Moderate-temperature water-based

bitumen recovery from tar sand

J. Hupka and J. D. Miller

Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT841 12, USA
(Received 3 April 1991; revised 25 April 1997)

A moderate-temperature water-based separation process for the recovery of bitumen from tar sand (with
an emphasis on tar sands containing bitumen of high viscosity) is presented. The new approach was
evaluated using samples of Asphalt Ridge and Whiterocks tar sands, originating from the Uinta Basin in
Utah. Digested tar sand slurry, subjected to dilution, was sedimented in a gravity cell and the stratified
layers investigated under a microscope. Different layers formed in the gravity cell were characterized in
terms of the extent of bitumen separation from sand. Selected problems associated with the design of the’
processing strategy are briefly discussed.

(Keywords: bitumen; tar sand; water-based recovery)

Expected energy demand in the future has renewed samples were sprayed with kerosene as a diluent (13 wt%
interest in the recovery of hydrocarbon values from tar with respect to bitumen, for both tar sands). A
sand deposits; interest, which has recently become very penetration time of 2 h was used to dilute the bitumen,
real in the US A significant amount of the US tar sand as discussed previously’.
reserves can be mined and processed using water-based Batch hot water (5560°C) separation tests were
separation techniques, which in general consist of three performed in an agitated, baffled stirred-tank reactor
major steps: tar sand digestion (or conditioning), (3.8 1) equipped with two turbine impellers (75 wt%
separation of bitumen from the sand and cleaning of the solids). Bitumen was separated from sand by gravity
bitumen concentrate. The efficiency of bitumen separ- separation (40 wt% solids) and by flotation in a flotation
ation from the sand, and the extent of the bitumen cell (20 wt% solids). The air Row rate was 5 1 min- ’ and
concentrate clean-up depend on the extent of bitumen a flotation time of 10 min was used for each test, the
disengagement during the digestion step. bitumen concentrate being collected according to the
In the moderate temperature water-based processing following time sequence 1 + 2 + 3 +4 min, in order to
strategy, bitumen viscosity is controlled by diluent establish the flotation kinetics. The aqueous phase
application in a pretreatment step’. Bitumen viscosity alkalinity was adjusted by addition of Na,CO,. In some
remains < 1.5 Pa s through the entire process which experiments 0.5 g Na,P,O,, kg-’ tar sand was added
facilitates disengagement of bitumen from sand but also during digestion in order to improve the ability of the
leads to the further breakage of bitumen droplets. With aqueous phase to wet the sand particles and thus
the application of a chelating agent, such as sodium disengage the bitumen. No flotation collectors or frothers
tripolyphosphate2, a significant part of the bitumen in were used.
the digested tar sand slurry exists as freely suspended The analysis of the feed and product streams included
drops, still containing dispersed water and fine mineral compositional measurements by Dean-Stark analysis,
particles. Such bitumen droplets, not loaded with larger electrophoretic mobility measurements, bitumen vis-
sand particles, can be rapidly separated in a gravity cell. cosity measurements with a microviscometer and particle
The objective of the present work is to discuss selected size analysis by wet screening. Stereo microscopes and a
aspects of the modified, diluent-assisted processing fluorescent microscope were used for the study of bitumen
strategy based on processing data obtained for samples disengagement from sand particles.
of Asphalt Ridge and Whiterocks tar sands originating
from the Uinta Basin in Utah. MICROSCOPIC OBSERVATIONS
The digested tar sand slurry was placed in a 2 litre
EXPERIMENTAL graduated cylinder, diluted with fresh, warm water (up
Tar sand surface samples from the Asphalt Ridge and Table 1 Characteristics of tar sand samples used in water-based
Whiterocks deposits were used for bitumen recovery in separation tests
____ __--.
laboratory experiments. Basic characteristics of the tar
sand samples used are presented in Table 1. Feed material Bitumen viscosity
Bitumen (Pa s) Mineral particles
was prepared by mechanical crushing, screening content -- (< 100 pm)
and mixing. Subsequently, prior to processing, the Tar sand (wt%) 50°C 90°C (wt%)
______.
__-
Asphalt Ridge 11.8 80 I.2 8
Presented at ‘Eastern Oil Shale Symposium’, 6-8 November 1990,
Whiterocks 1.6 110 2.5 22
Lexington, KY, USA _~~ ~_____ ~_.
0016-2361/91/l II30845
( 1991 Butterworth-Heinemann Ltd.

