WO2008063762A2 - Separating compositions and methods of use - Google Patents
Separating compositions and methods of use Download PDFInfo
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- WO2008063762A2 WO2008063762A2 PCT/US2007/080563 US2007080563W WO2008063762A2 WO 2008063762 A2 WO2008063762 A2 WO 2008063762A2 US 2007080563 W US2007080563 W US 2007080563W WO 2008063762 A2 WO2008063762 A2 WO 2008063762A2
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- Prior art keywords
- composition
- weight
- separating
- bitumen
- separating composition
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Classifications
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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
- C10G1/047—Hot water or cold water extraction processes
Definitions
- Oil sands also known as “tar sands” and “bituminous sands,” are a mixture of bitumen (tar), sand, and water Bitumen is a heavy, viscous crude oil, having relatively high sulfur content.
- bitumen When pioperly separated from the oil sands, bitumen may be processed to synthetic crude oil suitable for use as a feedstock for the production of liquid motor fuels, heating oil, and petrochemicals.
- Bitumen is very difficult to separate from oil sands in an efficient and environmentally acceptable manner.
- Current efforts to separate bitumen from oil sands typically yield only about 85-92% of the available bitumen.
- current efforts to separate bitumen from oil sands include the creation of emulsions, or "froth,” during processing, requiring the use of environmentally harmful organic solvents such as naphtha to "crack" the emulsions and allow for further processing.
- bitumen that remains in the sand (and other particulate matter, such as clay) component of the oil sands contributes to the creation of a heavy sludge, often ieferred to as "tailings"
- Tailings which aie comprised of unrecoveied bitumen, sand (and other particulate matter), and water is to pump the tailings into huge tailings ponds, where the sand and other particulate matter slowly settle and stratify over the course of several years
- the present exemplary embodiments describe compositions and methods for separating bitumen from oil sands in an efficient and environmentally acceptable manner, and for lecovering residual bitumen from existing tailings ponds.
- a composition comprising a separating composition comprising a wetting agent in the amount of from about 0 001 % to about 2 5% by weight of the separating composition, a hydiotropic agent, and a dispersant having flocculating characteristics, wherein the separating composition has a pH of greater than 7 5
- a sepaiating composition comprising from about 0.001% to about 2 5% by weight of a wetting agent; from about 0.1% to about 4.0% by weight of a hydrotiopic agent; and from about 0 25% to about 4 5% by weight of a dispersant having flocculating characteristics.
- a method for separating bitumen from oil sands comprising contacting a separating composition comprising a wetting agent, a hydrotropic agent, and a dispersant having flocculating characteristics with oil sands comprising bitumen and sand; heating the separating composition and the oil sands; agitating the separating composition and the oil sands; and recovering the bitumen and sand as separate products.
- a method for separating bitumen from tailings comprising contacting a separating composition comprising a wetting agent, a hydrotropic agent, and a dispersant having flocculating characteristics with tailings comprising bitumen and sand; heating the separating composition and the tailings; agitating the separating composition and the tailings; and recovering the bitumen and sand as separate products.
- essentially free means an amount less than about 0.1%.
- a composition comprising a separating composition comprising a wetting agent in the amount of from about 0.001% to about 2.5% by weight of the separating composition, a hydrotropic agent, and a dispersant having flocculating characteristics, wherein the separating composition has a pH of greater than 7,5,
- Suitable wetting agents may include, for example, one or more of
- DYNOLTM 607 Surfactant Air Products and Chemicals, Inc.
- SURFYNOL® 420 Air Products and Chemicals, Inc.
- SURFYNOL ⁇ 440 Air Products and Chemicals, Inc.
- SURFYNOL® 465 Air Products and Chemicals, Inc.
- SURFYNOL® 485 Air Products and Chemicals, Inc.
- DYNOLTM 604 Surfactant Air Products and Chemicals, Inc.
- TOMADOL® 91-2.5 Tomah Products, Inc.
