CA1308378C - Separation of bituminous material from tar sands - Google Patents
Separation of bituminous material from tar sandsInfo
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- CA1308378C CA1308378C CA000614783A CA614783A CA1308378C CA 1308378 C CA1308378 C CA 1308378C CA 000614783 A CA000614783 A CA 000614783A CA 614783 A CA614783 A CA 614783A CA 1308378 C CA1308378 C CA 1308378C
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Abstract
ABSTRACT
A method of separating bituminous fractions from tar sand is described. The tar sand is treated by electromagnetic radiation, of the frequency range generally referred to as microwave. Application of electromagnetic radiation, followed by conventional heating was also found to effect separation. The tar sand is preferably treated below the boiling point of water by electromagnetic radiation, more preferably below the initial boiling point of water, and yet more preferably in the presence of added water. The preferred frequency range is about 800 to about 1700 MHz. Frequencies of 920+90 and 1540+150 and 1250+130 MHz, have been successfully applied. The added water preferably is between a quarter and four time the volume of the tar sand.
A method of separating bituminous fractions from tar sand is described. The tar sand is treated by electromagnetic radiation, of the frequency range generally referred to as microwave. Application of electromagnetic radiation, followed by conventional heating was also found to effect separation. The tar sand is preferably treated below the boiling point of water by electromagnetic radiation, more preferably below the initial boiling point of water, and yet more preferably in the presence of added water. The preferred frequency range is about 800 to about 1700 MHz. Frequencies of 920+90 and 1540+150 and 1250+130 MHz, have been successfully applied. The added water preferably is between a quarter and four time the volume of the tar sand.
Description
SEPAR~TIO~ OF BITUMINOUS MATERIAL FROM 'rAR SANDS
This invention relates to treatment o~ mix.tures of bituminous, aqueous, and mineral matter of the type commonly referred to as tar sands, to separate them into bituminous and mineral fractions, by application oE
elec~romagnetic frequencies o~ the type commonly referred to as microwaves.
It is an o~ject of the invention to provlde a method of separating tar sand into two fraction~, one fraction cantaining bituminous matter, the other ~raction containing mineral matter. These two fractions are not neces-carily absolutes, the bituminous fraction will contain a greater proportion o~ bi~uminous matter than the original tar sand, while the ~ineral fraction will contain a g~eater proportion of mineral matter than the original ~ar sandO Desirably there will be no apparent bitumen in the mineral fraction, and no apparent mineral in the b ! tuminous fraction. More desirably there will be negligible bitumen in the mineral fraction, and negligible mineral in the bituminous fraction.
The electroma~netic radiation used is depending on definition and frequency, in that part of the electromagnetic spec~rum bordering radio waves and microwaves~ The usual definition of microwaves is that portion of the el~ctromagnetic spestrum having frequencies greater than thQse of radio waves and les5 than those of infrared waves. Microwaves are def,-ined as having frequencies ranging from a lower limit of 100 MHz (3 m), 300 MHz (1 m), or 1 GHz (30 cm),to an upper limit of 300 GHz (1 mm) or 1000 GHz (0.3 mm). Radio waves are usually defined as not including microwaves, but are sometimes regarded as including microwave frequencies, and having an upper frequency limit o~ 100 GHz (3 mm).
3~7~
Applicant has discovered that ~y treatm~t of tar sand by electromagnetic radiatlon of selected wavelength separation of bituminolls ancl mineral fractions can be observed.
Tar sand also known as "oil sand" is understood to mean in this applica~ion a naturally occurring mixture of tar, water and mineral matter. The m:ineral matter is usually a mixture of sand (95%), heavy minerals, carbonates, and clay Minerals~ The tar is bituminous in nature and typically comprises from about 5% to about 18% by weight of the mixture. Water typically comprises about 2% to about 12% by weight of the mixture. Mineral matter typically comprises about a3% by weight of the mixture, variation from these figures may be observed.
The mineral matter includes sand grains and fines. The sand grains are believed to form a nearly space filling arrangement with about 65~ by volume of the sand, with the bituminous material and water in the voids between the sand grains, totalling about 35~ by volume of the sand. The sand grains of the tar sand are wetted, the grains can range from strongly water wetted, to strongly oil (bitumen/tar) wetted, sands of intermediate wettability are known to exist.
DESCRIPTION OF THE PRIOR ART
General applications of electromagnetic waves to tar sands, oil shales and coals are known. Radio waves may be applied directly, or as a fluctuating electric or magnetic field, or by induction heating where an electric current is applied to generate another electric current in the material to be treated [as a primary coil current in a transformer qenerates a secondary coil current]. All these can be viewed as application of electromagnetic waves loosely termed of "radio"
frequency. General use of such frequencies for heating tar sand or oil shale in situ is taught by Rowland in ~3~&~3~7i3 U.S. Pa-tent 4,135,5'~9 ancl Dauphine in Canadiarl Patent 1,105,376, which utilize ~re~uencie~ between lO0 kiloher~z and 100 megahertz, ~or yeneral heating of oil shales. The Fishers in Canadian Patents 994,694, 994,695 and 1,105,376 teach similar treatment of tar sand by induction heating using alternatiny current o~
unspecified ~requencies, except that i~ i5 suggested that normal 60 cycle AC could be used.
Radio and microwave frequency heating of oil shales, tar sands and coals to liquefy, volatilize~ and pyrolyze the bituminous or organic component is well known. Microwaves are used to retort such materials by ~odge in U.S. Patent 2,542,028, Knapp in U.S. Patent 3,449,213 and 3,560,347, Stone in U.S. Patent 3,503,865, Wallace in U.S. Patent 4,118,282, Dumbaugh et al in Canadian Patent 1,108,081, Wall in U.S. Patent 4,376,034, Balint et al in U.S. Patent 4,419,214.
General frequencies are taught from 20 MHz to 1000 GHz, specific frequencies applied were 20 MHz ~Hodge), 0.4 to 1000 MHz (Balint), 915 MHz (Wall, Balint), 900 to 2500 MHz (Balint), 2450 MHz (Wallace, Dumbaugh, Wall,) 5800 MHz (Balint), ~napp and Stone are indi~ferent to the ~requency applied as long as it is above 1000 MHz ~1 GHz~ (Stone) or allowed by the FCC (Knapp). Ergun in U.S. Patent 3,463,310, teaches application o~ microwave heating to the mineral component of coal to change its magnetic proper~ies to allow separation by magnetic means over a frequency range of 400 to 10,000 MHz.
