Ind. Eng. Chem. Res., Vol. 33, No.

5, 1994 1329
3.00

log-noma1 bimodal
2.75

b 50 ~ 1 2 . MPa 2

2 5
6 2.50 N
; ; j
d

1.0

1.5

2.0

Log (Diameter, pm)

2.5

3.0 .3.5 1.0

1.5

2.0

2.5

3.0

3.5

*a

e2 0 2.25

2
B e2

3.00

Figure 11. Comparison of unimodal and bimodal log-normal functions fitted to asphaltene particle size averages: (a) Countess oil C and 2.2 MPa. at 0 *C and 2.2 MPa, (b) Border condensate at 50 O
, . . .

8
+ I

2.75

8
2.50 2.25
0

eBorder condensate Countess oil o Lindbergoil a Cold Lake bitumen

v

2,00
I

Countess oil Lindbere oil Cold Lake bitumen

5
4 5

1-

200

400

600 0

200

400

600

Molar Mass of Crude Oil ( k g h o l )

Figure 13. Relationship between molar mass of crude oils and mean asphaltene particle size.

25

50

7501w

Pressure, MPa

Temperature, C

Figure 12. Effects of pressure and temperature on mean asphaltene particle size: (a) at a constant temperature of 0 OC, (b) at a constant pressure of 2.2 MPa.

slight increase in the mean particle size with pressure for all crude oils except the Lindberg oil. Figure 12bpresents the mean particle sizes as a function of temperature for all crude oils. The Border condensate showed an interesting effect of temperature; there is a significant decrease in log E from 2.60 to 2.28 between 0 and 50 "C followed by an increase to 2.36 at 100 "C. The results are similar to those reported for Qaiyarah oil by Ali and Al-Ghannam (1981). It is possible that the asphaltene particles at 0 "C have a greater occlusion of the diluent and maltenes. The Cold Lake, Countess, and Lindberg oils show only slight change in the mean particle size over the temperature ranges. At higher temperatures (75-150 "C), it appears that the asphaltenes of the heavier crude oils soften to the point where the agglomeration of larger particles takes place due to increased adhesion. As suggested by Speight (19911, it may be caused by an increase in the amount of nearasphaltene molecules (resins of high molar mass) precipitating due to their decreased solubility. The viscosity measurements by Mehrotra et al. (1989) on the heaviest fraction (cut no. 5)of Cold Lake bitumen, which comprised 49 mass % asphaltenes, indicated a softening temperature of approximately 100 "C for the glasslike solid. Furthermore, the observation of Speight (1991) that a decrease in the solubility parameter would precipitate a "tacky" semisolid residue may explain the "super agglomerates" observed with Cold Lake bitumen and Lindberg oil at higher temperatures. Thus, the term "particle size" may not have any significance for asphaltene agglomerates at temperatures higher than approximately 75-100 "C. Effect of Crude Oil Molar Mass. Figure 13 shows the effect of oil molar mass on the mean asphaltene particle diameter. The experiments at 50 and 100 "C show discernible trends for an increase in particle size with molar mass of crude oils. There is limited agreement with Ferworn et al. (1993), who had found an increase in asphaltene particle size with crude oil molar mass at

22 "C and atmospheric pressure. However, for other temperature and pressure conditions, i.e., 0 "C and either 2.2 or 5.6 MPa, the results do not show any appreciable dependence of asphaltene particle size with molar mass. Overall, the results of this study suggest a slight increase of the mean asphaltene particle size with an increase in pressure and with a decrease in temperature; however, any effect of crude oil molar mass is not apparent.

Conclusions Modifications of the Brinkmann particle size analyzer were described for studying the effects of temperature and pressure on the size of asphaltene particles in crude oils diluted with n-pentane. Expanding the range for the particle size analyzer to 10-1200 pm proved invaluable to this investigation. Experiments were performed with four crude oil samples diluted (in a volumetric ratio of 1:60) with n-pentane at 0-150 "C and up to 5.6 MPa. Although the particle size distribution in most cases was log-normal, the Border condensate and Countess oil showed instances where bimodal distributions were clearly apparent. An increase in pressure yielded an increase in the mean asphaltene particle size for all oil samples except the Lindberg oil. Varying the temperature from 0 to 100 "C yielded a significant change in the mean particle size for the Border condensate. In experiments with the two higher molar mass crude oils (Cold Lake bitumen and Lindberg oil), "super agglomerates" were observed at temperatures of 75 "C and higher, which is attributed to the softening and adhesion of asphaltene particles. Acknowledgment Financial support provided by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Alberta Oil Sands Technology and Research Authority (AOSTRA), and the Department of Chemical and Petroleum Engineering (University of Calgary) is gratefully acknowledged.

Nomenclature
d, = mean particle diameter, pm rn = relative weight of the first log-normal curve