- TOMADOL® 91-6 Tomah Products, Inc.
- TOMADOL® 91-8 Tomah Products, Inc
- TOMADOL® 1-3 TOmah Products, Inc.
- TOMADOL® 1-5 Tomah Products, Inc.
- TOMADOL® 1-7 TOmah Products, Inc.
- TOMADOL® 1-73B TOmah Products, Inc.
- TOMADOL® 1-9 Tomah Products, Inc.
- the wetting agent may include one or more ethoxylated acetylenic alcohols, such as, for example, 2,5,8,1 l-tetramethyl-6-dodecyn-5,8-dioI ethoxylate.
- Suitable hydrotropic agents may include, for example, one or more of
- TRITON® H-66 (Dow Chemical Company), TRITON® H-55 (Dow Chemical Company), TRITON® QS-44 (Dow Chemical Company), TRITON® XQS-20 (Dow Chemical Company), TRITON® X-15 (Union Carbide Corporation), TRITON® X-35 (Union Carbide Corpoiation), TRITON® X-45 (Union Carbide Corporation), TRITON® X-114 (Union Carbide Corporation), TRITON® X-100 (Union Carbide Corporation), TRITON® X-165 (70%) active (Union Carbide Coiporation), TRITON® X- 305 (70%) active (Union Carbide Corporation), TRITON® X-405 (70%) active (Union Carbide Corporation), TRITON® BG Nonionic Surfactant (Union Caibide Corporation), TERGITOL® MinFoam IX (Dow Chemical Company), TERGITOL® L-61 (Dow Chemical Company), TERGITOL® L-
- the hydrotropic agent may be one or moie aromatic phosphate esters, such as, for example, an aromatic phosphate ester having the formula:
- Suitable dispersants having flocculating characteristics may include, for example, one or more of sodium acid pyrophosphate, tetrapotassium pyrophosphate, monosodium phosphate (H 6 NaO 6 P), monoamrnonium phosphate ((NHa)PO 4 ), sodium acid phosphate, trisodium phosphate, sodium tripolyphosphate, sodium trimetaphosphate, sodium laurel phosphate, sodium phosphate, pentapotassium triphosphate, potassium triphosphate, tetraborate potassium tripolyphosphate, potassium phosphate - monobasic, potassium phosphate - dibasic, monopotassium phosphate, and tripotassium phosphate, and mixtures thereof.
- the dispersant having flocculating characteristics may include one or more pyrophosphate salts, including, for example, one or more of sodium acid pyrophosphate and tetrapotassium pyrophosphate.
- the hydrotropic agent may be present in the amount of from about 0 1% to about 4.0% by weight of the separating composition.
- the dispersant having flocculating characteristics may be present in the amount of fiom about 0.25% to about 4 5% by weight of the separating composition.
- the separating composition may further comprise a strong base, such as, for example, hydroxides of alkali metals and alkaline earth metals, such as, for example, NaOH, KOH, Ba(OH) 2 , CsOH, SrOH, Ca(OH) 2 , LiOH, RbOH, NaH, LDA, and NaNH 2
- a "stiong base" is a chemical compound having a pH of greater than about 13 The stiong base may be piesent in the amount of fiom about 2% to about 9 5% by weight of the separating composition
- the separating composition may further comprise a heavy acid, such as, for example, phosphoric acid, nitric acid, sulfuric acid, hydronic acid, hydrobromic acid, perchloric acid, fluoromatic acid, magic acid (FSO 3 HSbF 5 ), carborane super acid [H(CHBi ]CIn)], triflic acid, ethanoic acid, and acetylsalicylic acid
- a heavy acid is an acid having a specific gravity greater than about 1.5.
