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Sommaire du brevet 2761201 

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Disponibilité de l'Abrégé et des Revendications

L'apparition de différences dans le texte et l'image des Revendications et de l'Abrégé dépend du moment auquel le document est publié. Les textes des Revendications et de l'Abrégé sont affichés :

  • lorsque la demande peut être examinée par le public;
  • lorsque le brevet est émis (délivrance).
(12) Brevet: (11) CA 2761201
(54) Titre français: LIQUIDES IONIQUES ANALOGUES POUR LA SEPARATION ET LA RECUPERATION DES HYDROCARBURES DE LA MATIERE PARTICULAIRE
(54) Titre anglais: ANALOGUE IONIC LIQUIDS FOR THE SEPARATION AND RECOVERY OF HYDROCARBONS FROM PARTICULATE MATTER
Statut: Octroyé
Données bibliographiques
(51) Classification internationale des brevets (CIB):
  • C10G 1/04 (2006.01)
(72) Inventeurs :
  • PAINTER, PAUL (Etats-Unis d'Amérique)
  • WILLIAMS, PHIL (Etats-Unis d'Amérique)
  • MANNEBACH, EHREN (Etats-Unis d'Amérique)
  • LUPINSKY, ARON (Etats-Unis d'Amérique)
(73) Titulaires :
  • THE PENN STATE RESEARCH FOUNDATION (Etats-Unis d'Amérique)
(71) Demandeurs :
  • THE PENN STATE RESEARCH FOUNDATION (Etats-Unis d'Amérique)
(74) Agent: LAVERY, DE BILLY, LLP
(74) Co-agent:
(45) Délivré: 2017-01-17
(22) Date de dépôt: 2011-12-05
(41) Mise à la disponibilité du public: 2013-04-04
Requête d'examen: 2016-02-19
Licence disponible: S.O.
(25) Langue des documents déposés: Anglais

Traité de coopération en matière de brevets (PCT): Non

(30) Données de priorité de la demande:
Numéro de la demande Pays / territoire Date
13/252,523 Etats-Unis d'Amérique 2011-10-04

Abrégés

Abrégé français

Des systèmes, des méthodes et des compositions destinés à la séparation et la récupération dhydrocarbure de la matière particulaire sont révélés aux présentes. Conformément à une réalisation, une méthode comprend la mise en contact de la matière particulaire avec au moins un liquide ionique analogue. La matière particulaire renferme au moins un hydrocarbure et au moins une particule solide. Lorsque la matière particulaire est mise en contact avec le liquide ionique analogue, lhydrocarbure se dissocie de la particule solide pour former un système multiphase.


Abrégé anglais

Systems, methods and compositions for the separation and recovery of hydrocarbons from particulate matter are herein disclosed. According to one embodiment, a method includes contacting particulate matter with at least one analogue ionic liquid. The particulate matter contains at least one hydrocarbon and at least one solid particulate. When the particulate matter is contacted with the analogue ionic liquid, the hydrocarbon dissociates from the solid particulate to form a multiphase system.

Revendications

Note : Les revendications sont présentées dans la langue officielle dans laquelle elles ont été soumises.


CLAIMS

What is claimed is
1. A method of separating and recovering hydrocarbon from particulate matter,
the method
comprising:
contacting particulate matter comprising at least one hydrocarbon and at least
one
solid particulate with at least one analogue ionic liquid to separate the at
least one
hydrocarbon from the at least one solid particulate, wherein the at least one
analogue ionic
liquid comprises at least two components selected from the following
components: a
tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal salt, water,
fructose, sucrose,
glucose, organic halide salt and an organic hydrogen bond donor; and
recovering the at least one hydrocarbon.
2. The method as recited in claim 1, further comprising forming a multiphase
system from the
at least one hydrocarbon, the at least one solid particulate and the at least
one analogue ionic
liquid; and recovering the at least one hydrocarbon from the multiphase
system.
3. The method as recited in claim 2, further comprising recovering the at
least one solid
particulate.
4. The method as recited in claim 1, wherein contacting the particulate matter
comprises
contacting the particulate matter with the at the least one analogue ionic
liquid and at least
one organic solvent as a composition to separate the at least one hydrocarbon
from the at least
one solid particulate.
5. The method as recited in claim 1, wherein contacting the particulate matter
comprises
contacting the particulate matter with the at least one analogue ionic liquid
and water as a
composition to separate the at least one hydrocarbon from the at least one
solid particulate.

36

6. The method as recited in claim 1, wherein contacting the particulate matter
comprises
contacting the particulate matter at a temperature of less than 100°C
to separate the at least
one hydrocarbon from the particulate matter.
7. The method as recited in claim 1, wherein contacting the particulate matter
comprises
contacting the particulate matter at a temperature of less than or equal to
50°C to separate the
at least one hydrocarbon from the particulate matter.
8. The method as recited in claim 2, further comprising at least one step
selected from:
decanting at least a portion of the multiphase system, evaporating at least a
portion of the
multiphase system, distilling at least a portion of the multiphase system,
centrifuging at least
a portion of the multiphase system and filtrating at least a portion of the
multiphase system.
9. The method as recited in claim 1, wherein the at least one hydrocarbon
comprises at least
one hydrocarbon selected from the group consisting of: bitumen, oil and
drilling fluid.
10. The method as recited in claim 1, wherein the at least one solid
particulate comprises at
least one solid particulate selected from the group consisting of: sand, soil,
silt, clay, rock,
minerals and drill cuttings.
11. The method as recited in claim 1, wherein the at least one analogue ionic
liquid comprises
a tetralkyl ammonium salt.
12. The method as recited in claim 2, wherein the multiphase system comprises
three phases.
13. The method as recited in claim 4, wherein the at least one organic solvent
is at least one
organic solvent selected from the group consisting of: toluene, naphtha,
hexane, kerosene and
paraffinic solvents.
14. The method as recited in claim 1, further comprising contacting the
particulate matter
and the at least one analogue ionic liquid to form a mixture; subjecting the
mixture to
electromagnetic heating to heat the mixture; and then recovering the at least
one hydrocarbon.

37

15. The method as recited in claim 14, wherein the electromagnetic heating is
microwave
heating.
16. The method as recited in any one of claims 1 to 15, wherein the tetraalkyl
ammonium
salt is 2-hydroxyethyl(trimethyl) ammonium chloride, 2-hydroxyethyl(trimethyl)
ammonium
bromide, 2-hydroxyethyl(triethyl) ammonium chloride, 2-hydroxyethyl(trimethyl)

ammonium tetrafluoroborate, or any combination thereof.
17. The method as recited in any one of claims 1 to 15, wherein the at least
one analogue
ionic liquid comprises urea and a tetraalkyl ammonium salt, wherein the
tetraalkyl
ammonium salt is 2-hydroxyethyl(trimethyl) ammonium chloride, 2-
hydroxyethyl(trimethyl)
ammonium bromide, 2-hydroxyethyl(triethyl) ammonium
chloride, 2-
hydroxyethyl(trimethyl) ammonium tetrafluoroborate, or any combination
thereof.
18. The method as recited in any one of claims 1 to 15, wherein the at least
one analogue
ionic liquid comprises 2-hydroxyethyl(trimethyl) ammonium chloride and urea.
19. The method as recited in any one of claims 1 to 15, wherein the analogue
ionic liquid
comprises a concentrated solution of 2-hydroxyethyl(trimethyl) ammonium
chloride in water.
20. The method as recited in any one of claims 2 to 5 and 8 to 19, wherein
contacting the
particulate matter comprises contacting the particulate matter at a
temperature of less than
100 C to separate the at least one hydrocarbon from the particulate matter.
21. The method as recited in any one of claims 2 to 5 and 8 to 19, wherein
contacting the
particulate matter comprises contacting the particulate matter at a
temperature of less than or
equal to 50 C to separate the at least one hydrocarbon from the particulate
matter.
22. The method as recited in any one of claims 1 to 21, wherein the at least
one analogue
ionic liquid separates at least 90% of the at least one hydrocarbon from the
particulate matter.
23. The method as recited in any one of claims 1 to 22, wherein the contacting
step
comprises contacting the particulate matter with a separating composition to
separate the at

38

least one hydrocarbon from the at least one solid particulate; and wherein the
at least one
analogue ionic liquid comprises at least 25 percent by weight of the
separating composition.
24. A method of separating bitumen or oil from particulate matter, the method
comprising:
contacting particulate matter comprising bitumen or oil with at least one
analogue
ionic liquid to separate the bitumen or oil from the particulate matter,
wherein the at least one
analogue ionic liquid comprises at least two components selected from the
following
components: a tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal
salt, water,
fructose, sucrose, glucose, organic halide salt and organic hydrogen bond
donor; and
recovering the bitumen or oil.
25. The method as recited in claim 24, wherein the particulate matter is
Canadian oil sands
comprising bitumen.
26. The method as recited in any one of claims 24 to 25, wherein the at least
one analogue
ionic liquid separates at least 90% of the bitumen or oil from the particulate
matter.
27. The method as recited in any one of claims 24 to 26, wherein the
contacting step
comprises mixing the particulate matter with a separating composition to
separate the
bitumen or oil from the particulate matter; and wherein the at least one ionic
liquid comprises
at least 25 percent by weight of the separating composition.
28. A method of separating hydrocarbon from oil sludge, the method comprising:
mixing oil sludge which comprises at least one hydrocarbon and at least one
solid
particulate with at least one analogue ionic liquid, wherein the at least one
analogue ionic
liquid comprises at least two components selected from the following
components: a
tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal salt, water,
fructose, sucrose,
glucose, organic halide salt and organic hydrogen bond donor; and
separating the at least one hydrocarbon from the oil sludge.
29. The method as recited in claim 28, wherein the at least one analogue ionic
liquid
separates at least 90% of the hydrocarbon from the solid sludge.

39

30. The method as recited in any one of claims 28 to 29, wherein the mixing
step comprises
mixing the oil sludge with a separating composition to separate the at least
one hydrocarbon
from the oil sludge; and wherein the at least one ionic liquid comprises at
least 25 percent by
weight of the separating composition.
31. A method of treating a mixture, the method comprising:
mixing the mixture which comprises at least one hydrocarbon, water and at
least one
solid particulate, with at least one analogue ionic liquid to separate the at
least one
hydrocarbon and/or the at least one solid particulate from the water, wherein
the at least one
analogue ionic liquid comprises at least two components selected from the
following
components: a tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal
salt, water,
fructose, sucrose, glucose, organic halide salt and organic hydrogen bond
donor; and
recovering the separated at least one hydrocarbon and/or the separated at
least one
solid particulate.
32. The method as recited in claim 31, wherein the mixture is from a
tailing pond.
33. The method as recited in claim 31, wherein the mixture is a feed stream
from a process to
recover bitumen from particulate matter.
34. The method as recited in claim 33, wherein the mixture is a slurry, froth,
or process water
from a process to recover bitumen from particulate matter
35. The method as recited in any one of claims 31 to 34, wherein the solid
particulate
comprises mineral fines and the process comprises separating the mineral fines
from the
mixture.
36. The method as recited in any one of claims 31 to 35, wherein the mixture
comprises a
suspension of the solid particulate and wherein mixing the mixture with the at
least one
analogue ionic liquid flocculates the solid particulate.
37. The method as recited in any one of claims 31 to 36, wherein the mixing
step comprises
mixing the mixture with a separating composition to separate the hydrocarbon
and/or the


solid particulate from the water; and wherein the at least one ionic liquid
comprises at least
25 percent by weight of the separating composition.
38. The method as recited in any one of claims 24 to 37, wherein the
tetraalkyl ammonium
salt is 2-hydroxyethyl(trimethyl) ammonium chloride, 2-hydroxyethyl(trimethyl)
ammonium
bromide, 2-hydroxyethyl(triethyl) ammonium chloride, 2-hydroxyethyl(trimethyl)

ammonium tetrafluoroborate, or any combination thereof.
39. The method as recited in any one of claims 24 to 37, wherein the at
least one analogue
ionic liquid comprises urea and a tetraalkyl ammonium salt, wherein the
tetraalkyl
ammonium salt is 2-hydroxyethyl(trimethyl) ammonium chloride, 2-
hydroxyethyl(trimethyl)
ammonium bromide, 2-hydroxyethyl(triethyl) ammonium
chloride, 2-
hydroxyethyl(trimethyl) ammonium tetrafluoroborate, or any combination
thereof.
40. The method as recited in any one of claims 24 to 37, wherein the at least
one analogue
ionic liquid comprises 2-hydroxyethyl(trimethyl) ammonium chloride and urea.
41. The method as recited in any one of claims 24 to 37, wherein the analogue
ionic liquid
comprises a concentrated solution of 2-hydroxyethyl(trimethyl) ammonium
chloride in water.
42. The method as recited in any one of claims 24 to 41, further comprising
including at least
one organic solvent with the at least one analogue ionic liquid in the
contacting or mixing
step.
43. The method as recited in any one of claims 24 to 30, further comprising
including water
with the at least one analogue ionic liquid in the contacting or mixing step.
44. The method as recited in any one of claims 24 to 43, wherein the
contacting or mixing
step is at a temperature of less than 100°C.
45. The method as recited in any one of claims 24 to 43, wherein the
contacting or mixing
step is at a temperature of less than or equal to 50°C.

