Abstract
In a concentric cylinder viscometer. Utah shale oils have different characteristics, both at equilibrium flow and during start-up from rest, depending on whether the wax has crystallized as needles or spherulites. Compared with waxy crude oils, which are thixotropic, shale oil had the added rheological property of being antithixotropic.
Introduction
The most likely liquid synthetic fuel to be produced initially in the U.S. will be raw shale oil from western oil shale. This abundant resource is located principally in the western Rocky Mountain states of Colorado. Utah. and Wyoming (Fig. 1). Ultimate commercial production probably will be transported to marketing, distribution, and refining centers by pipeline. It has been reported that Utah shale oils produced by the Union "B" and Paraho DH retorting processes gave similar physical and chemical properties. Some properties of the two Utah shale oils are given in Table 1. The only major difference is that the Union shale oil has a pour point of - 1 degree C compared with a pour point of 25 degrees C for the Paraho oil.
Wax Crystallization
The difference in the pour points of the oils from the Utah shale retorted by Union Oil Co of California and Paraho is caused mainly by the difference in how the wax in the respective oils crystallizes. In the high- pour-point (25 degrees C) Paraho DK oil, the wax, under a microscope, appears as fine (1 to 10 m) needles, as expected for normal paraffins. However, the wax in the low-pour-point (−1 degrees C) Union oil forms small spherulites.Wax spherulites have not been reported before: however, this type of crystal is seen commonly in polymer. Spherulites show up as round areas containing a maltese cross when observed between crossed polars under a microscope.Photomicrographs of these crystals are shown in Figs. 2 and 3. The former, showing spherulites, is of the Union oil. In contrast, they are very different from the customary needles as typified by the Paraho oil in the latter micrograph. Presumably, these highly ordered spheres are made up of wax needles grown out radially from the center as described by Hartshorne and Stuart. The polarized light is scattered only by those needles not parallel nor perpendicular to the plane of polarization.
Viscometer Measurements
To understand the effect of these spherulites on the flow characteristics of raw shale oil at flow conditions expected in a long-distance pipeline, typical stress-rate measurements were made in a rotating cylinder viscometer, the Haake Rotovisco RV3 with MK500 measuring head and MVI coaxial cylinder sensor having an 82-mm cup and radii ratio of 0.95. This equipment has provisions for varying shear rate continuously at selected values down to 23.4 sec(−1)/min and can produce and record shear stress as a function of either shear rate or time. Calibration of the sensor was verified with a sucrose/water solution at several temperatures.Changes in temperature always were made from lower to higher to keep the sensor full of oil. Also, the shear-stress/ shear-rate curves were obtained by starting at high shear, down to zero, and then back up.
SPEJ
P. 679^
