WO2001081502A2 - Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) - Google Patents
Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) Download PDFInfo
- Publication number
- WO2001081502A2 WO2001081502A2 PCT/US2001/011152 US0111152W WO0181502A2 WO 2001081502 A2 WO2001081502 A2 WO 2001081502A2 US 0111152 W US0111152 W US 0111152W WO 0181502 A2 WO0181502 A2 WO 0181502A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- oil
- emulsion
- residuum
- viscosity
- Prior art date
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
Definitions
- the present invention relates to a method for reducing the viscosity of crude oils and crude oil residuum by mineral acid enhanced thermal treatment of crude oil or crude oil residuum
- the product from the combination of acid and thermal treatment process affords oil with a substantially lower viscosity than the starting oil or product oil derived from thermal treatment without acid addition
- the instant process provides an improved visbreaking method and can be utilized as an upgrading process in pipeline transportation, or to reduce the viscosity of a water-in-oil emulsion used in enhanced oil recovery (EOR) operations.
- EOR enhanced oil recovery
- viscosity reduction of heavy crude oils can play a role in new upstream technology related to recovering hydrocarbons from subterranean formations using enhanced oil recovery methods
- Solids-stabilized water-in-oil emulsions have a viscosity that is greater than that of the crude oil to be recovered, and as such, can serve as an effective drive fluid to displace the crude oil to be recovered, such as described in U.S. Patents Nos. 5,927,404, and 5,855,243.
- the solids-stabilized water-in-oil emulsions can also be used as a barrier fluid, to fill in subterranean zones of high rock permeability, or "thief zones.”
- a barrier fluid such as the solids-stabilized water-in-oil emulsion, can be used to fill these "thief zones" to divert pressure energy into displacing oil from adjacent lower-permeability zones.
- the solids-stabilized water-in-oil emulsion is too viscous to be injected or is too viscous to otherwise be efficiently used as a drive or barrier fluid. Therefore, there is a need to be able to reduce the viscosity of the emulsion to obtain the optimum rheological properties for the type of enhanced oil recovery method used and for the particular type and viscosity of crude oil to be recovered
- Viscosity reduction of heavy oils is also important for downstream operations. 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 are practiced commercially. The prior art in the area of thermal treatment or additive enhanced visbreaking of hydrocarbons teach methods for improving the quality, or reducing the viscosity, of crude oils, crude oil distillates or residuum by several different methods.
- this invention addresses Provided is a method of reducing the viscosity of oil or a water-in-oil emulsion by an acid enhanced thermal treatment process
- the product from the acid enhanced thermal treatment process has a substantially lower viscosity than the untreated oil or the untreated water-in-oil emulsion, respectively
- crude oil residuum is defined as residual crude oil obtained from atmospheric or vacuum distillation
- the process comprises, consists and consists essentially of the steps herein described
- Another embodiment of the process is directed to a thermal visbreaking method for reducing the viscosity of crude oils and crude oil residuum by thermally treating the oils and residuum wherein the improvement comprises contacting the crude oil or residuum with an effective amount of an acid consisting essentially of or consisting of acid and heating said crude oil or residuum and said acid at a temperature and for a time and at a pressure sufficient to decrease the viscosity of said crude oil or residuum
- the invention is also directed to a crude oil or crude residuum having decreased viscosity prepared by
- a solids-stabilized emulsion having a reduced viscosity may also be made using this method by adding solid particles to the oil after the step of heating the acid treated oil (step b), but before emulsification by adding water and mixing (step c)
- Figures 1A and IB are plots of viscosity versus shear rate for the untreated and thermally treated T and K crude oils at 25 C
- the X axis is Shear rate (sec " ') and the Y axis is viscosity (cP)
- the line with diamonds is the untreated crude oil
- the line with squares is heat treatment alone
- the line with triangles is the acidic heat treatment combination described herein
- Figures 2A and 2B depict viscosity versus temperature plots for the untreated and thermally treated T and K crude oils
- the X axis is temperature 1000/T(1/K) and the Y axis is viscosity (cp ) expressed as ln(v ⁇ s) @ 0 204 sec '
- the line with diamonds is the untreated crude oil.
