USE OF FREE BODIES TO INCREASE SIZE OF DISPERSED PHASE PARTICLES

UTILISATION DE CORPS LIBRES POUR AUGMENTER LA TAILLE DES PARTICULES D'UNE PHASE DISPERSEE

English Abstract

ABSTRACT OF THE INVENTION
A mixture containing a dispersed bitumen, oil or
hydrocarbon phase and a continuous aqueous phase is passed
for treatment through a rotating horizontal tumbler, containing
oleophilic free bodies, for the purpose of increasing the
particle size of the dispersed phase and facilitating
subsequent separation of the phases of the mixture. Alternately,
a mixture containing a dispersed aqueous phase and a
continuous bitumen, oil or hydrocarbon phase is passed for
treatment through a rotating horizontal tumbler, containing
hydrophilic and oleophilic free bodies, for the purpose of
increasing the particle size of the dispersed phase and
facilitating subsequent separation of the phases of the mixture.
The free bodies tumbling with the mixture in the drum have
affinity for the dispersed phase particles and cause an increase
in the particles size of the dispersed phase of the mixture
through a process of cyclic coalescence, agglutination,
condensation and/or coherence of dispersed phase particles
from the mixture onto the surface of the free bodies and
cyclic shedding or sloughing off of coalesced dispersed phase
back into the mixture. Some mixtures that may be treated
include oil sand slurries, effluent streams from a hot sands
extraction plant, oil-in-water emulsions from processes that
use enhanced oil well recovery, and bitumen froth.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for increasing the mean particle size of dis-
persed phase particles in a liquid mixture of continuous phase
and dispersed phase which comprises the steps of:
(a) introducing said mixture into a generally horizontal
rotating drum that contains free bodies having surfaces
that have affinity for dispersed phase particles, said drum
rotating at a rate not exceeding twice the critical rota-
tion rate.
(b) agitating said mixture in the rotating drum so that
said free bodies continually mix with said mixture and come
in contact with said dispersed phase particles causing said
particles to unite to form particles that are larger in
size than the particles of said dispersed phase in the
mixture when introduced into said drum, and
(c) removing said mixture containing said larger particles
from said drum for subsequent separation of dispersed
phase particles from the continuous phase.
2. A method according to Claim 1 wherein the dispersed
phase is an oil phase, the continuous phase is an aqueous phase,
and the free bodies have oleophilic surfaces.
3. The method as set forth in Claim 2 wherein the dis-
persed oil phase has a viscosity in the range from 1.0 to 5000
poises.
4. The method as set forth in Claim 3 wherein the dis-
persed oil phase has a viscosity in the range from 10 to 500
poises.
5. The method as set forth in Claim 3 wherein the free
bodies have a density of from 60 to 600 pounds per cubic foot.
33

6. The method as set forth in Claim 5 wherein the free
bodies have a density range of from 100 to 300 pounds per cubic
foot.
7. The method as set forth in Claim 5 wherein the free
bodies have dimensions within the range of 0.1 to 10.0 inches.
8. The method as set forth in Claim 7 wherein the free
bodies have dimensions within the range of 0.5 to 2.0 inches.
9. The method according to Claim 7 wherein the free bodies
have a rough surface.
10. The method according to Claim 7 wherein the free bodies
have a porous surface.
11. The method as set forth in claim 7 wherein the free
bodies have both oleophilic and hydrophilic surfaces.
12. The method according to Claim 1, 2 or 7 wherein the
drum rotates at a speed sufficient to cause agitation of the
mixture by the free bodies but at a speed not in excess of
2 x <IMG> r.p.m. wherein r is the inner radius of the drum
measured in feet.
13. The method as set forth in Claim 7 wherein said drum
also contains free bodies with hydrophilic surfaces.
14. The method as set forth in Claim 7 wherein internal
surfaces of said drum are oleophilic.
15. The method as set forth in Claim 7 wherein one or more
emulsion breaking chemicals are added to said mixture.
34

16. The method as set forth in Claim 15 wherein said chemical
is a inorganic alkaline earth salt or hydroxide.
17. The method as set forth in Claim 7 wherein said mixture
is an oil-in-water emulsion produced by enhanced oil well
recovery methods.
18. The method as set forth in Claim 7 wherein said mixture
is an aqueous stream from a hot water oil sands extraction plant
19. The method as set forth in Claim 7 wherein said mixture
is an aqueous oil sand slurry from which debris, rocks and/or
oversize lumps have been removed.
20. The method as set forth in Claim 7 wherein said mixture
is an oil-in-water emulsion produced by enhanced oil well
recovery methods to recover bitumen from buried oil sands.
21. A method according to Claim 1 wherein the dispersed
phase is an aqueous phase, the continuous phase is an oil
phase and the free bodies have hydrophilic surfaces.
22. The method as set forth in Claim 21 wherein the continuous
phase has a viscosity within the range 1.0 to 50 poises.
23. A method as set forth in Claim 21 wherein said drum
also contains free bodies with oleophilic surfaces.
24. A method as set forth in Claim 21 wherein internal surfaces
of said drum are hydrophilic.

25. The method as set forth in Claim 1 wherein one or more
emulsion breaking chemicals are added to said mixture.
26. The method as set forth in Claim 21 wherein a hydrophilic
surface active agent is added to the mixture to encourage
particulate solids to collect into the dispersed phase.
27. The method as set forth in Claim 21 wherein a chelating
agent is added to the mixture for the purpose of transferring
particulate solids from the continuous phase to the dispersed
phase.
28. The method as set forth in Claim 21 wherein said mixture:
is a bituminous froth containing entrapped gas bubbles
wherein said gas bubbles collapse during said agitation
in said drum thereby enhancing subsequent separation of water
and particulate solids from said froth.
29. The method as set forth in Claim 21 wherein said continu-
ous phase consists of bitumen that contains water droplets and
particulate solids.
30. The method as set forth in Claim 21 wherein said continuous
phase consists of heavy petroleum oil.
31. An apparatus for increasing the size of dispersed phase
particles in a feed mixture of dispersed phase and continuous
phase, comprising:
(a) a generally horizontal rotating drum provided with a feed inlet
and a product outlet, said drum being partly filled with
free bodies that have an affinity for dispersed phase drum
36

feed contents,
(b) drum mounting means and rotating means supporting said
drum so as to be able to rotate the drum as a tumbler at a
rate not exceeding twice the critical rotation rate,
(c) means that permits introduction of feed to the rotat-
ing drum such that drum contents will not spill out of the
drum at the feed inlet, and
(d) adjustable means that permits exit of product mixture
from the drum at a rate that maintains a desired mixture
level in the drum but that prevents free bodies from
leaving the drum.
32. Apparatus according to Claim 31 which includes longi-
tudinal ribs along the drum internal periphery to prevent drum
contents from sliding along drum wall and to cause the mixture
to tumble inside said drum.
33. Apparatus according to Claim 31 wherein the free bodies
contain oleophilic surfaces.
34. Apparatus according to Claim 31 wherein the free
bodies contain hydrophilic surfaces.
35. Apparatus according to Claim 31 wherein the free bodies
contain both oleophilic and hydrophilic surfaces.
36. Apparatus according to Claim 31 wherein at least a
portion of the internal drum wall surface is oleophilic.
37. Apparatus according to Claim 31 wherein at least a
portion of the internal drum wall surface is hydrophilic.
38. Apparatus according to Claim 31 wherein the products
outlet is positioned in the drum such that under steady state
conditions the composition of the drum contents is caused to be
37

different from the composition of the feed and products
streams.
39. Apparatus according to Claim 38 wherein the products
outlet is positioned in an end wall of the drum.
40. Apparatus according to Claim 39 wherein the products
outlet is an annular ring.
41. Apparatus according to Claim 39 wherein the products
outlet is a circular opening at the center of the end wall.
42. Apparatus according to Claim 39 wherein the products
outlet size is determined by an adjustable sliding gate.
43. Apparatus according to Claim 31, 32 or 33 wherein the
drum rotates at a speed sufficient to cause agitation of the
mixture by the free bodies but at a speed not in excess of
2 x <IMG> r.p.m. wherein r is the inner radius of the drum
measured in feet.
44. A method for increasing the mean particle size of
dispersed oil phase particles in a liquid mixture of continuous
aqueous phase, with or without solids, and dispersed oil phase,
with or without solids, which comprises the steps of:
a. introducing said mixture into a generally
enclosed horizontal rotating drum that contains retained free
bodies having oleophilic surfaces that have affinity for oil
phase particles,
b. agitating said mixture in the rotating drum so
that said oleophilic surfaced free bodies continually mix with
said mixture and come in contact with said dispersed oil phase
particles causing said dispersed oil phase particles to tem-
porarily adhere to the surface of said free bodies and unite
to form enlarged oil phase particles until such enlarged oil
38

