CA2304972A1 - A process for low temperature separation and isolation of crude heavy oil - Google Patents
A process for low temperature separation and isolation of crude heavy oil Download PDFInfo
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- CA2304972A1 CA2304972A1 CA 2304972 CA2304972A CA2304972A1 CA 2304972 A1 CA2304972 A1 CA 2304972A1 CA 2304972 CA2304972 CA 2304972 CA 2304972 A CA2304972 A CA 2304972A CA 2304972 A1 CA2304972 A1 CA 2304972A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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Abstract
A Process for the dendritic separation of a soluble maltene based oil fraction from insoluble pitches and tars also known as asphaltenes and from oxidized hydrocarbons known as naphthenates. The process has the further simultaneous capability to confine /
concentrate the vanadium, nickel, and iron constituents to specific separated fractions.
concentrate the vanadium, nickel, and iron constituents to specific separated fractions.
Description
Flow Chart of the Process:
Isolated bitumen from the M.O.R.E and Clark process and I or crude heavy oils and I
or refinery distillation column residuum and I or oil sludge I slop is treated with Solvent A / Solvent 8 jwhose composition mixture is made up of Solvent A and Solvent B in the ratio of xA to (1-x) B where x is the fraction proportion of Solvent A]
ratio mixture of known pH and lower critical solution temperature (LCST).
The temperature of the mixture is maintained above its LCST while the mixture partitions into distinct layers based on the constituent densities, solvent specific gravity,mineraJ particle size and the hydrocarbon solubility. Centrifugation speeds up the separation process of the constituents into distinct fractions or layers.
All ingredients that are soluble in the upper layer and have a combined ingredient I
solvent specific gravity of less than 0.82 gram I cc congregate in the upper layer.
Entrapment of iron, nickel and vanadium in this layer is low.
All insoluble ingredients whose densities are greater than 0.82 and less than 0.99 gram ! cc gravitate to the interface between the two layers. It has a high r:nncPntratinn of irnn an~i tha hinh~ect cnncRntratinnR of nickRl and vanaeiimm_ The lower layer, if basic, may contain soluble naphthenic acid and mercaptan salts that can be liberated by acidification. Inorganic, water-soluble salts'may dissolve in this layer.
Ali insoluble organic ingredients whose densities are greater than 0.88 gram I
cc and which are bound to colloidal clay consolidate at the bottom of the lower layer. It is highest in iron concentration and relatively high in nickel and vanadium.
Centrif~rgal forces cause the clay and silt particles to pack tightly together leaving little void space for the insoluble organic fraction.
Specifications I Background of the Invention This invention relates to the dendritic separation and isolation of 1) hydrocarbons, 2) derivatives of hydrocarbons, 3) clays and silts (particle sizes of less than 80 um) and 4) sand, gravel and added minerals (particle sizes of greater than 80wm).
The invention also relates to the dendritic redistribution of the metals to specifically partitioned fractions.
The three distinct hydrocarbon layers, which form, have specifically partitioned fractions of heavy metals. The fop Layer is almost devoid of iron and nickel and has a substantially reduced concentration of vanadium. The concentration ratio of the second to the third layer is slightly less than one for iron and slightly less than two for nickel and vanadium.
In total numbers, the greater portion of the iron, nickel and vanadium is found in the third layer.
By dendr'rtic is meant the simultaneous ! all at once separation and isolation of various consfrtuents from the raw material such as crude oil and oil sand extracted bitumen as opposed to the seauential I consecutive one step followed by another separation and isolation of the organic and inorganic constituents from the raw material.
A dendritic chemical reaction example is the side by side conversion of ethylene into copolymer polyethylene using a mufti site instead of a single site polymerization catalyst.
(1]
(1] G.C. Bazan, Z.J. Komon J. Amer. Chem. Soc.,122,1830 (2000) Simultaneous as opposed to sequential I consecutive is one way of reducing profligate process steps. C.R Strauss j2] refers to such processes as containing tandem /
cascade steps that contribute to the logic {described by Haggin (3]) that reduced reactor size becomes an attitude, and mobile portability due to reduced equipment size becomes an asset. Such thinking gts in quite well with present day Total Quality demands for portable, multipurpose self sustaining systems that concomitantly shorten process cycle time, increase step efficiency and have less impact on the environment while meeting today's and tommorow's needs.
Isolated bitumen from the M.O.R.E and Clark process and I or crude heavy oils and I
or refinery distillation column residuum and I or oil sludge I slop is treated with Solvent A / Solvent 8 jwhose composition mixture is made up of Solvent A and Solvent B in the ratio of xA to (1-x) B where x is the fraction proportion of Solvent A]
ratio mixture of known pH and lower critical solution temperature (LCST).
The temperature of the mixture is maintained above its LCST while the mixture partitions into distinct layers based on the constituent densities, solvent specific gravity,mineraJ particle size and the hydrocarbon solubility. Centrifugation speeds up the separation process of the constituents into distinct fractions or layers.
All ingredients that are soluble in the upper layer and have a combined ingredient I
solvent specific gravity of less than 0.82 gram I cc congregate in the upper layer.
Entrapment of iron, nickel and vanadium in this layer is low.
All insoluble ingredients whose densities are greater than 0.82 and less than 0.99 gram ! cc gravitate to the interface between the two layers. It has a high r:nncPntratinn of irnn an~i tha hinh~ect cnncRntratinnR of nickRl and vanaeiimm_ The lower layer, if basic, may contain soluble naphthenic acid and mercaptan salts that can be liberated by acidification. Inorganic, water-soluble salts'may dissolve in this layer.
Ali insoluble organic ingredients whose densities are greater than 0.88 gram I
cc and which are bound to colloidal clay consolidate at the bottom of the lower layer. It is highest in iron concentration and relatively high in nickel and vanadium.
Centrif~rgal forces cause the clay and silt particles to pack tightly together leaving little void space for the insoluble organic fraction.
Specifications I Background of the Invention This invention relates to the dendritic separation and isolation of 1) hydrocarbons, 2) derivatives of hydrocarbons, 3) clays and silts (particle sizes of less than 80 um) and 4) sand, gravel and added minerals (particle sizes of greater than 80wm).
The invention also relates to the dendritic redistribution of the metals to specifically partitioned fractions.
The three distinct hydrocarbon layers, which form, have specifically partitioned fractions of heavy metals. The fop Layer is almost devoid of iron and nickel and has a substantially reduced concentration of vanadium. The concentration ratio of the second to the third layer is slightly less than one for iron and slightly less than two for nickel and vanadium.