- the heavy acid may be present in the amount of from about 1 7% to about 8 6% by weight of the separating composition
- the pH of the separating composition may be greater than 7 5
- the pH of the separating composition may also be from about 7 0 to about 8 5
- the pH of the separating composition may also be from about 7 6 to about 7 8
- the composition may be essentially free of organic solvent
- organic solvent refers to solvents that are organic compounds and contain carbon atoms such as, for example, naphtha,
- the composition may also comprise hydrocarbon containing materials, such as oil sands, tailings, and the like.
- hydrocarbon containing materials such as oil sands, tailings, and the like.
- the ratio of the separating composition to the hydrocarbon containing materials may be from about 2:3 to about 3:2-
- a separating composition comprising from about 0.001% to about 2.5% by weight of a wetting agent; from about 0.1% to about 4.0% by weight of a hydrotropic agent; and from about 0,25% to about 4.5% by weight of a dispersa ⁇ t having flocculating characteristics.
- the separating composition may have a pH of greater than 7.5; from about 7.0 to about 8.5; or from about 7.6 to about 7 8.
- the wetting agent may be, for example, 2,5,8,1 l-tetramethyl-6-dodecyn-5,8-diol ethoxylate.
- the hydrotropic agent may be, for example, MAPHOS® 66H aromatic phosphate ester.
- the dispersant having flocculating characteristics may be, for example, one or more of sodium acid pyrophosphate and tetiapotassium pyrophosphate.
- the separating composition may further comprise a strong base, which may be, for example, sodium hydroxide.
- the strong base may be present in the amount of from about 2% to about 9.5% by weight of the separating composition.
- the separating composition may further comprise a heavy acid, which may be, for example, phosphoric acid. The heavy acid may be present in the amount of from about 1 ,7% to about 8.6% by weight of the separating composition.
- the separating composition may also be essentially free of organic solvent.
- a separating composition for separating bitumen from oil sands or tailings comprising from about 0.001% to about 2.5% by weight of 2,5,8,1 l-tetramethyl-6-dodecyn-5,8-diol ethoxylate; from about 0 1 % to about 4 0% by weight of an aromatic phosphate estei having the formula:
- the separating composition may have a pH of from about 7.0 to about 8-5.
- the separating composition may also be essentially free of organic solvent,
- a method for separating bitumen from oil sands comprising contacting a separating composition comprising a wetting agent, a hydrotropic agent, and a dispersant having flocculating characteristics with oil sands comprising bitumen and sand; heating the separating composition and the oil sands; agitating the separating composition and the oil sands; and recovering the bitumen and sand as separate products.
- the pH of the separating composition may be greater than 7 5; from about 7.0 to about 8.5; or from about 7.6 to about 7.8.
- the separating composition used in the exemplary method may be comprised of from about 0.001% to about 2.5% by weight of a wetting agent; from about 0.1% to about 4,0% by weight of a hydrotropic agent; and from about 0 25% to about 4.5% by weight of a dispersant having flocculating characteristics.
- the separating composition used in the exemplary method may be comprised of from about 0.001% to about 2.5% by weight of 2,5,8,1 1- tetramethyI-6-dodecyn-5,8-diol ethoxylate; from about 0.1% to about 4 0% by weight of an aromatic phosphate ester having the formula:
- the separating composition and the oil sands may be heated to greater than 25 0 C; from about 32°C to about 72°C; or from about 54 0 C to about 6O 0 C Any source of heat within the ambit of those skilled in the art may be used, Similarly, any device capable of providing sufficient agitation may be used to agitate the separating composition and the oil sands, including, for example, a high shear mixer, high speed attritor, high speed dispersers, fluidized beds, and the like, or any other device capable of providing sufficient agitation within the ambit of those skilled in the art. [0032] In one embodiment, the ratio of the separating composition to the oil sands may be from about 2:3 to about 3:2. In another embodiment, the ratio of the separating composition to the oil sands may be about 1 :1.
- the recovered bitumen may be essentially emulsion-free.