phase particles become sufficiently large that they are
redispersed into said mixture from the surface of said free
bodies as enlarged dispersed oil phase particles by the
physical forces operating within said rotating drum as a
result of said agitation, and
c. removing said mixture containing said enlarged
dispersed oil phase particles from said drum containing said
retained free bodies for subsequent separation of said enlarged
dispersed oil phase particles from said continuous aqueous
phase.
45. The method as set forth in Claim 44 wherein the
free bodies are spheres or spheroids.
46. A method for increasing the mean particle size of
dispersed aqueous phase particles in a liquid mixture of
continuous oil phase and dispersed aqueous phase which com-
prises the steps of:
a. introducing said mixture into a generally
enclosed horizontal rotating drum that contains retained free
bodies, at least a portion of said free bodies having at least
one hydrophilic surface that has affinity for aqueous phase.
b. agitating said mixture in the rotating drum so
that said free bodies continually mix with said mixture such
that the hydrophilic surface of said free bodies come in
contact with said dispersed aqueous phase particles causing
said dispersed aqueous phase particles to temporarily adhere
to the hydrophilic surface of said free bodies and unite to
form enlarged aqueous phase particles until such enlarged
aqueous phase particles become sufficiently large that they
are redispersed into said mixture from the hydrophilic surface
of said free bodies as enlarged dispersed aqueous phase
39

particles by the physical forces operating within said
rotating drum as a result of said agitation, and
c. removing said mixture containing said enlarged
dispersed aqueous phase particles from said drum containing
said retained free bodies for subsequent separation of
dispersed aqueous phase particles from the continuous oil
phase.
47. A method as set forth in Claim 46 wherein said drum
also contains free bodies with oleophilic surfaces or with at
least one oleophilic surface.
48. A method as set forth in Claim 46 wherein at least
part of the internal surfaces of said drum are hydrophilic.
49. The method as set forth in Claim 46 wherein one or
more emulsion breaking chemicals are added to said mixture to
remove from said aqueous phase particles any repulsive forces
that would prevent attachment of dispersed aqueous phase
to the hydrophilic surfaces of said free bodies.
50. The method as set forth in Claim 46 wherein a
hydrophilic surface active agent is added to the mixture to
encourage particulate solids to collect into the aqueous
dispersed phase instead of in the oil phase.
51. The method as set forth in Claim 46 wherein a
chelating agent is added to the mixture for the purpose of
transferring particulate solids from the continuous oil phase
to the dispersed aqueous phase.
52. The method as set forth in Claim 46 wherein said
mixture is a bitumous froth containing entrapped gas bubbles
wherein said gas bubbles collapse during said agitation in

said drum thereby enhancing subsequent separation of water and
particulate solids from said froth.
53. The method as set forth in Claim 46 wherein said
continuous phase consists of bitumen that contains water drop-
lets and particulate solids.
54. The method as set forth in Claim 46 wherein said
continuous phase consists of heavy petroleum oil.
55. An apparatus for increasing the size of dispersed
phase particles in a feed mixture of dispersed phase and
continuous phase, comprising:
a. generally enclosed horizontal rotatable drum
provided with a feed inlet and a product outlet, said drum
being partly filled with retained mechanical free bodies that
have an affinity for dispersed phase drum feed contents,
b. drum mounting means and rotating means supporting
said drum so as to be able to rotate the drum as a tumbler
at a predetermined rate of speed,
c. means that permits introduction of feed to the
rotating drum such that drum contents will not spill out of
the drum at the feed inlet, and
d. means that permit exit of product mixture from
the drum at a rate that maintains a desired mixture through the
drum but that prevents the retained free bodies from leaving
the drum.
56. Apparatus according to Claim 55 which includes
longitudinal ribs along the drum internal periphery to prevent
drum contents from sliding along drum wall and to cause the
mixture to tumble inside said drum.
41

57. Apparatus according to Claim 55 wherein at least a
portion of the free bodies contain at least one oleophilic
surface.
58. Apparatus according to Claim 55 wherein at least a
portion of the free bodies contain at least one hydrophilic
surface.
59. Apparatus according to Claim 55 wherein the free
bodies contain both oleophilic and hydrophilic surfaces.
60. Apparatus according to Claim 55 wherein at least a
portion of the internal drum surfaces is oleophilic.
61. Apparatus according to Claim 55 wherein at least a
portion of the internal drum surfaces is hydrophilic.
62. Apparatus according to Claim 55 wherein the products
outlet is positioned in the drum such that under steady
state conditions the composition of the drum contents is
caused to be different from the composition of the feed and
products streams.
63. Apparatus according to Claim 55 wherein the products
outlet is positioned in an end wall of the drum.
64. Apparatus according to Claim 63 wherein the products
outlet is an annular ring.
65. Apparatus according to Claim 63 wherein the products
outlet is a circular opening at the center of the end wall.
66. Apparatus according to Claim 63 wherein the products
outlet size is determined by an adjustable sliding gate.
67. A method for increasing the mean particle size of
42

aqueous particles dispersed in an oil phase which comprises
tumbling a mixture of oil phase having dispersed aqueous
particles in the presence of some free bodies having at least
one hydrophilic surface for a time sufficient to allow said
aqueous particles to come into contact with said bodies and
unite into larger particles.
68. A method for increasing the mean particle size of
oil particles dispersed in an aqueous phase which comprises
tumbling a mixture of aqueous phase having dispersed oil
particles in the presence of some free bodies having at least
one oleophilic surface for a time suffficient to allow said oil
particles to come into contact with said free bodies and unite
into larger particles.
43

CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE
69. The method as set forth in Claim 44 wherein the
dispersed oil phase has a viscosity in the range from 0.1 to
50,000 poises.
70. The method as set forth in Claim 69 wherein the
dispersed oil phase has a viscosity in the range from 1.0 to
5000 poises.
71. The method as set forth in Claim 70 wherein the free
bodies have a density of from 30 to 800 pounds per cubic foot.
72. The method as set forth in Claim 71 wherein the free
bodies have a density range of from 200 to 500 pounds per cubic
foot.
73. The method as set forth in Claim 71 wherein the free
bodies have dimensions within the range of 0.1 to 10.0 inches.
74. The method as set forth in Claim 73 wherein the free
bodies have dimensions within the range of 0.5 to 2.0 inches.
75. The method as set forth in Claim 73 wherein the
free bodies have a rough surface.
76. The method as set forth in Claim 73 wherein the free
bodies have a porous surface.
77. The method as set forth in Claim 73 wherein the free
bodies have both oleophilic and hydrophilic surfaces.
78. The method as set forth in Claim 73 wherein said
drum also contains free bodies with hydrophilic surfaces.
79. The method as set forth in Claim 73 wherein at least
a portion of the internal surfaces of said drum are oleophilic.
44

80. The method as set forth in Claim 74 wherein the free
bodies are fabricated from metal.
81. The method as set forth in Claim 80 wherein the free
bodies are pretreated to remove metal oxide from their surfaces
to cause them to become oleophilic and to permit dispersed oil
phase particles to form a coating on their surfaces.
82. The method as set forth in Claim 80 wherein the
mixture in the drum is abrasive, causing removal of any oxide
coating from the surface of said free bodies and causing the
surfaces of said free bodies to remain oxide free in order for
the free bodies to become and remain oleophilic and coated with
dispersed oil phase particles.
83. The method as set forth in Claim 73 wherein one or
more emulsion breaking chemicals are added to said mixture to
remove from said dispersed oil phase particles any repulsive
forces that would prevent attachment of dispersed phase to the
oleophilic surfaces of said free bodies.
84. The method as set forth in Claim 83 wherein said
chemical is an inorganic alkaline earth salt or hydroxide.
85. The method as set forth in Claim 73 wherein said
mixture is produced from an oil well.
86. The method as set forth in Claim 73 wherein said
mixture is derived from a hot water oil sands extraction plant.
87. The method as set forth in Claim 73 wherein said
mixture is an aqueous oil sand slurry from which debris, rocks
and/or oversize lumps have been removed.
88. The method as set forth in Claim 73 wherein said

mixture is an oil-in-water emulsion produced by enhanced oil
well recovery methods to recover bitumen from a buried tar
sands or heavy oil deposit.
89. The method as set forth in Claim 46 wherein the
continuous phase has a viscosity within the range 0.01 to
500 poises.
90. Apparatus according to Claim 55 wherein the product
mixture exits through perforations in the cylindrical wall of
said drum.
91. Apparatus according to Claim 90 wherein said drum is
partly immersed in a tank or cover and drum contents, after
passing through said perforations, leave said tank or cover to
the separator.
92. Apparatus according to Claim 91 wherein paddles on
said drum are adapted to prevent settling of solids in said
tank or cover.
46

