WO2002072734A2 - Viscosity reduction of oils by sonic treatment - Google Patents
Viscosity reduction of oils by sonic treatment Download PDFInfo
- Publication number
- WO2002072734A2 WO2002072734A2 PCT/US2002/002002 US0202002W WO02072734A2 WO 2002072734 A2 WO2002072734 A2 WO 2002072734A2 US 0202002 W US0202002 W US 0202002W WO 02072734 A2 WO02072734 A2 WO 02072734A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- crude oil
- residuum
- viscosity
- acids
- Prior art date
Links
Classifications
-
- 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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
-
- 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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
- C10G17/04—Liquid-liquid treatment forming two immiscible phases
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
Definitions
- the present invention relates to a method for reducing the viscosity of crude oils and crude oil residuum by treatment of crude oil or crude oil residuum with sound waves.
- the product from the sonic treatment process affords oil with a substantially lower viscosity than the starting oil.
- Heavy oils are generally referred to those oils with high viscosity or API gravity less than about 23.
- the origin of high viscosity has been attributed to high asphaltene and naphthenic acid content of the oils.
- Viscosity reduction of heavy oils is important in production, transportation and refining operations of crude oil. Transporters and refiners of heavy crude oil have developed different techniques to reduce the viscosity of heavy crude oils to improve its pumpability. Commonly practiced methods include diluting the crude oil with gas condensate and emulsification with caustic and water. Thermally treating crude oil to reduce its viscosity is also well known in the art. Thermal techniques for visbreaking and hydro-visbreaking (visbreaking with hydrogen addition) are practiced commercially.
- sonication the process of treatment of a fluid with sound waves is termed sonication or sonic treatment.
- the main drawback of sonic treatment for viscosity reduction of heavy oils is that the effect is reversible.
- the viscosity of the sonic treated oil recovers back to the original viscosity of the oil and in some crude oils viscosity of the product after sonication is higher than the starting oil.
- An embodiment of the invention is directed to a method for decreasing the viscosity of crude oils or crude oil residuum comprising the steps of:
- organic acid, mineral acid or mixtures thereof - sonicating said acid treated crude oil at a temperature and for a time sufficient to decrease the viscosity of said crude oil or residuum.
- Another embodiment of the invention is directed to a crude oil or crude residuum having decreased viscosity prepared by
- Figure 1 is a plot of viscosity versus shear rate plots for the untreated and sonic treated Kome crude oils at 25°C.
- the X axis is shear rate (sec _1 ) and the Y axis is viscosity (cP).
- the line with diamonds is the untreated crude oil.
- the line with squares is crude oil treated with acid and sonicated.
- Figure 2 is a plot of the elastic modulus (G') along the Y axis as a function of sweep frequency in radians/second along the X axis for a fixed sinusoidal oscillation at 25°C.
- the line with triangles is the untreated crude oil.
- the line with squares is crude oil treated with acid and sonicated.
- Figure 3 is a plot of the viscous modulus (G") as a function o sweep frequency in radians/second along the X axis for a fixed sinusoidal oscillation at 25°C.
- the line with triangles is the untreated crude oil.
- the line with squares is crude oil treated with acid and sonicated.
- a method for viscosity reduction of crude oils and crude oil residuum An acid is added to the crude or residuum followed by sonic treatment at temperatures in the range of about 25 to about 50°C for about 30 seconds to 1 hour. Typically, the amount of acid added will be about 10 to about 10, 000 ppm, preferably about 20 to 100 ppm, based on the amount of crude oil or crude oil residuum.
- the types of acids, which can be utilized include mineral acids such as sulfuric acid, hydrochloric acid and perchloric acid.
- Organic acids like acetic, para-toluene sulfonic, alkyl toluene sulfonic acids, mono di- and trialkyl phosphoric acids, organic mono or di carboxylic acids, formic, C3 to Ci g organic carboxylic acids, succinic acid, and low molecular weight petroleum naphthenic acid are also effective in this invention.
- Crude oil high in naphthenic acid content (TAN) can be used as the source of petroleum naphthenic acids.
- mineral acids may be used to produce the same effect.
- the preferred mineral acid is sulfuric or hydrochloric acid.
- the preferred organic acid is acetic acid. Nitric acid should be avoided since it could potentially form an explosive mixture.
- crude oil residuum is defined as residual crude oil obtained from atmospheric or vacuum distillation.
- Sonication is the act of subjecting a fluid to sound (acoustic) waves.
- a typical commercial sonicator is in the shape of a tapered rod or horn. While a horn type sonicator is preferred other shapes of sonicators can also be used.
- the velocity of sound in liquids is typically about 1500 meters/sec. Ultrasound spans the frequency of about 15 kHz to 10 MHz with associated wavelengths of about 10 to 0.02 cm. Frequencies of about 15 kHz to about 20 MHz can be used.