Nadkarni, in U.S. Patent 4,408,999 treats oil shale or coàl or the like in an acidic slurry with frequencies in the 100 KHz to 100,000 MHz range with 1,000 to 3,000 MHz preferred, which assists the solution o~ the mineral component in the acidic slurry. Canadian Patent 448,231 issued May 4, 1948 to Clark, teaches to heat and mix water with tar sand in a mill, -the water plus ail ~orming less than 30% weight of ~he mixture, air is beaten into the resulting pulp, which is then washed in ll3~`~3'7~3 warm water. T~hi~h releases the oil a.~ a froth, containing less than 5~ of the sand.
SUMMARY OF THE INVENTION
In a broad aspect the invention is directed to an improved process o~ physical separation of tar sand comprising bituminous, mineral an~ aqueous components in~o upper bituminous and lower mineral fraction~. The improvement is exposing the tar sand to microwave radiation, at a temperature less than the boilin~ point o~ water, in the absence of industrial solvent, and the presence of added water, at a level sufficient to allow the tar sand to separate by gravity into upper bituminous and lower mineral fractions. The upper bituminous fraction has a ~reater proportion of bituminous matter than the tar sand, and the lower mineral fraction has a greater proportion of mineral matter than the tar sand. The microwave frequency i5 in the ran~e of about 800 MHz to about 1700 MHz. Preferred microwave ~requency ranges are 920+90 MHzr 1250+130 MHz and 1540+150 M~z. The temperature i~ preferred to be below the initial boiling point of water. Preferably the added water i5 from about a quarter to about four times the volume of the tar sand.
In another broad aspect the invention i5 directed ~o an improved process of physical separation o~ tar sand having bituminous, mineral and aqueous components 30 into upper bituminous and lower mineral fractions. The improvement is exposin~ the tar sand to microwave radiation at a temperature less than the bolling poin-t of water r in the absence of industrial solvent, and the presence o~ added water, at a level su~ficient to allow the tar sand to separate by gravity into upper bituminous and lower mineral fractions. The upper bituminous fraction has no apparent mineral matter, and the lower mineral fraction has no apparent bituminous ' 13~1~3'7~
matter. Visually clean 3eparation appears to be achieved. The microwave ~requency is ln the ran~0 of about 800 MH2 to about 1700 M~z. Pre~erred microwave frequency ranges are 920+90 MHz, 1~50+130 MHz and l540+150 MHz. The temperature is preferred to be below the initial boiling point o~ water. Preferably the added water is from about a guarter to about four times the volume of the tar sand.
lQ The original samples, in the initial observations, separated fairly cleanly. Later attempts to reproduce the exact conditions and results were not as successful, although partîal separation wa~ achieved. The area from which the original samples were taken, near Fort McMurray, is often waterlogged. It was therefore considered probable, by those skilled in the art, that the original samples were extremely wet, possibly saturated with water. On addition o~ water much better separation was obtained. When the temperature reached a level sufficient to cause initial boiliny of the waterr below the local boiling point, (the later experiments were carried out about 1.2 km a~ove sea level), it was noted separation cease~.
In this application the term "boiling point of water" is understood to mean the temperature at which water and steam are in equilibrium and at which llquid water boils internally throughout. The term "initial boiling point of water" is understood to mean the temp~ratur~ at which the liquid water begins to boil internally, which is several degrees lower than the boiling point o~ water. Both these temperatures are ~unctions of the local pressure.
Tar sands were treated by variou~ microwave generators of standard commercial type, and also u~ing a , ' . : . ' .
~L3~ '7~
nonstandard ~lectromagnetic generator, in glass, pla~tic or metal containers. In some cases the operating microwave generator (magnetron) was replaced by another magnetron of different ~requency.
INITIAL OBSERVATIONS
Initially, wet gloves stained with tar sand were dried in a microwave oven of uncali~rated frequency, 10 believed to be about 950 MHz (0.95 GHz). The dried gloves were noted to have clean sand and tar separately adhering to them.
Bituminous tar sand in a glass container was treated by a magnetron believed to operate at 950 MH~.
Steam was generated, after completion of treating there was no visible water, light coloured sand on the bottom and above it, several layers ranging from medium yellow to very heavy black material of asphalt like appearance on the top.
A magnetron ra~ed at 950 MHz, was connected by TV
type coaxial cable to an electronic type antenna generator, which was introduced into a 5 gallon (20 litre) metal bucket ~ull o~ bituminous tar sand and the magnetron switched on, the bucket and contents rapidly became very hot. On cooling the bucket was about two thirds full and contained three layers - a top layer of black material resembllng partially set asphalt in appearance and smell, below ~his a second layer of yellowish rankish smelling mixture, below this again a third layer of a mixture of sand, water, and other unidentified matter. A ~ample of this third layer was allowed to settle, the sediment appeared largely ~and and other mineral matter and to have no apparent rust pre~ent..
A further test wa~ performed usin~ a magnetron .
-~:
' .
- ~3~3 "~3 believe~ to operat~ at 1500 MHz ~amples of ~hout loo ml of tar sand were treated, partial separation of bitumen and sand layers was observed A further test was performed using a ~agnetron rated at 1250 MHz and 500 watts, partlal s paration of bitumen and sand layers was observed.
The frequency ratings are generally believed to be lQ accurate within about 10~.
These observations su~gest to those skilled in the art, either that on the removal of the bitumen, that the sand settled, grea~ly reducing the void volume of the sand, and allowing the water present to fill the void volume, and thus preventing the separated bitumen from seeping back into the sand, or that there was suf~icient water there to fill the slightly reduced void volume of the sand on settling, that is that there was probably more water in the initial tar sand than was usually expected to be present. If the second possibility was correct, these initial observations must have been observed on tar sand containing sub~tantially more water than normal. In effect the initial observations were probably made on tar sand containing added-water.
EXPERIMENT~L OBSERVATIONS
A microwave generator was obtained, nominally a 950J1525 MHz L3315 magnetron, which was tested for leakage r output in watts and ~requency of emitted radiation. Leakage was found within tolerance. The generator emitted radiation at frequencies measured at 920 MHz and 1540 MHz. Thers was a possible variation of these frequencies of 10%, using this magnetron. Using a antenna connected by cable to the ma~netron power output was measured at about 100 watts for 920 MHz and about 80 watts for 1540 MHz, without the antenna the power was ~3(:~83'7~
measured at about 0.3 watts at g20 MHz, and 3.~ watts at 1540 MHz, The microwave output Wa8 directed to the inside of a conventional microwave oven, with the oven ma~netron removed.
