초록 ▼

A process for reducing the naphthenic acidity of petroleum oils or their fractions is described, said process comprising providing a hydrocarbon feed 103/203/303 having between 0.1 and 99 wt % of emulsified/dispersed water in oil, said feed containing salts and a content of naphthenic acids measured

A process for reducing the naphthenic acidity of petroleum oils or their fractions is described, said process comprising providing a hydrocarbon feed 103/203/303 having between 0.1 and 99 wt % of emulsified/dispersed water in oil, said feed containing salts and a content of naphthenic acids measured as TAN between 0.1 and 10 mg KOH/g oil; directing the said petroleum oil feed and emulsified/dispersed water towards an energy emitter device in the microwave range and submitting said feed 103/203/303 in liquid phase, under pressure between 0.7 and 4.5 MPa at temperatures between 50�� C. and 350�� C. to the microwave radiation, applied in the range of 1 mm to 30 cm to said feed so that the presence of salts, the applied temperature and the high dielectric constant of the water droplets make that the heat is absorbed on the spot by the water and heat said water preferentially to the oil, while the naphthenic compounds at the interface between the droplets and the oil catch said heat; effecting the decomposition of the carboxylic acids responsible for the naphthenic acidity in the petroleum feed at temperatures around 320�� C. and generating CO2; separating with the aid of any known device 106/106'/112/117/208/208'/214/219/310/310'/316/321 any gas phase generated, water and oil; and recovering the hydrocarbon oil stream 108/113/119/210/215/221/312/317/323 having a reduced content in naphthenic acids. The process is designed to be applied to the reduction of naphthenic acids in feeds of petroleum oils and their fractions in the oil production step, in refineries or any industrial installation.

대표청구항 ▼

We claim: 1. A process for reducing the naphthenic acidity of petroleum oils or their fractions, wherein said process comprises: a) providing a feed of petroleum oil or its fractions with between 0.1 and 99 wt % of emulsified/dispersed water in oil, said feed containing salts and a content of napht