- the exemplary method may be performed without the addition of organic solvent,
- the exemplary method further comprises contacting the separated, recovered bitumen with a second or subsequent aliquot of fresh separating composition; heating the fresh separating composition and the bitumen; agitating the fresh separating composition and the recovered bitumen; and recovering the resulting bitumen, Such a "rinse" cycle may be repeated until the bitumen is essentially free of any sand or other particulate matter.
- the separating composition may be recyclable
- the exemplary method further comprises recovering the separating composition; contacting the recovered separating composition with a second or subsequent aliquot of oil sands comprising bitumen and sand; heating the recovered separating composition and the second or subsequent aliquot of oil sands; agitating the recovered separating composition and the second or subsequent aliquot of oil sands; and recovering the bitumen and sand as separate products.
- a method for processing existing tailings, both to salvage remaining bitumen and to allow for redeposit of the essentially bitumen- free sand.
- the method may comprise contacting a separating composition comprising a wetting agent, a hydrotropic agent, and a dispersant having flocculating characteristics with tailings comprising bitumen and sand; heating the separating composition and the tailings; agitating the sepaiating composition and the tailings; and recovering the bitumen and sand as separate products
- the pH of the separating composition may be greater than 7 5; from about 7 O to about 8.5; or from about 7 6 to about 7 8,
- the separating composition used in the exemplary method for processing existing tailings may be comprised of from about 0,001% to about 2 5% by weight of a wetting agent; from about 0 1% to about 4.0% by weight of a hydrotiopic agent; and from about 0.25% to about 4 5% by weight of a dispersant having flocculating chaiacteiistics.
- the separating composition used in the exemplary method for processing existing tailings may be comprised of fiom about 0,001% to about 2 5% by weight of 2,5,8,1 l-tetramethy ⁇ -6-dodecyn-5,8-diol ethoxylate; from about 0 1% to about 4 0% by weight of an aromatic phosphate ester having the formula:
- the separating composition and the tailings may be heated to greater than 25°C; from about 32°C to about 72 0 C; or from about 54 0 C to about 6O 0 C.
- Any source of heat within the ambit of those skilled in the art may be used Simiiaily, any device capable of providing sufficient agitation may be used to agitate the sepaiating composition and the tailings, including, for example, a high shear mixer, high speed attritor, high speed dispersers, fluidized beds, and the like, or any other device capable of providing sufficient agitation within the ambit of those skilled in the art,
- the ratio of the separating composition to the tailings may be from about 2:3 to about 3:2. In another embodiment, ratio of the sepaiating composition to the tailings may be about 1 :1.
- the recovered bitumen may be essentially emulsion-ftee.
- the exemplary method may be performed without the addition of organic solvent,
- the exemplary method further comprises contacting the separated, recovered bitumen with a second or subsequent aliquot of fiesh sepaiating composition; heating the fresh separating composition and the bitumen; agitating the fresh separating composition and the recovered bitumen; and recovering the resulting bitumen.
- a "rinse" cycle may be repeated until the bitumen is essentially free of any sand or other particulate matter
- the separating composition may be recyclable.
- the exemplary method for processing existing tailings would further comprise recovering the separating composition; contacting the recovered separating composition with a second ot subsequent aliquot of tailings comprising bitumen and sand; heating the recovered separating composition and the second or subsequent aliquot of tailings; agitating the recovered separating composition and the second or subsequent aliquot of tailings; and recovering the bitumen and sand as separate products.
- the broken down oil sands are added to a mixing tank and contacted with the separating composition as described herein
- the separated bitumen is augered and pumped to storage, and then further refined to produce synthetic crude oil suitable for use as a feedstock for the production of liquid motor fuels, heating oil, and petrochemicals
- the beaker containing the separating composition was charged with 300 g of Athabasca oil sands.
- the resultant slurry was heated to between 54°C and 60 0 C
- a high shear lab mixer was lowered into the beaker and the slurry was stirred at 3500 ipm for 3 minutes.
