MX2008007551A - Process for upgrading heavy oil using a highly active slurry catalyst composition - Google Patents

Abstract

Applicants have developed a new residuum full hydroconversion slurry reactor system that allows the catalyst, unconverted oil and converted oil to circulate in a continuous mixture throughout an entire reactor with no confinement of the mixture. The mixture is partially separated in between the reactors to remove only the products and hydrogen gas, while permitting the unconverted oil and the slurry catalyst to continue on into the next sequential reactor. A portion of the unconverted oil is then converted to lower boiling point hydrocarbons, once again creating a mixture of unconverted oil, products, hydrogen, and slurry catalyst. Further hydroprocessing may occur in additional reactors, fully converting the oil. Additional oil may be added at the interstage feed inlet, possibly in combination with slurry. The oil may alternately be partially converted, leaving a highly concentrated catalyst in unconverted oil which can be recycled directly to the first reactor.

Description

PROCESS FOR THE IMPROVEMENT OF HEAVY OILS USING A CATALYST IN HIGHLY ACTIVE SUSPENSION FIELD OF THE INVENTION The present invention relates to a process for the improvement of heavy oils using a suspension catalyst composition. BACKGROUND OF THE INVENTION There is at this moment a growing interest in the processing of heavy oils, due to a greater global demand for petroleum products. Canada and Venezuela are sources of heavy oils. Processes that produce a complete conversion of feeds from heavy oils to useful products are of particular interest. The following patents, which are incorporated herein by reference, are directed to the preparation of high activity suspension catalyst compositions and their use in processes for the improvement of heavy oils: U.S. Serial No. 10 / 938,202 is directed to the preparation of a catalyst composition suitable for the hydroconversion of heavy oils. The catalyst composition is prepared by means of a series of steps, which involve mixing a Group VIB metal oxide and aqueous ammonia to form an aqueous mixture, and sulfurizing the mixture to form a suspension. The suspension is then promoted with a Group VIII metal. The stages Ref .: 193906 subsequent include mixing the suspension with a hydrocarbon oil and combining the resulting mixture with hydrogen gas and a second hydrocarbon oil having a lower viscosity than the first oil. An active catalyst composition is formed in this manner. U.S. Serial No. 10 / 938,003 is directed to the preparation of a suspension catalyst composition. The suspension catalyst composition is prepared in a series of steps, which involve mixing a Group VIB metal oxide and aqueous ammonia to form an aqueous mixture and sulfurizing the mixture to form a suspension. The suspension is then promoted with a metal, from Group VIII. Subsequent steps involve mixing the suspension with a hydrocarbon oil, and combining the resulting mixture with hydrogen gas (under conditions that hold the water in a liquid phase) to produce the catalyst in active suspension. U.S. Serial No. 10 / 938,438 is directed to a process employing suspension catalyst compositions in the improvement of heavy oils. It is not allowed that. catalyst composition in sediment suspension, which would result in possible deactivation. The suspension is recycled to a breeding reactor for the repeated use of products that do not require additional separation procedures for catalyst removal.

U.S. No. 10 / 938,200 is directed to a process for improving heavy oils using a suspension composition. The suspension composition is prepared in a series of steps, which involve mixing a Group VIB metal oxide with aqueous ammonia to form an aqueous mixture and sulfurizing the mixture to form a suspension. The suspension is then promoted with a Group VIII metal compound. Subsequent steps include mixing the suspension with a hydrocarbon oil, and combining the resulting mixture with hydrogen gas (under conditions that hold the water in a liquid phase) to produce the catalyst in active suspension. U.S. Serial No. 10 / 938,269 is directed to a process for improving heavy oils using a suspension composition. The suspension composition is prepared by a series of steps, which involve mixing a Group VIB metal oxide and aqueous ammonia to form an aqueous mixture, and sulfurizing the mixture to form a suspension. The suspension is then promoted with a group VIII metal. Subsequent steps involve mixing the suspension with a hydrocarbon oil and combining the resulting mixture with hydrogen gas and a second hydrocarbon oil having a lower viscosity than the first oil. In this way an active catalyst composition is formed.