In total numbers, the greater portion of the iron, nickel and vanadium is found in the third layer.
By dendr'rtic is meant the simultaneous ! all at once separation and isolation of various consfrtuents from the raw material such as crude oil and oil sand extracted bitumen as opposed to the seauential I consecutive one step followed by another separation and isolation of the organic and inorganic constituents from the raw material.
A dendritic chemical reaction example is the side by side conversion of ethylene into copolymer polyethylene using a mufti site instead of a single site polymerization catalyst.
(1]
(1] G.C. Bazan, Z.J. Komon J. Amer. Chem. Soc.,122,1830 (2000) Simultaneous as opposed to sequential I consecutive is one way of reducing profligate process steps. C.R Strauss j2] refers to such processes as containing tandem /
cascade steps that contribute to the logic {described by Haggin (3]) that reduced reactor size becomes an attitude, and mobile portability due to reduced equipment size becomes an asset. Such thinking gts in quite well with present day Total Quality demands for portable, multipurpose self sustaining systems that concomitantly shorten process cycle time, increase step efficiency and have less impact on the environment while meeting today's and tommorow's needs.
(2] C.R. Strauss Australian J. Chemistry 52 83-96 (1999) (3] J. Haggin Chemical and Engineering News 74 (23) 38 (1999) Seauential Multi-Steutaed Processing of Oil Extracted oils and tars are usually colloid systems that have entrapped bubbles, droplets of water with dissolved corrosive salts and fine mineral particles. De-emulsification (Step 1 ) by the addition of a light hydrocarbon and de-watering by centrifugation (Step 2) followed by drying with the aid of a desiccant such as calcium oxide (Step 3) is carried out in order to overcome this problem. The dried crude is subsequently centrifuged to remove entrapped fine particles of clay, calcium hydroxide from excess calcium oxide (Step 4). Tiny droplets of water containing corrosive salts and very fine solids contaminate the bitumen when desiccants are not used.
Naturally occurring colloid size silt and clay particles along with hydrocarbon residues are dispersed in the treabnent waters during the "oil sand conditioning" and "bitumen extraction" steps; hence creating unwanted toxic fine tails (Step 5).
"Bitumen extraction" entails the use of low concentrations of caustic, such as sodium hydroxide, as a process aid in the de-oiling of the oil sand. The caustic reacts with the naphthenic acids thus generating natural soaps that contribute to the entrapment of both hydrocarbons and fine silts in the aqueous phase. Step 5, which has not totally addressed the fine tails challenge, is being studied. It involves an attempt to decrease process toxic waste production in order to tower the process Environmental Quotient (EQ) as described by Sheldon [4~. EQ is the ratio of waste generated volume to the product volume multiplied by an "unfriendly" environmental quotient {Q) i.e.
toxic factor contributed by the waste. In this case, the volume of wastewater is 1-3 times the volume of the bitumen product, and Q is the toxicity and time for deposition of the bitumen loaded fine taitings produced.
[4j Sheldon R.A. Chem. Ind. (London) 199712.
Heavy crude oil and extracted bitumen is categorized in three major constituent categories : alkanes Iparaffins; cyclo alkanes i naphthenes and aromatics I
asphalts.
Traditionally, the constituents have been isolated either by fractional distillation (gases and liquids) or by fractional crystallization {waxy solids} (Step 6).
The following table gives some idea of the boiling point ranges and carbon chain lengths of fractional refinery distillation cuts.
Naturally occurring colloid size silt and clay particles along with hydrocarbon residues are dispersed in the treabnent waters during the "oil sand conditioning" and "bitumen extraction" steps; hence creating unwanted toxic fine tails (Step 5).
"Bitumen extraction" entails the use of low concentrations of caustic, such as sodium hydroxide, as a process aid in the de-oiling of the oil sand. The caustic reacts with the naphthenic acids thus generating natural soaps that contribute to the entrapment of both hydrocarbons and fine silts in the aqueous phase. Step 5, which has not totally addressed the fine tails challenge, is being studied. It involves an attempt to decrease process toxic waste production in order to tower the process Environmental Quotient (EQ) as described by Sheldon [4~. EQ is the ratio of waste generated volume to the product volume multiplied by an "unfriendly" environmental quotient {Q) i.e.
toxic factor contributed by the waste. In this case, the volume of wastewater is 1-3 times the volume of the bitumen product, and Q is the toxicity and time for deposition of the bitumen loaded fine taitings produced.
[4j Sheldon R.A. Chem. Ind. (London) 199712.
Heavy crude oil and extracted bitumen is categorized in three major constituent categories : alkanes Iparaffins; cyclo alkanes i naphthenes and aromatics I
asphalts.
Traditionally, the constituents have been isolated either by fractional distillation (gases and liquids) or by fractional crystallization {waxy solids} (Step 6).
The following table gives some idea of the boiling point ranges and carbon chain lengths of fractional refinery distillation cuts.
Carbon Chain Class Boiling Point Length Range C
CS-C,o Gasoline 37 -175 C,o-C,5 Kerosene/Jet 175-275 Fuel C,2 -C2o Diesel 190-330 C14 -C22 Fuel Oil 230-360 C20-C30 Lubricating >350 Oil C~-C4o Petroleum Jelly40-60 (m. pt.) C2s-Cso Paraffin Wax 50-65(m.pt.) Cso + poly Tar/bitumen > 400 cyclics The residuum of distillation is made up of mineral desiccant residues, naphthenic acid salts, high molecular weight paraffins, asphalt aromatics, sulfur and nitrogen compounds and heavy metals . Such products are sold as road asphalt constituents.
One Steu Dendritic Processing of Oil This invention relates to the separation and isolation of the raw material described above; taking advantage of a novel sustainable suitable alternative process which reduces the number of profligate process steps and the reactor size hence making the system more portable, self contained and possessing a much lower EQ.
The system simultaneously takes advantage of the following process variables:
1) A Solvent A which can act a) as a surface-active wetting agent for both the hydrocarbon and the mineral substrate by lowering interfacial tension, b) as de-emulsifying agent by absorbing water present, c) as a mineral clay precipitant consolidating agent and d) as a solubilizing solvent for the maltene fraction, 2) a biphasic solvent system that results when the solvent mixture A + B is raised above its LCST, (E.G. 40°C in the example case when A is Butoxy Ethanol in 10-57%
concentration and B is water), 3) a biphasic solvent system whose LCST may be altered by an aromatic propylene glycol ether (E.G. a decrease from 40°C to 22-26°C by the addition of 1-2% by volume phenyl propylene glycol ether to a 10-57% concentration of butoxy ethanol in water), 4) a biphasic solvent system whose LCST may be altered by salt concentration, (E.G.
