PREDICTION OF MOLECULAR DIFFUSION AT RESERVOIR CONDITIONS. PARTI---MEASUREMENT AND PREDICTION OF BINARY DENSE GAS DIFFUSION COEFFICIENTS P.M.

SIGMUND

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RECOVERY TECHNOLOGY JCPT76-02-05 JCPT-12 Prediction of Molecular Diffusion At Reservoir Conditions. Part I Measurement and Prediction of Binary Dense Gas Diffusion Coefficients Phillip M. Sigmund, Petroleum Recovery Institute, Calgary, Alberta Abstract Diffusion coefficients in binary dense fluid systems are measured and used along with data available in the literature to obtain a generalized correlation for predicting binary molecular diffusion coefficients in dense gases over a broad range of conditions. Introduction ATTEMPTS to quantify mixing phenomenal in porous media are often, encountered in design studies of processes(@ related to petroleum recovery. Dispersion, an important part of mixing phenomena, can be related to the distribution in travel times that results when a fluid passes through a porous media"1. On a micro- scopic scale, the two most important mechanisms con- tributing to dispersion are variations in velocity be- tween fluid elements flowing in neighbouring pores or groups of pores (often referred to as convective mixing) and molecular diffusion",', ". Although there is some controversy over the magnitude of convective effects, it has been thought that in vertical gravity- stabilized miscible floods, such as those carried out in the carbonate pinnacle reefs of Alberta, molecular diffusion played an important role in the mixing of the solvent bank with drive gas and oil('-, In other pro- cesses, such@h -as gas, solvent or C02 horizontal 'miscible floods, the effects of molecular diffusion are difficult to quantify, but are thought to be important in the recovery of non-flowing oil by mass transfer", ', "'. The estimation of molecular diffusion coefficients in low-pressure gases using .'the Chapman @@sk ?g Theory"." is adequate for a wide variety oi singie- Phillip M. Sigmund graduated from the University of Waterloo with a B.A.Sc. (c emical engineering) in 1963 and a M.A.Sc. (chemical en- gineering) in 1964. After obtaining his Pb.D. (chemical engineering) from the University of Texas in 1969, he joined the Petroleum Recovery Re- search Institute, where he is cur- rently employed as a senior research engineer. He has been involved in Institute research projects dealing _ with retrograde phenomena in porous media, diffusion and dispersion phenomena, hydrocarbon recovery from car- bonate reservoirs, and the use of CO, and SO, for en- hanc4@d oil recovery. Dr. Sigmund is a member of CIM, CIC, AIME and the Association of Professional Engineers of Alberta. 4a@ component and binary gases ... .... In liquids, the success of theoreticil models has been more limited, perhaps because of ilhe complex nature of molecular interac- tions in the liquid state. Nevertheless, except in the critical region, liquid diffusion coefficients can at present be predicted by empirical correlations, with sufficient accuracy for many engineering pur- poses"@ In the critical or dense fluid state, there are few exp@@rimental studies of diffusion coefficients inbinary mixtures. This has made it difficult t.o assess predictive t(@chniques, which have so far been tested largely on l-,he basis of self-diffusion data and are generally considered unreliable(',"). The pres(@nt two-part paper describes Petroleum Re(!overy Institute work that was directed toward de- veloping improved predictive methods for molecular diffusion coefficients in the high-pressure dense gas state which is commonly encountered under reservoir conditions. @rhe first part presents previously unob- tained data on binary diffusion coefficients for fluids in the dens(! gas state, and a general correlation for binary molecular diffusion coefficients at conditions ranging from ambient to those likely to exist in Alberta reservoirs. 'rhe second part presents a method., for using the binary correlation to estimate diffusion in multicompolient systems and shows how the effects of convection and diffusion can be combined to calculate concentration profiles for flu id mixtures flowing in porous media. Experimental APPARATUS AND PROCEDURE A Loschrriidt diffusion cell was used in the experi- ments. It consisted of three ball valves joined together with stainless steel tubing to form the upper and lower half cells. I'he ball valves were modified slightly to provide for circulation of dense gas mixtures above their upper dew point. The cell lengths in this version of the Loschmidt apparatus could be easily changed by using different lengths of tubing, allowing a broad range of pressures to be studied in gas systems. The diffusion cell was held in a vertical position by ring clamps and placed in a chromatographic air oven, which served as a thermostat. An illustration of the cell is shown in Figure 1. Diffusion was studied between mixtures of gases over some desired mole fraction interval (approxim- ately 0.20). The two mixtures of approximately desired composition were generated by metering appropriate amounts of each pure component into two storage ves- sels equipped with floating pistons. The volume and hence pressiire of each fluid was adjusted to ensure _ The Jburfial'of Canadian Petroleum