BRIEF DESCRIPTION OF THE INVENTION A process for the hydroconversion of heavy oils, the process employs at least two reactors of ascending flow in series with a separator between each reactor, the process comprising the following steps: (a) combining a heavy oil feed heated, an active suspension catalyst composition and a gas containing hydrogen to form a mixture; (b) transferring the mixture from step (a) to the bottom of the first reactor, which is maintained under hydroprocessing conditions, including elevated temperature and pressure; (c) removing a vapor stream comprising products and hydrogen, unconverted material and catalyst in suspension from the top of the first reactor and transferring it to a first separator; (d) in the first separator, remove the products and hydrogen from the dome as steam for further processing as unconverted material and catalyst in suspension as a liquid stream of funds; (e) combining the bottoms of step (d) with additional feed oil resulting in an intermediate mix; (f) transferring the intermediate mixture from stage (e) to the bottom of the second reactor, which is maintained under conditions of hydroprocessing, including elevated temperature and pressure; (g) removing a vapor mixture containing products and hydrogen, unconverted material and catalyst in suspension from the top of the second reactor and transferring it to a second separator; (h) in the second separator, remove the products and hydrogen from the dome as steam for further processing and transfer the liquid bottom stream, which comprises unconverted material and suspended catalyst to further processing. BRIEF DESCRIPTION OF THE FIGURES Figures 1-6 illustrate process schemes of the present invention with oil addition between stages. DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a process for hydrodisintegration in suspension activated with catalyst. The separation of unconverted products and material is effective to maintain the heat balance in the process. In Figure 1, stream 1 comprises a heavy feed, such as vacuum residue. The feed enters the furnace 80 where it is heated, leaving stream 4. The stream 4 is combined with a gas containing hydrogen (stream 2), and a stream comprising an active suspension composition (stream 23), resulting in a mix (stream 24). The stream 24 enters the bottom of the first reactor 10. The vapor stream 5 leaves the upper part of the reactor 10 and comprises product and hydrogen gas, as well as suspension and unconverted material. The stream 5 passes to a separator 40, which is preferably an instantaneous evaporation drum. Product and hydrogen is removed from the dome of the separator 40 as the stream 6. The liquid stream 7 is removed through the bottom of the flash drum. Stream 7 contains suspension in combination with unconverted oil. Stream 7 is combined with a gaseous stream comprising hydrogen (stream 15) and stream 41 (which comprises an additional feed such as a vacuum gas oil) to create stream 27. Stream 27 enters the bottom of the second reactor 20 The vapor stream 8 leaves the second reactor 20 and passes to the separator 50, which is preferably an instantaneous evaporation drum. Product and hydrogen are removed from the dome of the separator 50 as the stream 9. The liquid stream 11 is removed through the bottom of the flash drum. Stream 11 contains suspension in combination with unconverted oil. The stream 11 is combined with gaseous stream comprising hydrogen (stream 16) to create the stream 28. The stream 28 enters the bottom of the third reactor 30. The steam stream 12 leaves the third reactor 30 and passes to the separator 60, which preferably a drum of instantaneous evaporation. Product and hydrogen are removed from the dome like stream 13. Liquid stream 17 is removed through the bottom of the flash drum. Stream 17 contains suspension in combination with unconverted oil. A portion of this current can be drawn through the current 18. The currents of domes 6, 9 and 13 create the stream 14, which passes to a poor oil contactor 70. The stream 21, which contains a poor oil such as Vacuum gasoil, enters the top of the poor oil contactor 70 and flows downstream. Products and gas leave the dome of the poor oil contactor 70 through the stream 22, while the liquid stream 19 leaves the bottom. The stream 19 comprises a mixture of suspension and unconverted oil. Stream 19 is combined with stream 17, which also comprises a mixture of suspension and unconverted oil. Fresh suspension is added in stream 3, and stream 23 is created. Stream 23 is combined with feed to first reactor 10. Figure 2 illustrates a flow scheme identical to figure 1, except that stream 11 is combined with an additional feed stream such as vacuum gas oil, in addition to the hydrogen stream 16, in order to create the current 28. Figures 3, 4 and 5 are variations in a flow scheme of multiple reactors in which some reactors have internal phase separation means with the reactor and some employ external separation with an instantaneous evaporation drum. In Figure 3, stream 1 comprises