- the line with squares is heat treatment alone.
- the line with triangles is the acidic heat treatment combination described herein.
- Figure 3 depicts viscosity versus shear rate plots for a heavy vacuum resid at 60 ° C.
- the X axis is Shear rate (sec " ') and the Y axis is viscosity (cP).
- the line with diamonds is heat treatment alone.
- the line with squares is the acidic heat treatment combination described herein.
- Figure 4 depicts viscosity versus temperature plots for a heavy vacuum resid.
- the X axis is temperature 1000/T(1/K) and the Y axis is viscosity (cP) expressed as ln(vis) @ 9.6 sec "1 .
- the line with diamonds is heat treatment alone.
- the line with squares is the acidic heat treatment combination described herein.
- an improved method for viscosity reduction of crude oils and crude oil residuum An acid is added to the crude or residuum followed by thermal treatment at temperatures of about 250 to about 450°C at about 30 to about 300 psi for about 0.25 to 6 hours in an inert environment.
- the amount of acid added will be about 10 to about 1000 ppm, preferably about 20 to 100 ppm, based on the amount of crude oil or crude oil residuum.
- the acid utilized in the contacting step will not contain other components not inherent in the acid itself or not present in the acid as impurities.
- the acid will consist essentially of or consist of acid.
- one skilled in the art can choose process conditions to retain or degrade naphthenic acids in addition to reducing the viscosity of the crude.
- a purge gas is used as disclosed in US 5,820,750. Any inert purge gas (a gas non-reactive in the process) may be used. For example nitrogen, argon, etc.
- the instant invention allows for acid addition to crude oils which are high in naphthenic acids to achieve viscosity reduction. Such an addition of acid to acidic crude oil is counter intuitive since refiners are continuously looking for methods which reduce the amount of acid in crude oils and residuum.
- the types of acids which can be utilized in the instant invention 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 C16 organic carboxylic acids, succinic acid, & low molecular weight petroleum naphthenic acid are also effective in this invention.
- Mixtures of mineral acids, mixtures of organic acids or combinations of mineral and organic 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.
- Reaction time, temperature and pressure collectively define process severity.
- process severity One ordinarily skilled in the art can choose process severity within the preferred ranges to produce the desired level of viscosity decrease.
- the previously described method for reducing the viscosity of oil can be used to make a water-in-oil emulsion or a solids-stabilized water-in-oil emulsion with a reduced viscosity.
- the viscosity of the oil is reduced by the method previously described, prior to using the oil to make the emulsion. Though any decrease in the viscosity of the oil can be beneficial, preferably the viscosity will be decreased by at least about 2 to 30 times that of the viscosity of the oil prior to the treatment described herein
- water or brine is added to the acid enhanced thermally treated oil
- the water or brine is added in small aliquots or continuously with mixing, preferably at a rate of about 500 to about 12000 rpm, for a time sufficient to disperse the water as small droplets in the continuous oil phase, thereby forming the emulsion
- the amount of water in the emulsion water can range from 40 to 80 wt %, preferably 50 to 65 wt %, and more preferably 60 wt %
- formation water is used to make the emulsion, however, fresh water can also be used and the ion concentration adjusted as needed to help stabilize the emulsion under formation conditions
- the resulting emulsion will have a substantially lower viscosity than an emulsion made with an untreated oil, or an oil subjected only to thermal treatment
- a solids-stabilized water-in-oil emulsion with a reduced viscosity can also be made using the acid enhanced thermal treatment process described above
- the solids particles may be added to the oil before or after the acid addition and thermal treatment step, but should be added before adding water and emulsifying However note that if the solid particles are present during the thermal treatment step, the solid particles have the potential for fouling the process equipment, and this issue needs to be addressed to practice this embodiment Accordingly, it is preferred to add the solids particles to the oil after the acid and thermal treatment steps
- the solid particles preferably should be hydrophobic in nature
- a hydrophobic silica sold under the trade name Aerosil® R 972 (product of DeGussa Corp ) has been found to be an effective solid particulate material for a number of different oils
- Other hydrophobic (or oleophilic) solids can also be used, for example, divided and oil-wetted bentonite clays, kaolinite clays, organophihc clays or carbonaceous asphaltemc solids
- the individual solid particle size should be sufficiently small to provide adequate surface area coverage of the internal droplet phase.