10:90 and 60:40 concentrations of N-cyclohexyl pyrrolidone (CHP) in water are miscible at 50°C but form a biphasic solvent system when a 2% sodium chloride solution is made) [51, 5) a biphasic solvent system whose LCST may be altered by pH, (E.G. from 50°C to 5 °C
when the concentration of sodium hydroxide is raised from 0 to 0.5 Normal and from 50°C to 80°C when the concentration of sulfuric acid is raised from 0 to 1 Normal in the example case when A is CHP of approximately 30% concentration and B is water j6], 6) an upper layer that has a greater concentration of the less dense organic solvent component, 7) an upper layer that has a differing solubility capability than the lower layer because of the relative concentrations of the solvent A and B components, 8) an upper layer that has an enhanced organic solvating power because of the addition of the phenyl propylene giygol ether to the solvent mixture, 9) a system which possesses a) a higher flash point because of the water present in each of its layer components and b) a lower potential to burn because water acts as a heat sink, 10) a two phased system wherein one of the phases has a greater lipophilic and the other a greater hydrophilic character (increased penetrating I cleaning power, break down micelles, solvency difference in the layers) 11) a two phased system wherein one of the phases can be made more or less acidic or basic in order to separate organic acids or bases from the neutral components (E.G.
salt formation of naphtheneic acids and mercaptans) 12) a two phased system wherein isolation of the soluble maltene product is made possible in an enriched solvent A phase of controlled volume (E.G. the volume ratio of the Layers may be determined by the use of the formula: % BE in water =
0.47 volume of upper layer being sought in a 100 ml sample + 10) [5] GAF Corporation Bulletin 2550-0531985 [6] International Specialty Products Brochure 2302-219 5M-991 (1991 ) SOME OF THE INHERENT PROBLEMS ASSOCIATED WITH PRESENT DAY PROCESSES
ARE:
Enersw Usas~e:
The total crude volume determines the fractional distillation equipment size.
That is, equipment size must include low boiling temperature hydrocarbon volumes as well as greater than 360°C boiling point Fuel Oil.
Tailins~s and Storage Saace:
The process of bitumen recovery from oil sands generates large quantities of tailings that require indefinite storage space. [7]
[7] Strand, W. L. Canadian Pat. 2 124199 (1992 0611) Water usa~ae:
The volume of processing water required is 1 to 3 times the volume of the about to be extracted oil sands [8]. The volume of water required is inversely proportional to the clay fraction content [8] FTFC (Fine Tailings Fundamentals Consortium) "Vol. 2 - 3 " In: Advances in Oil Sands Tailings Research, Alberta Department of Energy, Oil Sands and Research Division, Publisher.
Environmental Concerns:
Because the spent water presently generated contains toxic naphthenates, oil and solvent residues, and fine tailings, storage and containment of the waste waters has become an integral part of the process. The presently projected required volume of settling ponds is used up every 400 days. This is expected to decrease to 300 days when the Aurora mine comes on stream in the year 2004 i.e. 460,000,000 m$ per annum of new storage space for spent water shall be required.
It has been estimated that it will take 100 - 300 years for the colloidal of the fine tailings to agglomerate to a soft clay before release of the above mentioned waters shall be permitted to the environment " Without further treatment of the existing fne tailings and withouf process modifications to reduce fhe rate of production of "new" fine tailings, by the year 2030, over one billion cubic meters of a non-consolidating gne tailings would exist at the bottom of these lakes."
...since "Containment of the entire watersystem with the operating process is required as part of the operating license agreement between the Provincial Government and the two commercial plants." (9,10 (9)~ FTFC (Fine Tailings Fundamentals Consortium) "Vol. 4 -5. " In: Advances in Oil Sands Tailings Research, Alberta Department of Energy, Oil Sands and Research Division, Publisher.
(10) Mac Kinnon, M. and Sethi, A.; A Comparison of the Physical and Chemical Properties of the Tailings Ponds of the Syncrude and Suncor OII Sands Plants, OII Sands Our Petroleum fufure Conference, Edmonton, Alberta, April 4-7, 1993.
SUMMARY OF THE INVENTION
The present invention provides a process whereby crude, recovered oil sand bitumen, distillate residuum or recovered waste oils can be separated from an inorganic agglomerate of various size particles. Because of the ability of the solvent to physically set up a phase mixture system which has inherent density and solubifrty ranges, tars can be separated from oils and sand or diatomaceous earths can be separated from clays and silts.
Such solvent mixtures have the ability to separate into biphasic mixtures simply by adjusting the temperature of the solution or by changing its inorganic salt or its non LCST organic concentrations.
The separating solvent solution is an aqueous mixture of lipophilic and hydrophilic liquids that possess a Lower Critical Solution Temperature.
Some liquids exhibit total solubility over a range of concentrations and temperatures but partition into biphasic systems at specific concentrations and temperatures.
They possess the specific ability to raise the lipophilic and hydrophilic characteristics of a solution by simple manipulation of the process variables. In other words, simple adjustment of the salt, organic concentration or temperature greatly expands the separation abilities of the constituent solvents.
An example is Butoxy Ethanol in water. Solutions of greater than 10% and less than 57%
Butoxy Ethanol will, below approximately 40°C remain in solution but partition into a biphasic system above 40°C.
For example,100 ml of totally miscible (15% by volume) Butoxy Ethanol (density 0.90 glml) will, at 40°C give a biphasic system of 10 mls 57% Butoxy Ethanol in Water as a top phase (density 0.92 glml) and 90 mls of 10% Butoxy Ethanol in Water as a bottom phase (density 0.99 glml).
Such phenomena are known as Lower Critical Solution Temperatures. When the reverse phenomena is exhibited i.e. a biphasic mixture at a low temperature becomes a single phase at a higher temperature the solvents are said to have an Upper Critical Solution Temperature (UCST). Some mixtures do not exhibit an UCST at atmospheric pressure only because their boiling points are lower than their UCST's. In order to exhibit an UCST
it becomes imperative that the solvent solution be held under pressure while being heated (11 ).
(11) Hyun- Song Lee and Huen Lee J. Chem. Eng. Data 1996,41,1358 -1360.