a heavy feed, such as vacuum residue. This feed enters the furnace 80 where it is heated, coming out in the stream 4. The stream 4 is combined with a gas containing hydrogen (stream 2) and a stream comprising an active suspension composition (stream 23), resulting in a mixture (stream 24). The stream 24 enters the bottom of the reactor 10. The steam 31 leaves the upper part of the reactor and comprises only products and gases, due to the separation apparatus inside the reactor. Stream 26 containing suspension in combination with unconverted oil leaves the bottom of reactor 10. Stream 26 is combined with a gaseous stream comprising hydrogen (stream 15) and stream 41 (comprising an additional feed such as vacuum gas oil) ) to create the current 27. Current 27 enters the bottom of the second reactor 20. The process continues as illustrated in Figure 1. In Figure 4, current 11 is combined with a additional feed (stream 42) as well as current 16 to create current 28. In the rest figure 4 is identical to figure 3. In figure 5, stream 1 comprises a heavy feed, such as vacuum residue. This feed enters the furnace 80 where it is heated, coming out in the stream 4. The stream 4 is combined with a gas containing hydrogen (stream 2), and a stream comprising an active suspension composition (stream 23), resulting in a mixture (stream 24). The stream 24 enters the bottom of the reactor 10. The steam stream 31 leaves the upper part of the reactor, and comprises only product and gases, due to the separation apparatus inside the reactor (not shown). Stream 26, which contains suspension in combination with unconverted oil, leaves the bottom of reactor 10. Stream 26 is combined with a gaseous stream comprising hydrogen (stream 15) and stream 41 (which comprises an additional feed such as a vacuum gasoil and may also contain a catalyst suspension) to create the stream 27. The stream 27 enters the bottom of the second reactor 20. The steam stream 32 leaves the reactor 20 comprising only products and gases, due to the separation apparatus within of the reactor (not shown). Stream 29, which contains suspension in combination with unconverted oil leaves the bottom of reactor 20. Stream 29 is combined with hydrogen-containing gas (stream 16) to create stream 28. Stream 28 enters bottom of reactor 30. Steam stream 12 leaves the reactor 30, passing to the separator 60, preferably an instantaneous evaporation drum. Product and gases are removed from the dome such as stream 13. Liquid stream 17 is removed through the bottom of separator 60. Stream 17 contains suspension in combination with unconverted oil. A portion of this current can be drawn through the current 18. The currents of domes 31, 32 and 13 create the stream 14, which passes to a poor oil contactor 70. The stream 21, which comprises a poor oil such as vacuum gasoil, enters the upper part of the high pressure separator 70. Products and hydrogen exit the high pressure separator 70 through the dome, while the stream 19 leaves the bottom. The stream 19 comprises a mixture of suspension and unconverted oil. Stream 19 is combined with stream 17, which also comprises a mixture of suspension and unconverted oil. Fresh suspension is added in stream 3, and current 23 is created. Stream 23 is combined with feed to the first reactor In Figure 6, the stream 29 is combined with an additional feed (stream 42) as well as with the stream 16 to create the stream 28. The rest in Figure 6 is identical to Figure 5. The process for preparing the The catalyst suspension composition used in the present invention is presented in the application Serial No. 10/938003, and No. of Series 10/938202 and are incorporated by reference. The catalyst composition is useful but not limited to hydrogenation improvement processes such as thermal hydrodisintegration, hydrotreating, hydrodesulfurization, hydrodenitrification and hydrodemetalization. Feeds suitable for use in the present invention are presented in US Serial No. 10/938269 and include atmospheric waste, vacuum residue, tar from a deasphalting unit with solvents, atmospheric gas oils, vacuum gas oils, deasphalted oils, olefins, oils derived from bituminous sands or bitumen, oils derived from mineral coal, heavy crude oils , synthetic oils from Fischer Tropsch processes, and oils derived from waste of recycled oils and polymers. The preferred type of reactor in the present invention is a liquid recirculation reactor, although they can other types of upflow reactors should be used. Recirculation reactors are discussed further in the pending application together with this Series No. (T-6493), which is incorporated by reference. A liquid recirculation reactor is an upflow reactor which feeds heavy hydrocarbon oil and a gas rich in hydrogen at high pressure and temperature for hydroconversion. Process conditions for the recirculation reactor include pressures in the range of 71.82 to 167.58 KPa absolute (1500 to 3500 psia) and temperature in the range of 371.1 to 482.2 ° C (700 to 900 ° C). Preferred conditions include 95.76 to 143.64 KPa absolute (2000 to 3000 psia) and a temperature in the range of 371.1 to 482.2 ° C (700 to 900 ° F). Hydroconversion includes processes such as hydrodisintegration and the removal of heteroatomic contaminants (such as sulfur and nitrogen). In the use of the suspension catalyst, the particles are extremely small (1-10 microns). Generally, recirculation pumps are not needed, although they can be used. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (20)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A process for the hydroconversion of heavy oils, the process employs at least two reactors of ascending flow in series with a separator located between each reactor , characterized in that it comprises the following steps: (a) combining a heated heavy oil feed, an active suspension catalyst composition and a hydrogen-containing gas to form a mixture; (b) transferring the mixture from step (a) to the bottom of the first reactor, which is maintained at hydroconversion conditions in suspension which include elevated temperature and pressure; (c) removing a vapor stream containing products and hydrogen, unconverted material and catalyst in suspension from the top of the first reactor and transferring it to a first separator; (d) in the first separator, remove the products and hydrogen from the dome as steam for further processing as unconverted material and catalyst in suspension as a liquid stream of funds; (e) combining the bottoms of step (d) with additional feed oil resulting in an intermediate mix; (f) transferring the intermediate mixture from step (e) to the bottom of the second reactor, which is maintained under hydroprocessing conditions, including elevated temperature and pressure; (g) removing a vapor mixture containing products and hydrogen, unconverted material and catalyst in suspension from the top of the second reactor and transferring it to a second separator; (h) in the second separator, remove the products and hydrogen from the dome as steam for further processing and transfer the liquid bottom stream, which comprises unconverted material and suspended catalyst to further processing.
2. 2. The process according to claim 1, characterized in that the feed to one or more additional reactors is combined with additional feed oil before entering the reactor. The process according to claim 2, characterized in that the additional feed oil is selected from the group consisting of atmospheric residue, vacuum residue, tar from a solvent deasphalting unit, atmospheric gas oils, vacuum gas oils, deasphalted oils , oils derived from bituminous sands or bitumen, oils derived from mineral coal, heavy crude oils, synthetic oils from Fischer-Tropsch processes, and oils derived from waste of recycled oils and polymers. 4. The process according to claim 3, characterized in that the additional feed oil is a vacuum gas oil. 5. The process according to claim 1, characterized in that the additional feed oil also comprises catalyst in suspension. The process according to claim 1, characterized in that the bottom material of step (h) is recycled to step (a), the mixture of step (a) additionally comprises recycled unconverted material and suspended catalyst . 7. The process according to claim 1 characterized in that the bottom material of step (h) is transferred to the bottom of a third reactor which is maintained at hydroprocessing conditions in suspension, including high temperature and pressure. 8. The process according to claim 1, characterized in that a liquid recirculation reactor is used in at least one of the reactors. 9. The process according to claim 8, characterized in that the recirculation reactor employs a bomb. The process according to claim 1, characterized in that the hydroprocessing conditions employed in each reactor have a total pressure in the range of 71.82 to 167.58 KPa absolute (1500 to 3500 psia), and a reaction temperature of 371.1 to 482.2 °. C (700 to 900 ° F). 11. The process according to claim 10, characterized in that the preferred total pressure is in the range of 9.58 to 143.64 KPa absolute (200 to 3000 psia), and the preferred temperature is in the range of 412.8 to 454.4 ° C (775 to 850 ° F). 12. The process according to claim 1, characterized in that the separator located between each reactor is an instantaneous evaporation drum. The hydroconversion process according to claim 1, characterized in that the heavy oil is selected from the group consisting of vacuum gas oils, deasphalted oils, oils derived from bituminous sands or bitumen, olefins, oils derived from mineral coal, crude oils heavy, synthetic oils from Fischer-Tropsch processes, and oils derived from recycled oil waste and polymers. 