We claim: 1. A process for reducing the naphthenic acidity of petroleum oils or their fractions, wherein said process comprises: a) providing a feed of petroleum oil or its fractions with between 0.1 and 99 wt % of emulsified/dispersed water in oil, said feed containing salts and a content of naphthenic acids measured as TAN between 0.1 and 10 mg KOH/g of oil; b) directing said feed of petroleum oil or its fractions with emulsified/dispersed water and salts towards a radiation emitting device in the microwave range and submitting said feed in the liquid phase under pressure between 0.7 and 4.5 MPa at temperatures between 50�� C. and 350�� C. to said microwave energy, applying said energy in the range of 1 mm to 30 cm on said petroleum feed, so that the presence of salts, the applied temperature and the high dielectric constant of water droplets make that the heat is absorbed on the spot by the water and heat it preferentially to oil, while the naphthenic compounds in the interface between the droplets and the oil receive said heat; c) effecting the decomposition of the carboxylic acids responsible for the naphthenic acidity in said feed of petroleum oil or its fractions at temperatures around 320�� C., generating CO2; d) with the aid of any known separating device, separating any generated gas phase, water and oil; e) recovering petroleum oil or its fractions of reduced content in naphthenic acids, and where: i) the feed of petroleum oil or its fractions is free from any added solid; ii) the migration trend of the naphthenic acids towards the emulsified phase, by concentrating said acids in a fraction of the overall feed, allows the application of the microwave radiation to a fraction that is smaller than the total feed. 2. A process according to claim 1, wherein the microwave radiation emitter is included in a phase separation device. 3. A process according to claim 1, wherein the microwave radiation emitter is an equipment independent of any phase separation device. 4. A process according to claim 1, wherein in step d) the phase separation device separates water and oil only. 5. A process according to claim 1, wherein said process comprises the following steps: a) combining a feed stream (101) and a water stream (102) at a concentration of at least 3% vol/vol obtaining a stream (103) directed to an in line mixing device (104) so as to form a water-in-oil emulsion/dispersion (105) directed to a device (106), said emulsion/dispersion being kept within said mixing device (106) for a residence time between 20 seconds and 40 minutes, at a temperature between 50�� C. and 350�� C. under a pressure between 0.7 and 4.5 MPa, in liquid phase, the device (106) being designed for phase separation and also including a microwave radiation emitter of 1,000 MHz to 300,000 MHz, the application of microwave radiation in emulsified water heating preferentially the water, whereby the naphthenic compounds in the interface between the drop and the oil catch on the spot the heat absorbed by water and are heated preferentially to oil; b) with the aid of the microwave radiation, decomposing the carboxylic acids responsible for the naphthenic acidity, at temperatures around 320�� C. and generating CO2; c) effecting the separation of the oil, gas and water streams; d) recovering the oil stream with a reduced content in naphthenic acids, and where: i) the hydrocarbon stream is free from any added solid; ii) the trend to migration exhibited by naphthenic acids towards the emulsified phase, by concentrating said acids in a fraction of the overall feed allows to apply the microwave radiation in a fraction that is smaller than the total feed. 6. A process according to claim 5, wherein the device (106) is a three-phase separator. 7. A process according to claim 6, wherein the separation yields a CO2-rich gas stream (l07) generated by the degradation of the carboxylic acids present in the feed, besides light hydrocarbons. 8. A process according to claim 6, wherein the separation yields product stream (l08), a hydrocarbon organic stream having a reduced content of naphthenic acids. 9. A process according to claim 6, wherein stream (l09) is an aqueous stream directed for discarding or recycled to the process and made up of water from feed stream (103), and a minor amount of hydrocarbons, entrained solids and dissolved gases such as CO2. 10. A process according to claim 5, wherein alternatively feed stream (105) is directed to a two-phase separator (106'), yielding a gaseous stream (110) and a hydrocarbon and water stream (111), said stream (111) being directed to a second two-phase separation device (112) wherefrom are separated a product hydrocarbon stream (113) and an aqueous stream (114). 11. A process according to claim 5, wherein still alternatively the feed stream (105) is directed to a two-phase separator (106') yielding an aqueous stream (115) and a gas and hydrocarbon stream (116) directed to a second two-phase separator (117) where are separated a gas stream (118) and a hydrocarbon product (119) stream. 12. A process according to claim 5, wherein alternatively the process stream is stream (105). 13. A process according to claim 1, wherein said process comprises the following steps: a) combining feed stream (201) and water stream (202) at a concentration of at least 3% vol/vol, obtaining stream (203) directed to the in-line mixing device (204) so as to form water-in-oil emulsion/dispersion (205), said emulsion/dispersion (205) being directed to device (206 containing a microwave radiation emitter in the range of 1,000 MHz to 300,000 MHz where the water of the emulsion/dispersion will be preferentially heated, whereby the naphthenic compounds at the interface between the drop and the oil receive on the spot the heat absorbed by water and are heated preferentially to oil, the ambient pressurized between 0.7 and 4.5 MPa, at temperatures between 50�� C. and 350�� C. keeping the droplets in emulsion and allowing the decomposition of the carboxylic acid and CO2 release so as to reduce naphthenic acidity; b) with the aid of the microwave radiation, decomposing carboxylic acids responsible for naphthenic acidity at temperatures around 320�� C., generating CO2; c) separating the oil, gas and water streams in a phase separator; and d) recovering the petroleum oil or its fractions having a reduced naphthenic acid content, and wherein: i) The feed of petroleum oil or its fractions is free from any added solid; ii) The trend of the naphthenic acids to migrate towards the emulsified phase so as to concentrate said acids in a fraction of the total feed allows the application of the microwave radiation to a fraction that is smaller than the total feed. 14. A process according to claim 3, wherein the residence time of the feed of petroleum oil or its fractions in the microwave radiation emitter (206) varies according to the feed flow rate and the pipe diameter. 15. A process according to claim 13, wherein the oil, gas and water streams are separated in a three-phase separator (208). 16. A process according to claim 13, wherein the separation yields a CO2-rich gas stream generated by the degradation of carboxylic acids present in the feed, besides light hydrocarbons. 17. A process according to claim 13, wherein the separation yields product stream (210), a hydrocarbon organic stream having a reduced content in naphthenic acids. 18. A process according to claim 13, wherein stream (211) is an aqueous stream directed to discarding or recycled to the process and made up of water from feed stream (203), a minor amount of hydrocarbons, entrained solids and dissolved gases such as CO2. 