- the average particle size should be smaller than the average diameter of pore throats in the porous subterranean formation.
- the solid particles may be spherical in shape, or non-spherical in shape. If spherical in shape, the solid particles should preferably have an average size of about five microns or less in diameter, more preferably about two microns or less, even more preferably about one micron or less and most preferably, 100 nanometers or less.
- the solid particles are non-spherical in shape, they should preferably have an average size of about 200 square micron total surface area, more preferably about twenty square microns or less, even more preferably about ten square microns or less and most preferably, one square micron or less.
- the solid particles must also remain undissolved in both the oil and water phase of the emulsion under the formation conditions.
- the preferred treat rate of solids is 0.05 to .25 wt% based upon the weight of oil.
- the resulting water-in-oil emulsion or solids-stabilized water-in-oil emulsion's pH can be adjusted by adding a calculated amount of weak aqueous base to the emulsion for a time sufficient to raise the pH to the desired level. If the pH of the emulsion is too low (less than 4), it may be desirable to adjust the emulsion's pH to the 5 to 7 range. Adjusting the pH is optional as in some cases it is desirable to inject an acidic emulsion and allow the reservoir formation to buffer the emulsion to the reservoir alkalinity.
- Ammonium hydroxide is the preferred base for pH adjustment. Stronger bases like sodium hydroxide, potassium hydroxide and calcium oxide have a negative effect on emulsion stability. One possible explanation for this effect is that strong bases tend to invert the emulsion, i.e. convert the water-in-oil emulsion to an oil-in- water emulsion. Such an inversion is undesirable for the purposes of this invention.
- the water-in-oil emulsion or the solids-stabilized water-in-oil emulsion can be used in a wide range of enhanced oil recovery applications.
- One typical application is using such an emulsion for displacing oil from a subterranean formation, i.e. using the emulsion as a drive fluid.
- the emulsion is prepared, as described above, and then injected into the subterranean formation, typically, but not necessarily through an injection well.
- the emulsion, which is injected under pressure, is used to displace the oil in the formation towards a well, typically a production well, for recovery
- Another application is for using the emulsion as a barrier fluid to divert the flow of hydrocarbons in a subterranean formation
- the emulsion is prepared and then injected into the subterranean formation
- the emulsion is used fill "thief zones" or to serve as a horizontal barrier to prevent coning of water or gas
- "thief zones” and coning events will reduce the efficiency of enhanced oil recovery operations.
- Tables 1 & 2 summarize the effect of thermal treatment and sulfuric acid catalyzed thermal treatment on key properties of T and K crude oils respectively. As can be seen from the data no significant changes are observed in the total acid number, distribution of naphthenic acids, toluene equivalence and n-heptane insolubles between the thermally treated and sulfuric acid catalyzed thermally treated samples. These data indicate that the chemistry of the crude oil is not significantly altered as a result of sulfuric acid addition prior to thermal treatment.
- Viscosity as a function of shear rate plots for the untreated and thermally treated T and K crude oils are shown on Figures 1 A and IB. Data are plotted for the neat crude, thermally treated crude and thermally treated crude with prior sulfuric acid addition. A reduction in viscosity as a result of thermal treatment is expected. However, it is observed that sulfuric acid addition prior to thermal treatment results in further reduction in viscosity.