Description

sACKGROUND OF THE INVENTION
The present invention relates to a method for
treating a mixture of continuous phase and dispersed phase
so as to facilitate subsequent separation oE the phases. The
intent of the present invention is to increase the average
size of dispersed phase particles in the mixture under
treatment.
This invention is primari:Ly concerned with recovering
bitumen from mined oil sand and for recovering bitumen or
oil phase from oil and water m:ixtures produced from oil wells.
Extensive deposits of oil sands, which are also known as
tar sands and bituminous sands, are found in Northern Alberta,
Canada. The sands are composed of siliceous material with
grains generally having a size greater than that passing a
325 mesh screen (44 microns) and a relatively heavy, viscous
petroleum, called bitumen, which fills the voids between the
grains in quantities of from 5 to 21 percent of total compo-
sition. (All percentages referred to herein are in weight
percent unless noted otherwise). Generally the bitumen
content of the sand is between 5 and 15 percent. This bitumen
contains typically 4.5 percent sulfur and 38 percent aromatics.
Its specific gravity at 60F. ranges generally from about 1.00
to about 1.06. The oil sands also contain clay and silt.
Silt is defined as siliceous material which will pass a 325
mesh screen, but which is larger than 2 microns. Clay is
material smaller than 2 microns, including some siliceous
material of that size. Extensive oil sand deposits are also
found elsewhere in the world, such as in the Orinoco heavy
oil belt of Venezuela and in the area near Vernal,-Utah.
The mineral and bitumen of these deposits differ somewhat
from those of the Alberta deposits. Compared with the Alberta
1`~' -. ~

q~q~
oil sands, the Utah deposit contains a coarser sand, less
clay and an even more viscous bitumen.
Much of the world resource of bitumen and heavy
oil is deeply buried by overburden. For example it has been
estimated that only about lO percent of the Alberta oil sand
deposit is close enough to the earth's surface to be
conveniently recovered by mining. The remainder is buried
too deeply to be economically surfaced mined. Hydraulic mining
or tunnel mining has been proposed for these deeper deposits.
Generally, however, it is considered that enhanced recovery
by steam injection, by injectlon of aqueous solutions, and/or
by in situ combustion may possibly be more e~fective for
obtaining bitumen or heavy oil from deeply buried formations.
Such enhanced recovery methods use one or more oil wells that
penetrate the formation and stimulate or recover the resource.
Recovery of bitumen from a well by steam stimulation is
described in Canadian Patent No. 822,985 granted on
September 16, 1969 to Fred D. Muggee. Depending upon the
procedure employed, enhanced recovery methods either produce
mixtures of oil, water and water-in-oil emulsions or produce
oil-in-water emulsions.
There are several well known procedures for separating
bitumen from mined oil sands. In a hot water method, such as
disclosed in Canadian Patent Mo. 841,581 issued May 12, 1979
to Paul H. Floyd et al.; the bituminous sands are jetted with
steam and ~ulled with a minor amount of hot water and sodium
hydroxide in a conditioning drum to produce a pulp which
passes from the conditioning drum through a screen, which
removes debris, rocks and oversize lumps, to a sump where it
is diluted with additional water. It is hereafter carried
into a separation cell.
~1

In the separation cell, sand settles to the bottom
as tailings which are discarded. Bitumen rises to the top of
the cell in the form of a bituminous froth which is called
the primary froth product. An aqueous middlings layer
containing some mineral and bitumen is formed between these
layers. A scavenging step :i~ normally conducted on this
middlings layer in a separate flotation zone. In this
scavenging step the middlings are ae!rated so as to produce
a scavenger tailings product, which is discarded, and a
scavenger froth product. The scavenger froth product is
thereafter treated to remove some of its high water and
mineral matter content and is thereafter combined with the
primary froth product Eor urther treatment. This combined
froth product typically contains about 52 percent bitumen,
6 percent minerals, 41 percent water, all by weight, and may
contain from 20 to 70 volume percent air. It resembles a
liquid foam that is difficult to pump and, for that reason,
is usually trea-ted with steam to improve its flow
characteri-stics.
The high water and mineral contents of the combined
froth product normally are reduced by diluting it with a
hydrocarbon diluent such as naptha. It is then centrifuged
to produce a tailings product and a final bitumen product
that typically contains essentially no water and about 1.3
percent solids and that is suitable for coking, hydrovis-
breaking and other refining techni~ues for producing a
synthetic crude oil. The tailings products, containing some
naptha, are discarded.
There are basically four effluent streams from the
Hot Water Process. Each carries with it some of the bitumen
of the feed; thereby reducing the efficiency of the process.
-- 3 --
..~

7~
These include the oversize material, the sand from the
separation cells, the silt and clay from the scavenger cells
and the tailings from the centrifuges. Up to 10 percent
of the bitumen in the original feed and up to 2 1/2 percent
of the naptha stream may be lost in this manner. Much of
this bitumen effluent finds its way into large retention ponds
that are typical of the Hot Water Process. The bottom of
one such retention pond may contain up to 50 percent dispersed
mineral matter substantially of clay and silt as well as 5 percent
bitumen. As disclosed in Canadian Patent No. 975,697 issued
on October 7, 1975 to Davitt H. James this part of the pond
contents, referred to as sludge, is a potential source of
bitumen.
The Hot Water Process described in the preceeding
paragraphs separates bitumen from a prepared oil sand slurry.
Various methods for preparing oil sand slurries are taught
in the prior art, as for example disclosed in Canadian Patent
No. 918,588 issued on January 9, 1973 to Marshall R. Smith et
al. and in United States Patent No. 3,968,572 issued on
July 13, 1976 to Frederick C. Stuchberry. These apparatus as
disclosed were especially designed to form a slurry that is
hot, that contains finely dispersed air bubbles and wherein
the bitumen is in the form of small flecks. Such a slurry
is amenable to subsequent separation in a hot water bath
after dilution, wherein bitumen forms into a froth that
rises to the top of the bath and is skimmed therefrom.
Alkaline reagents such as sodium hydroxide are normally
added in this Process to give to the slurry those properties
that provides for efficient flotation of the bitumen in said
water bath. However, in the presence of sodium hydroxide,
fine clay particles inthe effluent streams from this process

7~1~
do not settle readily. For this reason inordinately large
settling ponds are required to contain the e.ffluents from
commercial hot water oil sands extraction plants.
The present invention applies to a method of treating
various streams from oil sand operat:ions, having a dispersed
oil or aqueous phase, to cause combi.nation of dispersed
particles which combination improvec; the recovery of the oil
phase by the use o apertured oleophilic endless conveyor
belts to achieve oil phase~aqueous phase separations. These
processes are superior to -the Hot Water Process because
separations are conducted at lower process temperatures and with
lower water requirements. For comparable oil sand feedstocks
the bitumen produced by combination of dispersed phase
particles followed by oil phase-aqueous phase separation with
an apertured oleophilic belt as typically disclosed is of
higher quality than the froth produced by a Hot Water
Process.
The apertured oleophilic conveyor belt, that may
be used to separate emulsions, slurries, or mixtures of oil
phase and aqueous phase, typically consists o a mesh belt
that is woven from fibre, string or wire of high tensile
strength and atigue resistance, that is oleophilic by nature
or that will bond strongly with a belt coating that is
oleophilic. This belt typically is supportea by two conveyer
end rolls that provide tension and form to the belt.
Separation is achi.eved by passing a slurry, emulsion or mixture
of oil phase and water phase, with or without particulate
solids, through the belt one or more times. Water phase and
particulate solids in the water phase pass through the belt
apertures and are discarded while oil phase attaches itself
i ~
,~J,.,~