19. A process according to claim 13, wherein alternatively feed stream (205) is directed to a two-phase separator (208') yielding a gas stream (212) and a hydrocarbon and water stream (213) directed to a second two-phase separation device (214) wherefrom are separated a stream (215) of product hydrocarbon and an aqueous stream (216). 20. A process according to claim 13, wherein still alternatively feed stream (205) is directed to a two-phase separator (208') yielding an aqueous stream (217) and a hydrocarbon and gas stream (218) directed to a second two-phase separator (219) where are separated a gas stream (220) and a product hydrocarbon stream (221). 21. A process according to claim 13, wherein alternatively the feed stream is stream (205). 22. A process according to claim 5, wherein in step c) the phase separation device separates water and oil only. 23. A process according to claim 1, wherein said process comprises the following steps: a) combining feed stream (301) with water stream (302) in a concentration of at least 3% vol/vol, obtaining stream (303) directed to in-line mixing device (304) so as to form water-in-oil emulsion/dispersion (305) in turn directed to any phase separation device (306); b) in device (306), separating a water stream (308), a hydrocarbon stream (307) and a residual emulsion stream (309); c) directing said residual emulsion stream (309) to separator device (310), said separator including in its interior a microwave radiation emitter in the range of 1,000 MHz to 300,000 MHz and submitting the said residual emulsion stream (309) to microwave radiation, whereby the water of the residual emulsion will be preferentially heated, whereby the naphthenic compounds of the drop and oil interface catch on the spot the heat absorbed by water, being heated preferentially to the oil, the pressurized ambient between 0.7 and 4.5 MPa and the temperatures between 50�� C. and 350�� C. keeping the droplets in emulsion and allowing the carboxylic acid decomposition and CO2 release, so as to reduce naphthenic acidity; d) with the aid of the microwave radiation, decomposing the carboxylic acids responsible for the naphthenic acidity at temperatures around 320�� C., so as to generate CO2; e) separating the oil, gas and water streams in a phase separator; and f) recovering petroleum oil or its fractions having a reduced content in naphthenic acids; and wherein: i) the feed of petroleum oil or its fractions is free from any added solid; ii) the migration trend of the naphthenic acids towards the emulsified phase, by concentrating said acids in a fraction of the overall feed, allows the application of the microwave radiation to a fraction that is smaller than the total feed. 24. A process according to claim 2, wherein the residence time of the feed of petroleum oil or its fractions in the microwave radiation emitter varies between 20 seconds and 40 minutes. 25. A process according to claim 5, wherein the water concentration of stream (102/202/302) combined to stream (101/201/301) is between 5 and 10% vol/vol. 26. A process according to claim 23, wherein the separation yields a CO2-rich gas stream (311) generated by the carboxylic acids present in the feed, besides light hydrocarbons. 27. A process according to claim 23, wherein the separation yields product stream (312), a hydrocarbon organic stream having a reduced content in naphthenic acids. 28. A process according to claim 23, wherein stream (313) is an aqueous stream to be either discarded or recycled to the process and made up of water from feed stream (303), a minor amount of hydrocarbons, entrained solids and dissolved gases such as CO2. 29. A process according to claim 23, wherein alternatively residual emulsion stream (309) is directed to a two-phase separator (310') yielding a gas stream (314) and a water and hydrocarbon stream (315), directed to a second two-phase separation device (316) wherefrom are separated a product hydrocarbon stream (317) and an aqueous stream (318). 30. A process according to claim 23, wherein still alternatively residual emulsion stream (309) is directed to a two-phase separator (310') yielding an aqueous stream (319) and a gas and hydrocarbon stream (320) directed to a second two-phase separator (321) wherefrom are separated a gas stream (322) and a product hydrocarbon stream (323). 31. A process according to claim 23, wherein alternatively the process feed is stream (305). 32. A process according to claim 23, wherein in step e), the phase separation device separates water and oil only. 33. A process according to claim 1, wherein the pH of the emulsified/dispersed water in the feed of petroleum oil or its fractions is between 5 and 14. 34. A process according to claim 33, wherein the pH of the emulsified/dispersed water in the feed of petroleum oil or its fractions is between 10 and 11. 35. A process according to claims 33, wherein further the emulsified/dispersed water in the feed of petroleum oil or its fractions contains phenols, chlorides, sulfide, ammonia and sodium hydroxide. 36. A process according to claim 1, wherein said process is designed to be applied to petroleum production. 37. A process according to claim 1, wherein said process is designed to be applied in refineries. 38. A process according to claim 1, wherein said process is designed to be applied in any industrial installation. 39. A process according to claim 1, wherein the feed of petroleum oil or its fractions is a crude or a petroleum blend. 40. A process according to claim 1, wherein the feed of petroleum oil or its fractions is a petroleum fraction, alone or combined to other fractions in any amount. 41. A process according to claim 1, wherein the feed of petroleum oil or its fractions is a crude or a petroleum blend combined to a petroleum fraction, alone or combined to other fractions in any amount. 42. A process according to claim 1, wherein the feed of petroleum oil or its fractions is a residue from petroleum processing. 43. A process according to claim 1, wherein the naphthenic acid content of the feed measured as TAN is between 0.5 and 3 mg KOH/g oil. 44. A process according to claim 1, wherein it further includes a demulsifier. 45. A process according to claim 44, wherein the demulsifier addition is performed before, during or after the application of the microwave radiation, in the phase separation step. 46. A process according to claim 1, wherein further the hydrocarbon product having reduced content of naphthenic acids is analyzed for determining the remaining naphthenic acid content. 47. A process according to claim 46, wherein for higher than desired naphthenic acid contents in the product stream, a new cycle of naphthenic acid removal is carried out, whereby the hydrocarbon stream can be added of a further water stream equivalent to the initial stream utilized to prepare the emulsion/dispersion, with the same or different percent water based on the feed, the water being from the same source or not, so as to create in series a new cycle of mixing process, microwave radiation application and phase separation. 48. A process according to claim 47, wherein, according to the required severity, the process conditions of said further cycle can be the same or different from those practiced in the first cycle. 49. A process according to claim 1, wherein the phase separation carried out in a phase separation device is complemented downstream by centrifugation, gravity separation, ultrasound, hydrocyclones, electrostatic separation, filtration, membrane separation or a combination of these techniques. 50. A process according to claim 13, wherein the microwave radiation emitter is independent of the phase separator.