- the output energy at a given frequency is expressed as sonication energy in units of watts/cm .
- the sonication is typically accomplished at energies in the range of 200 watts/cm to 800 watts/cm .
- the time of sonication can vary in the range of 0.5 minutes to 6 hours.
- Sonic treatment can be continuous or in pulse mode.
- the crude oil can be at temperatures in the range of 15 to 70°C and atmospheric pressure. It is preferred mix the crude oil during treatment at low shear rates. The preferred shear rates are between 50 to 200 rpm.
- the sonic treatment process can be conducted in batch or flow- through process modes.
- the flow - through process mode is preferred in pipeline transportation applications.
- the crude oil is pumped through a pipe to which are attached the sonicator horn tips in a radial manner.
- the rate of crude oil flow is optimized for maximum desirable exposure of the crude oil to the cavitation field.
- a recycle loop can be introduced for repeated sonic treatment.
- the batch process mode is preferred in upgrading applications. It is preferred to introduce several sonicator horn tips at various heights of the reactor vessel. A stirred reactor with low shear stirring is preferred.
- Figure 2 is a plot of the elastic modulus (G') and viscous modulus (G") as a function of sweep frequency for a fixed sinusoidal oscillation.
- the elastic modulus (G') and viscous modulus (G") were determined using a Haake viscometer in the oscillatory mode of operation. Data for untreated Kome crude oil and sonic treated crude oil are shown. A decrease in the absolute value of G' and G" are observed upon sonic treatment. Further, a change in the value of the intercept of the G' versus frequency and G" versus frequency plots are also observed.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002438319A CA2438319A1 (en) | 2001-03-09 | 2002-01-25 | Viscosity reduction of oils by sonic treatment |
EP02702066A EP1379610A2 (en) | 2001-03-09 | 2002-01-25 | Viscosity reduction of oils by sonic treatment |
AU2002235451A AU2002235451A1 (en) | 2001-03-09 | 2002-01-25 | Viscosity reduction of oils by sonic treatment |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/803,734 US6544411B2 (en) | 2001-03-09 | 2001-03-09 | Viscosity reduction of oils by sonic treatment |
US09/803,734 | 2001-03-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002072734A2 true WO2002072734A2 (en) | 2002-09-19 |
WO2002072734A3 WO2002072734A3 (en) | 2002-12-27 |
Family
ID=25187298
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/002002 WO2002072734A2 (en) | 2001-03-09 | 2002-01-25 | Viscosity reduction of oils by sonic treatment |
Country Status (5)
Country | Link |
---|---|
US (2) | US6544411B2 (en) |
EP (1) | EP1379610A2 (en) |
AU (1) | AU2002235451A1 (en) |
CA (1) | CA2438319A1 (en) |
WO (1) | WO2002072734A2 (en) |
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US5824214A (en) * | 1995-07-11 | 1998-10-20 | Mobil Oil Corporation | Method for hydrotreating and upgrading heavy crude oil during production |
-
2001
- 2001-03-09 US US09/803,734 patent/US6544411B2/en not_active Expired - Lifetime
-
2002
- 2002-01-25 WO PCT/US2002/002002 patent/WO2002072734A2/en not_active Application Discontinuation
- 2002-01-25 AU AU2002235451A patent/AU2002235451A1/en not_active Abandoned
- 2002-01-25 EP EP02702066A patent/EP1379610A2/en not_active Ceased
- 2002-01-25 CA CA002438319A patent/CA2438319A1/en not_active Abandoned
-
2003
- 2003-01-21 US US10/348,371 patent/US20030132139A1/en not_active Abandoned
Patent Citations (4)
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US3422894A (en) * | 1967-06-05 | 1969-01-21 | Clarence W Brandon | Method of treating and producing fluids from reservoirs of variable permeability |
US4966685A (en) * | 1988-09-23 | 1990-10-30 | Hall Jerry B | Process for extracting oil from tar sands |
US5096566A (en) * | 1988-10-04 | 1992-03-17 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Process for reducing the viscosity of heavy hydrocarbon oils |
US5110443A (en) * | 1989-02-14 | 1992-05-05 | Canadian Occidental Petroleum Ltd. | Converting heavy hydrocarbons into lighter hydrocarbons using ultrasonic reactor |
Also Published As
Publication number | Publication date |
---|---|
US20020125174A1 (en) | 2002-09-12 |
US20030132139A1 (en) | 2003-07-17 |
WO2002072734A3 (en) | 2002-12-27 |
CA2438319A1 (en) | 2002-09-19 |
EP1379610A2 (en) | 2004-01-14 |
AU2002235451A1 (en) | 2002-09-24 |
US6544411B2 (en) | 2003-04-08 |
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