41

Description

Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.


CA 02761201 2016-02-19
ANALOGUE IONIC LIQUIDS FOR THE SEPARATION AND RECOVERY OF
HYDROCARBONS FROM PARTICULATE MATTER
[00011
FIELD OF TECHNOLOGY
100021 The present application is directed to systems, methods and
compositions for the
separation and recovery of hydrocarbons from particulate matter. More
specifically, the present
application is directed to analogue ionic liquids for the separation and
recovery of hydrocarbons
from particulate matter.
BACKGROUND
100031 Oil sands, also referred to as tar sands, contain a significant
quantity of the world's
known oil reserves. Large deposits of oil sands are found in Canada. Venezuela
and in the United
States in eastern Utah. Oil sands are a complex mixture of sands, clays, water
and viscous
hydrocarbon compounds, known as bitumen. Typically, the extraction and
separation of bitumen
from oil sands involves the use of significant amounts of energy and heated
water.
Approximately 19 barrels of water are required for every barrel of oil
produced. Water, sodium
hydroxide (NaOH) and other additives are mixed with the oil sands to form a
slurry. The Na011
releases surfactants from the oil sands and improves bitumen recovery. The
slurry is conditioned
by mixing and/or shearing the slurry to detach bitumen from the oil sands
particles. Bitumen is
separated from water by aeration to form an oil containing froth that can be
skimmed off the
surface of the water. The remaining process water is a complex mixture of
alkaline water,
dissolved salts. minerals, residual bitumen, surfactants released from the
bitumen and other
materials used in processing. Additional processing of the water is required
to remove residual
1

CA 02761201 2011-12-05
bitumen
[0004] The process water is ultimately stored in tailing ponds and is acutely
toxic to aquatic
life. The process water recycled from tailings ponds causes scaling and
corrosion problems that
often adversely affect the optimum recovery of bitumen. In addition, very fine
mineral particles
such as clays are co-extracted with the bitumen and must be removed in
subsequent processing
steps that ultimately reduce the yield of bitumen. Although a large proportion
of the water used
in the process (about 16 barrels) is now recycled from tailing ponds, the
production of each
barrel of oil still requires importing an additional 3 barrels of fresh water.
The necessity of large
quantities of water has prevented the recovery of bitumen deposits from oils
sands in arid areas
such as Utah.
[0005] Several other related scenarios require the removal of oil from sand or
solid particles in
oil and gas operations. For example, heavy oil (e.g., between 100 and 20 API
gravity) is also
found in sand deposits, particularly in Venezuela and Canada. Recovery of
heavy oil from sand
typically involves expensive thermal methods such as, steam injection. A
technique widely used
in Canada called cold heavy oil production with sand (CHOPS) has also been
used to separate
heavy oil from sand. CHOPS involves the continuous production of sand and oil,
which presents
separation and disposal constraints.
[0006] During drilling operations drilling fluids used to cool and clean the
drill bit become
contaminated with formation cuttings. Formation cuttings must be removed from
the drilling
fluid before reuse of drilling fluid. During production operations, crude oil
produced from
unconsolidated formations can also contain sand including mixtures of various
minerals and silt
that require removal prior to processing the oil. The oil coated sand must
also be cleaned before
disposal or re-depositing.
[0007] An increase in offshore drilling operations has also increased the risk
of coastal
communities and beaches being exposed to crude oil produced from offshore oil
rigs. As
described above, current methods for the removal of oil from sand require
large quantities of
water and energy. Physical methods for removing oil from beach sand including
the use of
shovels, cleaning forks and lift and screen systems require large amounts of
labor and do not
efficiently remove all the decontaminate from the sand.
[0008] In view of the foregoing, there is a need in the field of art for
improved systems,
2

CA 02761201 2016-02-19
methods and compositions for the separation and recovery of hydrocarbons from
particulate
matter.
SUMMARY
[00091 Systems, methods and compositions for the separation and recovery of
hydrocarbons
from particulate matter are herein disclosed. According to one embodiment, a
method includes
contacting particulate matter with at least one analogue ionic liquid. The
particulate matter
contains at least one hydrocarbon and at least one solid particulate. When the
particulate matter
is contacted with the analogue ionic liquid, the hydrocarbon dissociates from
the solid particulate
to form a multiphase system.
10009.11 Also disclosed herein is a method of separating and recovering
hydrocarbon from
particulate matter, the method comprising:
contacting particulate matter comprising at least one hydrocarbon and at least
one
solid particulate with at least one analogue ionic liquid to separate the at
least one hydrocarbon
from the at least one solid particulate, wherein the at least one analogue
ionic liquid comprises
at least two components selected from the following components: a tetraalkyl
ammonium salt.
urea, carboxylic acid, glycerol, metal salt, water, fructose, sucrose,
glucose. organic halide salt
and an organic hydrogen bond donor; and
recovering the at least one hydrocarbon.
10009.21 Also disclosed herein is a method of separating bitumen or oil from
particulate
matter, the method comprising:
contacting particulate matter comprising bitumen or oil with at least one
analogue
ionic liquid to separate the bitumen or oil from the particulate matter,
wherein the at least one
analogue ionic liquid comprises at least two components selected from the
following
components: a tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal
salt, water,
fructose. sucrose, glucose, organic halide salt and organic hydrogen bond
donor; and
recovering the bitumen or oil.
3

CA 02761201 2016-10-20
(0009.31 Also disclosed herein is a method of separating hydrocarbon from
oil
sludge, the method comprising:
mixing oil sludge which comprises at least one hydrocarbon and at least one
solid particulate with at least one analogue ionic liquid, wherein the at
least one
analogue ionic liquid comprises at least two components selected from the
following
components: a tetraalkyl ammonium salt, urea, carboxylic acid, glycerol, metal
salt,
water, fructose, sucrose, glucose, organic halide salt and organic hydrogen
bond
donor; and
separating the at least one hydrocarbon from the oil sludge.
10009.41 Also disclosed herein is a method of treating a mixture, the
method
comprising:
mixing the mixture which comprises at least one hydrocarbon, water and at
least one solid particulate, with at least one analogue ionic liquid to
separate the at
least one hydrocarbon and/or the at least one solid particulate from the
water, wherein
the at least one analogue ionic liquid comprises at least two components
selected from
the following components: a tetraalkyl ammonium salt, urea, carboxylic acid,
glycerol, metal salt, water, fructose, sucrose, glucose, organic halide salt
and organic
hydrogen bond donor; and
recovering the separated at least one hydrocarbon and/or the separated at
least
one solid particulate.
100101 The foregoing and other objects, features and advantages of the present
disclosure will
become more readily apparent from the following detailed description of
exemplary
embodiments as disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
100111 Embodiments of the present application are described, by way of example
only, with
reference to the attached Figures, wherein:
100121 FIG 1 illustrates an exemplary system for recovering bitumen from oil
sands according to
one embodiment;
100131 FIG. 2 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to one embodiment;
[001.1] FIG. 3 illustrates an exemplary system for recovering bitumen from oil
sands according to
3a

CA 02761201 2016-02-19
another embodiment;
[0015] FIG. 4 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to another embodiment;
100161 FIG. 5 illustrates an exemplary system for recovering bitumen from oil
sands according to
another embodiment;
100171 FIG. 6 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to another embodiment;
3b

CA 02761201 2011-12-05
[0018] FIG. 7 illustrates an exemplary three-phase system formed from mixing
oil sands and
ionic liquid according to one embodiment;
[0019] FIG. 8 illustrates a comparative example of bitumen encrusted minerals;
[0020] FIG. 9 illustrates exemplary three-phase systems formed from mixing oil
sands, ionic
liquid and organic solvent according to one embodiment;
[0021] FIG. 10 illustrates an exemplary infrared spectra of medium grade
Canadian oil sands and
component parts thereof before and after separation of bitumen;
[0022] FIG. 11 illustrates an exemplary infrared spectra of low-grade oil
sands and medium-
grade oil sands after separation of bitumen;
[0023] FIG. 12 illustrates exemplary three-phase systems formed from mixing an
exemplary
separating composition and toluene with low-grade and medium-grade oil sands
according to one
embodiment;
[0024] FIG. 13 illustrates the infrared spectra of extracted bitumen and
residual sand obtained in
the separation of low-grade oil sands using an exemplary separating
composition according to
one embodiment;
[0025] FIG 14 illustrates an exemplary three-phase system formed from mixing
ionic liquid,
organic solvent and contaminated sand according to one embodiment;
[0026] FIG. 15 illustrates the infrared spectra of contaminated drill cuttings
and component parts
thereof before and after separation of oil;
[0027] FIG. 16 illustrates exemplary and comparative multi-phase systems
formed from mixing
exemplary and comparative separation solutions with tar balls according to one
embodiment;
[0028] FIG. 17 illustrates tar contaminated sand prior to separation and sand
free of tar
contamination after separation with the use of an exemplary ionic liquid;
[0029] FIG. 18 illustrates comparative systems formed from mixing Canadian tar
sands with
comparative additive solutions;
[0030] FIG. 19 illustrates comparative systems formed from mixing Canadian tar
sands with
other comparative additive solutions;
4

CA 02761201 2011-12-05
[0031] FIG. 20 illustrates a comparative system formed from mixing Canadian
tar sands with
another comparative additive solution;
[0032] FIG. 21 illustrates an exemplary multi-phase system formed from mixing
Canadian tar
sands with an exemplary analogue ionic liquid according to one embodiment;
[0033] FIG. 22 illustrates an exemplary multi-phase system formed from mixing
Canadian tar
sands with an exemplary analogue ionic liquid according to another embodiment;
[0034] FIG. 23 illustrates exemplary three-phase systems formed from
centrifuging components
of the exemplary multi-phase system shown in FIG. 22;
[0035] FIG. 24 illustrates infra red spectra of the top hydrocarbon phase and
the bottom mineral
phase of the exemplary three-phase systems shown in FIG 23;
[0036] FIG. 25 illustrates tailing pond material before and after separation
with the use of an
exemplary ionic liquid according to one embodiment;
[0037] FIG. 26 illustrates tailing pond material before and after separation
with the use of
exemplary analogue ionic liquids according to one embodiment;
[0038] FIG. 27 illustrates concentrated tailing pond material before and after
separation with the
use of an exemplary analogue ionic liquid according to another embodiment;
[0039] FIG. 28 illustrates an exemplary three phase system formed from mixing
an exemplary
analogue ionic liquid with Canadian tar sands and tailing pond material
according to one
embodiment;
[0040] FIG. 29 illustrates an exemplary three phase system formed from mixing
an exemplary
analogue ionic liquid with Canadian tar sands according to another embodiment;
and
[0041] FIG. 30 illustrates an exemplary system for recovering hydrocarbons
from particulate
matter with the use of the exemplary ionic liquids or analogue ionic liquids
according to one
embodiment.
DETAILED DESCRIPTION
[0042] It will be appreciated that for simplicity and clarity of illustration,
where considered
appropriate, reference numerals may be repeated among the figures to indicate
corresponding or
analogous elements. In addition, numerous specific details are set forth in
order to provide a