~ ~ ~7t~
to the belt because of its attraction for the oleophilic
belt surfaces. The oil phase subsequently is recovered from
said belt as a product. Typical processes are disclosed in
United States Patent ~,224,13~ which issued September 23,
19~0 to Jan Kruyer and United States Patent 4,236,995 which
issued December 2, 1980 to ~an Kruyer.
BRIEF_DESCRIPTION OF T~IE INVENTION
The purpose of the invention is to treat a mixture
of water and immiscible hydrocarbon to facilitate subsequent
separation.
The subject matter that is claimed as the invention
herein is a method for increasing the mean particle size of
aqueous particles disposed in an oil phase, or of oil particles
disposed in an aqueous phase, which comprises tumbling a
mixture of an oil or water phase having dispersed aqueous or
oil particles in the presence of some free bodies having at
least one hydrophilic or oleophilic surface, for a time
sufficient to allow the particles to come in contact with
the bodies and unite into larger particles. The invention
also relates to an apparatus adapted to carry out this
process, comprising a horizontal rotatable drum which is
partly filled with retained mechanical free bodies that have
an affinity for the dispersed phase drum feed contents,
means to rotate the drum at a predetermined rate of speed,
means to introduce the feed into the drum so that
the drum contents will not spill out at the feed inlet and
means that permit exit of the product mixture from the drum
at a rate that maintains a desired mixture through the drum
but that prevents the retained free bodies from leaving the
drum.
In accordance with the one a~spect of the present
invention a mixture of continuous phase and dispersed phase
-- 6 ~

is tumbled with suitably surfaced free bodies in a horizontal
rotating drum to prepare a mi~ture suitable or separation
by an oleophilic apertured endless conveyor belt, wherein the
aqueous phase readily passes through the belt apertures and
is discarded while an optimum amount of oil phase is captured
by the oleophilic surfaces of the belt and is carried away
for removal from the belt surface for additional treatment
or upgrading or is treated on the belt prior to removal.
The free bodies of the present invention are spheres,
or more complex bodies, with surfaces that have af~inity for
dispersed phase particles. When tumbled in a drum together
with an emulsion or a slurry these free bodies cause particle
size growth of the dispersed phase in this drum. The free
bodies remain in the drum at all times while the mixture being
treated passes through the drum and is acted upon or processed
by the free bodies while in the drum.
In the preferred embodiment a continuous feed of
oil-in-water emulsion, obtained from enhanced oil well or
bitumen recovery, is tumbled in a drum with reagents and
oleophilic free bodies to produce a continuous product of oil
phase droplets and streamers in a continuous water phase.
In a second preferred embodiment a continuous feed
of bitumen froth, or a water-in-oil emulsion, is tumbled in
a drum with hydrophilic free bodies (and preferably many
oleophilic free bodies~ to produce a continuous bitumen, or
oil phase, product with reduced air content and/or wherein
the dispersed water phase particles have grown in size.
In a third preferred embodiment a continuous feed of
aqueous slurry, that contains dispersed bitumen, or oil, is
tumbled in a drum with oleophilic (and possibly some
hydrophilic or a combination thereof) free bodies to produce
a continuous slurry product wherein the dispersed bitumen, or

oil, particles have grown in size.
Following is a lis-t of feedstocks and/or particles
which may be treated according to the present invention:
1. An oil sand slurry, from which debris, rocks and
oversize lumps have been removed previously.
2. The middlings drag stream of a hot water oil sands
extraction plant containing dispersed bitumen particles.
3. One or more of the effluen-t streams of a hot water
oil sands extraction plant containing dispersed bitumen particles~
4. An effluent stream of a ho-t water oll sands extraction
plant containing dispersed bitumen with naptha particles.
5. A sludge obtained from the retention pond of a hot
water oil sands extraction plant containing dispersed bitumen
particles.
6. Oil-in-water and/or water-in-oil emulsions, such as
may have been obtained by enhanced oil recovery methods, tar
sand operations, oil shale operations and the like.
7. A bituminous froth such as from the primary froth
product or from the scavenger froth product of a hot water
oil sand extraction plant.
8. A water-in-oil emulsion containing dispersed water-
wet mineral particles.
9. A combination of two or more of the above sources
in one operation.
10. Any other mixture of oily or greasy substances with
water, with or without solids.
It is therefore an object of the present invention to
provide a process which will increase the particle size o~
dispersed phase particles by cyclic coalescence, colligation,
adsorbtion, concrescence, conglutination and/or coherence
-- 8
~,~

onto the surface of free bodies and subsequent cyclic shedding
or sloughing off of cohered dispersed phase back into the
mixture.
It is also an object of the present invention to
provide a process which will increase the particle size of
dispersed oil phase particles contained in a continuous water
phase to enhance oil recovery from oil sands operations and
secondary flooding of oil wells wit:h aqueous solutions or steam.
It is further an object of the present invention to
provide a process for the breaking of emulsions and reduction
of air in froths in the processing of oil sands which result in
increased particle sizes of the dispersed phase enabling more
efficient oil phase~aqueous phase separations.
PRIOR ART
In searching the patent literature the closest prior
art uncovered is an oil agglomeration process disclosed in
Canadian Patent 787,898 issued on June 18, 196~ to Ira A.
Puddington, et al. In that process a mi~ture of oil phase and
hydrophilic solids in an aqueous phase is subjected to cocurrent
milling, kneading and agitation until the oil phase separates
and is recovered as discrete agglomerates when the milling
surfaces are hydrophilic or is recovered as an adherent layer
when at least part of the milling surfaces are oleophilicO The
differences between the present invention and that prior art
are:
1. The prior art requires cocurrent milling, kneading
and agitation, while in contrast the present invention
only requires tumbliny in a horizontal rotating drum.
2. The prior art uses hydrophilic milling surfaces to
permit recovery of discrete semi-solid oil phase agglo-
merates, while in contrast the present invention uses free
bodies with oleophilic surfaces to increase the size of
_ g

t~
oil phase particles.
3. Alternately, the prior art uses oleophilic milling
surfaces to recover an adherent layer of oil phase there-
from whereas the present invention is not based upon oil
phase recovery from milling surfaces but permits oil phase
to accumulate on oleophilic surfaces of free bodies where
it unites or coalesces and encourages subsequent flowing
or dripping therefrom.
DRAWINGS
Figure 1 is a perspective view showing the horizontal
drum used in the present invention to tumble a feed with free
bodies for the purpose of increasing the size of dispersed
phase particles.
Figure 2 is a cross sectional view of the drum of
Figure 1 taken along the lines 2 2 of Figure 1 showing the
contents of the drum and adjustable means to control the rate
of product flow from the drum.
Figure 3 is a cross sectional view of the drum of
Figure 1 taken along the lines 3 - 3 of Figure 2.
Figure 4a is a view of a drum exit in the form of a
sieve covered central opening.
Figure 4b is a view of a drum exit in the shape of a
sieve covered pie with a sliding gate to control the size of
the exit.
Figure 4c is a view of a drum exit in the form of a
sieve covered annular opening.
Figures 5a, 5b and 5c are illustrative free bodies
having both oleophilic and hydrophilic surfaces.
DETAILED DESCRIPTION OF THE INVENTION
As used in the present invention "water-in-oil
emulsion", "oil phase" and "bit~men" all refer to greases or
-- 10 --

~5'77~
oils that may contain water droplets and particulate solids.
"Bitumen froth" refers to bitumen that contains water phase
and solids, and significant quantities of entrained gas.
"Oil-in-water emulsion" refers to a stable mixture of small
oil phase droplets dispersed in a continuous water phase and
may con-tain up to about 5 percent particulate solids. "Slurry"
refers to a mixture containing cont:inuous water phase, dispersed
oil phase and more than 5 percent particulate solids.
"Aqueous phase" refers to any type of continuous water phase;
it may contain particulate solids, oil particles and/or
chemicals and it generally is used to describe a slurry or
emulsion that has passed or is to be passed through an
apertured oleophilic belt. "Dispersed phase" refers to that
phase in the mixture, emulsion or slurry that is not continuous.
It is to be understood that the present invention
is to separate heavy or light oil from particulate solids and/or
water, no matter from where they originate. For example,
Canadian Patent No.: 726,683 issued on January 25, 1966 to
Albert F. Lenhart discloses that oils derived from solid
carbonaceous materials, such as from oil shales, coals, and
the like, usually are recovered in the form of oil-water
emulsions when in-situ combustion is practiced to convert these
solid carbonaceous materials to oils. That same patent also
discloses that in the recovery of conventional crude oil from
wells, oil-water emulsions are produced as well on many
occasions. A paper by L.S. ~ohnson et al. of the United
States Department of Energy, presented at the 13th Intersociety
Energy Conversion Engineering Converence in San Diego,
California on August 20-25, 1978 discloses that oil~water
emulsions, containing particulate solids, usually are produced
when oil is recovered by in-situ combustion of tar sands.