- Viscosity at 0.204 sec-1 as a function temperature plots for the untreated and thermally treated T and K crude oils are shown on Figures 2 A and 2B. Data are plotted for the neat crude, thermally treated crude and thermally treated crude with prior sulfuric acid addition. From the slope of each plot the corresponding energy of activation was calculated. A decrease in energy of activation is observed for samples subjected to sulfuric acid addition and thermal treatment relative to thermal treatment without prior acid addition. This suggests that sulfuric acid catalyzed thermal treatment has altered fundamental aggregation properties of the chemical species responsible for high viscosities of respective heavy crude oils.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0110282-6A BR0110282A (en) | 2000-04-25 | 2001-04-05 | Method for decreasing the viscosity of crude and waste oils, thermal visc reduction method for reducing the viscosity of crude and waste oils, crude oil or crude oil waste, methods for preparing a water-in-oil emulsion, and for recovering hydrocarbons from a underground formation and water-in-oil emulsion. |
AU2001251360A AU2001251360A1 (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) |
EA200201135A EA004090B1 (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) |
GB0223091A GB2381795A (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils ecb-0002 |
CA002405692A CA2405692C (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) |
MXPA02010423A MXPA02010423A (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002). |
DE10196133T DE10196133T1 (en) | 2000-04-25 | 2001-04-05 | Mineral acid improved thermal treatment to reduce viscosity of oils (ECB-0002) |
NO20025087A NO20025087L (en) | 2000-04-25 | 2002-10-23 | Mineral acid enhanced heat treatment for viscosity reduction for oils |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US19956500P | 2000-04-25 | 2000-04-25 | |
US60/199,565 | 2000-04-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001081502A2 true WO2001081502A2 (en) | 2001-11-01 |
WO2001081502A3 WO2001081502A3 (en) | 2002-03-28 |
Family
ID=22738081
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/011152 WO2001081502A2 (en) | 2000-04-25 | 2001-04-05 | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ecb-0002) |
Country Status (14)
Country | Link |
---|---|
US (2) | US6800193B2 (en) |
CN (1) | CN1426506A (en) |
AR (1) | AR028916A1 (en) |
AU (1) | AU2001251360A1 (en) |
BR (1) | BR0110282A (en) |
CA (1) | CA2405692C (en) |
DE (1) | DE10196133T1 (en) |
EA (1) | EA004090B1 (en) |
EG (1) | EG22907A (en) |
GB (1) | GB2381795A (en) |
MX (1) | MXPA02010423A (en) |
NO (1) | NO20025087L (en) |
OA (1) | OA12249A (en) |
WO (1) | WO2001081502A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011161116A1 (en) * | 2010-06-22 | 2011-12-29 | Ntnu Technology Transfer As | Synthetic crude oil |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7186673B2 (en) * | 2000-04-25 | 2007-03-06 | Exxonmobil Upstream Research Company | Stability enhanced water-in-oil emulsion and method for using same |
US6800193B2 (en) * | 2000-04-25 | 2004-10-05 | Exxonmobil Upstream Research Company | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ECB-0002) |
US6988550B2 (en) * | 2001-12-17 | 2006-01-24 | Exxonmobil Upstream Research Company | Solids-stabilized oil-in-water emulsion and a method for preparing same |
US20050279673A1 (en) * | 2003-05-16 | 2005-12-22 | Eppig Christopher P | Delayed coking process for producing free-flowing coke using an overbased metal detergent additive |
US7645375B2 (en) * | 2003-05-16 | 2010-01-12 | Exxonmobil Research And Engineering Company | Delayed coking process for producing free-flowing coke using low molecular weight aromatic additives |
