal is cooled below this temperature, a so-called gel phase is formed. The hydrocarbon chains in the lipid bilayers of this phase are extended, and they can be regarded as crystalline. The gel phase and the transitions between ordered and disordered chains are considered separately. 

FIGU RE 1.2 Phase diagrams for some simple natural gas hydrocarbons that form hydrates. Ql lower quadruple point Q2 upper quadruple point. (Modified from Katz, D.L., Cornell, D., Kobayashi, R., Poettmann, F.H., Vary, J.A., Elenbaas, J.R., Weinaug, C.F., The Handbook of Natural Gas Engineering, McGraw Hill Bk. Co. (1959). With permission.)... 

Hydrate phase diagrams for water-hydrocarbon systems provide a convenient overview of the calculation types. These diagrams differ substantially from the normal hydrocarbon phase diagrams primarily due to hydrates and the hydrogen bonds inherent in aqueous systems. The phase diagrams of Section 4.1 provide an overview for the calculation methods in this chapter and the next. 

Hydrate Phase Diagrams for Water + Hydrocarbon Systems... 

The phase behavior of hydrocarbon + water mixtures differs significantly from that of normal hydrocarbon mixtures. Differences arise from two effects, both of which have their basis in hydrogen bonding. First, the hydrate phase is a significant part of all hydrocarbon + water phase diagrams for hydrocarbons with a molecular size lower than 9 A. Second, water and hydrocarbon molecules are so different that, in the condensed state, two distinct liquid phases form, each with a very low solubility in the other. 

In Figure 4.2c for natural gases without a liquid hydrocarbon (or when liquid hydrocarbons exist below 273 K), the lower portion of the pressure-temperature phase diagram is very similar to that shown in Figure 4.2a. Two changes are (1) the Lw-H-V line would be for a fixed composition mixture of hydrocarbons rather than for pure methane (predictions methods for mixtures are given in Section 4.2 and in Chapter 5) and (2) quadruple point Qi would be at the intersection of the Lw-H-V line and 273 K, at a pressure lower than that for methane. The other three-phase lines of Figure 4.2a (for I-Lw-H and I-H-V) have almost the same slope at Qj. Otherwise, the same points in Section 4.1.1 apply. 

A comprehension of Figure4.3 has value because a similar phase diagram could be drawn for a natural gas of fixed composition between the quadruple points (Qi and QaJ. The same phase transitions and boundaries would qualitatively occur, with the artificial constraint that all hydrocarbon phases be of the same composition as the original gas. A second useful outcome of binary phase diagrams like Figure 4.3 is the use of the lever rule (Koretsky, 2004, p. 367) at constant temperature to determine relative phase amounts note that the lever rule can be applied for quantitatively correct phase diagrams. 

Figure 5.13 is the equivalent ethane + water pressure versus temperature phase diagram. Note that the Aq-sI-V line intersects the Aq-V-Lhc line at 287.8 K and 35 bar. Due to differences in the volume and enthalpy of the vapor and liquid hydrocarbon, the three-phase hydrate formation line changes slope at high temperature and pressure from Aq-sI-V to Aq-sI-Lhc, due to the intersectiion of Aq-sI-V line with the Aq-V-Lhc line (slightly higher than the ethane vapor pressure). Note that the hydrate formation pressure for ethane hydrates at 277.6 K is predicted to be 8.2 bar. 

To evaluate the phase equilibria of binary gas mixtures in contact with water, consider phase diagrams showing pressure versus pseudo-binary hydrocarbon composition. Water is present in excess throughout the phase diagrams and so the compositions of each phase is relative only to the hydrocarbon content. This type of analysis is particularly useful for hydrate phase equilibria since the distribution of the guests is of most importance. This section will discuss one diagram of each binary hydrate mixture of methane, ethane, and propane at a temperature of 277.6 K. 

PCB phase diagrams with carbon dioxide Effect of temperature and pressure on extraction of PCB and polyaromatic hydrocarbons Combination of solid-phase carbon trap with supercritical fluid chromatography for PCB, pesticides, polychlorodibenzo-p-dioxins and polychlorofurans... 

---