'7~
It has been found that when an oil-in-water emulsion
is tumbled in a drum in the presence of free bodies that have
oleophilic surfaces, this emulsion undergoes a partial
separation in which oil phase droplets of the emulsion unite
together to produce larger droplets and streamers of dispersed
oil phase tha-t readily may be separated subsequently from the
continuous water phase. Additions of emulsion breaking
chemicals such as alkaline earth salts to such emulsions
significantly increase the production of such droplets and
streamers by removing repulsive forces from the dispersed
phase which permits cohesion of dispersed phase particles on
the oleophilic surfaces of free bodies.
When a slurry of dispersed particles of oil phase,
continuous water phase and particulate solidsl are tumbled in
a drum in the presence of free bodies that have oleophilic
surfaces, these dispersed oil phase particles unite to produce
droplets and streamers tha-t are larger in size than the
dispersed oil particles originally present in the slurry.
When a water-i.n-oil emulsion, that may contain
particulate solids and air, is tumbled in a drum in the
presence of free bodies that have hydrophilic surfaces, this
emulsion undergoes a partial separation in which water droplets
trapped by the continuous oil phase form into larger droplets
or bodies of water which subsequently can be more easily
separated from the oil phase. Air bubbles collapse and water-
wet particulate solids gather with the water phase. Emulsion
breaking chemicals when added to the mixture, help in this
mechanism of particle size growth by removing repulsive
forces from the particles and permitting cohesion of dispersed
phase particles on the hydrophilic surfaces of free bodies.
- 12 -

7~2
The present invention takes advantage of these
discoveries to prepare mixtures of dispersed phase and continu-
ous phase for separation by an apertured oleophilic belt or
other appropriate means.
Figures 1 to 5 illustrate an apparatus for treating,
with free bodies a continuous feed mixture of oil phase and
aqueous phase to enlarge the particle size of dispersed parti-
cles enabling better subsequent separation of the two phases.
The drum 10 of Figure 1 is a horiztonal, rotating
cylinder having rear 12 and front 13 ends, each partially
closed by a washer. The cylindrical side wall 11 is provided
with internal protrusions or ribs 14 that encourage mixing of
the drum contents by the rotating drum. The drum is supported
on rollers 15 connected to a frame 16 and contains a drive
motor 17 and drive means 18.
When conditions require, steam may be introduced into
the interior of the drum 10, illustrated in Figures 2 and 4,
through a rotatable distributor valve 19, which feeds it to a
series of perforated pipes 20. These pipes 20 extend longitu-
dinally along the interior cylindrical surface 21 of the drum
10 in spaced relationship about its circumference. The valve
19 feeds the steam to the pipes 20 only when they are submerged
within the drum contents 22. The mixture to be treated 23 is
fed into the rear end 12 of the drum by way of a pipe 24~ A
seal 25 prevents drum contents 22 from spilling out of the rear
12 of the drum. Alternately, the mixture may be fed to the
drum 10 through a flexible rotating hose that is attached to the
central part of the drum rear 12. The drum contains free bodies
26 that tumble through the drum contents 22. Product 27 leaves
the drum 10 through an opening 28 that is covered with an aper-
tured wall 29 such as a mesh screen, or a perforated plate, to
permit passage of prepared product but which prevents passage
- 13 -
~r !

~ ~ ~9~
of free bodies 26 from the drum 10.
Various types of drum product exits 28 are illustra-
ted in Figures 4a, 4b and 4c. Figure 4a illustrates a central
opening 28a in the drum wall. Figure 4b illustrates a pie
shaped opening 28b whereof the si~e may be controlled by a
sliding gate 31 and Figure 4c illustrates an annular opening
28c. The flow rate of product frorn the drum and hence the
level in the drum may be controlled by means of the cover plate
30 of Figure 2 by adjusting the dis~ance between the cover
plate 30 and the drum front wall 13. The type of product exit
selected determines to some degree the concentration in the
drum contents 22. For example, if an oil sand slurry 23 i.s fed
to the drum wherein mineral particles readily settle to the
wall 21 of the drum 10, but wherein bitumen preferably occupies
the central regions of the drum 10, then, with an annular exit
28c as in Figure 4c, bitumen wilL accumulate in the drum so
that ~or steady state conditions the bitumen concentration in
the drum 10 will be higher than the bitumen concentration in
either the feed 23 or the product 27. Conversely, when for the
same feed 23 a central exit opening 28a as shown in Figure 4a,
is chosen, concentration of solids will take place in the drum
10. Thus, for steady state conditions, the solids concentration
in the drum 10 may be higher than the solids concentration in
either the feed 23 or the product 27 streams. Other types of
opening 28 may be chosen to reduce such concentration change as
for example by the use of an annular opening 2~c of smaller
radius than the opening of Figure 4c. The pie shaped opening
28b of Figure 4b may provide for a cyclic variation in the
level o~ contents in the drum.
The drum 10 may be rotated by the motor 17 and
associated drive 18 at any rate of rotation that is most

7~
effective Eor the m:ixture 23 to be treated, fro~l very slow
up to but not exceeding two times the critical rate. The
critical rate of rotation i.s reached when at the apex of the
inside drum surface 21 the centri.fugal force equals the force
of gravity. Critical rotation is defined in revolutions per
minute as:
Critical rotation rate = ~ rr
where r is the drum inner radius in feet. Above this critical
rate, some drum content commences to attach itself to the drum
wall and does not readily mix with the remainder of the drum
contents. At rotation rates between one and two times the
critical rate, progressi.vely more of the drum content attaches
itself to the drum wall and does not take part in the tumbling
process operating in the drum 10. Rotating the drum 10 at more
than twice the critical rate is not the intent of the present
invention. The desired rate of drum 10 rotation varies with
each type of feed 23 being treated and is influenced among others
by the viscosity of the mixture 22, the density difference
between the mixture 22 and the free bodies 26, the solids
content of the mixture 22, and the level of the drum contents 22.
In the specification, the term "critical rotation
rate" denotes a drum rotation rate such that the centrifugal
force at the inside drum surface at the apex of the drum equals
the force due to gravity.
For many of the mixtures 22 treated, the drum 10
will be maintained more than half full, level 32, and for
some mixtures 22 the drum 10 may be kept substantially filled,
level 33, as long as the viscosity of the feed mixture 22,
the solids concentration and the density difference between
the components of the mixture 22 and the free bodies 26 permit
for a continuous thorough mixing of the drum contents, with
- 15 ~

said free bodies 26.
Without in any way attempting -to :Limit the scope of
this invention the following theory is offered. It is believed
that the oil phase particle size growth that takes place when
a mixture of continuous aqueous phase and dispersed oil phase
is tumbled in a drum in the presence of oleophilic free body
surfaces may be explained as a mechanism of oil film building
and shedding. In this mechanism, dispersed oil phase particles
of the mixture in the drum come in c~ontact with an oleophilic
surface, adhere thereto, unite on that surface with other oil
phase particles and form into a coat that continues to grow
in thickness until the forces of self adhesion in the oil
phase coat cannot resist the forces of erosion on the coat
surface caused by the movement of mixture past this coat. At
that instant the coat begins to shed oil phase particles which,
for the conditions of the present inven-tion on the average, are
larger than the oil phase particles originally present in the
mixture fed to the drum. The force of erosion varies with lo-
cation in the drum contents and since the free bodies in the
drum are mixing and moving in the drum, therefore the force
of erosion on the oleophilic surface of a free body varies
with time; thus permitting a cyclic accumulation of oil phase
on free bodies and a cyclic shedding of accumulated oil phase
therefrom. The shed oil phase particles appear to increase in
size with an increase in oil phase viscosity.
Similarly, free bodies with hydrophilic surfaces
may be used to collect water phase on their surfaces and to
provide for an increase of particle size of aqueous phase in a
mixture with continuous oil phase. A combination of
oleophilic and hydrophilic free bodies may be used to advantage
in cases where it is desirable to remove particles of
- 16 -