The tar sand samples used in these experiments ~except Experiment 19), were all from the same source.
It is not known whether these tar sands were the same as~ or different from, the tar sands of the initial observations.
The following experiments were performed at an altitude of approximately 1.2 km at Calgary.
About 15 ml of tar sand was treated for 30 minutes at 920 MHz at 0.3 watts on a plate, no visible change was noted, a smell of light crude lacking the typical sulfur odour was observed.
About 30 ml of tar sand was treated for 7 minutes at 920 MHz at 100 watts in a plastic tube, the antenna was inserted into the tar sand in the tube, the plastic tube began to melt after 7 minutes. A water sample was present as a check.
About ~00 ml of tar sand was treated for 2.25 hour~
at 920 MHz at lQ0 watts in a glas~ container placed upside dawn on a microwave plate, the antenna was inside the container. The sand reached 117~F at the end of this period, the tar sand shrank slightly, condensed water, and clean sand grains were observed on the inside of the container, smudges of oil yellow to light brown in colour were noted on the inside of the container.
The observed separation was minuscule. A water sample was present as a check~ at the end of treating it was ,~.
31 3~3~8 12~OF.
About 30 ml of tar sand was placed in a glass test tube upside down over the an~enna, tin ~oil wa~ placed on the closed end of the tube, which was treated for 2.5 hours at 920 MHz at 100 watts. A water sample waQ
present as a check. The sand settled slightly, water vapour and droplets were observed, but no visible separation.
The magnetron-antenna cable was shortened to increase power delivery to an estimated 160 watts at 920 MH2. About 300 ml of tar sand was treated for 3 hours at 920 MHz at an estimated 160 watts, in an inverted glass container on a plate, with ihe antenna inside the container. The tar sand temperature rose to 143~F. A
water sample was present as a check, its temperature ~0 rose to the ran~e 99 to 109~F. At the end of treating, clean sand grains and a small amount (estimated at 1 ml) of oil and water on the inside of the container was observed. The observed separation was minuscule.
About 20Q ml of tar sand was treated for 9 hours at 920 MHz at an estimated 160 watts, in an inver~ed glass container on a perforated plate, spaced above a second plate r the antenna was insid~ the cont~iner. At the end of treating, clean sand grains and a small amount of oil and water on the inside o~ the container was observed.
A water sample was present as a check. The observed separation was minuscule.
EXPERIMENT ~
About 200 ml of tar sand was treated for 20 minutes at 1540 MHz at an estimated 160 watts, in an inverted glass container on a per~orated plate, spa~ed above a :
.
.
second plate, t-he antenna was in~:ide the conta~ner. The water check sample began to boll at the end of 20 minutes. At the end of treatiny, clean sand grains and a small amount of water on the inside of the container was observed. The observed separation was mlnuscule.
The residual material from experiment 5, together with added water was treated to boiling on an electric kitchen stove in a pyrex container. Three layer separation was observed with an oily bituminous top layer, a water middl~ layer and a sand bottom layer.
A similar sample to that of experiment 5, not previously treated with microwave radiation at 920 MHz was treated to boiling with added water on an electric kitchen stove in a pyrex container. No separation was observed.
A similar sample to that of experiment 5, not previously treated with microwave radiation, was treated to boiling with added water by a magnetron rated at 2450 MHz. No separation was observed.
EXPERIMENT ll About 160 ml of tar sand and 80 ml of water was placed in a 250 ml glass container, ad~acent the antenna, and treated on and off ~or 1 hour at 920 MHz and 160 watts. The initial temperature was 71~F, both water and ~and. After 5 minutes oP treating the water was 200F, the sand 154F, an oily layer began to separate, the oil was skimmed. Another 3 minutes treating gave water 195F, sand 170F, with oil easily Ploatlng to the top. 1.5 extra minutes of treating gave water 189~F, sand 170F, with a very black oil layer filled with gas bubbles, which was skimme~. 2 more ~3(3~3'7~
, .
minutes of treating gave water 198~F, sand 187~F, with an oil layer over clear water and clean sand, oil floated to the top without visible sand vlbration or agitation, or convection currents. Another 2 ~inutes of treatin~ gave water 194~F, sand 184F, the oil layer was skimmed. A further 2 minutes of treating gave water 193~F, sand 181F, the oil layer was skimmed, the ~and was ve~y clear not much tar being lePt. 2 more minute~
of treating gave water 199F (boiling), sand 192~F, the oil layer was skimmed. About 80 to 90% of the tar was estimated to have separated. A further four treatin~
periods each of two minutes gave water temperatures of 195, 199, 199, 19~F (boiling) and sand temperatures of 197, 201, 204, 20sF, respectively, very little additional oil separated. It was estimated that 90 to 95~ of the tar had been removed from the sand.
About 80 ml of tar sand and 160 ml of water was placed in a 250 ml glass container, adjacent the antenna, and treated at 1540 MH~ and 160 watts. The initial temperature was 78F, water, and 73~F, sand.
After 2.5 minutes of treating the temperature of the water rose to 101F and the sand to 93~F, without separation. 3 ex-tra minute~ of treating yave water 129F, ~and 110F, without separation. A further 5 minutes of treating gave water 186~F, sand 141F, with a very thin light o~l layer. 2 more minutes of treating gave water 198F, sand 165~F, t~e oil layer was ~ki~med.
Another 2 minutes of treating gave water 201aF, sand 174 F. the thin oil layer waY skimmed, not much extra separation was noted. A further series of treating periods of 2, 1, 2, 2, 3, 2, 4.5 minutes gave water temperatures of 203, 202, 204, 204, 204, 204, 204 F
(boiling) and sand temperatures of 176, 195, 202, 199, 201, 199, 198 F ~respectively) with very little additional separation. It was estimated that only 20 to 25% of ~the tar had been removed from the sand.
~,1'3~
About 80 ml of tar sand and 80 ml of water wa~
placed in a 250 ml glas~ container, adjacent the antenna, and treate~ at 920 MHz and 160 watt~. The initial temperature was 74F, both water and sand.