The present invention provides a method of separating the organic constituents from each other and from the inorganic phase in crude, bitumen, residuum and recovered waste by a recyclable solvent solution. By way of example, Butoxy Ethanol :
Water, which is not limiting to the solvent solution that can be used in the process, has a LCST
of 40°C. The constituents of the treatment solution may be:
Sodium silicate ...........................................................................0 -2.5%
Sodium hydroxide .......................................................................0 -2.5%
Alkyl orland aryl or di alkyl glycol or di glycol ether and I or the corres-ponding propylene glycol ether derivatives................ Ingredient dependant Triethyl amine and I or diethyl methyl and I or dimethyl pyridine and I or °
methyl pyridyl and i or methyl piperidene ......................................0 -10 /o Water ...............................................................................
..........to 100 /o at a pressure of 1 - 3 atmospheres depending on the glass transition temperature (To ) or pour points of the target crude, bitumen, residuum or waste oil being extracted.
In preferred embodiments of the inventions the following proportions of chemical components can be used:
Sodium Hydroxide andlor Sodium Silicate 0-2.5%, preferably 0.5 to 2.5, particularly preferable 1-2°!° when a high pH is required as an extraction aid by ionizing the free organic acid fraction of the oil sand extract or the distillate residuum. A
titration curve for a Califoria residuum sample gave a starting pH of 3.03 and showed the pH
transition point at approximately 7.6.
Aryl glycol ether or their corresponding propylene glycol derivative (such as propylene glycol phenyl ether) can act as a colloid disrupter, i.e. a susceptor extraction aid at 0-5%, preferably 0 to 2%, particularly preferable 1% when colloidal clay acts as an asphalt binder and requires an extraction aid.
All glycol ethers 0-100°l°, preferably 10 to 5T particularly 15 -25%, and especially 20% In the case of butoxy ethanol.
In preferred embodiments of the inventions the following properties of the mechanical components can be used:
A high shearing force in a hydrocyclone to enhance the removal of oil from the sand and clay surface.
Separation of the sand from the clay based on particle size and density.
Compaction of the clay and silt particles by centrifugal forces leaving extremely small voids, hence causing the asphaltenes to form a layer of oil on the surface of the compacted clay.
~n A depiction of the experimental dendritic I simultaneous separations follow:
Top liquid layer ---1 Soluble lipophilics (maltenes) Liquid-liquid interface --~ Insolubles (den.<0.99>0.92) Bottom liquid layer Soluble naphthenates Raw material Mercaptans ~ high pH
+ Suspended (clay +
den. >0.99 asphaltene) Solvent Liquid-solid interface Centrifugation causes Solution asphaltenes to deposit on top of clay layer Solid ---1 Sand ADVANTAGE OF OUR PROCESS OVER THE PAST ART
Some obvious advantages of the process are:
1 Simplicity of the equipment and Reduction in capital costs ) the process and maintenance fees.
2) One step dendritic separation of Smaller portable reactors the organic (pre- with distillation) and inorganic constituentsshorter cycle times.
of the raw material mixture 3) Performing the extraction and separationEliminating the costs of of constituents in one step. profligate process steps.
4) Facile separation of the semi-solidShort cycle time and therefore hydrocarbons from their liquid counterparts reduced equipment size requirements.
5) Reduction in the viscosity of the Increased pipeline flow heavier oil fractions by disolving (57:431 capabilities at lower butoxy ethanol :
~y water mixtures. temperatures..
6) Up-grading the constituents by concentratingReduction of the volumes which precious metals into fewer product require de-contamination streams.
treatment.
T) Concentration of the liquid hydrocarbonConcentration of the fraction up-graded by partitioning it between the two fraction into smaller phases of the volumes of solvent mixture at temperatures just solvent.
above the LCST
8) Generate two separate hydrocarbon Eliminate transportation streams at of the the mine site (Maitenes and Asphaltenes)inorganic phases.
8) Generate a solvent system in the Reduction of the pour case of butoxy point to ethanol which has a freezing point lower temperatures..
of -10C
10) Work with non- flammable solvents Insurance premiums are i.e. flash points above 100C lowered.
11 ) Reduce energy usage Process ores just above 12) Eliminate the need for waste waterNo toxic waste and no containment fine ponds tailings.
CS-C,o Gasoline 37 -175 C,o-C,5 Kerosene/Jet 175-275 Fuel C,2 -C2o Diesel 190-330 C14 -C22 Fuel Oil 230-360 C20-C30 Lubricating >350 Oil C~-C4o Petroleum Jelly40-60 (m. pt.) C2s-Cso Paraffin Wax 50-65(m.pt.) Cso + poly Tar/bitumen > 400 cyclics The residuum of distillation is made up of mineral desiccant residues, naphthenic acid salts, high molecular weight paraffins, asphalt aromatics, sulfur and nitrogen compounds and heavy metals . Such products are sold as road asphalt constituents.
One Steu Dendritic Processing of Oil This invention relates to the separation and isolation of the raw material described above; taking advantage of a novel sustainable suitable alternative process which reduces the number of profligate process steps and the reactor size hence making the system more portable, self contained and possessing a much lower EQ.
The system simultaneously takes advantage of the following process variables:
1) A Solvent A which can act a) as a surface-active wetting agent for both the hydrocarbon and the mineral substrate by lowering interfacial tension, b) as de-emulsifying agent by absorbing water present, c) as a mineral clay precipitant consolidating agent and d) as a solubilizing solvent for the maltene fraction, 2) a biphasic solvent system that results when the solvent mixture A + B is raised above its LCST, (E.G. 40°C in the example case when A is Butoxy Ethanol in 10-57%
concentration and B is water), 3) a biphasic solvent system whose LCST may be altered by an aromatic propylene glycol ether (E.G. a decrease from 40°C to 22-26°C by the addition of 1-2% by volume phenyl propylene glycol ether to a 10-57% concentration of butoxy ethanol in water), 4) a biphasic solvent system whose LCST may be altered by salt concentration, (E.G.