EP2428549A1 (en) * | 2003-05-16 | 2012-03-14 | ExxonMobil Research and Engineering Company | Delayed coking process for producing free-flowing shot coke |
US7658838B2 (en) * | 2003-05-16 | 2010-02-09 | Exxonmobil Research And Engineering Company | Delayed coking process for producing free-flowing coke using polymeric additives |
US20100098602A1 (en) | 2003-12-19 | 2010-04-22 | Opinder Kishan Bhan | Systems, methods, and catalysts for producing a crude product |
US7780844B2 (en) * | 2003-12-19 | 2010-08-24 | Shell Oil Company | Systems, methods, and catalysts for producing a crude product |
US7745369B2 (en) | 2003-12-19 | 2010-06-29 | Shell Oil Company | Method and catalyst for producing a crude product with minimal hydrogen uptake |
US7117722B2 (en) * | 2003-12-23 | 2006-10-10 | Exxonmobil Research And Engineering Company | Method for determining viscosity of water-in-oil emulsions |
MXPA06011746A (en) * | 2004-05-14 | 2007-01-16 | Exxonmobil Res & Eng Co | Delayed coking process for the production of substantially fre-flowing coke from a deeper cut of vacuum resid. |
WO2005113707A1 (en) | 2004-05-14 | 2005-12-01 | Exxonmobil Research And Engineering Company | Viscoelastic upgrading of heavy oil by altering its elastic modulus |
EP1751257A2 (en) * | 2004-05-14 | 2007-02-14 | Exxonmobil Research And Engineering Company | Inhibitor enhanced thermal upgrading of heavy oils |
BRPI0510522A (en) * | 2004-05-14 | 2007-10-30 | Exxonmobil Res & Eng Co | process to produce and remove coke and coke |
AU2005245863A1 (en) * | 2004-05-14 | 2005-12-01 | Exxonmobil Research And Engineering Company | Blending of resid feedstocks to produce a coke that is easier to remove from a coker drum |
BRPI0609416A2 (en) | 2005-04-11 | 2011-10-11 | Shell Int Research | method to produce a gross product |
CA2632526C (en) | 2005-12-22 | 2014-03-11 | Exxonmobil Upstream Research Company | Method of oil recovery using a foamy oil-external emulsion |
WO2008024147A1 (en) | 2006-08-23 | 2008-02-28 | Exxonmobil Upstream Research Company | Composition and method for using waxy oil-external emulsions to modify reservoir permeability profiles |
US7871510B2 (en) * | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
US7794587B2 (en) * | 2008-01-22 | 2010-09-14 | Exxonmobil Research And Engineering Company | Method to alter coke morphology using metal salts of aromatic sulfonic acids and/or polysulfonic acids |
US9150472B2 (en) | 2011-12-21 | 2015-10-06 | Shell Oil Company | Method and composition for inhibiting asphaltene deposition in a hydrocarbon mixture |
WO2013096215A1 (en) * | 2011-12-21 | 2013-06-27 | Shell Oil Company | Method and composition for reducing viscosity of a hydrocarbon mixture |
WO2013096216A1 (en) | 2011-12-21 | 2013-06-27 | Shell Oil Company | Method and composition for inhibiting foam in a hydrocarbon mixture |
BR112014015256A8 (en) | 2011-12-21 | 2017-07-04 | Shell Int Research | method and composition for inhibiting wax formation or deposition, and, inhibited wax mixture |
US20140166538A1 (en) * | 2012-12-17 | 2014-06-19 | Conocophillips Company | Bitumen based indirect steam boiler |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3796266A (en) * | 1972-12-13 | 1974-03-12 | Texaco Inc | Surfactant oil recovery process |
US4085799A (en) * | 1976-11-18 | 1978-04-25 | Texaco Inc. | Oil recovery process by in situ emulsification |
US4096914A (en) * | 1976-12-06 | 1978-06-27 | Shell Oil Company | Acidizing asphaltenic oil reservoirs with acids containing salicylic acid |
US4216828A (en) * | 1978-06-19 | 1980-08-12 | Magna Corporation | Method of recovering petroleum from a subterranean reservoir incorporating an acylated polyether polyol |