A~ter 6.5 ~inutes oF treating separatlon Wc-15 no~ed at 7 minutes, the water boiled. The temperature of the ~ater was ls8F and the sand to 174~F, and an oil layer was skimmed. A further 2 minutes of treating boiled the water, water 195F, sand 188aF, lots of oil came off, and was skimmed. An extra minute of treating boiled the water, the experiment was discontinued.
About 80 ml of tar ~and and 80 ml water was placed in a 250 ml glass container, a distance from the antenna, and treated at 920 MHz and 160 watts. The initial te~perature was 74~F, both water and sand.
A~ter 7 minutes of treating separation was observed. 10 minutes gave water 144F, sand 128~F, a very thin oily layer was noted. Further treating periods of 1, 1.5, 0.5, and 0.5 minutes boiled the water without noticeable additional separation. The experiment was discontinued.
About 80 ml of tar sand and 160 ml of water was placed in a 250 ml glass ~ontainer, a distance from the antenna, and treated at 920 MH~ and 160 watts. 5 minutes of treatin~ gave water 170 F, sand 131F, no separation was noted. An extra 1 minute oP treating gave tar gobs floatlny to the surface at water 168F, sand 13~F. 3.5 minutes more treating gave water 183F, sand 156F, and oil gob~ floating to the surPace. A
further 2 minutes treating gave water 199F (boiling) and sand 169F. Another 2 minutes gave water 200 F
(boiling), sand 169~F, with heavy tar gobs floating to the surface and sinking. About 20X of the tar separated from the sand prior t~ boiling, no separation was ~1.3~3~
observed after boiling.
About 80 ml of tar sand and 320 ml of water was placed in a 500 ml glass container, adjacent the ~ntenna, and treated at 920 MHz and 160 watts. After 10 minutes of treating the temperature of the water rose ~o 185~F and the sand to 151 F. Oil be~an to ~eparate.
After a further 3 minutes of treating water was 19 P F, sand 165VF, slow separation continued. After a Purther 3 minutes oP treating the water boiled at 205~F, sand was 179F, slow separation continued. After a further 1 minute of treatin~ the water went into rapid boil and separation stopped. The separation was very slight.
About 80 ml of tar sand and 40 ml o~ water was placed in a 250 ml glass container, adjacent the antenna, and treated at 920 MHz and 160 watts. After 4 minutes of treating the temperature of the water rose to 85F. A further 5 minutes o~ treating raised the water temperature to 105F, no separation was noted. A
further 6 minutes o~ treating rai~ed the water temperature to 125~F at which point separation was noted, i.e. the sand and oil began to separate.
Although the oil did not rise to the surface oP the water, clean sand gralns were observed at the bottom.
About 120 ml o~ tar ~and and 40 ml water in a 250 ml glass container was treated at 920 MHz and 160 watts, near the antenna. APter 6 minutes oP treating, no separation was observed. After a Purther 3 minutes of treating, water was 14~F, separation was observed. A
further 7 minutes of treating be~an to produce noticeable ~eparation with an oil layer, water was lBl F. The sand was beginning to compact and some tar was trapped in the sand. A Purther 6 minut~ oP treatin~
~ . -13~337~3 .
produced a thick clean bubbling oil at -the top, beneath this a mixed sand oil layer (oil carryiny san~ grains), then a water sand layer, below ~hich was clean sand.
The mixture was treated ~urther 6 minutes, the oil was 12'~, and climbing the sides o~ the container, the sand and water was 139F, about 50 to 70% of the oil had migrated to the top. In a further 2 minutes the water boiled and separation stopped, the oil was 131F, ~he sand and water was 191 F.
A shaley tar sand sample was broken into chunks forming about 5 cm cubes, and placed in about 375 ml water, in a glass container. The container wa~ placed adjacent the antenna, and treated at 920 MHz and 160 watts. After 2 minute~ treating, water was 121 F, the shaley blocks started to break down to silt, with alr bubbling out o~ the sand. 1.~ minutes more treating produced water at 159~F, and 50% break down to silt, and more air bubbles, some pieces floated. 2 ~urther minutes treating produced more air bubbles, water at l~'O~F and no separation, some water was removed. A
furthex 2 minutes treatin~ produced the beginning of separation, clay and silt at the bo-ttom, most of the air bubbles had gone, and an oil layer at the top, which was skimmed. Another minute of treating produced more oil, air bubbles originating in the silt were bringing oil and silt to the top, and water at 1920F. A further 0.25 minutes treating boiled the water ending separation.
As those skilled in the art would realise these preferred details can be subjected to substantial variation, modification, change, alteration, and substitution without affecting or modifying the function of the especially preferred described embodiment.
Although embodiments of the invention have heen described above, it is not limited thereto, and it will . . . ~ .
13~ 7~
, be apparent to persons skilled in the art that null1erou~
modifications and variation~ form part of the present invention insofar as they do not depart ~rom the spirit, nature and ~cope of the claimed and described invention.
; - ~
, :
This invention relates to treatment o~ mix.tures of bituminous, aqueous, and mineral matter of the type commonly referred to as tar sands, to separate them into bituminous and mineral fractions, by application oE
elec~romagnetic frequencies o~ the type commonly referred to as microwaves.
It is an o~ject of the invention to provlde a method of separating tar sand into two fraction~, one fraction cantaining bituminous matter, the other ~raction containing mineral matter. These two fractions are not neces-carily absolutes, the bituminous fraction will contain a greater proportion o~ bi~uminous matter than the original tar sand, while the ~ineral fraction will contain a g~eater proportion of mineral matter than the original ~ar sandO Desirably there will be no apparent bitumen in the mineral fraction, and no apparent mineral in the b ! tuminous fraction. More desirably there will be negligible bitumen in the mineral fraction, and negligible mineral in the bituminous fraction.
The electroma~netic radiation used is depending on definition and frequency, in that part of the electromagnetic spec~rum bordering radio waves and microwaves~ The usual definition of microwaves is that portion of the el~ctromagnetic spestrum having frequencies greater than thQse of radio waves and les5 than those of infrared waves. Microwaves are def,-ined as having frequencies ranging from a lower limit of 100 MHz (3 m), 300 MHz (1 m), or 1 GHz (30 cm),to an upper limit of 300 GHz (1 mm) or 1000 GHz (0.3 mm). Radio waves are usually defined as not including microwaves, but are sometimes regarded as including microwave frequencies, and having an upper frequency limit o~ 100 GHz (3 mm).