10:90 and 60:40 concentrations of N-cyclohexyl pyrrolidone (CHP) in water are miscible at 50°C but form a biphasic solvent system when a 2% sodium chloride solution is made) [51, 5) a biphasic solvent system whose LCST may be altered by pH, (E.G. from 50°C to 5 °C
when the concentration of sodium hydroxide is raised from 0 to 0.5 Normal and from 50°C to 80°C when the concentration of sulfuric acid is raised from 0 to 1 Normal in the example case when A is CHP of approximately 30% concentration and B is water j6], 6) an upper layer that has a greater concentration of the less dense organic solvent component, 7) an upper layer that has a differing solubility capability than the lower layer because of the relative concentrations of the solvent A and B components, 8) an upper layer that has an enhanced organic solvating power because of the addition of the phenyl propylene giygol ether to the solvent mixture, 9) a system which possesses a) a higher flash point because of the water present in each of its layer components and b) a lower potential to burn because water acts as a heat sink, 10) a two phased system wherein one of the phases has a greater lipophilic and the other a greater hydrophilic character (increased penetrating I cleaning power, break down micelles, solvency difference in the layers) 11) a two phased system wherein one of the phases can be made more or less acidic or basic in order to separate organic acids or bases from the neutral components (E.G.
salt formation of naphtheneic acids and mercaptans) 12) a two phased system wherein isolation of the soluble maltene product is made possible in an enriched solvent A phase of controlled volume (E.G. the volume ratio of the Layers may be determined by the use of the formula: % BE in water =
0.47 volume of upper layer being sought in a 100 ml sample + 10) [5] GAF Corporation Bulletin 2550-0531985 [6] International Specialty Products Brochure 2302-219 5M-991 (1991 ) SOME OF THE INHERENT PROBLEMS ASSOCIATED WITH PRESENT DAY PROCESSES
ARE:
Enersw Usas~e:
The total crude volume determines the fractional distillation equipment size.
That is, equipment size must include low boiling temperature hydrocarbon volumes as well as greater than 360°C boiling point Fuel Oil.
Tailins~s and Storage Saace:
The process of bitumen recovery from oil sands generates large quantities of tailings that require indefinite storage space. [7]
[7] Strand, W. L. Canadian Pat. 2 124199 (1992 0611) Water usa~ae:
The volume of processing water required is 1 to 3 times the volume of the about to be extracted oil sands [8]. The volume of water required is inversely proportional to the clay fraction content [8] FTFC (Fine Tailings Fundamentals Consortium) "Vol. 2 - 3 " In: Advances in Oil Sands Tailings Research, Alberta Department of Energy, Oil Sands and Research Division, Publisher.
Environmental Concerns:
Because the spent water presently generated contains toxic naphthenates, oil and solvent residues, and fine tailings, storage and containment of the waste waters has become an integral part of the process. The presently projected required volume of settling ponds is used up every 400 days. This is expected to decrease to 300 days when the Aurora mine comes on stream in the year 2004 i.e. 460,000,000 m$ per annum of new storage space for spent water shall be required.
It has been estimated that it will take 100 - 300 years for the colloidal of the fine tailings to agglomerate to a soft clay before release of the above mentioned waters shall be permitted to the environment " Without further treatment of the existing fne tailings and withouf process modifications to reduce fhe rate of production of "new" fine tailings, by the year 2030, over one billion cubic meters of a non-consolidating gne tailings would exist at the bottom of these lakes."
...since "Containment of the entire watersystem with the operating process is required as part of the operating license agreement between the Provincial Government and the two commercial plants." (9,10 (9)~ FTFC (Fine Tailings Fundamentals Consortium) "Vol. 4 -5. " In: Advances in Oil Sands Tailings Research, Alberta Department of Energy, Oil Sands and Research Division, Publisher.
(10) Mac Kinnon, M. and Sethi, A.; A Comparison of the Physical and Chemical Properties of the Tailings Ponds of the Syncrude and Suncor OII Sands Plants, OII Sands Our Petroleum fufure Conference, Edmonton, Alberta, April 4-7, 1993.
SUMMARY OF THE INVENTION
The present invention provides a process whereby crude, recovered oil sand bitumen, distillate residuum or recovered waste oils can be separated from an inorganic agglomerate of various size particles. Because of the ability of the solvent to physically set up a phase mixture system which has inherent density and solubifrty ranges, tars can be separated from oils and sand or diatomaceous earths can be separated from clays and silts.
Such solvent mixtures have the ability to separate into biphasic mixtures simply by adjusting the temperature of the solution or by changing its inorganic salt or its non LCST organic concentrations.
The separating solvent solution is an aqueous mixture of lipophilic and hydrophilic liquids that possess a Lower Critical Solution Temperature.
Some liquids exhibit total solubility over a range of concentrations and temperatures but partition into biphasic systems at specific concentrations and temperatures.
They possess the specific ability to raise the lipophilic and hydrophilic characteristics of a solution by simple manipulation of the process variables. In other words, simple adjustment of the salt, organic concentration or temperature greatly expands the separation abilities of the constituent solvents.
An example is Butoxy Ethanol in water. Solutions of greater than 10% and less than 57%
Butoxy Ethanol will, below approximately 40°C remain in solution but partition into a biphasic system above 40°C.
For example,100 ml of totally miscible (15% by volume) Butoxy Ethanol (density 0.90 glml) will, at 40°C give a biphasic system of 10 mls 57% Butoxy Ethanol in Water as a top phase (density 0.92 glml) and 90 mls of 10% Butoxy Ethanol in Water as a bottom phase (density 0.99 glml).
Such phenomena are known as Lower Critical Solution Temperatures. When the reverse phenomena is exhibited i.e. a biphasic mixture at a low temperature becomes a single phase at a higher temperature the solvents are said to have an Upper Critical Solution Temperature (UCST). Some mixtures do not exhibit an UCST at atmospheric pressure only because their boiling points are lower than their UCST's. In order to exhibit an UCST
it becomes imperative that the solvent solution be held under pressure while being heated (11 ).
(11) Hyun- Song Lee and Huen Lee J. Chem. Eng. Data 1996,41,1358 -1360.
The present invention provides a method of separating the organic constituents from each other and from the inorganic phase in crude, bitumen, residuum and recovered waste by a recyclable solvent solution. By way of example, Butoxy Ethanol :
Water, which is not limiting to the solvent solution that can be used in the process, has a LCST
of 40°C. The constituents of the treatment solution may be:
Sodium silicate ...........................................................................0 -2.5%
Sodium hydroxide .......................................................................0 -2.5%
Alkyl orland aryl or di alkyl glycol or di glycol ether and I or the corres-ponding propylene glycol ether derivatives................ Ingredient dependant Triethyl amine and I or diethyl methyl and I or dimethyl pyridine and I or °
methyl pyridyl and i or methyl piperidene ......................................0 -10 /o Water ...............................................................................
..........to 100 /o at a pressure of 1 - 3 atmospheres depending on the glass transition temperature (To ) or pour points of the target crude, bitumen, residuum or waste oil being extracted.
In preferred embodiments of the inventions the following proportions of chemical components can be used:
Sodium Hydroxide andlor Sodium Silicate 0-2.5%, preferably 0.5 to 2.5, particularly preferable 1-2°!° when a high pH is required as an extraction aid by ionizing the free organic acid fraction of the oil sand extract or the distillate residuum. A
titration curve for a Califoria residuum sample gave a starting pH of 3.03 and showed the pH
transition point at approximately 7.6.