~6~
continuous phase out of dispersed phase particles that are
being increased in size. Thus free bodies with hydrophilic
surfaces may be added to the free bodies with oleophilic
surfaces in the drum to treat a mixlure containing continuous
aqueous phase. Conversely, free bodies with oleophilic
surfaces may be added to the free bodies with hydrophilic
surfaces in the drum to treat a mixt;ure containing continuous
oil phase~
Free bodies may be in the form of spheres, spheroids,
pebbles, teardrops, rods, discs, sacldles, snowflakes or of any
other shape, simple or cornplex, which is effective in searching
out dispersed phase particles in the mixture. The free bodies
may be solid, hollow, or apertured. They may also be smooth,
but are preferably of a rough or of a porous surface. The
size of the free bodies used in said drum depends to a large
degree upon the consistency of the mixture in the drum that
is to be treated. The mean dimension of these free bodies
preferably is within the range 0.1 to 10.0 inches and most
preferably within the range 0.5 to 2.0 inches. However, free
bodies larger than 10 inches and smaller than 0.1 inch can
be used without departing from the scope of the present
invention.
The free bodies may also be configured to contain
both oleophilic and hydrophilic surfaces. Examples of such
bodies are disclosed in Figures 5a, 5b and 5c. However, these
Figures are not intended to be self limiting as any other
configuration, simple or complex, may be used. Figure 5a shows
a free body 34 consisting of a hydrophilic head 35 and an
oleophilic tail 36 or streamer. Figure 5b shows a free body
37 consisting of a frayed oleophilic rope fibre 38 secured

7,~32
in a crimped hydrophilic ring 39. Figure 5c illustrates a
body 40 consisting o~ a series of oleophilic strands or
straps 41 secured by molding into a ceramic hydrophilic ring 42.
The desired density of the free bodies varies with
the shape and size of the bodies used, -the viscosity of the
oil phase, the solids content of the mixture and the level
of the contents maintained in the drum. ~t is preferably
within the range 60 to 600 pounds per cubic foot and ~ost
preferably within the range 100 to 300 pound.s per cubic foot.
Free bodies may be cast, molded, formed or fabricated
in other ways. Oleophilic free bodies may be made with
oleophilic materials or they may be made from othex materials
and then covered with a coating of a strongly oleophilic material
that is abrasion resistant, resistant to oil phase of the
mixture under treatment and that may be made to adhere strongly
to the body. Suitable oleophilic materials that may be used
in the fabrication of oleophilic free bodies are neoprene,
urethane, polypropylene, plastics and artificial rubkers.
Hydrophilic free bodies may be made using ceramics, glass,
carbides or other strongly hydrophilic materials. Pebbles
or flint may be used as well.
The particulate solids content of the mixture
preferably is within the range of 0.0 to 0.9 pounds of solids
per pound of mixture and most preferably 0.0 to 0.4 pounds
of solids per pound of mixture.
The desired viscosity of the phases of the mixture
depends upon which is the continuous phase. When oil is the
continuous phase of the mixture, the preferred viscosity of
the o~ll phase is such that permits the free bodies to freely
travel through the mixture and is within the range 0.10 to 500
poises, with the most preferred range being 1.0 to 50 poises.
- 18 -

3~7~
When oil is the dispersed phase of the mixture, the preferred
viscosity of the oil phase is such as to provide optimum
"tackiness" to the oil phase particles and is within the
range 1.0 to 5000 poises, with the most preferred range being
10 to 500 poises. Generally, "tackiness" refers to the ability
of oil particles to adhere to themselves and to oleophilic
surfaces.
While particle size enlargement may be achieved in
small rotatlng horizontal drums, effectiveness of the present
invention may be enhanced by the use of large diameter drums
since these, for a given mixing action, may rotate at a slower
rate. Such a slower rate of rotation in larger drum sizes may
provide for longer accumulation and shedding cycles of
dispersed phase on and from free body surfaces and in many cases
provides for improved performance of the present invention.
The preferred drum diameter is within the range 7 to 70 feet
and the preferred drum length i5 within the range 10 to 200 feet.
Reagents may be added to the mixture before it enters
the drum or while it is in the drum, for the purpose of aiding
in the process of the present invention, for breaking emulsions,
for increasing the affinity of the dispersed phase for the
surfaces of the free bodies, for increasing the affinity of
the surfaces of the free bodies for the dispersed phase, and/or
for increasing the affinity of particulate solids in the mixture
for one of the phases of the mixture. Addition of inorganic
alkaline earth hydroxides or salts, such as for example
calcium sulphate or calcium hydroxide, is very effective for
breaking tight oil sand oil-in-water emulsions and for rapid
accumulation of bi-tumen coatings on the free bodies in the
mixture. Non-ionic, water soluble-polyethylene oxide polymers
having a molecular weight in the range of 10,000 to 7,000,000
-- 19 --
'' ''"~1

~;77~
added to the mixture may serve to aid the alkaline earth
chemicals in breaking tight oil-in-water emulsions. A
suitable temperature for adding such polymers to the mixture
is when the mixture is in the range of 120 to 210F. Depending
upon the desired temperature for uniting of dispersed oil
phase particles, this polymer addition may be made to the drum
contents or it may be made to the feed prior to entering the
drum. In this latter case, the feed may be cooled prior to
entering the drum for the purpose oE operating both the
chemical treatment step and the dispersed particle size growth
step at differing optimum temperatures. United States Patent
No. 4,058,453 issued on November 15, 1977 to Mahendra S. Patel
et al. discloses the use of such a polymer mixture to break
an oil-in-water emulsion. However, instead of using free
bodies for that purpose, as disclosed in the present invention,
Patel et al. disclose the need for a hydrocarbon diluent to
collect the dispersed phase, which is not required in the
present invention.
Non-ionic surface active compounds, as for example a
chemical demulsifier comprising polyethoxyalkene compound
sold under the trade name of NALCO D-1645 produced by the
Nalco Chemical Company, may be added to the feed or to the
drum for the purpose of breaking a water-in-oil emulsion and
of making it easier for the free bodies to enlarge dispersed
water phase particles.
Another demulsifier for adding to a water-in-oil
emulsion in the present invention is sold under the trade
name of BREAXIT 79~1 and comprises a mixture of: (1) One part
of the reaction product of diethyl ethanolamine with premixed
propylene oxide and ethylene oxide; and (2) approximately
three parts of a palmitic acid ester of the reaction product
- 20 -

7~
of an alkyl phenol formaldehyde resin with ethylene oxide. Other
demulsifiers that may aid free bodies in increasing the mean
water particle size of a water-in-oil emulsion in the present
invention are polyoxypropylene glycols produced by the
Wyandotte Chemical Company under the trade name "Pluronic".
An enhanced transfer of particulate solids to the
water phase of the mixture tumbling with free bodies in the
drum of the present invention may, in some mixtures, be effected
by addition to these mixtures of hydrophilic surface active
transfer agènts, such as polyphosphates. Any water soluble
salt of pyrophosphoric acid, ~I2P2O7, such as for example
tetrasodium pyrophosphate or sodium tripolyphosphate, are
transfer agents and may be mixed with the feed or the drum
contents in proportion of 0.01 percent to 1.0 percent to effect
an improvement in the recovery of particulate solids in the
water phase. Addition of sodium hydroxide with said
polyphosphate reagent in about equal proportion may aid in
effecting the improvement.
In instances where the oil phase of the mixture may
contain heavy mineral; for example, bitumen may contain as
high as 1 to 50 percent of heavy minerals as for example
zircon, rutile, ilmenite, tourmaline, apatite, staurolite,
garnet, etc. it may be desirable to employ chelating agents
to make these particulate heavy minerals water wet and cause them
to report to the water phase. Examples of suitable chelating
agents are ethylenediamine-tetraacetic acid, sodium gluconate,
gluconic acid, sod:ium oxalate and diethylene glycol. Chelating
agents may be added to mixtures wherein oil is the continuous
phase or they may be added to mixtures where water is the
continuous phase. Generally they are the most cost effective
when added to mixtures in which oil is the continuous phase.
- 21 -