US6022471A (en) * | 1996-10-15 | 2000-02-08 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite and rare earth oxide |
US6068054A (en) * | 1997-05-23 | 2000-05-30 | Exxon Production Research Company | Oil recovery method using an emulsion |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1761328A (en) * | 1928-07-31 | 1930-06-03 | Richfield Oil Company | Process of purifying lubricating-oil distillates |
US2396646A (en) * | 1940-03-11 | 1946-03-19 | Russell G Dressler | Art of preparation of valuable substances from tall oil |
US2358004A (en) * | 1940-03-11 | 1944-09-12 | Russell G Dressler | Treatment of tall oil |
US2568738A (en) * | 1947-04-15 | 1951-09-25 | Visco Products Co | Process for resolving emulsions |
US2952634A (en) * | 1955-09-14 | 1960-09-13 | Scholten Chemische Fab | Heat-resistant drilling fluid |
US2996450A (en) * | 1957-04-23 | 1961-08-15 | Atlas Powder Co | Water-in-oil emulsion drilling fluid |
US3095368A (en) * | 1957-07-31 | 1963-06-25 | Exxon Research Engineering Co | Process for removing metallic contaminants from oils |
US3169113A (en) * | 1961-07-17 | 1965-02-09 | Nalco Chemical Co | Emulsifier compositions and uses thereof |
US3804760A (en) * | 1969-12-02 | 1974-04-16 | Shell Oil Co | Well completion and workover fluid |
US3707459A (en) | 1970-04-17 | 1972-12-26 | Exxon Research Engineering Co | Cracking hydrocarbon residua |
US4012329A (en) * | 1973-08-27 | 1977-03-15 | Marathon Oil Company | Water-in-oil microemulsion drilling fluids |
US4384997A (en) * | 1978-09-29 | 1983-05-24 | Reed Lignin, Inc. | Lignosulfonated derivatives for use in enhanced oil recovery |
US4219082A (en) * | 1979-03-23 | 1980-08-26 | Texaco Inc. | Lignosulfonate-formaldehyde condensation products as additives in oil recovery processes involving chemical recovery agents |
US4298455A (en) | 1979-12-31 | 1981-11-03 | Texaco Inc. | Viscosity reduction process |
US4411770A (en) | 1982-04-16 | 1983-10-25 | Mobil Oil Corporation | Hydrovisbreaking process |
AU580617B2 (en) | 1984-09-10 | 1989-01-19 | Mobil Oil Corporation | Process for visbreaking resids in the presence of hydrogen- donor materials and organic sulfur compounds |
US4592830A (en) | 1985-03-22 | 1986-06-03 | Phillips Petroleum Company | Hydrovisbreaking process for hydrocarbon containing feed streams |
US4659453A (en) | 1986-02-05 | 1987-04-21 | Phillips Petroleum Company | Hydrovisbreaking of oils |
US4795478A (en) * | 1986-06-17 | 1989-01-03 | Intevep, S.A. | Viscous hydrocarbon-in-water emulsions |
US4790382A (en) * | 1986-12-29 | 1988-12-13 | Texaco Inc. | Alkylated oxidized lignins as surfactants |
US5095986A (en) * | 1990-12-24 | 1992-03-17 | Texaco, Inc. | Enhanced oil recovery using oil soluble sulfonates from lignin and benzyl alcohol |
US5294353A (en) * | 1991-06-27 | 1994-03-15 | Halliburton Company | Methods of preparing and using stable oil external-aqueous internal emulsions |
US5350014A (en) * | 1992-02-26 | 1994-09-27 | Alberta Oil Sands Technology And Research Authority | Control of flow and production of water and oil or bitumen from porous underground formations |
US5603863A (en) * | 1993-03-01 | 1997-02-18 | Tioxide Specialties Limited | Water-in-oil emulsions |
US5820750A (en) | 1995-02-17 | 1998-10-13 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
BR9700727A (en) * | 1997-01-21 | 1998-08-11 | Petroleo Brasileiro Sa | Thermo-chemical process for dewaxing pipelines under oil flow condition |
US5855243A (en) | 1997-05-23 | 1999-01-05 | Exxon Production Research Company | Oil recovery method using an emulsion |
US6387840B1 (en) * | 1998-05-01 | 2002-05-14 | Intevep, S.A. | Oil soluble coking additive |