Aryl glycol ether or their corresponding propylene glycol derivative (such as propylene glycol phenyl ether) can act as a colloid disrupter, i.e. a susceptor extraction aid at 0-5%, preferably 0 to 2%, particularly preferable 1% when colloidal clay acts as an asphalt binder and requires an extraction aid.
All glycol ethers 0-100°l°, preferably 10 to 5T particularly 15 -25%, and especially 20% In the case of butoxy ethanol.
In preferred embodiments of the inventions the following properties of the mechanical components can be used:
A high shearing force in a hydrocyclone to enhance the removal of oil from the sand and clay surface.
Separation of the sand from the clay based on particle size and density.
Compaction of the clay and silt particles by centrifugal forces leaving extremely small voids, hence causing the asphaltenes to form a layer of oil on the surface of the compacted clay.
~n A depiction of the experimental dendritic I simultaneous separations follow:
Top liquid layer ---1 Soluble lipophilics (maltenes) Liquid-liquid interface --~ Insolubles (den.<0.99>0.92) Bottom liquid layer Soluble naphthenates Raw material Mercaptans ~ high pH
+ Suspended (clay +
den. >0.99 asphaltene) Solvent Liquid-solid interface Centrifugation causes Solution asphaltenes to deposit on top of clay layer Solid ---1 Sand ADVANTAGE OF OUR PROCESS OVER THE PAST ART
Some obvious advantages of the process are:
1 Simplicity of the equipment and Reduction in capital costs ) the process and maintenance fees.
2) One step dendritic separation of Smaller portable reactors the organic (pre- with distillation) and inorganic constituentsshorter cycle times.
of the raw material mixture 3) Performing the extraction and separationEliminating the costs of of constituents in one step. profligate process steps.
4) Facile separation of the semi-solidShort cycle time and therefore hydrocarbons from their liquid counterparts reduced equipment size requirements.
5) Reduction in the viscosity of the Increased pipeline flow heavier oil fractions by disolving (57:431 capabilities at lower butoxy ethanol :
~y water mixtures. temperatures..
6) Up-grading the constituents by concentratingReduction of the volumes which precious metals into fewer product require de-contamination streams.
treatment.
T) Concentration of the liquid hydrocarbonConcentration of the fraction up-graded by partitioning it between the two fraction into smaller phases of the volumes of solvent mixture at temperatures just solvent.
above the LCST
8) Generate two separate hydrocarbon Eliminate transportation streams at of the the mine site (Maitenes and Asphaltenes)inorganic phases.
8) Generate a solvent system in the Reduction of the pour case of butoxy point to ethanol which has a freezing point lower temperatures..
of -10C
10) Work with non- flammable solvents Insurance premiums are i.e. flash points above 100C lowered.
11 ) Reduce energy usage Process ores just above 12) Eliminate the need for waste waterNo toxic waste and no containment fine ponds tailings.
13) Eliminate the projected volumes Holding ponds not needed.
of toxic fine tallS
of toxic fine tallS
14) Eliminate the need for Tailings No wastewater.
Oil Recovery 15) Fexible pH capabilities. Extraction of the naphthenates and thio compounds 16) Recycle the solvent since the systemLess fresh water required.
is closed loop.
1T) Segregation of the mineral clays Recovery of >99~ pure from the sand for silicon further processing dioxide 18) Provide the opportunity to recoverCreation of a profit precious metals center.
from the isolates.
19) Extension of the process to cleaningUse the previously generated up man made spills ponds as the water source.
20) Reduction of the extraction processDecreasing the cycle to 3 - 4 time and minutes using a solvent system under reducing the extraction pressure. process to in (pipe) line processing.
21 ) Reduction of the solvent volumes Reduction of solvent to half the weight and water of the sand being processed. vole~rne needs, 22) Substantial reduction of iron, Concentration of precious nickel and vanadium m in specific fractions before process refining. ~ metals into smaller but specific process streams.
Experimental Example of an OII Sand Extraction 1 ) To a 6-12% by weight sample of tar sand isadded an equivalent weight of 20% by volume Butoxy Ethanol in Water. The solvent mixture may require up to 0.75% of sodium hydroxide and mete sodium silicate respectively andlor a 1% propylene glycol phenyl ether. This is especially true of tar sands that have a large proportion of very fine particles and low API asphalts such as the tar sands found in Trinidad Pitch Lake.
2) Sodium mete silicate reacts with free calcium ions to precipitate insoluble calcium silicate.
3) The mixture was subjected to shear forces from a 1735 rpm stirrer while being heated above 40°C preferably around 90°C.
4) Heating the mixture above 40°C causes the liquid to separate into two layers or phases when no caustic or propylene glycol phenyl ether is present. The upper layer and lower layers are 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
5) Soluble maltenes dissolve in the upper layer.
6) Propylene glycol phenyl ether dissolves exclusively in the top layer.
7) Insoluble heavy oils whose densities are less than 0.99 glcc and are greater than 0.92 rise to the interface between the two layers.
8) These tars and pitches can be isolated by centrifuging I or by a gravity generated density gradient.
9) The bottom solvent layer contains asphalt laden clay particulates plus dissolved naphthenates when caustic soda and sodium silicates were used.
10) Hard to extract samples were sometimes encountered. Running the extraction at a temperature of 120 to 130 °C (1-2 bar) encourages the clay to release asphaltenes.
Centrifugation deposited the separated asphalt and clay.
11) Neutralization of the clear (post centrifugation) bottom phase liquid regenerates the naphthenic acid and precipitates very fine colloidal clay.
12) Recovery of the solvent is attained by heating the clay. Butoxy Ehanol forms a 20%
azeotrope at 99°C from the 10% solvent.
m 13) Within the scope of our experiment we used an aspirator and a Buchner funnel lined with a 94 mesh Fourdriner fabric [121 to collect the sand. The bitumen free sand layer was stripped of solvent. The semi dry, silt free sand was flash evaporated in order to recover the 20% Butoxy Ethanol azeotrope.
14) Heating the clay in the presence of the 120-130°C or in the presence of a 1.9%
solution of propylene glycol phenyl ether solvent solution ensured bitumen free clay was obtained at less than 100°C . The clay is dried by stripping the azeotrope.
15) Depending on the source of the ore, the cleaned clays (mainly kaolinite and illite) may have commercial applications.
18) Precious metals were concentrated in the insoluble fraction layers.
Oil Recovery 15) Fexible pH capabilities. Extraction of the naphthenates and thio compounds 16) Recycle the solvent since the systemLess fresh water required.
is closed loop.