3~7~
Applicant has discovered that ~y treatm~t of tar sand by electromagnetic radiatlon of selected wavelength separation of bituminolls ancl mineral fractions can be observed.
Tar sand also known as "oil sand" is understood to mean in this applica~ion a naturally occurring mixture of tar, water and mineral matter. The m:ineral matter is usually a mixture of sand (95%), heavy minerals, carbonates, and clay Minerals~ The tar is bituminous in nature and typically comprises from about 5% to about 18% by weight of the mixture. Water typically comprises about 2% to about 12% by weight of the mixture. Mineral matter typically comprises about a3% by weight of the mixture, variation from these figures may be observed.
The mineral matter includes sand grains and fines. The sand grains are believed to form a nearly space filling arrangement with about 65~ by volume of the sand, with the bituminous material and water in the voids between the sand grains, totalling about 35~ by volume of the sand. The sand grains of the tar sand are wetted, the grains can range from strongly water wetted, to strongly oil (bitumen/tar) wetted, sands of intermediate wettability are known to exist.
DESCRIPTION OF THE PRIOR ART
General applications of electromagnetic waves to tar sands, oil shales and coals are known. Radio waves may be applied directly, or as a fluctuating electric or magnetic field, or by induction heating where an electric current is applied to generate another electric current in the material to be treated [as a primary coil current in a transformer qenerates a secondary coil current]. All these can be viewed as application of electromagnetic waves loosely termed of "radio"
frequency. General use of such frequencies for heating tar sand or oil shale in situ is taught by Rowland in ~3~&~3~7i3 U.S. Pa-tent 4,135,5'~9 ancl Dauphine in Canadiarl Patent 1,105,376, which utilize ~re~uencie~ between lO0 kiloher~z and 100 megahertz, ~or yeneral heating of oil shales. The Fishers in Canadian Patents 994,694, 994,695 and 1,105,376 teach similar treatment of tar sand by induction heating using alternatiny current o~
unspecified ~requencies, except that i~ i5 suggested that normal 60 cycle AC could be used.
Radio and microwave frequency heating of oil shales, tar sands and coals to liquefy, volatilize~ and pyrolyze the bituminous or organic component is well known. Microwaves are used to retort such materials by ~odge in U.S. Patent 2,542,028, Knapp in U.S. Patent 3,449,213 and 3,560,347, Stone in U.S. Patent 3,503,865, Wallace in U.S. Patent 4,118,282, Dumbaugh et al in Canadian Patent 1,108,081, Wall in U.S. Patent 4,376,034, Balint et al in U.S. Patent 4,419,214.
General frequencies are taught from 20 MHz to 1000 GHz, specific frequencies applied were 20 MHz ~Hodge), 0.4 to 1000 MHz (Balint), 915 MHz (Wall, Balint), 900 to 2500 MHz (Balint), 2450 MHz (Wallace, Dumbaugh, Wall,) 5800 MHz (Balint), ~napp and Stone are indi~ferent to the ~requency applied as long as it is above 1000 MHz ~1 GHz~ (Stone) or allowed by the FCC (Knapp). Ergun in U.S. Patent 3,463,310, teaches application o~ microwave heating to the mineral component of coal to change its magnetic proper~ies to allow separation by magnetic means over a frequency range of 400 to 10,000 MHz.
Nadkarni, in U.S. Patent 4,408,999 treats oil shale or coàl or the like in an acidic slurry with frequencies in the 100 KHz to 100,000 MHz range with 1,000 to 3,000 MHz preferred, which assists the solution o~ the mineral component in the acidic slurry. Canadian Patent 448,231 issued May 4, 1948 to Clark, teaches to heat and mix water with tar sand in a mill, -the water plus ail ~orming less than 30% weight of ~he mixture, air is beaten into the resulting pulp, which is then washed in ll3~`~3'7~3 warm water. T~hi~h releases the oil a.~ a froth, containing less than 5~ of the sand.
SUMMARY OF THE INVENTION
In a broad aspect the invention is directed to an improved process o~ physical separation of tar sand comprising bituminous, mineral an~ aqueous components in~o upper bituminous and lower mineral fraction~. The improvement is exposing the tar sand to microwave radiation, at a temperature less than the boilin~ point o~ water, in the absence of industrial solvent, and the presence of added water, at a level sufficient to allow the tar sand to separate by gravity into upper bituminous and lower mineral fractions. The upper bituminous fraction has a ~reater proportion of bituminous matter than the tar sand, and the lower mineral fraction has a greater proportion of mineral matter than the tar sand. The microwave frequency i5 in the ran~e of about 800 MHz to about 1700 MHz. Preferred microwave ~requency ranges are 920+90 MHzr 1250+130 MHz and 1540+150 M~z. The temperature i~ preferred to be below the initial boiling point of water. Preferably the added water i5 from about a quarter to about four times the volume of the tar sand.
In another broad aspect the invention i5 directed ~o an improved process of physical separation o~ tar sand having bituminous, mineral and aqueous components 30 into upper bituminous and lower mineral fractions. The improvement is exposin~ the tar sand to microwave radiation at a temperature less than the bolling poin-t of water r in the absence of industrial solvent, and the presence o~ added water, at a level su~ficient to allow the tar sand to separate by gravity into upper bituminous and lower mineral fractions. The upper bituminous fraction has no apparent mineral matter, and the lower mineral fraction has no apparent bituminous ' 13~1~3'7~
matter. Visually clean 3eparation appears to be achieved. The microwave ~requency is ln the ran~0 of about 800 MH2 to about 1700 M~z. Pre~erred microwave frequency ranges are 920+90 MHz, 1~50+130 MHz and l540+150 MHz. The temperature is preferred to be below the initial boiling point o~ water. Preferably the added water is from about a guarter to about four times the volume of the tar sand.
lQ The original samples, in the initial observations, separated fairly cleanly. Later attempts to reproduce the exact conditions and results were not as successful, although partîal separation wa~ achieved. The area from which the original samples were taken, near Fort McMurray, is often waterlogged. It was therefore considered probable, by those skilled in the art, that the original samples were extremely wet, possibly saturated with water. On addition o~ water much better separation was obtained. When the temperature reached a level sufficient to cause initial boiliny of the waterr below the local boiling point, (the later experiments were carried out about 1.2 km a~ove sea level), it was noted separation cease~.