- the mixer was removed from the beaker Over the course of the next 5-30 minutes, complete phase separation occurred within the beaker. Four separate, distinct phases were observed.
- the top, first layer contained bitumen.
- the second layer contained the separating composition.
- the third layer contained clay.
- the bottom, fourth layer contained sand and other particulate matter.
- bitumen was lemoved from the beaker.
- the bitumen was determined to be greater than 99% free of contaminants, including sand and clay.
- Approximately 45 g of bitumen was recovered, representing greater than 99% of all of the available bitumen in the sample of oil sands
- the sand was also recovered and determined to be greater than 99% free of bitumen.
- the sand was placed in a drying oven at 72°C for 8 hours and, after cooling to room tempetature, was able to be sifted through a 20-25 rnesh sieve.
- the original separating composition was removed from the first IL beaker after the bitumen was removed. 275 g of this separating composition was added to a 1 L beaker. The beaker was charged with 275 g of a new aliquot of Athabasca oil sands The slurry was heated to 72°C and was stirred at 3000 rpm for 3 minutes
- bitumen was determined to be greater than 99% free of contaminants, including sand and clay, Approximately 41 g of bitumen was recovered, representing greater than 99% of the available bitumen in the sample of oil sands [0055] The sand was also recovered and determined to be greater than 99% free of bitumen. The sand was placed in a drying oven at 72°C for 8 hours and, after cooling to room temperature, was able to be sifted through a 20-25 mesh sieve.
- Example 2 200 g of the separating composition was prepared as in Example 1. The separating composition was placed in a 1 L beaker. The beaker was charged with 300 g of tailings from an Athabasca tailings pond. The slurry was heated to 72 0 C and was stirred at 3000 ipm for 2 minutes. The mixer was removed from the beaker. Over the course of the next 5-30 minutes, complete phase separation occurred within the beaker. Four separate, distinct phases were observed. The top, first layer contained bitumen. The second layer contained the separating composition. The third layer contained clay. The bottom, fourth layer contained sand and other particulate matter,
- bitumen was determined to be greater than 99% free of contaminants, including sand and clay. Approximately 12 g of bitumen was recovered, representing greater than 99% of the available bitumen in the sample of tailings [0060]
- the sand was a ⁇ so recovered and determined to be greater than 99% free of bitumen. The sand was placed in a drying oven at 72°C for 8 hours and, after cooling to room temperature, was able to be sifted through a 20-25 mesh sieve.
- bitumen was determined to be greater than 99% free of contaminants, including sand and clay. Approximately 40 g of bitumen was recovered, iepresenting greater than 99% of the available bitumen in the sample of oil sands. [0065] The sand was also recovered and deteimined to be greater than 99% free of bitumen The sand was placed in a drying oven at 72 0 C for 8 hours and, after cooling to room tempeiature, was able to be sifted through a 20-25 mesh sieve.
- the original separating composition was removed from the first IL beaker after the bitumen was removed. 275 g of this separating composition was added to a 1 L beaker. The beaker was chaiged with 275 g of a new aliquot of Utah oil sands. The slurry was heated to 72 0 C and was stirred at 3000 rpm for 3 minutes. The mixer was removed fiom the beaker Over the course of the next 5-30 minutes, complete phase separation occurred within the beaker. Four separate, distinct phases were observed. The top, first layer contained bitumen. The second layer contained the separating composition The third layer contained clay. The bottom, fourth layer contained sand and other particulate matter
- bitumen was determined to be greater than 99% free of contaminants, including sand and clay. Approximately 44 g of bitumen was recovered, iepiesenting greater than 99% of the available bitumen in the sample of oil sands. [0069] The sand was also recovered and determined to be greater than 99% fiee of bitumen- The sand was placed in a drying oven at 72 0 C for 8 hours and, after cooling to room temperature, was able to be sifted through a 20-25 mesh sieve.