1T) Segregation of the mineral clays Recovery of >99~ pure from the sand for silicon further processing dioxide 18) Provide the opportunity to recoverCreation of a profit precious metals center.
from the isolates.
19) Extension of the process to cleaningUse the previously generated up man made spills ponds as the water source.
20) Reduction of the extraction processDecreasing the cycle to 3 - 4 time and minutes using a solvent system under reducing the extraction pressure. process to in (pipe) line processing.
21 ) Reduction of the solvent volumes Reduction of solvent to half the weight and water of the sand being processed. vole~rne needs, 22) Substantial reduction of iron, Concentration of precious nickel and vanadium m in specific fractions before process refining. ~ metals into smaller but specific process streams.
Experimental Example of an OII Sand Extraction 1 ) To a 6-12% by weight sample of tar sand isadded an equivalent weight of 20% by volume Butoxy Ethanol in Water. The solvent mixture may require up to 0.75% of sodium hydroxide and mete sodium silicate respectively andlor a 1% propylene glycol phenyl ether. This is especially true of tar sands that have a large proportion of very fine particles and low API asphalts such as the tar sands found in Trinidad Pitch Lake.
2) Sodium mete silicate reacts with free calcium ions to precipitate insoluble calcium silicate.
3) The mixture was subjected to shear forces from a 1735 rpm stirrer while being heated above 40°C preferably around 90°C.
4) Heating the mixture above 40°C causes the liquid to separate into two layers or phases when no caustic or propylene glycol phenyl ether is present. The upper layer and lower layers are 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
5) Soluble maltenes dissolve in the upper layer.
6) Propylene glycol phenyl ether dissolves exclusively in the top layer.
7) Insoluble heavy oils whose densities are less than 0.99 glcc and are greater than 0.92 rise to the interface between the two layers.
8) These tars and pitches can be isolated by centrifuging I or by a gravity generated density gradient.
9) The bottom solvent layer contains asphalt laden clay particulates plus dissolved naphthenates when caustic soda and sodium silicates were used.
10) Hard to extract samples were sometimes encountered. Running the extraction at a temperature of 120 to 130 °C (1-2 bar) encourages the clay to release asphaltenes.
Centrifugation deposited the separated asphalt and clay.
11) Neutralization of the clear (post centrifugation) bottom phase liquid regenerates the naphthenic acid and precipitates very fine colloidal clay.
12) Recovery of the solvent is attained by heating the clay. Butoxy Ehanol forms a 20%
azeotrope at 99°C from the 10% solvent.
m 13) Within the scope of our experiment we used an aspirator and a Buchner funnel lined with a 94 mesh Fourdriner fabric [121 to collect the sand. The bitumen free sand layer was stripped of solvent. The semi dry, silt free sand was flash evaporated in order to recover the 20% Butoxy Ethanol azeotrope.
14) Heating the clay in the presence of the 120-130°C or in the presence of a 1.9%
solution of propylene glycol phenyl ether solvent solution ensured bitumen free clay was obtained at less than 100°C . The clay is dried by stripping the azeotrope.
15) Depending on the source of the ore, the cleaned clays (mainly kaolinite and illite) may have commercial applications.
18) Precious metals were concentrated in the insoluble fraction layers.
17) All recovered solvents and washings were recycled. They were used "as is"
from the bottom layer and after purification by distillation from the top and insoubie layers.
from the bottom layer and after purification by distillation from the top and insoubie layers.
18) The various fractions that in total made up the bitumen resulted in yields of greater than 99%.
Ex~erimentai Example of Crude OII Extraction 1) To a thermal steam stimulation sample of heavy oil from Kern County, California was added an equal volume of 20% butoxy ethanol in water.
2) Heating the mixture above 40°C causes the liquid to separate into two layers or phases. The upper layer and lower layers are 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
3) Soluble maltenes dissolve in the upper layer.
4) Insoluble Heavy Oils whose densities are less than 0.99 glcc and are greater than 0.92 rise to the interface between the two layers.
5) These tars and pitches could now be isolated by centrifuging I density gradient.
6) The bottom solvent layer contained naphthenic acid and mercaptan salts where present and strong bases such as sodium hydroxide and sodium mete silicate is used.
7) Centrifugation of the bottom layer deposits the asphaltic hydrocarbons.
8) A trace of sand is found below the bottom layer.
9) The various fractions that in total made up the bitumen resulted in yields of greater than 99%.
m 10) All recovered solvents and washings were recycled. They could be used "as is" from the bottom layer or after purification by distillation from the top and insoluble layers.
Exuerimental Examale of Peroleum Distillate Residuum Extraction 1) To an accumulated residuum sample (approximately 50% organic material and 50%
inorganic) from a heavy oil distillate column (Kern County, California) was added an equal volume of 20% butoxy ethanol in water containing 0.75% (by weight) sodium hydroxide and 0.75% weight sodium silicate.
Z) Heating the mixture to above its softening point (90-95°C) caused the solid portions to soften and separate into two layers or phases. The upper layer and lower layers were 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
3) The bottom solvent layer contained dissolved naphthenic acid salts which are recoverable by neutralization.
4) Recovered solvents are recycled.
5) Insoluble calcium silicates and residuum minerals were isolated by centrifugation.
embodiment of the invention in which an exclusive property or privilege is claimed are de'ti0.ed as follows:
1) A process tha~ses the separation of crude oil into 'rte constituent hydrocarbon parts and their deriva'ti~es without the generation of pond tailings.
2) A process that causes the 3e~aration of oil sands and distillate bottoms into their hydrocarbon and mineral parts w out the generation of pond tailings.
3) A solvent system that simultaneously a ' es its solvency, density, lipolhydrophilicity,surface active wetting, de- Isifying and mineral precipitating characteristics to separate the organic and inorgan onstituents of crude oil and oil derived from oil containing mineral ores.
4) A solvent system which has a freezing point of less than 0°C an~ence can be used to hydrostatically transport solid ores at less than 0°C while condition~the ore.
5j A process as defined in claims 182 in which the solvent has a pH range 11 than 1 to more than 14 but preferably between 7 and 12 in order to isolate acids.
l5
Ex~erimentai Example of Crude OII Extraction 1) To a thermal steam stimulation sample of heavy oil from Kern County, California was added an equal volume of 20% butoxy ethanol in water.
2) Heating the mixture above 40°C causes the liquid to separate into two layers or phases. The upper layer and lower layers are 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
3) Soluble maltenes dissolve in the upper layer.
4) Insoluble Heavy Oils whose densities are less than 0.99 glcc and are greater than 0.92 rise to the interface between the two layers.