1308 FUEL, 1991, Vol 70, November

 Water-based
COMPOSITION
[wt.X]
ZONE DESCRIPTlON Bitumen Water Solids
1 BitumenConcentrate* 50-85 lo-40 5-20
50-85 10-40 5-20
<3.0 88-96 4-10
Figure 1 Stratification of tar sand slurry in a gravity cell (40% solids)
to 40 wt% solids), resuspended by stirring with a rod,
and left for stratification of the dispersed phases (bitumen
droplets and sand particles). After 20 min of sedimen-
tation several layers were formed, as indicated in Figure I,
and samples were taken for microscopic analysis. At the
very top there was a continuous layer of bitumen
concentrate which, depending on the tar sand origin and
processing conditions, contained from 50 to 85 wt%
organic phase (bitumen and kerosene) and 15 to 50 wt%
dispersed water with suspended fine minerals. The size
of water droplets in this first layer was < 2 pm, while the
size of mineral particles was < 1 pm. The second layer
was also a bitumen-rich layer. In this case the bitumen
was present as separate drops of 60-500 pm in size. These
bitumen drops also contained emulsified water and would
not coalesce even after a period of 1 week. Numerous
fine particles were present at the oil-water interface. This
second layer of bitumen-rich material could be easily
resuspended in the supernatant by gentle stirring. The
third layer formed in the cylinder was more or less a
turbid aqueous phase. Unlike the aqueous phase from
the digested slurry (75 wt% tar sand) in which an
oil-in-water emulsion was observed with droplets from a
few micron to 10 pm in size, the third layer contained
practically no bitumen droplets.
As shown in Figure I the sedimented mineral particles
were also stratified (layers 4, 5 and 6), with the largest
grains settling in < 30 s and forming the bottom layer
(layer 6; analysis has shown < 1.5 wt% bitumen,
Figure 1). Above the bottom layer there was an
intermediate zone of sediment, well distinguished by its
dark colour, originating from its relatively high bitumen
content. This intermediate zone (layer 5) had a bitumen
grade comparable to the tar sand feed. Microscopic
analysis revealed numerous undigested tar sand aggre-
gates in the intermediate layer, very irregular in shape,
with bitumen serving as the binding medium. Some
aggregates had air bubbles entrapped in the bitumen,
which accounted for their slower settling velocity. The
hydrated sludge layer (layer 4) can be described as a
flocculated sediment, containing 300 mg l- ’ bitumen
with a droplet size of < 10-100 pm in diameter. Bitumen
droplets in layer 4 were spherical but their surface
frequently contained attached fine mineral particles.
PROCESSING STRATEGY
A block diagram of the hot water separation process for
a 100 tons per day tar sand pilot plant is shown in
bitumen recovery: J. Hupka and J. D. Miller
Figure 2. Tar sand, which undergoes size reduction
[stream (l)] is conditioned with diluent (2) and fed (3)
into the digester together with steam (6), recycled water
(5), wetting solution (4) [which was prepared from fresh
water (46), sodium carbonate (47) and sodium
tripolyphosphate (48)], recycled sludge (25 and 27)
combined into stream (7) and recycled low grade bitumen
concentrate (8). Digested slurry (9) is diluted with
recycled water (lo), screened to ~0.6 cm (11) and
transferred (12) to the gravity cell, yielding three
products: bitumen concentrate (17), slurry and/or
middlings (15) and coarse sand (16). The slurry/middlings
stream (15) undergoes flotation. The bitumen-rich
concentrate (19) is directed to clean-up, while the low
grade concentrate (8) is recycled for digestion.
The tailings sand (20) is subjected to size separation
in a spiral classifier, from which coarse sand (40) is stock-
piled, and the turbid tailings water (31) is pumped to a
thickener. An alternative to this treatment is direct size
separation of the coarse sand (16) from the gravity cell
in the spiral classifier, recycle of the aqueous phase with
suspended matter (32) into the flotation cell and
bypassing the size separation after flotation (34). The
supernatant from the thickener (36) is heated and
recycled (38). Make-up water (13), serving also as a
cooling medium during diluent removal from bitumen,
is added to the recycled water prior to heating.
Periodically, sediment (58) has to be pumped from
recycled water tank to a tailings pond. The run-off water
(41). thickened sludge (35) and various discharges (43)
are also collected in the tailings pond. The bitumen
skimmed from the thickener (37) and from the tailings
pond (44) is combined in one stream (14) and recycled.
The bitumen concentrates (17 and 19) are mixed with
diluent (21), and subjected to sedimentation and to a final
clean-up, if necessary, as indicated by streams (24) and
(26). When removal of fine mineral particles and fine
water droplets is not required, diluted bitumen
concentrate (39) is directed to distillation. After
distillation, the bitumen (28 and 30) can be utilized or
further processed, while the diluent (29) is recycled. Water
precipitated during diluent storage (50) is recycled. Other
stream numbers in the schematic stand for the following
media: demulsifier (23), air (56), optional flocculant (33),
make-up diluent (49) and heating steam (51-55).
Depending on tar sand properties, different versions of
the processing strategy are available and will be tested
in a pilot plant operation. Selected problems associated
with the design of key operations are briefly discussed
below.
Pretreutment with diluent
Undisturbed operation of the tar sand processing plant
(using hot water technology) will strongly depend on a
uniform composition of the feed material. This becomes
even more critical when diluent is used prior to digestion
in order to reduce bitumen viscosity. The amount of
diluent required to lower the digestion-separation
temperature to 5(1_55”C for most Utah tar sands is from
10 to 35 wt% with respect to the bitumen content, and
can be predicted from bitumen viscosity curvesl. Two
phenomena control diluent mixing into the bitumen
phase, namely capillary action and diffusion. Depending
on origin and properties, the tar sand feed generally exists
as particle aggregates from 1 to 5 cm (larger feed
FUEL, 1991, Vol 70, November 1309
Water-based bitumen recovery: J. Hupka and J. 0. Miller