In this application the term "boiling point of water" is understood to mean the temperature at which water and steam are in equilibrium and at which llquid water boils internally throughout. The term "initial boiling point of water" is understood to mean the temp~ratur~ at which the liquid water begins to boil internally, which is several degrees lower than the boiling point o~ water. Both these temperatures are ~unctions of the local pressure.
Tar sands were treated by variou~ microwave generators of standard commercial type, and also u~ing a , ' . : . ' .
~L3~ '7~
nonstandard ~lectromagnetic generator, in glass, pla~tic or metal containers. In some cases the operating microwave generator (magnetron) was replaced by another magnetron of different ~requency.
INITIAL OBSERVATIONS
Initially, wet gloves stained with tar sand were dried in a microwave oven of uncali~rated frequency, 10 believed to be about 950 MHz (0.95 GHz). The dried gloves were noted to have clean sand and tar separately adhering to them.
Bituminous tar sand in a glass container was treated by a magnetron believed to operate at 950 MH~.
Steam was generated, after completion of treating there was no visible water, light coloured sand on the bottom and above it, several layers ranging from medium yellow to very heavy black material of asphalt like appearance on the top.
A magnetron ra~ed at 950 MHz, was connected by TV
type coaxial cable to an electronic type antenna generator, which was introduced into a 5 gallon (20 litre) metal bucket ~ull o~ bituminous tar sand and the magnetron switched on, the bucket and contents rapidly became very hot. On cooling the bucket was about two thirds full and contained three layers - a top layer of black material resembllng partially set asphalt in appearance and smell, below ~his a second layer of yellowish rankish smelling mixture, below this again a third layer of a mixture of sand, water, and other unidentified matter. A ~ample of this third layer was allowed to settle, the sediment appeared largely ~and and other mineral matter and to have no apparent rust pre~ent..
A further test wa~ performed usin~ a magnetron .
-~:
' .
- ~3~3 "~3 believe~ to operat~ at 1500 MHz ~amples of ~hout loo ml of tar sand were treated, partial separation of bitumen and sand layers was observed A further test was performed using a ~agnetron rated at 1250 MHz and 500 watts, partlal s paration of bitumen and sand layers was observed.
The frequency ratings are generally believed to be lQ accurate within about 10~.
These observations su~gest to those skilled in the art, either that on the removal of the bitumen, that the sand settled, grea~ly reducing the void volume of the sand, and allowing the water present to fill the void volume, and thus preventing the separated bitumen from seeping back into the sand, or that there was suf~icient water there to fill the slightly reduced void volume of the sand on settling, that is that there was probably more water in the initial tar sand than was usually expected to be present. If the second possibility was correct, these initial observations must have been observed on tar sand containing sub~tantially more water than normal. In effect the initial observations were probably made on tar sand containing added-water.
EXPERIMENT~L OBSERVATIONS
A microwave generator was obtained, nominally a 950J1525 MHz L3315 magnetron, which was tested for leakage r output in watts and ~requency of emitted radiation. Leakage was found within tolerance. The generator emitted radiation at frequencies measured at 920 MHz and 1540 MHz. Thers was a possible variation of these frequencies of 10%, using this magnetron. Using a antenna connected by cable to the ma~netron power output was measured at about 100 watts for 920 MHz and about 80 watts for 1540 MHz, without the antenna the power was ~3(:~83'7~
measured at about 0.3 watts at g20 MHz, and 3.~ watts at 1540 MHz, The microwave output Wa8 directed to the inside of a conventional microwave oven, with the oven ma~netron removed.
The tar sand samples used in these experiments ~except Experiment 19), were all from the same source.
It is not known whether these tar sands were the same as~ or different from, the tar sands of the initial observations.
The following experiments were performed at an altitude of approximately 1.2 km at Calgary.
About 15 ml of tar sand was treated for 30 minutes at 920 MHz at 0.3 watts on a plate, no visible change was noted, a smell of light crude lacking the typical sulfur odour was observed.
About 30 ml of tar sand was treated for 7 minutes at 920 MHz at 100 watts in a plastic tube, the antenna was inserted into the tar sand in the tube, the plastic tube began to melt after 7 minutes. A water sample was present as a check.
About ~00 ml of tar sand was treated for 2.25 hour~
at 920 MHz at lQ0 watts in a glas~ container placed upside dawn on a microwave plate, the antenna was inside the container. The sand reached 117~F at the end of this period, the tar sand shrank slightly, condensed water, and clean sand grains were observed on the inside of the container, smudges of oil yellow to light brown in colour were noted on the inside of the container.
The observed separation was minuscule. A water sample was present as a check~ at the end of treating it was ,~.
31 3~3~8 12~OF.
About 30 ml of tar sand was placed in a glass test tube upside down over the an~enna, tin ~oil wa~ placed on the closed end of the tube, which was treated for 2.5 hours at 920 MHz at 100 watts. A water sample waQ
present as a check. The sand settled slightly, water vapour and droplets were observed, but no visible separation.
The magnetron-antenna cable was shortened to increase power delivery to an estimated 160 watts at 920 MH2. About 300 ml of tar sand was treated for 3 hours at 920 MHz at an estimated 160 watts, in an inverted glass container on a plate, with ihe antenna inside the container. The tar sand temperature rose to 143~F. A
water sample was present as a check, its temperature ~0 rose to the ran~e 99 to 109~F. At the end of treating, clean sand grains and a small amount (estimated at 1 ml) of oil and water on the inside of the container was observed. The observed separation was minuscule.
About 20Q ml of tar sand was treated for 9 hours at 920 MHz at an estimated 160 watts, in an inver~ed glass container on a perforated plate, spaced above a second plate r the antenna was insid~ the cont~iner. At the end of treating, clean sand grains and a small amount of oil and water on the inside o~ the container was observed.
A water sample was present as a check. The observed separation was minuscule.
EXPERIMENT ~
About 200 ml of tar sand was treated for 20 minutes at 1540 MHz at an estimated 160 watts, in an inverted glass container on a per~orated plate, spa~ed above a :
.
.
second plate, t-he antenna was in~:ide the conta~ner. The water check sample began to boll at the end of 20 minutes. At the end of treatiny, clean sand grains and a small amount of water on the inside of the container was observed. The observed separation was mlnuscule.
The residual material from experiment 5, together with added water was treated to boiling on an electric kitchen stove in a pyrex container. Three layer separation was observed with an oily bituminous top layer, a water middl~ layer and a sand bottom layer.