CA 02761201 2011-12-05
thorough understanding of the example embodiments described herein. However,
it will be
understood by those of ordinary skill in the art that the example embodiments
described herein
may be practiced without these specific details. In other instances, methods,
procedures and
components have not been described in detail so as not to obscure the
embodiments described
herein. The terms oil sands and tar sands are used interchangeably throughout
this disclosure.
[0043] Systems, methods and compositions for the separation and recovery of
hydrocarbons
from particulate matter are herein disclosed. One or more ionic liquids or
analogue ionic liquids
herein disclosed can be mixed with or otherwise placed in contact with
particulate matter
comprising at least one hydrocarbon and at least one solid particulate. When
contacted with an
ionic liquid or analogue ionic liquid, the hydrocarbon separates or
dissociates from the solid
particulate. The particulate matter can include, but is not limited to the
following: oil sands,
drilling fluid containing drill cuttings, tailing pond material, crude oil
containing sand, beach
sand contaminated with oil, oil sludge, any hydrocarbon containing sand, soil,
rock, silt, clay or
other solid particulate or any hydrocarbon contained within sand, soil, rock,
silt, clay or other
solid particulate.
[0044] The ionic liquids disclosed herein are thermally stable, chemically
stable, have negligible
vapor pressure, and are soluble in water and insoluble in organic solvents,
such as non-polar
hydrocarbon solvents. The ionic liquids substantially degrade into a
corresponding amino acid at
room temperature when reacted with hydrogen peroxide and ions, such as iron
ions. Therefore,
the ionic liquids can be contained or reacted into innocuous amino acids if
they are inadvertently
or deliberately released into the environment. The ionic liquids can include
at least one
compound formed from imidazolium cations and at least one anion. The ionic
liquids can include
at least one compound including, but not limited to: 1-buty1-2,3-dimethyl-
imidazolium;
borontetrafluoride; 1-buty1-2,3-dimethyl-imidazolium; trifluoro-
methanesulfonate; 1-buty1-3-
methyl-imidazolium; trifluoromethanesulfonate; 1-butyl-3-methyl-imidazolium
chloride; 1-
ethy1-3-methyl-imidazolium chloride; tetraalkyl ammonium salts; pyrrolidinium
based salts or
any other ionic liquid that is soluble in water and insoluble in non-polar
organic solvents.
[0045] The ionic liquids disclosed herein are used to separate particulate
matter at relatively low
temperatures of below 100 C, preferably below 50 C and more preferably 25 C
and lower.
Optionally, the separation temperature can be raised to lower the viscosity of
the hydrocarbon
6

CA 02761201 2011-12-05
being separated and aid in separation from particulate material. The
separation temperature can
be raised by any heating means including electric heating means,
electromagnetic heating means,
microwave heating means or other heating means.
[0046] One or more analogue ionic liquids herein disclosed can also be mixed
with or otherwise
placed in contact with particulate matter comprising at least one hydrocarbon
and at least one
solid particulate to effect separation of the hydrocarbon from the solid
particulate. When
contacted with the analogue ionic liquids, the hydrocarbon separates or
dissociates from the solid
particulate. This separation is promoted by the presence of an organic
solvent, particularly if the
hydrocarbon to be separated is highly viscous. Examples of such viscous
hydrocarbons are
bitumen and tar. The particulate matter can include, but is not limited to the
following: oil sands,
drilling fluid containing drill cuttings, tailing pond material, crude oil
containing sand, beach
sand contaminated with oil, oil sludge, any hydrocarbon containing sand, soil,
rock, silt, clay or
other solid particulate or any hydrocarbon contained within sand, soil, rock,
silt, clay or other
solid particulate.
[0047] Analogue ionic liquids herein disclosed are relatively non-toxic and
biodegradable.
Analogue ionic liquids herein disclosed include at least two components. The
analogue ionic
liquids have melting temperatures that are significantly less than the melting
temperature of the
components making up the analogue ionic liquids. Analogue ionic liquids can
include, but are
not limited to at least two components selected from the following components:
tetralkyl
ammonium salts, urea, carboxylic acids, glycerol, metal salts, water,
fructose, sucrose, glucose,
organic halide salts and organic hydrogen bond donors.
[0048] The tetralkyl ammonium salts can include, but are not limited to 2-
hydroxyethyl(trimethyl) ammonium chloride (choline chloride), 2-
hydroxyethyl(trimethyl)
ammonium bromide, 2-hydroxyethyl(triethyl) ammonium chloride, 2-
hydroxyethyl(trimethyl)
ammonium tetrafluoroborate.
[0049] The organic halide salts can include, but are not limited to methyl
triphenyl
phosphoni um bromide.
[0050] The organic hydrogen bond donors can include, but are not limited to
glycerol, ethylene
glycol, or triethylene glycol.
7

CA 02761201 2011-12-05
[0051] An organic solvent and/or water can also be added to or mixed with the
ionic liquid or
analogue ionic liquid and the particulate matter to obtain optimal separation
of hydrocarbon from
the solid particulate. The organic solvent lowers the viscosity of the
hydrocarbon and aids in the
separation from the solid particulate. The organic solvents herein disclosed
dissolve non-polar
hydrocarbons such as bitumen, oil or drilling fluid and are immiscible with
the ionic liquids
disclosed above. The organic solvent can include, but is not limited to at
least one of the
following compounds: toluene, naphtha, hexane, kerosene, paraffinic solvents
or any other non-
polar hydrocarbon solvent that dissolves the hydrocarbon and is immiscible
with the ionic liquid.
[0052] FIG. 1 illustrates an exemplary system for recovering bitumen from oil
sands 102
according to one embodiment. Oil sands 102 can include sand, clay, other
minerals, and bitumen.
The oil sands 102 are mixed with an organic solvent 104 and an ionic liquid
106 in a primary
mixing vessel 100. The primary mixing vessel 100 can be any vessel known in
the art for mixing
or containing liquids, solids or slurries. When mixed with the organic solvent
104 and the ionic
liquid 106, the bitumen is separated from the oil sands 102 and a three-phase
system including a
top phase, middle phase and bottom phase is formed.
[0053] The bottom phase 110 consists of ionic liquid 106 with suspended sand
and clay. The
middle phase 109 consists of ionic liquid 106 with small amounts of dissolved
or suspended
bitumen particles and mineral fines. The top phase 108 consists of organic
solvent 104 and
bitumen. The bottom phase 110, the middle phase 109 and the top phase 108 can
be drained from
the primary mixing vessel 100 for further processing and/or recycling through
the system.
[0054] The bitumen in the top phase 108 can be recovered after separating or
evaporating the
organic solvent 104 from the bitumen in a primary separator 122. The primary
separator 122 can
be a decanter, distillation column, pressure separator, centrifuge, open tank,
hydroclone, settling
chamber or other separator known in the art for separating mixtures. The
organic solvent 104 can
be condensed, recycled to the primary mixing vessel 100 and mixed with
additional oil sands
102, organic solvent 104 and ionic liquid 106 to achieve three-phase
separation.
[0055] The middle phase 109 and substantially all of the ionic liquid 106
introduced into the
system can be retained in the mixing vessel 100. In this way, the ionic liquid
106 in the middle
phase 109 is not moved throughout the system. If removed for additional
processing, the middle
phase 109 can be recycled to the primary mixing vessel 100 and mixed with
additional oil sands
8

CA 02761201 2011-12-05
102, organic solvent 104 and ionic liquid 106 to achieve three-phase
separation. The
concentration of bitumen within the middle phase 109 is expected to reach
equilibrium and
therefore will not accumulate. If necessary, organic solvent 104 can be added
to the middle phase
109 in an additional processing step to separate any entrained or suspended
bitumen from the
ionic liquid 106 before the ionic liquid 106 is recycled to the primary mixing
vessel 100.
[0056] The bottom phase 110 consisting of ionic liquid 106 with suspended sand
and clay can be
fed into a secondary mixing vessel 118 and mixed with water to form a solution
of ionic liquid
106, water, and suspended sand and clay particles. The mixing vessel 118 can
be any vessel
known in the art for mixing or containing liquids, solids or slurries. The
sand and clay can be
filtered from the ionic liquid and water. The ionic liquid 106 can be
recovered after separating or
evaporating the water in a secondary separator 120. The separator 120 can be a
decanter,
distillation column, pressure separator, centrifuge, open tank or other
separator known in the art
for separating mixtures. After separation and/or evaporation, the water can be
condensed before
it is recycled to the secondary mixing vessel 118. The ionic liquid 106 can be
recycled to the
primary mixing vessel 100 and mixed with additional oil sands 102, organic
solvent 104 and
ionic liquid 106 to achieve three-phase separation.
100571 The exemplary system for recovering bitumen from oil sands illustrated
in FIG. 1 can
also be used to separate other particulate matter including, but not limited
to the following: oil
sands, drilling fluid containing drill cuttings, crude oil containing sand,
beach sand contaminated
with oil, oil sludge, any hydrocarbon containing sand, soil, rock, silt, clay
or other solid
particulate or any hydrocarbon contained within sand, soil, rock, silt, clay
or other solid
particulate. The ionic liquid 106 and organic solvent 104 can be mixed with or
otherwise placed
in contact with the particulate matter to separate or dissociate the
hydrocarbon from the solid
particulate and recover the hydrocarbon as described above.
100581 FIG. 2 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to one embodiment. The oil sands are mixed with an organic
solvent and an
ionic liquid at step 201 to form a three-phase system including a top phase,
middle phase and
bottom phase. The top phase consists of organic solvent and bitumen. The
middle phase consists
of ionic liquid with small amounts of dissolved bitumen particles and mineral
fines. The bottom
phase consists of ionic liquid with suspended sand and clay. The top phase,
middle phase and
9

CA 02761201 2011-12-05
bottom phase may be separated at step 202 for further processing or recycling
back through the
process.
[0059] At step 203, the bitumen and the organic solvent in the top phase are
separated through
decantation, distillation, evaporation or centrifugation and the bitumen is
recovered. The organic
solvent can be condensed, recycled and mixed with additional oil sands,
organic solvent and
ionic liquid to achieve three-phase separation.
[0060] At step 204, the middle phase is recycled and mixed with additional
organic solvent,
ionic liquid and oil sands to achieve three-phase separation. Optionally, the
middle phase and/or
substantially all of the ionic liquid can be retained in a primary mixing
vessel within which the
original oil sands, organic solvent and ionic liquid are mixed.
[0061] At step 205, water is added to the bottom phase to form a solution of
water, ionic liquid
and suspended sand and clay particles. The sand and clay is removed from
suspension at step 206
through filtration. At step 207, the water is separated from the ionic liquid
through decantation,
distillation, evaporation or centrifugation and the ionic liquid is recovered.
At step 208 the ionic
liquid is recycled and mixed with additional organic solvent, ionic liquid and
oil sands to achieve
three-phase separation. The water can be condensed, recycled and mixed with
the bottom phase
at step 209 to separate additional ionic liquid from sand and clay.
[0062] The exemplary process for recovering bitumen from oil sands illustrated
in FIG. 2 can
also be used to separate other particulate matter including, but not limited
to the following: oil
sands, drilling fluid containing drill cuttings, crude oil containing sand,
beach sand contaminated
with oil, oil sludge, any hydrocarbon containing sand, soil, rock, silt, clay
or other solid
particulate or any hydrocarbon contained within sand, soil, rock, silt, clay
or other solid
particulate. The ionic liquid and organic solvent can be mixed with or
otherwise placed in
contact with the particulate matter to separate the hydrocarbon from the solid
particulate and
recover the hydrocarbon as described above.
[0063] FIG. 3 illustrates an exemplary system for recovering bitumen from oil
sands 302
according to another embodiment. Oil sands 302 can include sand, clay, other
minerals, and
bitumen. The oil sands 302 are mixed with an ionic liquid 306 in a primary
mixing vessel 300.
The primary mixing vessel 300 can be any vessel known in the art for mixing or
containing
liquids, solids or slurries. When mixed with the ionic liquid 306, the bitumen
is separated from