I DIMSTZON
I

38

.O18

Figure 2 Block diagram of hot water separation process for bitumen recovery from tar sands

1310 FUEL, 1991, Vol 70, November


._
0 1 2 3 4 r ‘e
5 18
Time [h]
Figure 3 The uniformity of bitumen distribution in the Asphalt
tar sand: w, with diluent; 0, without diluent
fragments are expected for less consolidated tar sand,
such as Asphalt Ridge). Diluent is sprayed on the surface
of these feed particle aggregates and the capillary action
enables the diluent to penetrate and wet the bitumen
contained therein. After penetration and wetting,
diffusion finally leads to a uniform mixture of bitumen
and diluent. The lower the tar sand porosity and the
higher the bitumen viscosity, the longer the penetration
time required for complete and uniform bitumen dilution.
The wetting ability of the diluent is of pronounced
importance, particularly when capillaries are filled with
water. Diluent penetration will also depend on the
ambient temperature (water may freeze in tar sand pores
in the winter season).
The data shown in Figure 3 suggest that the time
necessary for uniform distribution of kerosene as a diluent
in the Asphalt Ridge tar sand was ~2 h. The
measurements reflect mostly the capillary action within
the ore, and indicate almost nothing about diluent
diffusion into the bitumen bulk. For low bitumen
viscosity tar sands, such as Asphalt Ridge, diffusion and
capillary penetration may be completed at the same time,
while for tar sands containing more viscous bitumen,
penetration of diluent by capillary action is much faster
than dilution of the bitumen phase by diffusion.
Digestion
Negative electrical charges at the bitumen droplet and
sand particle interfaces should facilitate disengagement
during tar sand digestion. The zeta potential curves for
Asphalt Ridge bitumen are presented in Figure 4. Above
pH 5 the zeta potential remains practically unchanged
while below pH 5 it becomes increasingly less negative
due to protonation of carboxylate surfactants and
hydroxyl groups, which provide the negative electrical
charge. Nevertheless the isoelectric point is not attained
even at pH 2, which may mean that other surfactants
(sulphonate and sulphate3) contribute significantly to
the surface charge of the bitumen droplets. The stable
negative charge may also result from fine mineral
particles (clays and carbonates with adsorbed organic
matter) present in the bitumen. Droplets originating from
the bitumen concentrate appear to be more stabilized by
negatively charged hydrophilic groups than droplets from
toluene-extracted bitumen. This observation is in
agreement with previous observations that bitumen
hydrophobicity can be destroyed during digestion4.
As reported in the literature, small amounts of calcium
Water-based bitumen recovery: J. Hupka and J. D. Miller
can be beneficial in the mineral-bitumen separation step
provided that appropriate anions are also present, on the
other hand larger amounts of calcium are not
recommended’. Tripolyphosphate which acts as a
complexing agent for calcium may be used to effectively
control the calcium concentration.
Gravity separation
A microscopic investigation revealed that bitumen
droplets from a digested tar sand slurry (containing
75 wt% solids, as typically obtained during water-based
separation processes) exist as a broad size distribution
with droplets from a few microns to 1 mm in size. The
large bitumen droplets can be rapidly separated in a
Ridge gravity cell. Fine bitumen droplets and bitumen-sand
aggregates require flotation for fast and complete
recovery. After gravity separation only small bitumen
droplets (~0.3 mm) remain in suspension and flotation
of negatively charged mineral particles competes with the
flotation of negatively charged bitumen droplets resulting
in an inferior flotation concentrate quality, when
compared to gravity separation. Gravity separation
applied to Utah tar sands yielded concentrates containing
5&80 wt% bitumen on a dry basis.
Flotation
As in most mineral processing systems, particles with
different degrees of liberation are present in digested tar
sand slurry, as revealed by microscopic observations. The
most distinctive flotability difference is between bitumen
droplets and bitumen-sand aggregates, nevertheless it
can be expected that both particle types will report to the
concentrate. It is much more difficult to describe the
flotation behaviour of mineral particles which appear to
be bitumen free under the microscope but in fact still
contain some organic matter chemically bound to the