- Example 2 300 g of the separating composition was prepared as in Example 1. The separating composition was placed in a 1 L beaker. The beaker was charged with 300 g of tailings from a Utah tailings pond. The slurry was heated to 72°C and was stirred at 3000 rpm fot 3 minutes. The mixer was removed from the beaker. Over the course of the next 5-30 minutes, complete phase separation occurred within the beakei. Four separate, distinct phases were observed. The top, first layer contained bitumen. The second layer contained the separating composition The third layer contained clay. The bottom, fourth layer contained sand and other particulate matter
- bitumen was determined to be greater than 99% free of contaminants, including sand and clay. Approximately 4 g of bitumen was recovered, representing greater than 99% of the available bitumen in the sample of tailings. [0074J The sand was also recovered and determined to be greater than 99% free of bitumen. The sand was placed in a drying oven at 72°C for 8 hours and, after cooling to room temperature, was able to be sifted through a 20-25 mesh sieve.
Abstract
Description
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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DK07871125.6T DK2069467T3 (en) | 2006-10-06 | 2007-10-05 | Various compositions and methods of use |
CA2665579A CA2665579C (en) | 2006-10-06 | 2007-10-05 | Separating compositions and methods of use |
PL07871125T PL2069467T3 (en) | 2006-10-06 | 2007-10-05 | Separating compositions and methods of use |
UAA200904469A UA102990C2 (en) | 2006-10-06 | 2007-10-05 | Spacer compositions and methods for using thereof |
CN200780037487.9A CN101589135B (en) | 2006-10-06 | 2007-10-05 | Separating compositions and methods of use |
EP07871125.6A EP2069467B1 (en) | 2006-10-06 | 2007-10-05 | Separating compositions and methods of use |
ES07871125.6T ES2517597T3 (en) | 2006-10-06 | 2007-10-05 | Separation compositions and methods of use |
EA200970356A EA015626B1 (en) | 2006-10-06 | 2007-10-05 | Separating compositions and methods of use |
NO20091322A NO337631B1 (en) | 2006-10-06 | 2009-04-01 | Separation of compositions and methods of use |
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US82850106P | 2006-10-06 | 2006-10-06 | |
US60/828,501 | 2006-10-06 |
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WO2008063762A2 true WO2008063762A2 (en) | 2008-05-29 |
WO2008063762A3 WO2008063762A3 (en) | 2008-11-06 |
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US (4) | US7749379B2 (en) |
EP (1) | EP2069467B1 (en) |
CN (1) | CN101589135B (en) |
CA (1) | CA2665579C (en) |
DK (1) | DK2069467T3 (en) |
EA (1) | EA015626B1 (en) |
ES (1) | ES2517597T3 (en) |
NO (1) | NO337631B1 (en) |
PL (1) | PL2069467T3 (en) |
UA (1) | UA102990C2 (en) |
WO (1) | WO2008063762A2 (en) |
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DK2069467T3 (en) | 2014-10-20 |
EA015626B1 (en) | 2011-10-31 |
WO2008063762A3 (en) | 2008-11-06 |
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EP2069467A2 (en) | 2009-06-17 |
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US8147680B2 (en) | 2012-04-03 |
EA200970356A1 (en) | 2009-10-30 |
US8414764B2 (en) | 2013-04-09 |
NO20091322L (en) | 2009-04-06 |
CA2665579A1 (en) | 2008-05-29 |
US7749379B2 (en) | 2010-07-06 |
EP2069467A4 (en) | 2009-12-30 |
CA2665579C (en) | 2015-06-30 |
PL2069467T3 (en) | 2015-02-27 |
CN101589135A (en) | 2009-11-25 |
NO337631B1 (en) | 2016-05-18 |
UA102990C2 (en) | 2013-09-10 |
US7862709B2 (en) | 2011-01-04 |
CN101589135B (en) | 2014-04-02 |
US20120193567A1 (en) | 2012-08-02 |
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