US6410488B1 (en) * | 1999-03-11 | 2002-06-25 | Petro-Canada | Drilling fluid |
US6734144B2 (en) * | 2000-04-25 | 2004-05-11 | Exxonmobil Upstream Research Company | Solids-stabilized water-in-oil emulsion and method for using same |
AU2001249902A1 (en) | 2000-04-25 | 2001-11-07 | Exxonmobil Upstream Research Company | Solids-stabilized water-in-oil emulsion and method for using same |
US6800193B2 (en) * | 2000-04-25 | 2004-10-05 | Exxonmobil Upstream Research Company | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ECB-0002) |
US20020011022A1 (en) * | 2000-06-21 | 2002-01-31 | Osami Nishida | Low cost, low pollution and low viscosity fuel oil using heavy oil |
US6544411B2 (en) * | 2001-03-09 | 2003-04-08 | Exxonmobile Research And Engineering Co. | Viscosity reduction of oils by sonic treatment |
-
2001
- 2001-03-28 US US09/819,269 patent/US6800193B2/en not_active Expired - Lifetime
- 2001-04-05 BR BR0110282-6A patent/BR0110282A/en not_active Application Discontinuation
- 2001-04-05 EA EA200201135A patent/EA004090B1/en not_active IP Right Cessation
- 2001-04-05 GB GB0223091A patent/GB2381795A/en not_active Withdrawn
- 2001-04-05 MX MXPA02010423A patent/MXPA02010423A/en not_active Application Discontinuation
- 2001-04-05 CA CA002405692A patent/CA2405692C/en not_active Expired - Lifetime
- 2001-04-05 AU AU2001251360A patent/AU2001251360A1/en not_active Abandoned
- 2001-04-05 WO PCT/US2001/011152 patent/WO2001081502A2/en active Application Filing
- 2001-04-05 DE DE10196133T patent/DE10196133T1/en not_active Withdrawn
- 2001-04-05 CN CN01808538.5A patent/CN1426506A/en active Pending
- 2001-04-05 OA OA1200200320A patent/OA12249A/en unknown
- 2001-04-20 AR ARP010101858A patent/AR028916A1/en unknown
- 2001-04-24 EG EG20010414A patent/EG22907A/en active
-
2002
- 2002-10-23 NO NO20025087A patent/NO20025087L/en not_active Application Discontinuation
-
2004
- 2004-06-16 US US10/869,513 patent/US7419939B2/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3796266A (en) * | 1972-12-13 | 1974-03-12 | Texaco Inc | Surfactant oil recovery process |
US4085799A (en) * | 1976-11-18 | 1978-04-25 | Texaco Inc. | Oil recovery process by in situ emulsification |
US4096914A (en) * | 1976-12-06 | 1978-06-27 | Shell Oil Company | Acidizing asphaltenic oil reservoirs with acids containing salicylic acid |
US4216828A (en) * | 1978-06-19 | 1980-08-12 | Magna Corporation | Method of recovering petroleum from a subterranean reservoir incorporating an acylated polyether polyol |
US6022471A (en) * | 1996-10-15 | 2000-02-08 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite and rare earth oxide |
US6068054A (en) * | 1997-05-23 | 2000-05-30 | Exxon Production Research Company | Oil recovery method using an emulsion |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011161116A1 (en) * | 2010-06-22 | 2011-12-29 | Ntnu Technology Transfer As | Synthetic crude oil |
Also Published As
Publication number | Publication date |
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EG22907A (en) | 2003-10-30 |
CA2405692A1 (en) | 2001-11-01 |
US7419939B2 (en) | 2008-09-02 |
MXPA02010423A (en) | 2003-04-25 |
AU2001251360A1 (en) | 2001-11-07 |
NO20025087L (en) | 2002-12-27 |
CN1426506A (en) | 2003-06-25 |
DE10196133T1 (en) | 2003-05-22 |
GB2381795A (en) | 2003-05-14 |
US20020033265A1 (en) | 2002-03-21 |
CA2405692C (en) | 2008-12-30 |
US6800193B2 (en) | 2004-10-05 |
AR028916A1 (en) | 2003-05-28 |
OA12249A (en) | 2006-05-10 |
US20040222128A1 (en) | 2004-11-11 |
NO20025087D0 (en) | 2002-10-23 |
EA004090B1 (en) | 2003-12-25 |
GB0223091D0 (en) | 2002-11-13 |
EA200201135A1 (en) | 2003-04-24 |
BR0110282A (en) | 2003-02-11 |
WO2001081502A3 (en) | 2002-03-28 |
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