A similar sample to that of experiment 5, not previously treated with microwave radiation at 920 MHz was treated to boiling with added water on an electric kitchen stove in a pyrex container. No separation was observed.
A similar sample to that of experiment 5, not previously treated with microwave radiation, was treated to boiling with added water by a magnetron rated at 2450 MHz. No separation was observed.
EXPERIMENT ll About 160 ml of tar sand and 80 ml of water was placed in a 250 ml glass container, ad~acent the antenna, and treated on and off ~or 1 hour at 920 MHz and 160 watts. The initial temperature was 71~F, both water and ~and. After 5 minutes oP treating the water was 200F, the sand 154F, an oily layer began to separate, the oil was skimmed. Another 3 minutes treating gave water 195F, sand 170F, with oil easily Ploatlng to the top. 1.5 extra minutes of treating gave water 189~F, sand 170F, with a very black oil layer filled with gas bubbles, which was skimme~. 2 more ~3(3~3'7~
, .
minutes of treating gave water 198~F, sand 187~F, with an oil layer over clear water and clean sand, oil floated to the top without visible sand vlbration or agitation, or convection currents. Another 2 ~inutes of treatin~ gave water 194~F, sand 184F, the oil layer was skimmed. A further 2 minutes of treating gave water 193~F, sand 181F, the oil layer was skimmed, the ~and was ve~y clear not much tar being lePt. 2 more minute~
of treating gave water 199F (boiling), sand 192~F, the oil layer was skimmed. About 80 to 90% of the tar was estimated to have separated. A further four treatin~
periods each of two minutes gave water temperatures of 195, 199, 199, 19~F (boiling) and sand temperatures of 197, 201, 204, 20sF, respectively, very little additional oil separated. It was estimated that 90 to 95~ of the tar had been removed from the sand.
About 80 ml of tar sand and 160 ml of water was placed in a 250 ml glass container, adjacent the antenna, and treated at 1540 MH~ and 160 watts. The initial temperature was 78F, water, and 73~F, sand.
After 2.5 minutes of treating the temperature of the water rose to 101F and the sand to 93~F, without separation. 3 ex-tra minute~ of treating yave water 129F, ~and 110F, without separation. A further 5 minutes of treating gave water 186~F, sand 141F, with a very thin light o~l layer. 2 more minutes of treating gave water 198F, sand 165~F, t~e oil layer was ~ki~med.
Another 2 minutes of treating gave water 201aF, sand 174 F. the thin oil layer waY skimmed, not much extra separation was noted. A further series of treating periods of 2, 1, 2, 2, 3, 2, 4.5 minutes gave water temperatures of 203, 202, 204, 204, 204, 204, 204 F
(boiling) and sand temperatures of 176, 195, 202, 199, 201, 199, 198 F ~respectively) with very little additional separation. It was estimated that only 20 to 25% of ~the tar had been removed from the sand.
~,1'3~
About 80 ml of tar sand and 80 ml of water wa~
placed in a 250 ml glas~ container, adjacent the antenna, and treate~ at 920 MHz and 160 watt~. The initial temperature was 74F, both water and sand.
A~ter 6.5 ~inutes oF treating separatlon Wc-15 no~ed at 7 minutes, the water boiled. The temperature of the ~ater was ls8F and the sand to 174~F, and an oil layer was skimmed. A further 2 minutes of treating boiled the water, water 195F, sand 188aF, lots of oil came off, and was skimmed. An extra minute of treating boiled the water, the experiment was discontinued.
About 80 ml of tar ~and and 80 ml water was placed in a 250 ml glass container, a distance from the antenna, and treated at 920 MHz and 160 watts. The initial te~perature was 74~F, both water and sand.
A~ter 7 minutes of treating separation was observed. 10 minutes gave water 144F, sand 128~F, a very thin oily layer was noted. Further treating periods of 1, 1.5, 0.5, and 0.5 minutes boiled the water without noticeable additional separation. The experiment was discontinued.
About 80 ml of tar sand and 160 ml of water was placed in a 250 ml glass ~ontainer, a distance from the antenna, and treated at 920 MH~ and 160 watts. 5 minutes of treatin~ gave water 170 F, sand 131F, no separation was noted. An extra 1 minute oP treating gave tar gobs floatlny to the surface at water 168F, sand 13~F. 3.5 minutes more treating gave water 183F, sand 156F, and oil gob~ floating to the surPace. A
further 2 minutes treating gave water 199F (boiling) and sand 169F. Another 2 minutes gave water 200 F
(boiling), sand 169~F, with heavy tar gobs floating to the surface and sinking. About 20X of the tar separated from the sand prior t~ boiling, no separation was ~1.3~3~
observed after boiling.
About 80 ml of tar sand and 320 ml of water was placed in a 500 ml glass container, adjacent the ~ntenna, and treated at 920 MHz and 160 watts. After 10 minutes of treating the temperature of the water rose ~o 185~F and the sand to 151 F. Oil be~an to ~eparate.
After a further 3 minutes of treating water was 19 P F, sand 165VF, slow separation continued. After a Purther 3 minutes oP treating the water boiled at 205~F, sand was 179F, slow separation continued. After a further 1 minute of treatin~ the water went into rapid boil and separation stopped. The separation was very slight.
About 80 ml of tar sand and 40 ml o~ water was placed in a 250 ml glass container, adjacent the antenna, and treated at 920 MHz and 160 watts. After 4 minutes of treating the temperature of the water rose to 85F. A further 5 minutes o~ treating raised the water temperature to 105F, no separation was noted. A
further 6 minutes o~ treating rai~ed the water temperature to 125~F at which point separation was noted, i.e. the sand and oil began to separate.
Although the oil did not rise to the surface oP the water, clean sand gralns were observed at the bottom.
About 120 ml o~ tar ~and and 40 ml water in a 250 ml glass container was treated at 920 MHz and 160 watts, near the antenna. APter 6 minutes oP treating, no separation was observed. After a Purther 3 minutes of treating, water was 14~F, separation was observed. A
further 7 minutes of treating be~an to produce noticeable ~eparation with an oil layer, water was lBl F. The sand was beginning to compact and some tar was trapped in the sand. A Purther 6 minut~ oP treatin~
~ . -13~337~3 .
produced a thick clean bubbling oil at -the top, beneath this a mixed sand oil layer (oil carryiny san~ grains), then a water sand layer, below ~hich was clean sand.