CA 02761201 2016-10-20
the oil sands 302 and a three-phase system including a top phase, middle phase
and bottom
phase is formed. The bottom phase 310 consists of ionic liquid 306, sand and
clay slurry. The
middle phase 309 consists of ionic liquid 306, with some bitumen and minerals.
The top
phase 308 consists of bitumen. The bottom phase 310, the middle phase 309 and
the top
phase 308 can be drained from the primary mixing vessel 300 and the bitumen
can be
recovered.
[0064] The middle phase 309 and substantially all of the ionic liquid 306
introduced into the
system can be retained in bulk in the mixing vessel 300. In this way, the
ionic liquid 306 in
the middle phase 309 is not moved throughout the system. If removed for
additional
processing, the middle phase 309 can be recycled to the primary mixing vessel
300 and
mixed with additional oil sands 302 and ionic liquid 306 to achieve three-
phase separation.
The bitumen within the recycled middle phase 309 is expected to reach
equilibrium and
therefore will not accumulate.
[0065] The bottom phase 310 containing ionic liquid 306, sand and clay slurry
can be fed
into a secondary mixing vessel 318 and mixed with water to form a solution of
ionic liquid
306, water, and suspended sand and clay particles. The mixing vessel 318 can
be any vessel
known in the art for mixing or containing liquids, solids or slurries. The
sand and clay can be
filtered from the ionic liquid and water. The ionic liquid 306 can be
recovered by separating
and/or evaporating the water in a secondary separator 320. The separator 320
can be a
decanter, distillation column, pressure separator, centrifuge, open tank
hydroclone, settling
chamber or other separator known in the art for separating mixtures. After
separation and/or
evaporation, the water can be condensed before it is recycled to the secondary
mixing vessel
318. The ionic liquid 306 can be recycled to the primary mixing vessel 300 and
mixed with
additional oil sands 302 and ionic liquid 306 to achieve three-phase
separation.
[0066] The exemplary system for recovering bitumen from oil sands illustrated
in FIG 3 can
also be used to separate other particulate matter including, but not limited
to the following:
oil sands, drilling fluid containing drill cuttings, crude oil containing
sand, beach sand
contaminated with oil, oil sludge, any hydrocarbon containing sand, soil,
rock, silt, clay or
other solid particulate or any hydrocarbon contained within sand, soil, rock,
silt, clay or other
solid particulate. The ionic liquid 306 can be mixed with or otherwise placed
in contact with
the particulate matter to separate or dissociate the hydrocarbon from the
solid particulate and
recover the hydrocarbon as described above.
11

CA 02761201 2011-12-05
[0067] FIG. 4 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to another embodiment. The oil sands are mixed with an ionic
liquid at step 401
to form a three-phase system including a top phase, middle phase and bottom
phase. The top
phase consists of bitumen. The middle phase consists of ionic liquid, with
some bitumen and
minerals. The bottom phase is ionic liquid, sand and clay slurry. The top
phase, middle phase and
bottom phase can be separated at step 402 for further processing or recycling
back through the
process.
[0068] At step 403, the middle phase is recycled and mixed with additional
ionic liquid and oil
sands to achieve three-phase separation. Optionally, the middle phase and/or
substantially all of
the ionic liquid can be retained in a primary mixing vessel within which the
original oil sands
and ionic liquid are mixed.
[0069] At step 404, water is added to the bottom phase to form a solution of
water, ionic liquid
and suspended sand and clay particles. The sand and clay is removed from the
solution at step
405 through filtration. At step 406, the water is separated from the ionic
liquid through
decantation, distillation, evaporation or centrifugation and the ionic liquid
is recovered. At step
407 the ionic liquid is recycled and mixed with additional ionic liquid and
oil sands to achieve
three-phase separation. The water can be condensed, recycled and mixed with
the bottom phase
at step 408 to separate additional ionic liquid from sand and clay.
[0070] The exemplary process for recovering bitumen from oil sands illustrated
in FIG. 4 can
also be used to separate other particulate matter including, but not limited
to the following: oil
sands, drilling fluid containing drill cuttings, crude oil containing sand,
beach sand contaminated
with oil, oil sludge, any hydrocarbon containing sand, soil, rock, silt, clay
or other solid
particulate or any hydrocarbon contained within sand, soil, rock, silt, clay
or other solid
particulate. The ionic liquid can be mixed with or otherwise placed in contact
with the particulate
matter to separate or dissociate the hydrocarbon from the solid particulate
and recover the
hydrocarbon as described above.
[0071] FIG 5 illustrates an exemplary system for recovering bitumen from oil
sands according
to another embodiment. Oil sands 502 can include sand, clay, other minerals,
and bitumen. The
oil sands 502 are mixed with or otherwise placed in contact with an ionic
liquid 506, water and
optionally an organic solvent 504 in a primary mixing vessel 500 or other
separation vessel or
12

CA 02761201 2011-12-05
column. The primary mixing vessel 500 can be any vessel known in the art for
mixing or
containing liquids, solids or slurries.
[0072] The water may be present within the oil sands in order to economically
transport or pump
the oil sands to the process facility. Water may also be added to the system
to dilute the ionic
liquid and reduce cost. When mixed with the organic solvent 504, ionic liquid
506 and water, the
bitumen is separated from the oil sands 502 and a three-phase system including
a top phase,
middle phase and bottom phase is formed. The bottom phase 510 consists of
ionic liquid 506,
water and suspended sand and clay. The middle phase 509 consists of ionic
liquid 506, water and
small amounts of dissolved or suspended bitumen particles and mineral fines.
The top phase 508
consists of organic solvent 504 and bitumen. The bottom phase 510, the middle
phase 509 and
the top phase 508 can be drained from the primary mixing vessel 500 for
further processing
and/or recycling through the system.
[0073] The bitumen in the top phase 508 can be recovered after separating or
evaporating the
organic solvent 504 from the bitumen in a primary separator 522. The primary
separator 522 can
be a decanter, distillation column, pressure separator, centrifuge, open tank,
hydroclone, settling
chamber or other separator known in the art for separating mixtures. The
organic solvent 504 can
be condensed, recycled to the primary mixing vessel 500 and mixed with
additional oil sands
502, organic solvent 504 and ionic liquid 506 to achieve three-phase
separation.
[0074] The middle phase 509 and substantially all of the ionic liquid 506
introduced into the
system can be retained in the mixing vessel 500. In this way, the ionic liquid
506 in the middle
phase 509 is not moved throughout the system. If removed for additional
processing, the middle
phase 509 can be recycled to the primary mixing vessel 500 and mixed with
additional oil sands
502, organic solvent 504 and ionic liquid 506 to achieve three-phase
separation. The
concentration of bitumen within the middle phase 509 is expected to reach
equilibrium and
therefore will not accumulate. If necessary, organic solvent 504 can be added
to the middle phase
509 in an additional processing step to separate any entrained or suspended
bitumen from the
ionic liquid 506 before the ionic liquid 506 is processed and/or recycled to
the primary mixing
vessel 500.
[0075] The bottom phase 510 consisting of ionic liquid 506, water and
suspended sand and clay
can be fed into a secondary mixing vessel 518 and mixed with additional water
(if necessary) to
13

CA 02761201 2011-12-05
form a solution of ionic liquid 506, water, and suspended sand and clay
particles. The mixing
vessel 518 can be any vessel known in the art for mixing or containing
liquids, solids or slurries.
The sand and clay can be filtered from the ionic liquid and water. The ionic
liquid 506 can be
recovered after separating or evaporating the water in a secondary separator
520. The separator
520 can be a decanter, distillation column, pressure separator, centrifuge,
open tank or other
separator known in the art for separating mixtures. After separation and/or
evaporation, the water
can be condensed before it is recycled to the secondary mixing vessel 518 or
primary mixing
vessel 500. The ionic liquid 506 can be recycled to the primary mixing vessel
500 and mixed
with additional oil sands 502, organic solvent 504 and ionic liquid 506 to
achieve three-phase
separation.
[0076] The exemplary system for recovering bitumen from oil sands illustrated
in FIG. 5 can
also be used to separate other particulate matter including, but not limited
to the following: oil
sands, drilling fluid containing drill cuttings, crude oil containing sand,
beach sand contaminated
with oil, oil sludge, any hydrocarbon containing sand, soil, rock, silt, clay
or other solid
particulate or any hydrocarbon contained within sand, soil, rock, silt, clay
or other solid
particulate. The ionic liquid 506, water and optionally organic solvent 504
can be mixed with or
otherwise placed in contact with the particulate matter to separate or
dissociate the hydrocarbon
from the solid particulate and recover the hydrocarbon as described above.
[0077] FIG. 6 illustrates a flow chart of an exemplary process for recovering
bitumen from oil
sands according to one embodiment. The oil sands are mixed with an organic
solvent, an ionic
liquid and water at step 601 to form a three-phase system including a top
phase, middle phase
and bottom phase. The top phase consists of organic solvent and bitumen. The
middle phase
consists of ionic liquid, water and small amounts of dissolved bitumen
particles and mineral
fines. The bottom phase consists of water, ionic liquid and suspended sand and
clay. The top
phase, middle phase and bottom phase may be separated at step 602 for further
processing or
recycling back through the process.
[0078] At step 603, the bitumen and the organic solvent in the top phase are
separated through
decantation, distillation, evaporation or centrifugation and the bitumen is
recovered. The organic
solvent can be condensed, recycled and mixed with additional oil sands,
organic solvent and
ionic liquid to achieve three-phase separation.
14

CA 02761201 2011-12-05
[0079] At step 604, the middle phase is recycled and mixed with additional
organic solvent,
ionic liquid and oil sands to achieve three-phase separation. Optionally, the
middle phase and/or
substantially all of the ionic liquid can be retained in a primary mixing
vessel within which the
original oil sands, organic solvent, ionic liquid and water are mixed.
[0080] At step 605, water is added to the bottom phase to form a solution of
water, ionic liquid
and suspended sand and clay particles. The sand and clay is removed from
suspension at step 606
through filtration. At step 607, the water is separated from the ionic liquid
through decantation,
distillation, evaporation or centrifugation and the ionic liquid is recovered.
At step 608 the ionic
liquid is recycled and mixed with additional organic solvent, ionic liquid and
oil sands to achieve
three-phase separation. The water can be condensed, recycled and mixed with
the bottom phase
at step 609 to separate additional ionic liquid from sand and clay.
[0081] The exemplary process for recovering bitumen from oil sands illustrated
in FIG. 6 can
also be used to separate other particulate matter including, but not limited
to the following: oil
sands, drilling fluid containing drill cuttings, tailing pond material, crude
oil containing sand,
beach sand contaminated with oil, oil sludge, any hydrocarbon containing sand,
soil, rock, silt,
clay or other solid particulate or any hydrocarbon contained within sand,
soil, rock, silt, clay or
other solid particulate. The ionic liquid, water and optionally organic
solvent can be mixed with
or otherwise placed in contact with particulate matter to separate or
dissociate the hydrocarbon
from the solid particulate and recover the hydrocarbon as described above.
[0082] One or more analogue ionic liquids herein disclosed can also be mixed
with or otherwise
placed in contact with particulate matter comprising at least one hydrocarbon
and at least one
solid particulate to effect separation of the hydrocarbon from the solid
particulate. When
contacted with the analogue ionic liquids, the hydrocarbon separates or
dissociates from the solid
particulate. This separation is promoted by the presence of an organic
solvent, particularly if the
hydrocarbon to be separated is highly viscous. Examples of such viscous
hydrocarbons are
bitumen and tar. The particulate matter can include, but is not limited to the
following: oil sands,
drilling fluid containing drill cuttings, tailing pond material, crude oil
containing sand, beach
sand contaminated with oil, oil sludge, any hydrocarbon containing sand, soil,
rock, silt, clay or
other solid particulate or any hydrocarbon contained within sand, soil, rock,
silt, clay or other
solid particulate.