7t~ ~
~ n summary, the present .invention uses free bodies,
some or all having surfaces with affinity ~or the dispersed
phase of a mixture being tumbled with said free bodies, in a
horizontal rotating drum for the purpose of increasing the
average particle size of said dispersed phase in the mixture.
Reayents may be added to the feed of said drum, or to said
drum, to enhance the process of dispersed phase particle size
growth, or to collect particulate solids into the water phase.
The "oil-in-water" emulsions that may be treated in
this manner may include mixtures of dispersed oil phase contain-
ing either medium crude oils, heavy crude oils or bitumen.
The "water-in-oil" emulsions that may be treated in this manner
may include bitumen froth, bitumen, heavy crude oil or medium
crude oil. The "oil-in-water and solids" slurries that may
be treated in this manner include oil sand slurries from which
oversize materials have been removed, bitumen depleted oil
sand slurries~ the middlings stream of a hot water oil sands
extraction plant, or slurries of sludge from the effluents
settling pond of a hot water oil sandsextraction plant.
Internal drum walls may be made oleophilic and such
walls may contain oleophilic inwardly extending baffles such
~ )6
as disclosed in copending~pplication Serial No. -~7i&r~
filed of even date herewith to aid the operation of oleophilic
free bodies or such wall and baffles may be made hydrophilic
to aid the operation of hydrophilic free bodies.
The method of the present invention may be more
fully understood by the following examples illustrating the
same.
The efficacy of the invention as shown in the examples
is judged by comparing a raw feed stock with a feed treated
according to the present invention using the Oleophilic Sieve
- 22 -

Test. The Oleophilic Sieve Test involves the followiny steps:
1. A neoprene coated ~ mesh Tyler screen and bottom
cover are cleaned, dried and weighed.
2. The cover is removed. The feed stock is passed
through the screen while the screen is immersed 1.0 inch below
the level of a water bath, maintained at 110F. The screen is
shaken gently while in the water and then is removed Erom the
water bath.
3. The bottom cover is fitted onto the screen and then
both are dried ln an oven at 212F, cooled and then weighed.
4. The increase in weight is recorded as being the
bitumen left on the screen. This bitumen usually contains
some solids which for purposes of the test are part of the
bitumen.
EXAMPLE I
An oil sand feed, consisting of 80.5 percent solids,
6.9 percent bitumen and 12.6 percent water is treated with
water and steam in a conditioning drum according to the method
disclosed in Canadian Patent ~o. 918,588 issued on January 9,
1973 to Marshall R. Smith, to produce a slurry product of oil
sand and water. Slurry product from this conditioning drum
is then treated by the process of the present invention. It is
first screened through a 5 mesh sieve to remove oversize
materials. The screened product is introduced into a drum
such as is illustrated in Figure 1. The drum is 6.0 feet in
diameter and 6.0 feet long and is filled to 30 percent of its
volume with 0.5 inch diameter steel ~alls that have been
coated with a 0.05 inch thick urethane layer. These spheres
are oleophilic. Lengthwise baffles on the interior cylindrical
wall of the drum cause mixing of the drum contents and prevent
the cylinder wall from sliding past the drum contents. The
- 23 -
~'

screened slurry product is introduced into the rear of the drum
through a flexible hose at a constant rate of 12.0 tons per
hour. Slurry water content is about 2S percent and its
temperature is approximately 170 to 180F. Water at about
70 is added to the rear of the drum at the rate of six tons
per hou~ to cool and dilute -the slurry. The drum is rotated
at approximately 10 rpm. Product mixture leaves the drum
through a concentric annular port in the drum front wall that
has been covered with reinforced 2 mesh screening. The por~
size is adjusted to maintain more than g0 percent of the drum
volume occupied by slurry and spheres. Temperature in the
drum stabilizes at about 115F. After steady state conditions
have been achieved, samples taken from the slurry feed
entering the drum are cooled to 35F and are compared with
samples taken from the slurry product leaving the drum. A
visual inspection of the feed sample shows bitumen flecks
generally smaller than 0.05 inch, while a visual inspec-tion of
the product sample shows bitumen streamers and globules very
much larger than 0.10 inch. One pound of feed sample,
maintained at 110F, is passed through a standard 4 mesh Tyler
screen according to the Oleophilic Sieve Test. The slurry
passes through the mesh apertures and 0.14 pound of bitumen
remains behind on the screen. Similarly, one pound of treated
product sample at 110F is passed throuyh the same test but in
this case 0.39 pound of bitumen remains behind on the screen.
The recovery of bitumen from treated product is 2.8 times greater
than from untreated product.
EX~PLE II
. _
A middlings feed material from a hot water oil sands
extraction plant, comprising 72.5 percent water, 25.0 percent
silt and clay and 2.5 percent bitumen, is cooled to about 110F.
- 24 -

'7~
and then is treated in the same drum used in Example I. Dough-
nut shaped free bodies, vulcanized from a mixture o~ brass
particles and neoprene that are 1.0 inch in diameter 0.5 inch
in cross-section, and have 0.5 inch holes in the center, fill
the drum to about 40 percent of its volume. These free bodies
have a density of 200 pounds per cubic foot and their surfaces
are oleophilic. A flow of 9.0 tons per hour of feed is treated
in the drum, which rotates at 15 rpm and which is lcept filled
to 70 percent of its capacity. A sample of untreated feed is
cooled to 35F and is inspected. Bitumen drops can be observed
in the continuous water phase. On the average these drops in
the untreated feed are much smaller than 0.02 inch in size.
A pound of this untreated slurry, passed through the Oleophilic
Sieve Test at 110F. leaves less than 0.01 pound of bitumen
thereon. A sample of treated product mixture cooled to 35F.
shows by inspection that more than half of the bitumen is in
the form of droplets and streamers that are much larger than
0.05 inch. A pound of -treated product passed through the
Oleophilic Sieve Test at 110F. leaves more than 0.02 pound of
bitumen thereon. Thus, it is evident that increasing bitumen
particle size prior to recovery results in a recovery that is
at least twice as great as bitumen recovered from the untreated
feed.
EXAMPLE III
A bitumen-in-water emulsion product from a pilot plant
that used steam injection to recover bitumen from deeply buried
oil sand formations is cooled to 105F. and then is treated in
a drum as shown in Figure l. No water is added. The emulsion
consists of about 10 percent bitumen and about 90 percent water
and less than 1.0 percent clay particles. Spheres of neoprene,
0.35 inch in diameter, fill the drum to about three quarters
~ 25 -

7~2
full. One ton per hour is treated in a 2.0 feet diameter, 3
feet long drum that is kept filled to about 95 percent of its
volume by the mixture of emulsion and spheres. The drum
rotates at 25 rpm. Five pounds per hour of calcium sulphate
is continuously added to the emulsion feed as it en-ters the
drum and thoroughly mixes with the drum contents. A sample of
untreated feed emulsion is cooled to 35 F. and is inspected
visually through a microscope. The average bitumen particles
in this emulsion are found to be smaller than 0.01 inch in
diameter. Very little bitumen remains behind on the screen
during an Oleophilic Sieve Test and the emulsion passing
through this screen analyzes 9.2 percent bitumen. Inspection
of the treated product of the drum, however, shows streamers of
bitumen and a flow of water leaving the drum. When one pound
of product water is passed through the Oleophilic Sieve Test at
110F. and is thereafter analyzed, it is found to contain less
than 1.0 percent bitumen. A sampl~ of dried bitumen product
from the drum is tested for viscosity by means of a Model LVT
Brookfield Synchro-Lectric viscometer with a No. 4 spindle.
At 105F. its viscosity is found to be approximately 275
poises. According to the above results the recovery of bitumen
from untreated product is about 10 percent whereas the recovery
of bitumen from treated product is in excess of 90 percent.
EXAMPLE IV
A scavenger froth product from a hot water oil sands
extraction plant containing 42 percent bitumen, 12 percent
solids and 46 percent water is treated in the apparatus used
in Example I at a temperature of 160F. The 6.0 feet diameter
6.0 feet long drum is filled to one half full with 0.75 inch
flint pebbles and 0.75 inch spheres molded from a mixture of
litharge and neoprene to give these spheres a density of 150
- 26 -
.~