The mixture was treated ~urther 6 minutes, the oil was 12'~, and climbing the sides o~ the container, the sand and water was 139F, about 50 to 70% of the oil had migrated to the top. In a further 2 minutes the water boiled and separation stopped, the oil was 131F, ~he sand and water was 191 F.
A shaley tar sand sample was broken into chunks forming about 5 cm cubes, and placed in about 375 ml water, in a glass container. The container wa~ placed adjacent the antenna, and treated at 920 MHz and 160 watts. After 2 minute~ treating, water was 121 F, the shaley blocks started to break down to silt, with alr bubbling out o~ the sand. 1.~ minutes more treating produced water at 159~F, and 50% break down to silt, and more air bubbles, some pieces floated. 2 ~urther minutes treating produced more air bubbles, water at l~'O~F and no separation, some water was removed. A
furthex 2 minutes treatin~ produced the beginning of separation, clay and silt at the bo-ttom, most of the air bubbles had gone, and an oil layer at the top, which was skimmed. Another minute of treating produced more oil, air bubbles originating in the silt were bringing oil and silt to the top, and water at 1920F. A further 0.25 minutes treating boiled the water ending separation.
As those skilled in the art would realise these preferred details can be subjected to substantial variation, modification, change, alteration, and substitution without affecting or modifying the function of the especially preferred described embodiment.
Although embodiments of the invention have heen described above, it is not limited thereto, and it will . . . ~ .
13~ 7~
, be apparent to persons skilled in the art that null1erou~
modifications and variation~ form part of the present invention insofar as they do not depart ~rom the spirit, nature and ~cope of the claimed and described invention.
; - ~
, :
Claims (32)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process of physical separation of tar sand comprising bituminous, mineral and aqueous components into upper bituminous and lower mineral fractions, the improvement comprising exposing said tar sand to microwave radiation, at a temperature less than the boiling point of water, in the absence of industrial solvent, and the presence of added water, at a level sufficient to allow said tar sand to separate by gravity into upper bituminous and lower mineral fractions, wherein said upper bituminous fraction comprises a greater proportion of bituminous matter than said tar said, and said lower mineral fraction comprises a greater proportion of mineral matter than said tar sand, and said microwave frequency is in the range of about 800 MHz to about 1700 MHz.
2. A process of claim 1, wherein said frequency is 920+90 MHz.
3. A process of claim 1, wherein said frequency is 1250+130 MHz.
4. A process of claim 1, wherein said frequency is 1540+150 MHz.
5. A process of claim 1, wherein said temperature is below the initial boiling point of water.
6. A process of claim 5, wherein said frequency is 920+90 MHz.
7. A process of claim 5, wherein said frequency is 1250+130 MHz.
8. A process of claim 5, wherein said frequency is 1540+150 MHz.
9. A process of claim 1, wherein said added water is from about a quarter to about four times the volume of the tar sand.
10. A process of claim 2, wherein said added water is from about a quarter to about four times the volume of the tar sand.
11. A process of claim 3, wherein said added water is from about a quarter to about four times the volume of the tar sand.
12. A process of claim 4, wherein said added water is from about a quarter to about four times the volume of the tar sand.
13. A process of claim 5, wherein said added water is from about a quarter to about four times the volume of the tar sand.
14. A process of claim 6, wherein said added water is from about a quarter to about four times the volume of the tar sand.
15. A process of claim 7, wherein said added water is from about a quarter to about four times the volume of the tar sand.
16. A process of claim 8, wherein said added water is from about a quarter to about four times the volume of the tar sand.
17. In a process of physical separation of tar sand comprising bituminous, mineral and aqueous components into upper bituminous and lower mineral fractions, the improvement comprising exposing said tar sand to microwave radiation at a temperature less than the boiling point of water, in the absence of industrial solvent, and the presence of added water, at a level sufficient to allow said tar sand to separate by gravity into upper bituminous and lower mineral fractions, wherein said upper bituminous fraction comprises no apparent mineral matter, and said lower mineral fraction comprises no apparent bituminous matter, and said microwave frequency is in the range of about 800 MHz to about 1700 MHz.
18. A process of claim 17, wherein said frequency is 920+90 MHz.
19. A process of claim 17, wherein said frequency is 1250+130 MHz.
20. A process of claim 17, wherein said frequency is 1540+150 MHz.
21. A process of claim 17, wherein said temperature is below the initial boiling point of water.
22. A process of claim 17, wherein said frequency is 920+90 MHz.
23. A process of claim 17, wherein said frequency is 1250+130 MHz.
24. A process of claim 17, wherein said frequency is 1540+150 MHz.
25. A process of claim 17, wherein said added water is from about a quarter to about four times the volume of the tar sand.
26. A process of claim 18, wherein said added water is from about a quarter to about four times the volume of the tar sand.
27. A process of claim 19, wherein said added water is from about a quarter to about four times the volume of the tar sand.
28. A process of claim 20, wherein said added water is from about a quarter to about four times the volume of the tar sand.
29. A process of claim 21, wherein said added water is from about a quarter to about four times the volume of the tar sand.
30. A process of claim 22, wherein said added water is from about a quarter to about four times the volume of the tar sand.
31. A process of claim 23, wherein said added water is from about a quarter to about four times the volume of the tar sand.
32. A process of claim 24, wherein said added water is from about a quarter to about four times the volume of the tar sand.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000614783A CA1308378C (en) | 1989-09-29 | 1989-09-29 | Separation of bituminous material from tar sands |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000614783A CA1308378C (en) | 1989-09-29 | 1989-09-29 | Separation of bituminous material from tar sands |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1308378C true CA1308378C (en) | 1992-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000614783A Expired - Fee Related CA1308378C (en) | 1989-09-29 | 1989-09-29 | Separation of bituminous material from tar sands |
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| Country | Link |
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| CA (1) | CA1308378C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016064586A1 (en) | 2014-10-20 | 2016-04-28 | Exxonmobil Upstream Research Company | Microwave-assisted bitumen extraction with vacuum-assisted sediment filtration |
-
1989
- 1989-09-29 CA CA000614783A patent/CA1308378C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016064586A1 (en) | 2014-10-20 | 2016-04-28 | Exxonmobil Upstream Research Company | Microwave-assisted bitumen extraction with vacuum-assisted sediment filtration |
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