CA 02761201 2011-12-05
[0083] Analogue ionic liquids herein disclosed include at least two
components. The analogue
ionic liquids have melting temperatures that are significantly less than the
melting temperature of
the components making up the analogue ionic liquids. Analogue ionic liquids
can include, but are
not limited to at least two components selected from the following components:
tetralkyl
ammonium salts, urea, carboxylic acids, glycerol, metal salts, water,
fructose, sucrose, glucose,
organic halide salts and organic hydrogen bond donors.
[0084] The tetralkyl ammonium salts can include, but are not limited to 2-
hydroxyethyl(trimethyl) ammonium chloride (choline chloride), 2-
hydroxyethyl(trimethyl)
ammonium bromide, 2-hydroxyethyl(triethyl) ammonium chloride, 2-
hydroxyethyl(trimethyl)
ammonium tetrafluoroborate.
[0085] The organic halide salts can include, but are not limited to methyl
triphenyl
phosphonium bromide.
[0086] The organic hydrogen bond donors can include, but are not limited to
glycerol, ethylene
glycol, or triethylene glycol.
[0087] In an exemplary embodiment, the analogue ionic liquid includes choline
chloride and
urea. In another exemplary embodiment, the analogue ionic liquid includes urea
and choline
chloride present at a molar ratio of 2:1 urea to choline chloride.
[0088] In yet another exemplary embodiment, the analogue ionic liquid includes
a concentrated
solution of choline chloride in water. In yet another exemplary embodiment,
the analogue ionic
liquid includes an 80% mixture of choline chloride with 20% water, by weight.
[0089] The analogue ionic liquid herein disclosed can be used instead of or in
combination with
the ionic liquids herein disclosed in any of the exemplary systems or
processes described with
respect to FIGS. 1-6. The analogue ionic liquid can also be used to separate
other particulate
matter including, but not limited to the following: oil sands, drilling fluid
containing drill
cuttings, tailing pond material; crude oil containing sand, beach sand
contaminated with oil, oil
sludge, any hydrocarbon containing sand, soil, rock, silt, clay or other solid
particulate or any
hydrocarbon contained within sand, soil, rock, silt, clay or other solid
particulate. The analogue
ionic liquid, water and optionally organic solvent can be mixed with or
otherwise placed in
16

CA 02761201 2011-12-05
contact with the particulate matter to separate or dissociate one or more
hydrocarbons from solid
particulate for recovery as described with respect to FIGS. 1-6.
EXAMPLES
[0090] The following examples are provided to illustrate the exemplary methods
for recovering
hydrocarbons from particulate matter as herein disclosed. The examples are not
intended to limit
the scope of the present disclosure and they should not be so interpreted.
[0091] In Examples 1-5 and Comparative Example 1, medium-grade Canadian oil
sands
comprising 10 weight percent bitumen was purchased from the Alberta Research
Council and
used in separation experiments described below.
Example 1
[0092] The ionic liquid 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride
was mixed with oil
sands at 50 C. A three-phase system was formed. The top phase consisted of
bitumen. The
middle phase consisted of 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride,
suspended
minerals and bitumen. The bottom phase consisted of a slurry of 1-buty1-2,3-
dimethyl-
imidazolium borontetrafluoride, sand and clay.
[0093] FIG. 7 illustrates the three-phase system formed from mixing 1-buty1-
2,3-dimethyl-
imidazolium borontetrafluoride with oil sands at 50 C. It is a surprising and
unexpected result
that a highly polar ionic liquid that is immiscible with non-polar
hydrocarbons, such as bitumen,
toluene and naphtha would be suitable for separating bitumen from sand. It is
also unexpected
that 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride would separate
bitumen from sand at a
low temperature of 50 C or less. It was also observed that a two-phase mixture
including a
viscous top layer and bottom layer is formed when relatively smaller amounts
of ionic liquid are
used. The viscous top layer of the two-phase system consisted of bitumen and
the bottom layer
consisted of ionic liquid, suspended mineral particles and residual bitumen.
Comparative Example 1
[0094] The ionic liquid 1-buty1-3-methyl imidazolium trifluoro-
methanesulfonate was mixed
with oil sands. The ionic liquid did not separate bitumen from the oil sands,
but instead resulted
in the formation of agglomerated, spherical, black balls of bitumen-encrusted
minerals illustrated
17

CA 02761201 2016-02-19
in FIG. 8. However, as illustrated in Examples 4 and 6, when an organic
solvent is added in
combination with 1-buty1-3-methyl imidazolium trifluoro-methanesulfonate a
clean separation of
bitumen from oil sands is unexpectedly achieved.
Example 2
[0095] A composition of 50 weight percent of the ionic liquid 1-buty1-2,3-
dimethyl-imidazolium
borontetrafluoride, 33.3 weight percent toluene and 16.7 weight percent oil
sands was mixed at
temperatures between 50 C and 60 C. A three-phase system was formed and a
clean separation
of bitumen from oil sands was unexpectedly achieved. The top phase consisted
of toluene and
bitumen. The middle phase consisted of 1-butyl-2,3-dimethyl-imidazolium
borontetrafluoride
with small amounts of dissolved and/or suspended bitumen particles and mineral
fines. The
bottom phase consisted of 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride
with suspended
sand and clay. FIG. 9 illustrates the three-phase system (in the right vial)
formed from mixing 50
weight percent 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride, 33.3
weight percent
toluene and 16.7 weight percent oil sands.
[0096] The top phase was removed using a pipette. The toluene was evaporated
from the top
phase. Upon evaporation of the toluene from the top phase, a residual amount
of 1-buty1-2,3-
dimethyl-imidazolium borontetrafluoride that was entrained during the
separation process
remained in the vial below the bitumen phase. Toluene was added to the vial
containing the 1-
buty1-2,3-dimethyl-imidazolium borontetrafluoride and bitumen and the
resulting
toluene/bitumen phase was decanted. Due to its high viscosity, the 1-buty1-2,3-
dimethyl-
imidazolium borontetrafluoride remained at the bottom of the vial while
pouring the
toluene/bitumen phase into a new vial to achieve a clean separation. The
bitumen was recovered
after evaporating the toluene. The recovered bitumen comprised about 12-13
weight percent of
the original oil sands. The 1-butyl-2,3-dimethyl-imidazolium
borontetrafluoride in the middle
phase was separated from the sand and clay by adding water to the middle phase
and filtering.
The water is easily removed from the ionic liquid/water solution by
evaporation or any other
standard method of liquid-liquid separation.
Example 3
[0097] A composition of 50 weight percent of the ionic liquid 1-butyl-2,3-
dimethyl-imidazolium
trifluoro-methanesulfonate, 33.3 weight percent toluene and 16.7 weight
percent oil sands was
18

CA 02761201 2011-12-05
mixed at temperatures between 50 C and 60 C. A three-phase system was formed
and a clean
separation of bitumen from oil sands was unexpectedly achieved. The top phase
consisted of
toluene and bitumen. The middle phase consisted of 1-butyl-2,3-dimethyl-
imidazolium trifluoro-
methanesulfonate with small amounts of dissolved and/or suspended bitumen
particles and
mineral fines. The bottom phase consisted of 1-buty1-2,3-dimethyl-imidazolium
trifluoro-
methanesulfonate with suspended sand and clay. FIG. 9 illustrates the three-
phase system (in the
middle vial) formed from mixing 50 weight percent of the ionic liquid 1-buty1-
2,3-dimethyl-
imidazolium trifluoro-methanesulfonate, 33.3 weight percent toluene and 16.7
weight percent oil
sands.
100981 The top phase was removed using a pipette. The toluene was evaporated
from the top
phase. Upon evaporation of the toluene from the top phase, a residual amount
of 1-buty1-2,3-
dimethyl-imidazolium trifluoro-methanesulfonate that was entrained during the
separation
process remained in the vial below the bitumen phase. Toluene was added to the
vial containing
the 1-butyl-2,3-dimethyl-imidazolium trifluoro-methanesulfonate and bitumen
and the resulting
toluene/bitumen phase was decanted. Due to its high viscosity, the 1-buty1-2,3-
dimethyl-
imidazolium trifluoro-methanesulfonate remained at the bottom of the vial
while pouring the
toluene/bitumen phase into a new vial to achieve a clean separation. The
bitumen was recovered
after evaporating the toluene. The recovered bitumen comprised about 12-13
weight percent of
the original oil sands. The 1-butyl-2,3-dimethyl-imidazolium trifluoro-
methanesulfonate in the
middle phase was separated from the sand and clay by adding water to the
middle phase and
filtering. The water is easily removed from the ionic liquid/water solution by
evaporation or any
other standard method of liquid-liquid separation.
Example 4
[00991 A composition of 50 weight percent of the ionic liquid 1-butyl-3-methyl-
imidazolium
trifluoromethanesulfonate, 33.3 weight percent toluene and 16.7 weight percent
oil sands was
mixed at temperatures between 50 C and 60 C. A three-phase system was formed
and a clean
separation of bitumen from oil sands was unexpectedly achieved. The top phase
consisted of
toluene and bitumen. The middle phase consisted of 1-butyl-3-methyl-
imidazolium
trifluoromethanesulfonate with small amounts of dissolved and or suspended
bitumen particles
and mineral fines. The bottom phase consisted of 1-buty1-3-methyl-imidazolium
19

CA 02761201 2011-12-05
trifluoromethanesulfonate with suspended sand and clay. FIG. 9 illustrates the
three-phase system
(in the left vial) formed from mixing 50 weight percent of the ionic liquid 1-
buty1-3-methyl-
imidazolium trifluoromethanesulfonate, 33.3 weight percent toluene and 16.7
weight percent oil
sands.
[00100] The top phase was removed using a pipette. The toluene was evaporated
from the top
phase. Upon evaporation of the toluene from the top phase, a residual amount
of 1-buty1-3-
methyl-imidazolium trifluoromethanesulfonate that was entrained during the
separation process
remained in the vial below the bitumen phase. Toluene was added to the vial
containing 1-butyl-
3-methyl-imidazolium trifluoromethanesulfonate and bitumen and the resulting
toluene/bitumen
phase was decanted. Due to its high viscosity, the 1-butyl-3-methyl-
imidazolium
trifluoromethanesulfonate remained at the bottom of the vial while pouring the
toluene/bitumen
phase into a new vial to achieve a clean separation. The bitumen was recovered
after evaporating
the toluene. The recovered bitumen comprised about 12-13 weight percent of the
original oil
sands. The 1-buty1-3-methyl-imidazolium trifluoromethanesulfonate in the
middle phase was
separated from the sand and clay by adding water to the middle phase and
filtering. The water is
easily removed from the ionic liquid/water solution by evaporation or any
other standard method
of liquid-liquid separation.
[00101] FIG 10 illustrates infrared spectra of medium-grade Canadian oil sands
and component
parts thereof before and after separation of bitumen. Upon evaporation of the
second addition of
toluene in Examples 2-4, the original oil sands sample, the recovered bitumen
and the separated
sand/clay were analyzed using infrared spectrometry. Bands due to methylene
and methyl groups
near 1450 cm-1 and 1370 cm-1 are prominent in the spectrum of the bitumen, and
appear with
very weak intensity in the spectrum of the oil sands. The mineral bands
(predominantly quartz
and clay) near 1100 cm-1, 800 cm-1 and 500 cm-' absorb very strongly in the
infrared and mask
bands due to organic groups. However, these hydrocarbon absorption modes are
essentially
undetectable in the spectrum of the sand/clay mixture recovered from the
bottom phase, even in
scale-expanded spectra. Similarly, the mineral bands are absent from the
spectrum of the
bitumen. This is most easily seen by examining the right hand end of the
plots, near 500 cm-1.
This demonstrates that the bitumen was separated from the oil sands without
carrying over fine
particles, unlike the hot or warm water processes presently used in the prior
art. In Examples 1-4,
a bitumen yield in excess of 90 percent was achieved.