surface as confirmed by FT-i.r. spectroscopy and
electrophoretic mobility measurements.
Flotation of bitumen at 20 wt% solids follows
gravity separation and produces concentrates containing
-7d
3 4 5 6 7 8 9
PH
Figure 4 Zeta potential of toluene-extracted bitumen droplets and
bitumen concentrate droplets in Asphalt Ridge tailings water (TW)
and in distilled water (DW): A, TW bitumen concentrate, 95°C pH
8.5, 80% grade; n , DW bitumen concentrate, 95°C pH 8.5, 80%
grade; x , TW toluene-extracted bitumen; 0, DW toluene-extracted
bitumen
FUEL, 1991, Vol 70, November 1311
Water-based bitumen recovery: J. Hupka and J. D. Miller
--.
w Fast Floating
‘!
-2.01 I I ,I I , , , , ,
0 1 2 3 4 5 6 7 9 9 lo
Time [minute]
Figure 5 Whiterocks tar sand flotation kinetics after bitumen
preliminary separation in a gravity cell
~55 wt% (dry basis) bitumen in the first minute.
Subsequently lower grade concentrate products are
recovered as the flotation continues. When easily
sedimenting bitumen droplets are removed from the tar
sand slurry as a gravity concentrate the impact of particle
diversity is even more pronounced. Flotation rate data,
which are presented in Figure 5, can be described by
first-order kinetics considering both fast and slow floating
particle types.
Water recycle
Most process water is recycled. A series of hot water
experiments with recycled water and the impact of water
recycle on the efficiency of bitumen recovery as well as
on tailings sedimentation is presented elsewhere*.
Bitumen concentrate clean-up
The combined bitumen concentrate, i.e. from the
gravity cell and from flotation, contains 2&60 wt%
dispersed water and fine minerals. Up to 40% of the fine
mineral particles can pass a 400 mesh screen. Larger sand
grains, most of which have undigested or residual
bitumen on the surface, report to the concentrate during
flotation. In bitumen clean-up tests the bitumen-diluent
ratio was 1:2. Usually fine particles reside at the oil-water
interface according to the following condition:
Yaw’ 1/sw+ Ys0
where Ye,.,,ysw and ysOare the interfacial tensions for
oil-water, solids-water and solids-oil, respectively. The
separation would be more efficient if solid particles could
be transferred from the oil-water interface into the water
droplets, which means that the solids should be well
1312 FUEL, 1991, Vol 70, November
wetted by the aqueous phase:
Stable water-in-oil emulsions have also been encountered
in our bitumen clean-up experiments, even when
microscopic investigation revealed almost a lack of
mineral particles at the water-oil interface. In this case
asphaltenes are responsible for the surface activity6.
Preliminary sedimentation tests have shown that in order
to reduce water and solids content to < 5 wt% in a
reasonable period of time centrifugation or other
separation techniques must be used.
,
11 12
CONCLUSIONS
A water-based moderate temperature (5&60”(Z) process
for bitumen recovery from tar sands (particularly those
containing bitumen of high viscosity, which is typical for
most US deposits) has been presented. Adequate diluent
pretreatment combined with application of sodium
tripolyphosphate, as a chelating/dispersing agent, made it
possible to recover a significant part of the bitumen in
a gravity cell as a high grade concentrate.
The process which includes the recovery of a gravity
concentrate offers the following advantages:
0 Low temperature processing, resulting in significant
thermal energy savings
l Moderate mechanical energy requirement for phase
disengagement, thus there is a possibility for digestion
under low shear conditions in a rotating drum
l Higher grade bitumen product from combined gravity
and flotation concentrates
l Process water recycle (cf. Ref. 2).
ACKNOWLEDGEMENTS
This research has been supported by the US Department
of Energy, Contract Number DEFC2189MC26268.
Mr R. White’s and Mr Y. Yang’s assistance in
the experimental part of this work is gratefully
acknowledged.
REFERENCES
Hupka, J., Miller, J. D. and Cortez, A. Mining Eng. 1983,35,1635
Huoka. J.. Drelich. J.. Miller. J. D. et 01. ‘Proc. 1990 Eastern Oil
ShLle &mposium’, Institute ior Mining and Minerals Research,
Lexington, 1991, p. 39; Fuel 1991, 70, 1313
Schramm, L. L. and Smith, R. G. Can. J. Chem. Eng. 1987,65,799
Misra, M., Aguilar, R. and Miller, J. D. Sep. Sci. Technol. 1981,
16(10), 1523
Hall, E. S. and Tollefson, E. L. Can. J. Chem. Eng. 1982,60, 812
Gonzalez, G. and Moreira, M. B. C. Poster Session Abstracts of
the International Symposium on Contact Angles and Wetting
Phenomena, 21-23 June, 1990, University ofToronto, Canada, p. 13