14. The hydroconversion process according to claim 1, characterized in that the process is selected from the group consisting of hydrodisintegration, hydrotreating, hydrodesulfurization, hydrodenitrification, and hydrodesmetalization. The process according to claim 1, characterized in that the suspension catalyst composition according to claim 1 is prepared by the following steps: (a) mixing a metal oxide of Group VIB and aqueous ammonia to form a mixture aqueous metal compound of Group VIB; (b) sulfur, in an initial reaction zone, the aqueous mixture of step (a) with a gas comprising hydrogen sulfide at a dosage greater than 0.5 m3 standard kilogram of hydrogen sulfide per kilogram (8 SCF of sulfur hydrogen per pound) of Group VIB metal to form a suspension; (c) promoting the suspension with a Group VIII metal compound; (d) mixing the suspension of step (c) with a hydrocarbon oil having a viscosity of at least 2 cSt at 100 ° C (212 ° F) to form an intermediate mixture; (e) combining the intermediate mixture with hydrogen gas in a second reaction zone, under conditions which keep the water in the intermediate mixture in a liquid phase, thereby forming an active catalyst composition mixed with a liquid hydrocarbon; Y (f) recovering the active catalyst composition. 16. The process according to claim 1, characterized in that at least 90% by weight of the heavy oil feed is converted to lighter boiling products. 17. A process for heavy oil hydroconversion, the process employs at least two upflow reactors in series with a separator located internally in the first reactor, characterized in that it comprises the following steps: (a) combining a heavy oil feed heated, an active suspension catalyst composition and a gas containing hydrogen to form a mixture; (b) transferring the mixture from step (a) to the bottom of the first reactor, which is maintained at hydroconversion conditions in suspension which include elevated temperature and pressure; (c) internally separating into the first reactor a vapor stream comprising reaction product, hydrogen gas, unconverted material and catalyst in suspension in two streams, a vapor stream comprising products and hydrogen, and a liquid stream comprising non-converted material and catalyst in suspension; (d) remove the steam stream that comprises products and dome gases for further processing, and removing the liquid stream, comprising unconverted material and catalyst in suspension, from the first reactor as a stream of bottoms; (e) combining the bottoms of step (d) with additional feed oil resulting in an intermediate mix; (f) transferring the intermediate mixture from step (e) to the bottom of the second reactor, which is maintained under hydroprocessing conditions, including elevated temperature and pressure; (g) removing a vapor mixture containing products and hydrogen, unconverted material and catalyst in suspension from the top of the second reactor and transferring it to a separator; (h) in the separator, remove the products and hydrogen from the dome as steam for further processing and transfer the liquid bottom stream, which comprises unconverted material and suspended catalyst to further processing. 18. The process according to claim 16, characterized in that the feed to one or more additional reactors is combined with additional feed oil before entering the reactor. 19. A process for the hydroconversion of heavy oils, the process employs at least two reactors of ascending flow in series with a separator located internally in both reactors, characterized in that it comprises the following steps: (a) combining a heated heavy oil feed, an active suspension catalyst composition and a hydrogen-containing gas to form a mixture; (b) transferring the mixture from step (a) to the bottom of the first reactor, which is maintained at hydroconversion conditions in suspension which include elevated temperature and pressure; (c) internally separating into the first reactor a vapor stream comprising reaction product, hydrogen gas, unconverted material and catalyst in suspension in two streams, a vapor stream comprising products and hydrogen, and a liquid stream comprising non-converted material and catalyst in suspension; (d) removing the vapor stream comprising products and gases from the dome for further processing, and drawing the liquid stream, comprising unconverted material and catalyst in suspension, from the first reactor as a stream of bottoms; (e) combining the bottoms of step (d) with additional feed oil resulting in an intermediate mix, - (f) transferring the intermediate mixture from step (e) to bottom of the second reactor, which is maintained at hydroprocessing conditions, including elevated temperature and pressure; (g) internally separating in the second reactor a vapor stream comprising reaction product, hydrogen gas, unconverted material and catalyst in suspension in two streams, a vapor stream comprising products and hydrogen, and a liquid stream comprising non-converted material and catalyst in suspension; (h) removing the vapor stream comprising products and hydrogen from the dome for further processing, and removing the unconverted material and catalyst in suspension, from the first reactor as a liquid stream of bottoms for further processing. The process according to claim 18, characterized in that the feed to one or more additional reactors is combined with additional feed oil before entering the reactor.