CA 02761201 2011-12-05
Example 5
[00102] A composition of 50 weight percent of the ionic liquid 1-buty1-2,3-
dimethyl-
imidazolium borontetrafluoride, 33.3 weight percent toluene and 16.7 weight
percent oil sands
was mixed at a temperatures of 25 C. A three-phase system was formed and a
clean separation of
bitumen from oil sands was unexpectedly achieved. The top phase consisted of
toluene and
bitumen. The middle phase consisted of 1-butyl-2,3-dimethyl-imidazolium
borontetrafluoride
with small amounts of dissolved and/or suspended bitumen particles and mineral
fines. The
bottom phase consisted of 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride
with suspended
sand and clay.
[00103] The top phase was removed using a pipette. The toluene was evaporated
from the top
phase. Upon evaporation of the toluene from the top phase, a residual amount
of 1-buty1-2,3-
dimethyl-imidazolium borontetrafluoride that was entrained during the
separation process
remained in the vial below the bitumen phase. Toluene was added to the vial
containing the 1-
buty1-2,3-dimethyl-imidazolium borontetrafluoride and bitumen and the
resulting
toluene/bitumen phase was decanted. Due to its high viscosity, the 1-buty1-2,3-
dimethyl-
imidazolium borontetrafluoride remained at the bottom of the vial while
pouring the
toluene/bitumen phase into a new vial to achieve a clean separation. The
bitumen was recovered
after evaporating the toluene. The recovered bitumen comprised about 12-13
weight percent of
the original oil sands. The 1-buty1-2,3-dimethyl-imidazolium
borontetrafluoride in the middle
phase was separated from the sand and clay by adding water to the middle phase
and filtering.
The water is easily removed from the ionic liquid/water solution by
evaporation or any other
standard method of liquid-liquid separation.
[00104] Examples 1-5 involve the separation of bitumen from medium-grade oil
sands. No
detectable mineral fines were recovered with the bitumen in Examples 1-5.
Bitumen in low-
grade oil sand feedstock is more difficult to recover free of mineral fine.
The prior art warm
water separation processes leave a significant amount of mineral fines in the
separated and
recovered bitumen, which leads to subsequent processing problems and reduces
the economic
viability of the process. The separation and recovering of bitumen with the
use of the exemplary
systems, methods and ionic liquids herein disclosed left no detectable mineral
fines at separation
21

CA 02761201 2011-12-05
temperatures below 100 C, preferably below 50 C and more preferably at
temperatures of 25 C
and lower.
Example 6
[00105] Examples 1-5 were also conducted at mixing ratios of 25 weight percent
ionic liquid, 50
weight percent organic solvent and 25 weight percent low-grade oil sands at a
temperature of
25 C and lower. A three-phase separation of low grade oil sands and yields of
bitumen in excess
of 90 percent were unexpectedly achieved.
[00106] FIG. 11 illustrates the infrared spectra of low-grade oil sands and
medium-grade oil
sands after separation of bitumen at 25 C using the mixing ratio of Example 6.
Strong infrared
absorption bands due to minerals near 1000 cm-1 cannot be detected in the low-
grade oil sands
spectra or the medium-grade oil sands spectra. It was surprisingly found that
low-grade oil sands
can be separated to produce bitumen free of mineral fines at low temperatures
(e.g., 25 C and
lower) using the systems, methods and ionic liquids herein disclosed.
[00107] In Examples 1-6, a separation of bitumen from both medium-grade and
low-grade oil
sands was achieved without the use of water in the primary separation step.
Some water was
used in Examples 1-6 to remove ionic liquid from sand, but as disclosed
herein, the water can be
separated and recycled through the system with substantially no loss. In some
circumstances, the
particulate matter including hydrocarbons and solid particulate is mixed with
significant
quantities of water to transport or pump the particulate matter. For example,
in some oil sands
mining operations, water is used to transport the mixture as slurry to a
processing plant. With the
use of the systems, methods and compositions herein disclosed the water does
not have to be
removed prior to separation of hydrocarbon from the solid particulate.
[00108] Examples 7-8 are provided to illustrate exemplary methods for
recovering bitumen from
low-grade and medium-grade Canadian oils sands with the use of water in the
primary separation
step. The examples are not intended to limit the scope of the present
disclosure and they should
not be so interpreted.
Example 7
[00109] A separating composition of 50 weight percent of the ionic liquid 1-
butyl-2,3-dimethyl-
imidazolium borontetrafluoride and 50 weight percent water was created. 2
grams of the
22

CA 02761201 2011-12-05
separating composition and 3 grams of toluene were mixed respectively with 1
gram of low-
grade oil sands and 1 gram of medium-grade oil sands in two separate
experiments at a
temperature of 25 C. The separating composition created a three phase system
when mixed with
low-grade oil sands and medium-grade oil sands.
[00110] FIG 12 illustrates exemplary three-phase systems formed from mixing
the separating
composition of Example 7 and toluene with low-grade and medium-grade oil
sands. The vial on
the left of in FIG. 12 illustrates a three phase system formed from separating
low-grade oil sands
and the vial on the right illustrates a three phase system formed from
separating medium-grade
oil sands. The bottom phase 706 of the vials contains a slurry of ionic
liquid, water and sand. The
middle phase 704 of the vials contains ionic liquid, water and small amounts
of mineral fines.
The top phase 702 of the vials contains a dark organic layer of bitumen
dissolved in toluene. The
top phase of the vials was separated using a pipette. Toluene was then
evaporated from the
bitumen in the top phase in a vacuum oven. A yield of 3.6 percent bitumen was
achieved in low-
grade oil sands using the separating composition of Example 7. A yield of 14.6
percent bitumen
was achieved in medium-grade oil sands using the separating composition of
Example 7.
Example 8
[00111] A separating composition of 25 weight percent of the ionic liquid 1-
buty1-2,3-dimethyl-
imidazolium borontetrafluoride and 75 weight percent water was created. 2
grams of the
separating composition was mixed with 3 grams of toluene and 1 gram of low-
grade oil sands at
a temperature of 25 C. The separating composition created a three phase system
when mixed
with low-grade oil sands. The bottom phase contained a slurry of ionic liquid,
water and sand.
The middle phase contained ionic liquid, water and small amounts of mineral
fines. The top
phase contained a dark organic layer of bitumen dissolved in toluene. The top
phase was
separated using a pipette. Toluene was then evaporated from the bitumen in the
top phase in a
vacuum oven. A yield of 5.1 percent bitumen was achieved in low-grade oil
sands using the
separating composition of Example 8.
[00112] FIG. 13 illustrates the infrared spectra of extracted bitumen and
residual sand obtained in
the separation of low-grade oil sands using the separating composition of
Example 8. It was
surprisingly found that bitumen bands between 2800 cm-1 and 3000 cm-1 are
absent in the
spectrum of the residual materials and mineral bands between 1000 cm-1 and 800
cm-1 are absent
23

CA 02761201 2011-12-05
in the spectrum of bitumen. Therefore, a clean separation of low-grade oil
sands with no residual
sand in separated bitumen and no residual bitumen in separated sand was
achieved.
[00113] The Canadian oil sands that were separated in Examples 1-8 were
unconsolidated
samples of oil sands. Utah oil sands are consolidated rock-like formations
that cannot be
processed directly with the prior art warm water processes presently used for
unconsolidated oil
sands. Example 9 is provided to illustrate the effectiveness of the systems,
methods and
compositions herein disclosed in separating consolidated Utah oil sands. The
example is not
intended to limit the scope of the present disclosure and should not be so
interpreted.
Example 9
[00114] A composition of 33.3 weight percent of the ionic liquid 1-buty1-2,3-
dimethyl-
imidazolium borontetrafluoride, 50.0 weight percent toluene and 16.7 weight
percent
consolidated Utah oil sands was mixed at a temperatures of 25 C. A three-phase
system was
formed and a clean separation of bitumen from oil sands was unexpectedly
achieved. The top
phase consisted of toluene and bitumen. The middle phase consisted of 1-buty1-
2,3-dimethyl-
imidazolium borontetrafluoride with small amounts of dissolved and/or
suspended bitumen
particles and mineral fines. The bottom phase consisted of 1-butyl-2,3-
dimethyl-imidazolium
borontetrafluoride with suspended sand and clay. The top phase was removed
using a pipette.
The toluene was evaporated from the top phase. The bitumen was recovered after
evaporating the
toluene. A yield of over 90 percent bitumen from the original sample of oil
sands was obtained
with no detectable mineral fines in the bitumen.
Example 10
[00115] In this example, the ionic liquid 1-buty1-2,3-dimethyl-imidazolium
borontetrafluoride,
and toluene were used to separate oil from sand in a contaminated sand sample.
The ionic liquid
1-butyl-2,3-dimethyl-imidazolium borontetrafluoride, toluene and the
contaminated sand sample
were mixed in the proportions 1:2:3 by weight respectively at 25 C to achieve
three phase
separation. Other proportions can also be used to achieve three phase
separation.
[00116] FIG. 14 illustrates an exemplary three-phase system formed from mixing
ionic liquid
(e.g., 1-buty1-2,3-dimethyl-imidazolium borontetrafiuoride), organic solvent
(e.g., toluene) and
contaminated sand according to Example 10. The top phase 802 contained oil and
toluene. The
24

CA 02761201 2011-12-05
middle phase 804 contained ionic liquid, residual mounts of oil and mineral
fines. The bottom
phase 806 contained ionic liquid and sand.
1001171 The three phases are easily separated in the laboratory using a
pipette as described in the
previous examples. Any inadvertent entraining of one phase in another can be
alleviated by
washing the phase with water or a non-polar solvent (e.g., toluene) depending
on the phase
which requires purification. The toluene is readily removed from the top phase
through
distillation. It is important to note, that the top phase containing oil and
toluene contained no
detectable mineral fines. The ionic liquid in the bottom phase was removed by
washing with
water. The sand in the bottom phase contained no detectable toluene or oil
contamination after
the ionic liquid was removed.
Example 11
1001181 In this example, ionic liquid 1-butyl-2,3-dimethyl-imidazolium
borontetrafluoride, and
toluene were used to separate oil from drill cuttings in a contaminated drill
cuttings sample. The
ionic liquid 1-buty1-2,3-dimethyl-imidazolium borontetrafluoride, toluene and
the contaminated
drill cuttings were mixed at 25 C to achieve three phase separation. The top
phase contained oil
and toluene. The middle phase contained ionic liquid, residual mounts of oil,
residual mineral
fines and residual drill cuttings. The bottom phase contained ionic liquid and
drill cuttings.
[00119] The three phases are easily separated in the laboratory using a
pipette as described in the
previous examples. Any inadvertent entraining of one phase in another can be
alleviated by
washing the phase with water or a non-polar solvent (e.g., toluene) depending
on the phase. The
toluene in the top phase is removed through distillation. The ionic liquid in
the bottom phase was
removed by washing with water.
[00120] FIG. 15 illustrates infrared spectra of the original contaminated
drill cuttings, oil after
separation and material after removal of oil in Example 11. The spectrum of
the original drill
cuttings is dominated by silicate (sand) absorption between 1000 and 1100 cm-
1. There is also a
strong absorption due to carbonates near 1450 cm-I, similar to what is
observed in the spectrum
of chalk. Minerals absorb infrared radiation far more strongly than oil, but
only weakly
absorbing modes between 2800 and 3000 crn-1 are observed. An absorption scale-
expanded
insert, which reveals the bands due to the oil in the spectrum of the drill
cuttings, is also
illustrated in FIG. 15. However, these absorptions are absent from the
spectrum of the residual

CA 02761201 2011-12-05
materials after removal of oil. Therefore, the residual materials including
drill cuttings are free
from oil contamination. It can also be seen from the spectrum of oil, that the
oil was recovered
free of minerals and drill cuttings.
Example 12
[00121] In this example, samples in the form of tar balls were obtained from a
beach in the Gulf
of Mexico after the Deepwater Horizon oil spill. Tar ball samples were mixed
with various
separation solutions to effect separation. One exemplary separation solution
contained the ionic
liquid 1-ethyl-3-methyl-imidazolium chloride, water and toluene. A comparative
separation
solution included water and toluene only. In the experiments where ionic
liquid and water were
used in the separation solution, 1-part by weight tar balls were mixed with 2-
parts by weight
ethyl-3-methyl-imidazolium chloride and water and 1-part by weight toluene.
Both separation
solutions were mixed with tar balls and stirred at a temperature of 20 C. The
degree of phase
separation strongly depended on the concentration of the ionic liquid 1-ethy1-
3-methyl-
imidazolium chloride in the separation solution.
[00122] FIG 16 illustrates exemplary and comparative multi-phase systems
formed from mixing
both separation solutions with tar balls according to Example 12. The vial on
the far left
illustrated in FIG. 16 is a four phase system formed from mixing tar balls
with the comparative
separation solution containing water and toluene. The other three vials
illustrated in FIG 16 are
multi-phase systems formed from mixing tar balls with the exemplary separation
solution
containing 25% by weight 1-ethyl-3-methyl-imidazolium chloride, 50% by weight
1-ethy1-3-
methyl-imidazolium chloride and 75% by weight 1-ethyl-3-methyl-imidazolium
chloride
respectively from left to right.
[00123] The four phase system (far left vial of FIG. 16) formed from mixing
tar balls with the
comparative separation solution included a top hydrocarbon phase appearing
lighter than the top
phase in the other multi-phase systems. The lighter top hydrocarbon phase is
due to suspended
sand particles in the top phase of the far left vial. Similarly the middle
water phase of the far left
vial is murky in appearance due to the presence of sand in the form of fine
particles. A thin white
phase of material separating the hydrocarbon phase and water phase is also
present. An infrared
spectrum of the thin white phase showed that the phase contains some proteins
and
polysaccharides potentially from seaweed and/or other biological matter from
sea water.
26