5) These tars and pitches could now be isolated by centrifuging I density gradient.
6) The bottom solvent layer contained naphthenic acid and mercaptan salts where present and strong bases such as sodium hydroxide and sodium mete silicate is used.
7) Centrifugation of the bottom layer deposits the asphaltic hydrocarbons.
8) A trace of sand is found below the bottom layer.
9) The various fractions that in total made up the bitumen resulted in yields of greater than 99%.
m 10) All recovered solvents and washings were recycled. They could be used "as is" from the bottom layer or after purification by distillation from the top and insoluble layers.
Exuerimental Examale of Peroleum Distillate Residuum Extraction 1) To an accumulated residuum sample (approximately 50% organic material and 50%
inorganic) from a heavy oil distillate column (Kern County, California) was added an equal volume of 20% butoxy ethanol in water containing 0.75% (by weight) sodium hydroxide and 0.75% weight sodium silicate.
Z) Heating the mixture to above its softening point (90-95°C) caused the solid portions to soften and separate into two layers or phases. The upper layer and lower layers were 57:43 and 10: 90 solutions of butoxy ethanol: water respectively.
3) The bottom solvent layer contained dissolved naphthenic acid salts which are recoverable by neutralization.
4) Recovered solvents are recycled.
5) Insoluble calcium silicates and residuum minerals were isolated by centrifugation.
embodiment of the invention in which an exclusive property or privilege is claimed are de'ti0.ed as follows:
1) A process tha~ses the separation of crude oil into 'rte constituent hydrocarbon parts and their deriva'ti~es without the generation of pond tailings.
2) A process that causes the 3e~aration of oil sands and distillate bottoms into their hydrocarbon and mineral parts w out the generation of pond tailings.
3) A solvent system that simultaneously a ' es its solvency, density, lipolhydrophilicity,surface active wetting, de- Isifying and mineral precipitating characteristics to separate the organic and inorgan onstituents of crude oil and oil derived from oil containing mineral ores.
4) A solvent system which has a freezing point of less than 0°C an~ence can be used to hydrostatically transport solid ores at less than 0°C while condition~the ore.
5j A process as defined in claims 182 in which the solvent has a pH range 11 than 1 to more than 14 but preferably between 7 and 12 in order to isolate acids.
l5
Claims (19)
1) A process that causes the separation of crude oil into its constituent hydrocarbon parts and their derivatives without the generation of pond tailings.
2) A process that causes the separation of oil sands and distillate bottoms into their hydrocarbon and mineral parts without the generation of pond tailings.
3) A solvent system that simultaneously utilizes its solvency, density, lipo/hydrophilicity,surface active wetting, de-emisifying and mineral precipitating characteristics to separate the organic and inorganic constituents of crude oil and oil derived from oil containing mineral ores.
4) A solvent system which has a freezing point of less than 0°C and hence can be used to hydrostatically transport solid ores at less than 0°C while conditioning the ore.
5) A process as defined in claims 1&2 in which the solvent has a pH range from less than 1 to more than 14 but preferably between 7 and 12 in order to isolate naphthenic acids.
6) A process as defined in claims 1&2, in which the solvent mixture phase transition is controlled by the addition of either inorganic acids and bases or organic solvents.
7) A process as defined in claims 1&2 in which the ionic strength and hence the LCST is controlled by the addition of salts.
8) A process as defined in claims 1&2 in which the freezing point is controlled by the ratio of the solvents in the mixture.
9) A process as defined in claims 1&2 in which the solid ore gradually distributes itself into "sized particle layers" of clay silt and sand.
10) A process as defined in claim 9 in which the isolated layers can be removed for further processing.
11) A process as defined in claim 9 in which either liquid phase can be regenerated by azeotropic distillation.
12) A process as defined in claims 1&2 in which the column of liquid is comprised of an upper layer of lower density that contains the major portion of the oils and a lower layer of higher density that contains the extracted inorganic salts, naphthenates and thio compounds.
13) A process as defined in claims 1&2, which can be executed at a tower than critical temperature and hence require less energy.
14) A process as defined in claims 1&2, which can be executed with non-flammable solvent mixtures.
15) A process as defined in claims 1&2 which eliminates toxic wastewater.
16) A process as defined in claims 1&2 which eliminates the need for holding ponds.
17) A process as defined in claim 12 that reduces the viscosity of the insoluble heavy oil fractions by disolving a percentage of its weight with 57:43 butoxy ethanol.
18) A process which provides a mechanism to separate the oils from mineral ores much closer to the mine site because of the reduced size of the required processing equipment.
19) A process which, on a small scale, can be mounted on a transportation vehicle and which, in the case of oil spillage and / or contamination of the land could be used to rejuvenate said land. An example would be sand on beaches that have become oil laden because of oil spillage disasters on the high seas. Another example would be contamination of a land site as the result of spillage and / or leakage of oils from holding tanks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2304972 CA2304972A1 (en) | 2000-04-12 | 2000-04-12 | A process for low temperature separation and isolation of crude heavy oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2304972 CA2304972A1 (en) | 2000-04-12 | 2000-04-12 | A process for low temperature separation and isolation of crude heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2304972A1 true CA2304972A1 (en) | 2001-10-12 |
Family
ID=4165856
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|---|---|---|---|
| CA 2304972 Abandoned CA2304972A1 (en) | 2000-04-12 | 2000-04-12 | A process for low temperature separation and isolation of crude heavy oil |
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| CA (1) | CA2304972A1 (en) |
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| WO2015148296A1 (en) * | 2014-03-27 | 2015-10-01 | Dow Global Technologies Llc | Method to extract bitumen from oil sands |
| US9207019B2 (en) | 2011-04-15 | 2015-12-08 | Fort Hills Energy L.P. | Heat recovery for bitumen froth treatment plant integration with sealed closed-loop cooling circuit |
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| US10041005B2 (en) | 2011-03-04 | 2018-08-07 | Fort Hills Energy L.P. | Process and system for solvent addition to bitumen froth |
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| US9546323B2 (en) | 2011-01-27 | 2017-01-17 | Fort Hills Energy L.P. | Process for integration of paraffinic froth treatment hub and a bitumen ore mining and extraction facility |
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| US9207019B2 (en) | 2011-04-15 | 2015-12-08 | Fort Hills Energy L.P. | Heat recovery for bitumen froth treatment plant integration with sealed closed-loop cooling circuit |
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| RU2680407C2 (en) * | 2014-03-27 | 2019-02-21 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Method of extracting bitumen from oil sands with propylene oxide capped glycol ether |
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