pounds per cubic Eoot. There are about an equal number of
pebbles and spheres in the drum that rotates at 10 rpm. Six
tons per hour of froth, containing 35 volume percent air, is
fed to the drum that is kept filled completely. Air bubbles
of the froth feed collapse in the drum because of the tumbling
and stirring action of the free bodies. The product of the
drum that leaves through a mesh covered exit consists of water,
that contains particulate solids, and a bitumen product that
contains less than 20 percent water and less tllan 10 percent
solids.
EXAMPLE V
An oil sand feed, consisting of 80.5 percent solids,
6.9 percent bitumen and 12.6 percent water is treated with
water and steam in a conditioning drum to produce a slurry
product of oil sand and water. The slurry product is then
screened to remove large oversize materials. After that,
coarse sand and additional oversize material is removed by
means of elutriation. The elutriation apparatus consists of a
vessel filled with water -that flows upward through the vessel.
The slurry is introduced into this apparatus. Oversize mineral
material and undigested oil sand fall to the bottom of the
vessel through the upward flowing water stream and are
discarded. The water spills over the top of the vessel and
carries with it bitumen particles and fine mineral particles in
the form of an overflow slurry. This overflow slurry is
treated by the method of the present invention for the purpose
of increasing the bitumen particle size to facilitate subse-
quent separation of bitumen therefrom. Said overflow slurry
is introduced into a drum such as is illustrated in Figure 1.
The drum is 6.0 feet in diameter and 6.0 feet long and is
filled to 40 percent o~ its volume with 1 inch long pieces of
- 27 -

~
1 inch diameter tubing that has a wall thickness of 0.065 inchand of whlch each piece has been coated with a 0.005 inch layer
of tin. Under the conditions existing in the drum these free
bodies made from steel and tin are oleophilic. The overflow
slurry is introduced into the rear of the drum at a rate of 12
tons per hour through a pipe that conveys the slurry from a
collar around the elutriation apparatus, through said pipe into
the rear of said drum. A seal is provided between said pipe
and said rear of the drum to prevent slurry from spilling out
of the drum at the rear. The drum is rotated at approximately
10 r.p.m. Product mixture leaves the drum through a concentric
annular port in the drum front wall that has been covered with
reinforced 2 mesh screening. The port size is adjusted to
maintain more than 75 percent of the drum volume occupied by
slurry and free bodies. Oleophilic baffles mounted along the
drum inside wall encourage mixing of the free bodies with the
slurrry. Temperature of the drum contents is 120F. After
steady state conditions have been achieved, samples taken from
the feed to the drum and samples taken from the product of the
drum are cooled to 35F and are compared with each oth~r. The
bitumen particles in the product from the drum are significant-
ly larger than the bitumen particles in the feed to the drum.
One pound of feed sample is treated by the Oleophilic Sieve
Test. The slurry passes through the apertures and 0.018 pound
of bitumen remains behind on the screen. Similarly, one pound
of product is also treated by the Oleophilic Sieve Test, but
in this case 0.045 pound of bitumen remains behind on the
sieve.
In addition to enhanced bitumen recovery this example
also illustrates the feasibility of removing oversize materials
prior to contacting the oil sands slurry with free bodies to
- 28 -

~6~7~7~
increase oil phase particle size.
Although the inventi.on as has been described isdeemecl to be that which forms the preferred embodiments
thereof, it is recognized that departures may be made there-
from and still be within the scope of the invention which is
not to be limited to the details d.isclosed but is to be
accorded the full scope of the clalms so as to include an~ and
all equivalent methods and apparatus. For example, the drum
may be inclined instead oE beinc~ perfectly horizontal without
departing from the scope of the invention. Other similar
modifications will also become apparent to those skilled in the
art.
_ 29 _
~.,

~7~7~
SUPPLE~lENTARY DISCLOSURE
A process for agglomerating inorganic materials (ash)
from pulverized coal is taught in U.S. Patent ~,033,729 issued
on July 5, 1977 -to Capes, et al. In that process a continuous
oil phase contains the dispersed coal and ash particles. Water
and hydrophilic surfaced free bodies are added to the oil phase
in a rotating drum. The water wets both the ash and the hydro-
philic materials and serves as a form of glue such that when an
ash particle contacts the hydrophilic surfaced free bodies, the
ash adheres thereto. The ash buildup on the hydrophilic free
bodies continues over a predetermined period of time to form an
agglomerate of combined ash and free body which is then screened
from the continuous oil phase containing the coal particles.
The agglomerated ash must be held to the free bodies
and discharged from the drum in that form. If too much water is
used it cannot effectively function as a glue and is displaced
from the hydrophilic free body back into the oil phase carrying
non-agglomerated suspended ash in water bubbles which pass
through the screen along with the oil phase when the water-in-
oil mixture containing the hydrophilic free bodies are dis-
charged from the rotating drum onto the screen. In this
process, hydrophilic free bodies must be continuously introduced
into the drum and also be removed therefrom. If the free bodies
are reused it is with the agglomerated ash still adhering to
their surfaces. It therefore follows that the capacity of
absorption of the free bodies will eventually reach a point
where they will become inefficient since the patent teaches that
efficiency decreases as free body size increases.
In the present invention the free bodies are
preerably oleophilic and always remain in the rotating drum.
They function to bring suspended oil phase particles in an
30 -
-!' -` .

7~7~
aqueous phase together on their surface where they unite to form
larger oil phase particles which are then shed from the surface
of the oleophilic free body by physical forces back in-to the
aqueous phase for discharge from the drum. Thus the function is
significantly different. No glue is rec~uired to adhere the oil
particles to the free body and keep them there and the relative
proportion of oil phase to water phase is not critical as in the
Capes, et al. patent. The free bod:ies can be used continuously
and indefinitely. Moreover, the size oE the free bodies
utilized in the present invention are considerably larger than
the free bodies advocated in the Capes, et al. patentO
An alternate method of removing contents from the drum
is to provide a perforated cylindrical wall on the horizontal
rota-ting drum and to permit the contents to flow out unhindered
through the perforations, or to immerse the thus perforated drum
partly in a tank or cover in such a way as to maintain a level
of contents in the tumbler; the contents flowing through the
perforations into the tank and spilling over an endwall of the
tank, thus controlling said level. The contents that flow from
said tank or cover is then sent to the separator for processing
while the free bodies are kept in the drum by making the
perforations smaller than the free bodies. Paddles may be
attached to the outside of the perforated drum wall to prevent
settling of solids in the tank which, if permitted to settle,
would hinder rotation of said perforated drum.
It has been found that the density of the free bodies
is preferably within the range 30 to 800 pounds per cubic foot
and most preferably within the range 200 to 500 pounds per cubic
foot.
Free bodies made from steel coated with a layer of
cadmium, tin or molybdenum have been found to be surprisingly
- 31 -
.

~7'~
efEective. rrhese coatings are oleophilic but are not suffi-
cient abrasion resistant for prolonged usage. However, it is
thought that as the coating is abraded from the free body the
exposed steel surface is impregnated by the oil phase before an
oxide layer can be formed thereby preserving the oleophilic
nature of the steel surface. Thus when using steel, alloy
steel, brass or other metals which may be covered with a thin
layer of metal oxide, it may be necessary to first remove such
layer by abrasion or other means to maximize the oleophilic
nature of that free body.
When oil is the continuous phase of the mixture, the
preferred viscosity of the oil phase is within the range 0.01
to 500 poises, with the most preferred range being 0.1 to 50
poises. When oil is the dispersed phase of the mixture, the
preferred viscosity of the oil phase is within the range 0.1 to
50,000 poises, with the most preferred range being 0.1 to 5000
poises.
A possible modification of the present invention
would be to apply the process to the recovery of oils, fats
and greases from plant and animal sources. For example,
effluent streams from slaughter houses, potato chip plants,
rapeseed or cottonseed oil pressing operations could be:treated
to remove the fat or oil content from such streams.