CA 02761201 2011-12-05
[00124] The exemplary four phase system (2"d vial from the left of FIG 16)
formed from mixing
tar balls with separation solution containing 25% by weight 1-ethyl-3-methyl-
imidazolium
chloride produced a better separation. The top hydrocarbon phase was much
darker than the far
left vial indicating a higher degree of tar separation. The top hydrocarbon
phase contained a
small amount of sand. The middle phase containing 1-ethyl-3-methyl-imidazolium
chloride and
water remained murky due to the presence of suspended minerals. There remained
a thin white
layer containing biopolymers separating the top hydrocarbon phase from the
middle phase
containing 1-ethy1-3-methyl-imidazolium chloride and water.
1001251 The exemplary three-phase systems (3rd vial from the left and far
right vial of FIG. 16)
formed from mixing tar balls with separation solutions containing 50% and 75%
by weight 1-
ethy1-3-methyl-imidazolium chloride produced even more pronounced phase
separation. The
middle phase of ionic liquid and water in the vials were clear and
substantially free of sand.
Visual examination of the bottom sand phase also indicates a more pronounced
phase separation
substantially free of tar when separation solutions containing greater than or
equal to 50% by
weight 1-ethyl-3-methyl-imidazolium chloride are used. Furthermore, three
phase systems (e.g.,
-rd vial from the left and far right vial of FIG. 16) formed from mixing tar
balls with separation
solutions containing greater than or equal to 50% by weight 1-ethyl-3-methyl-
imidazolium
chloride no longer contained a biomaterial phase separating the top
hydrocarbon phase from the
middle phase of ionic liquid and water. Infrared spectroscopy indicated that
the bottom sand
phase contained no detectable residual tar and the recovered tar from the top
phase contained
only trace amounts of minerals. Therefore, higher concentrations of ionic
liquid are necessary for
sufficient phase separation in Example 12.
[00126] FIG. 17 illustrates tar contaminated sand prior to separation and sand
free of tar
contamination after separation with the use an exemplary ionic liquid
according to Example 12.
The uncontaminated sand appears clean after separation of hydrocarbons such as
tar when
exemplary ionic liquids of Example 12 are used to effect separation.
Comparative Example 2
[00127] In this example, comparative additives and a comparative separation
process was used to
separate bitumen from Canadian tar sands. Additive solutions containing 0%,
25%, 50% and
75% by weight acrylamide/sodium acrylate acid copolymer (hydrolyzed
polyacrylamide) in
27

CA 02761201 2011-12-05
water were prepared. 2 parts by weight additive solution was mixed with 1 part
by weight
toluene and 1 part by weight Canadian tar sands at room temperature. High
molecular weight
polymers or copolymers such as, hydrolyzed polyacrylamide form thick, viscous
gels at high
concentrations in solution due to chain entanglements. As shown in FIG. 18,
aqueous solutions of
the polyacrylamide copolymer were no exception.
[00128] FIG. 18 illustrates comparative systems formed from mixing Canadian
tar sands with
additive solutions and toluene according to Comparative Example 2. Additive
solutions
containing 0%, 25%, 50% and 75% by weight acrylamide/sodium acrylate acid
copolymer
(hydrolyzed polyacrylamide) in water were used in the vials in FIG. 18 from
left to right
respectively. Unlike the results obtained with ionic liquids, segregation into
easily separated
phases did not occur at any concentration. Polyacrylamide copolymers did not
result in the type
of facile phase separations observed with ionic liquids.
Comparative Example 3
[00129] In this example, a comparative additives and a comparative separation
process was used
to separation bitumen from Canadian tar sands. Additive solutions containing
0%, 25%, 50% and
75% by weight polyacrylic acid in water were prepared. 2 parts by weight
additive solution was
mixed with I part by weight toluene and 1 part by weight Canadian tar sands at
room
temperature.
[00130] FIG. 19 illustrates comparative systems formed from mixing Canadian
tar sands with
additive solutions and toluene according to Comparative Example 3. Additive
solutions
containing 0%, 25%, 50% and 75% by weight polyacrylic acid in water were used
in the vials in
FIG. 19 from left to right respectively. Conglomerations of polymer gel were
observed on the
sides of the vials. Unlike the results obtained with ionic liquids,
segregation into easily separated
phases did not occur at any concentration.
Comparative Example 4
[00131] In this example, a comparative additive and separation process was
used to separation
bitumen from Canadian tar sands. An additive solution containing 75% by weight
citric acid in
water was prepared. 2 parts by weight additive solution was mixed with 1 part
by weight toluene
and 1 part by weight Canadian tar sands at room temperature.
28

CA 02761201 2011-12-05
[00132] FIG. 20 illustrates a comparative system formed from mixing Canadian
tar sands with
the additive solution and toluene according to Comparative Example 3. The vial
on the left
shown in FIG 20 illustrates the additive solution containing 75% by weight
citric acid in water.
Concentrated aqueous solutions of low molecular weight additives such as
citric acid do not gel
in the same way as polymers, but at high concentrations citric acid does not
completely dissolve
in water. The vial on the right in FIG. 20 illustrates the system formed from
mixing 2 parts by
weight additive solution (containing 75% by weight citric acid in water) with
1 part by weight
toluene and 1 part by weight Canadian tar sands at room temperature. High
concentrations of
citric acid (greater than or equal to 25% by weight in water) did not result
in the type of facile
separations observed with the use of concentrated ionic liquid solutions.
[00133] At low concentrations (parts per million), citric acid, polyacrylamide
and other additives
disclosed herein aid separation by sequestering ions present in tar sands that
act to attach mineral
fines to bitumen. The surprising phase separations observed when using
concentrated ionic liquid
separation solutions disclosed herein is facilitated by a significant
reduction in adhesion between
silica (sand) or other mineral particles and the hydrocarbon to be separated.
Example 13
[00134] In this example, an analogue ionic liquid of choline chloride and urea
was prepared by
mixing urea and choline chloride in the weight ratio of 1.2 to 1.4
respectively (2:1 molar ratio).
This mixture of powders was placed in a vial and heated to about 80 C
whereupon a liquid was
formed. Upon cooling to room temperature, the mixture remained a liquid but
was very viscous.
The liquid (1 part by weight) was mixed with Canadian tar sands (1 part by
weight) and toluene
(1 part by weight) and stirred in a laboratory vial at room temperature.
Although a degree of
phase separation occurred after a few minutes, with a top hydrocarbon phase
present in the vial, a
separation into easily distinguishable phases was not achieved under these
conditions.
[00135] FIG. 21 illustrates an exemplary multi-phase system formed from mixing
Canadian tar
sands with an exemplary analogue ionic liquid according to Example 13. As
shown in the right
vial in FIG. 21, the vial appears almost uniformly black due to the viscous
nature of the analogue
ionic liquid. The high viscosity hindered separation under the action of
density differences and
gravity alone. A separation was achieved after centrifugation. Alternatively,
when a mixture of
the exemplary analogue ionic liquid of Example 13 was diluted with water (1:1
by weight) to
29

CA 02761201 2011-12-05
lower the viscosity of the mixture, a separation into three phases was
achieved shown in the left
vial of FIG. 21. This result was surprising, because as demonstrated in
Comparative Example 2,
concentrated solutions of other common salts or materials used in current
extraction processes do
not result in a separation.
Example 14
1001361 In this example, an analogue ionic liquid of choline chloride and urea
was prepared by
mixing urea and choline chloride in the weight ratio of 1.2 to 1.4 (2:1 molar
ratio) and diluting
with 0.33 parts by weight water. The analogue ionic liquid and water were
mixed with 1 part by
weight Canadian tar sands and 1 part by weight toluene. The mixture was
stirred for about I
minute and left to stand for 15 minutes.
[001371 FIG. 22 illustrates an exemplary multi-phase system formed from mixing
Canadian tar
sands with an exemplary analogue ionic liquid according to Example 14. A
partial separation into
three phases was achieved under the action of density differences and gravity
alone. To speed the
process, the top phase and about half of the middle (cloudy) phase was
decanted and placed in
one centrifuge tube. The bottom mineral phase together with the other half of
the middle phase
was placed in a second centrifuge tube. The liquids were centrifuged for 15
minutes at 3000 rpm.
100138] FIG. 23 illustrates exemplary three phase systems formed from
centrifuging components
of the exemplary multi-phase system shown in FIG 22. Centrifugation of top
phase with '/2
middle phase (left vial) and the bottom phase with '/2 middle phase (right
vial) resulted in a
pronounced three phase separation having a top hydrocarbon phase, a middle
analogue ionic
liquid with water phase and a bottom mineral phase shown in FIG. 23. The
hydrocarbon phase
was removed using a pipette and a film was cast for infrared analysis. The
mineral phase was
washed with water to remove any entrained analogue ionic liquid and a small
amount of the
dried sample was also analyzed by infrared spectroscopy.
[00139] FIG. 24 illustrates infra red spectra of the top hydrocarbon phase and
the bottom mineral
phase of the exemplary three-phase systems shown in FIG. 23. The spectrum of
the top
hydrocarbon phase displays characteristic strong absorption bands between 2800
and 3000 cm-1.
These absorptions are absent in the spectrum of the bottom mineral phase,
indicating that within
the detection limits of infrared spectroscopy, essentially all of the bitumen
has been removed
from the sand. Similarly, the strong bands due to silica observed near 1100 cm-
1, 800 cm-1 and

CA 02761201 2011-12-05
500 cm -I are absent in the spectrum of the top hydrocarbon phase, indicating
that within the
detection limits of infrared spectroscopy, the recovered bitumen was not
contaminated with fine
sand particles. Weak bands near 1030 crn-1 indicate that only trace amounts of
fine clay particles
are present in the top hydrocarbon phase. The ash content of this sample was
determined to be
0.3% by weight.
Example 15
[00140] In this example, water used in prior art warm water processes and
stored in tailing ponds
is processed with the systems, methods and compositions disclosed herein. The
warm water
extraction process presently used to separate bitumen from tar sands in Canada
generates large
amounts of waste process water mixed with hydrocarbons, extracted sand and
minerals. It is
presently stored in vast tailing ponds. The water in these ponds is
contaminated with residual
hydrocarbons (e.g., bitumen) and the chemicals used in processing. It is toxic
to aquatic life and
has resulted in the death of a large number of ducks. Coarse sand quickly
sinks to the bottom of
these ponds, while water and some residual bitumen remains on the surface of
the pond. A layer
of fluid fine tailings and about 6% bitumen contamination sits in between
these two layers where
water is trapped in a thick soup of mineral fines (mainly clays). Ionic
liquids and analogue ionic
liquids herein disclosed can also be used to extract hydrocarbons such as,
bitumen from tailing
ponds material resulting in a flocculation or fast settling of mineral fines.
[00141] FIG. 25 illustrates tailing pond material before and after separation
with the use of an
exemplary ionic liquid. The far left container in FIG. 25 illustrates a dilute
but cloudy suspension
of mineral fines and settled solids obtained from the top liquid layer in a
drum of tailing pond
liquids. The containers on the right of FIG. 25 illustrate the top liquid
layer before (middle
container) and after (far right container) addition of the ionic liquid 1-
ethy1-3-methyl-
imidazolium chloride. The ionic liquid 1-ethy1-3-methyl-imidazolium chloride
was added as a
solid to obtain a concentration of 50% by weight in the top liquid layer
(other concentrations are
also effective). Upon stirring, the suspension became clear in seconds. The
liquid turned yellow
due to the yellow color and lower purity (95%) of the ionic liquid used.
Agglomerated or
flocculated mineral particles could be observed at the bottom of the far right
container shown in
FIG 25 Mineral fines in tailing ponds can take years to settle. Therefore, it
was surprising to
achieve settling so rapidly with the use of exemplary ionic liquids.
31

CA 02761201 2011-12-05
Example 16
[00142] In this example, tailing pond material was processed with the use of
exemplary analogue
ionic liquids. Analogue ionic liquids herein disclosed can also be used to
extract hydrocarbons
(e.g., bitumen) from tailing pond material resulting in a flocculation or fast
settling of mineral
fines. A dilute but cloudy suspension of mineral fines and settled solids
obtained from the top
liquid layer in a drum of tailing pond liquids was used as particulate matter
in this example. An
analogue ionic liquid of choline chloride and urea combined in the proportions
1.4 to 1.2 by
weight was mixed with the tailing pond material to produce a concentration of
50% by weight
analogue ionic liquid in the tailing pond material. Separately, another
exemplary analogue ionic
liquid was formed by mixing choline chloride and tailing pond material at a
concentration of 80
% by weight choline chloride in 20% by weight water.
[00143] FIG. 26 illustrates tailing pond material before and after separation
with the use of
exemplary analogue ionic liquids. The far left container of FIG. 26
illustrates a dilute but cloudy
suspension of mineral fines and settled solids obtained from the top liquid
layer in a drum of
tailing pond liquids. The middle container of FIG. 26 illustrates the tailing
pond material after
mixing with the analogue ionic liquid according to Example 16. The far right
container of FIG.
26 illustrates a tailing pond suspension after addition of sufficient analogue
ionic liquid to bring
the concentration of analogue ionic liquid to 80% by weight in tailing pond
material.
[00144] All containers of FIG. 26 were stirred to dissolve the analogue ionic
liquid. After being
left to stand overnight for about 16 hours, the liquid layers in the
containers of FIG 26 appeared
clear. The tailing pond material in the far left container of FIG. 26
containing no analogue ionic
liquid was also left to settle for the same amount of time as the middle and
far right containers.
The agglomerated and flocculated mineral particles can be observed at the
bottom of the middle
and far right container of FIG. 26.
Example 17
[00145] In this example, concentrated tailing pond material is processed with
the use of an
exemplary analogue ionic liquid. FIG. 27 illustrates concentrated tailing pond
material before and
after separation with the use of an exemplary analogue ionic liquid. The far
right container of
FIG. 27 illustrates a 30% by weight suspension of mineral solids in tailing
pond liquids. A
analogue ionic liquid of 50% by weight choline chloride and urea in water was
produced. The
32

CA 02761201 2011-12-05
analogue ionic liquid and an organic solvent were mixed with the concentrated
tailing pond
material for about 1 minute and centrifuged at 800 rpm. As show in the middle
container of FIG
27, a sharp phase separation was achieved and a top hydrocarbon phase and a
bottom mineral
phase were formed. The bottom mineral phase was dried and organic solvent was
removed from
the top hydrocarbon phase to produce a sample of bitumen and sand in the right
containers of
FIG. 27. Similar results were obtained using imidazolium ionic liquids such as
1-ethy1-3-methyl-
imidazolium chloride.
Example 18
[00146] In this example, tailing pond material and Canadian tar sands were
processed with the
use of an exemplary analogue ionic liquid. An analogue ionic liquid was
produced by mixing
75% by weight choline chloride and urea in water at a proportion of 1.4 parts
by weight choline
chloride and 1.2 parts by weight urea. 1 part by weight Canadian tar sands was
mixed with the
analogue ionic liquid, 2 parts by weight tailing pond material and 1 part by
weight toluene. After
stirring for a few minutes at ambient temperatures (about 20 C), vials
containing these samples
were allowed to stand. Phase separation occurred over a period of about one
hour due to the
immiscibilty and density differences of the hydrocarbon and analogue ionic
liquid phases.
[00147] FIG. 28 illustrates an exemplary three phase system formed from mixing
an exemplary
analogue ionic liquid with Canadian tar sands and tailing pond material
according to Example
18. The phase-separated layers are shown in FIG 28, which illustrates a top
bitumen phase a
middle phase containing analogue ionic liquid and water and a bottom sand
phase. The bottom
sand phase contained no detectable bitumen, and the top bitumen phase showed
only trace
amounts of clays, as determined by infrared spectroscopy. The intensities of
the clay bands were
equivalent to those bitumen samples having an ash content of 0.3% by weight.
Example 19
[00148] In this example, Canadian tar sands was processed using an exemplary
analogue ionic
liquid. The analogue ionic liquid was produced by mixing 80% by weight choline
chloride with
20% by weight water. 1 part by weight Canadian tar sands was mixed with 1 part
by weight
analogue ionic liquid in water and 1 part by weight toluene and stirred in a
container at room
temperature. The mixture was allowed to stand for 1 hour. Upon centrifugation
at 3000 rpm for
15 minutes, a phase separation into three distinct phases occurred.
33

CA 02761201 2011-12-05
[00149] FIG. 29 illustrates an exemplary three phase system formed from mixing
an exemplary
analogue ionic liquid with Canadian tar sands according to Example 19. A
separation into three
phases was achieved. The top hydrocarbon phase consisted of a solution of
bitumen in toluene,
with trace amounts of clays. The bottom mineral phase contained detectable but
small amounts
of bitumen. The middle phase consisted of analogue ionic liquid in water.
[00150] FIG. 30 illustrates an exemplary system for recovering hydrocarbons
from particulate
matter with the use of the exemplary ionic liquids or analogue ionic liquids
according to one
embodiment. The ionic liquids and analogue ionic liquids herein disclosed can
be used in the
system illustrated in FIG. 30 to separate hydrocarbons from particulate matter
including but not
limited to oil sands, drilling fluid containing drill cuttings, tailing pond
material, crude oil
containing sand, beach sand contaminated with oil, oil sludge, any hydrocarbon
containing sand,
soil, rock, silt, clay or other solid particulate or any hydrocarbon contained
within sand, soil,
rock, silt, clay or other solid particulate.
[00151] The system includes a mixing vessel 902 wherein a feed stream 900 of
particulate
matter, ionic liquid or analogue ionic liquid and optionally an organic
solvent, water or
combinations thereof are fed and mixed. The feed stream 900 can also be split
into one or more
streams containing one or more streams of particulate matter, ionic liquid,
analogue ionic liquid,
organic solvent, water or combinations thereof.
[00152] The feed stream remains in the mixing vessel 902 for a predetermined
or average
residence time sufficient to allow phase separation and break up of larger
mineral/hydrocarbon
particles (e.g., tar sand balls). The separation is accelerated by the
application of shear forces.
Therefore, the feed stream can be placed in slurry form and also fed through a
high-shear mixer
904 to assure detachment of hydrocarbons from sand or other minerals.
[00153] An inclined plate separator 906 can be used to separate ionic liquid,
analogue ionic
liquid, liquid hydrocarbons or organic solvent from solid particulate such as
silica, sand, clay,
other minerals or drill cuttings. The separator 906 can be a centrifuge,
hydrocyclone, settling
chamber or other separator known in the art for separating particulates from
liquids. A solid
particulate product stream 912 can be provided to recover solid particulate
free of hydrocarbons
generated in the inclined plate separator 906. The solid particulate can be
washed with water to
remove any ionic liquid, analogue ionic liquid or organic solvent used during
processing.
34

CA 02761201 2016-02-19
However, because small amounts of analogue ionic liquid herein disclosed are
non-toxic,
biodegradable and actually support plant growth, washing is optionally when
using analogue
ionic liquid.
[00154] A liquid phase separator 908 can be used to separate immiscible
process liquids. For
example, the liquid phase separator can be used to separate ionic liquid or
analogue ionic liquid
from the oil or bitumen or organic hydrocarbon solvent. The liquid phase
separator 908 can be a
continuous coalescing separator or other unit known to the art for separating
liquids. The liquid
phase separator 908 can simultaneously allow the separation of any lines that
have carried over
from other process streams or units. The liquid phase separator 908 can
operate at room
temperature (e.g., about 20T). If necessary, higher temperatures can be used
during separation.
A mineral fines product stream 914 can be provided to recover any mineral
fines generated in the
liquid phase separator 908. A hydrocarbon product stream 910 can be provided
to recover
hydrocarbons free of solid particulate generated in the liquid phase separator
908.
[001551 Any ionic liquid or analogue ionic liquid recovered from the liquid
phase separator 908
can be recycled in a recycle stream 916 and mixed with additional feed stream
900 components
in the mixing vessel 902.
1001561 Example embodiments have been described hereinabove regarding improved
systems,
methods and compositions for the separation and recovery of hydrocarbons from
particulate
matter. The systems, methods and compositions herein disclosed require
significantly less water
and less energy to recover hydrocarbons in processes such as the recovery of
bitumen from oil
sands. Various modifications to and departures from the disclosed example
embodiments will
occur to those having ordinary skill in the art. The subject matter that is
intended to be within the
spirit of this disclosure is set forth in the following claims.

Dessin représentatif

Désolé, le dessin représentatatif concernant le document de brevet no 2761201 est introuvable.

États administratifs

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États administratifs

Titre Date
Date de délivrance prévu 2017-01-17
(22) Dépôt 2011-12-05
(41) Mise à la disponibilité du public 2013-04-04
Requête d'examen 2016-02-19
(45) Délivré 2017-01-17

Historique d'abandonnement

Il n'y a pas d'historique d'abandonnement

Taxes périodiques

Dernier paiement au montant de 263,14 $ a été reçu le 2023-10-10


 Montants des taxes pour le maintien en état à venir

Description Date Montant
Prochain paiement si taxe générale 2024-12-05 347,00 $
Prochain paiement si taxe applicable aux petites entités 2024-12-05 125,00 $

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Historique des paiements

Type de taxes Anniversaire Échéance Montant payé Date payée
Le dépôt d'une demande de brevet 400,00 $ 2011-12-05
Taxe de maintien en état - Demande - nouvelle loi 2 2013-12-05 100,00 $ 2013-11-19
Taxe de maintien en état - Demande - nouvelle loi 3 2014-12-05 100,00 $ 2014-11-18
Taxe de maintien en état - Demande - nouvelle loi 4 2015-12-07 100,00 $ 2015-11-18
Requête d'examen 800,00 $ 2016-02-19
Enregistrement de documents 100,00 $ 2016-02-19
Taxe de maintien en état - Demande - nouvelle loi 5 2016-12-05 200,00 $ 2016-12-05
Taxe finale 300,00 $ 2016-12-07
Taxe de maintien en état - brevet - nouvelle loi 6 2017-12-05 200,00 $ 2017-11-15
Taxe de maintien en état - brevet - nouvelle loi 7 2018-12-05 200,00 $ 2018-11-14
Taxe de maintien en état - brevet - nouvelle loi 8 2019-12-05 200,00 $ 2019-11-14
Taxe de maintien en état - brevet - nouvelle loi 9 2020-12-07 200,00 $ 2020-11-11
Taxe de maintien en état - brevet - nouvelle loi 10 2021-12-06 255,00 $ 2021-10-13
Taxe de maintien en état - brevet - nouvelle loi 11 2022-12-05 254,49 $ 2022-10-12
Taxe de maintien en état - brevet - nouvelle loi 12 2023-12-05 263,14 $ 2023-10-10
Titulaires au dossier

Les titulaires actuels et antérieures au dossier sont affichés en ordre alphabétique.

Titulaires actuels au dossier
THE PENN STATE RESEARCH FOUNDATION
Titulaires antérieures au dossier
S.O.
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Description du
Document 
Date
(yyyy-mm-dd) 
Nombre de pages   Taille de l'image (Ko) 
Abrégé 2011-12-05 1 12
Description 2011-12-05 35 1 907
Revendications 2011-12-05 2 62
Page couverture 2013-04-12 1 30
Dessins 2016-02-19 21 2 995
Revendications 2016-02-19 7 247
Description 2016-02-19 37 1 949
Description 2016-10-20 37 1 957
Revendications 2016-10-20 6 267
Page couverture 2016-12-21 1 29
Correspondance 2011-12-28 1 22
Correspondance 2011-12-28 1 45
Correspondance 2011-12-16 2 81
Cession 2011-12-05 4 118
Correspondance 2012-01-11 2 85
Correspondance de la poursuite 2016-09-16 2 43
Modification 2016-02-19 47 3 966
Correspondance 2016-02-25 1 28
Demande d'examen 2016-09-21 3 192
Modification 2016-10-20 17 727
Taxe finale 2016-12-07 1 42