TWI486435B - Residue hydrocracking processing - Google Patents

Description

Residue hydrocracking technology Expose the field

The examples disclosed herein are generally directed to a hydrogen conversion process comprising a process for hydrocracking residues and other heavy hydrocarbon fractions. More particularly, the embodiments disclosed herein relate to solvent deasphalting of a residual hydrocarbon feedstock, treating the formed deasphalted oil in a residue desulfurization unit and a residue hydrocracking unit, and The bitumen from the solvent deasphalting unit is treated in a separate residue hydrocracking unit.

background

Because of the steady increase in demand for gasoline and other distillate refining products such as kerosene, jet engine oil and diesel, there has been a significant trend to convert higher boiling compounds to lower boiling points. To meet the increased demand for distillate fuels, refiners have investigated various reactions such as hydrocracking, residue desulfurization (RDS), and solvent deasphalting (SDA) to remove residues, vacuum gas oil (VGO). And other heavy petroleum raw materials are converted into jet engine oil and diesel fuel.

Catalysts that exhibit excellent distillate selectivity, reasonable conversion activity, and stability to heavier feedstocks have been developed. But by various methods The achievable conversion rate is limited. For example, a single RDS unit can produce 1% by weight of sulfur fuel from a high sulfur residue, but conversion is generally limited to about 35% to 40%. Others have proposed using the SDA unit to deasphalt the residual feed solvent and to treat the deasphalted oil in only one residue hydrocracking unit (RHU). Further, the others process the unconverted vacuum residue from a RHU in an SDA unit and recycle the deasphalted oil (DAO) back to the front end of the RHU. Still others have proposed to treat SDA bitumen directly in a RHU. However, economical methods for achieving high hydrocarbon conversion and sulfur removal are desirable.

summary

In one aspect, the embodiments disclosed herein relate to a method for upgrading residual hydrocarbons. The method may comprise the steps of: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; and passing the bitumen fraction and hydrogen with a first hydrogen conversion catalyst in a first bubbling bed hydrogen Contact in the conversion reactor system; recovery of an effluent from the first ebullated bed hydrogen conversion reactor system; fractionation of the effluent from the first ebullated bed hydrogen conversion reactor system to recover one or more hydrocarbon fractions.

In another aspect, the embodiments disclosed herein relate to a method for upgrading residual hydrocarbons, which can include the steps of: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and an asphalt. Distilling; contacting the bitumen fraction and hydrogen with a first hydrogen shift catalyst in a first bubbling bed hydrogen shift reactor system; recovering an effluent from the first ebullated bed hydrogen shift reactor system; Fluidized bed hydrogen conversion reactor system The effluent is fractionated to recover one or more hydrocarbon fractions; the deasphalted oil fraction and hydrogen are contacted with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; and a residue is hydrolyzed from the residue. An effluent of the sulfur unit; contacting the residue hydrodesulfurization unit effluent with a third hydrogen conversion catalyst in a hydrocracking reactor system; recovering an effluent from the hydrocracking reactor system; The effluent of the hydrocracking reactor system is fractionated to recover one or more hydrocarbon fractions.

In another aspect, the embodiments disclosed herein relate to a method of upgrading residual hydrocarbons, which can include the steps of: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction. Passing the bitumen fraction with hydrogen and a first hydrogen shift catalyst in a first bubbling bed hydrogen shift reactor system; recovering an effluent from the first ebullated bed hydrogen shift reactor system; from the first bubbling bed The effluent of the hydrogen conversion reactor system is fractionated to recover one or more hydrocarbon fractions; the deasphalted oil fraction and hydrogen are contacted with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; An effluent of the residue hydrodesulfurization unit; fractionating the effluent from the hydrocracking reactor system to recover one or more hydrocarbon fractions comprising a vacuum residual hydrocarbon fraction; and subjecting the vacuum residual hydrocarbon fraction to a first The trihydrogen conversion catalyst is contacted in a hydrocracking reactor system; and an effluent from the hydrocracking reactor system is recovered; the effluent from the hydrocracking reactor system is fractionated to recover one or Kind of hydrocarbon fractions.

Other aspects and advantages will be apparent from the description and drawings.

10‧‧‧Residual hydrocarbon fractions

12‧‧‧Solvent deasphalting unit

14‧‧‧Deasphalted oil fraction

15‧‧‧Asphalt fraction

16‧‧‧Residue desulfurization unit

17‧‧‧ Thinner

18‧‧‧ effluent

19‧‧‧Diluted bitumen fraction

20‧‧‧ Hydrocracking Reactor System

21‧‧‧ hydrogen

22‧‧‧Flow pipeline

23‧‧‧Gas-rich gas

24‧‧‧ fractionation system

26‧‧‧Exhaust

28‧‧‧Light naphtha fraction

30‧‧‧Heavy naphtha fraction

32‧‧‧kerosene fraction

34‧‧‧ diesel fraction

36‧‧‧Light vacuum gas oil fraction

38‧‧‧ Heavy vacuum gas oil fraction

40‧‧‧vacuum residue

42‧‧‧Boiled bed reactor system

44‧‧‧Flow pipeline

46‧‧‧ fractionation system

48‧‧‧Exhaust

50‧‧‧Light naphtha fraction

52‧‧‧Heavy naphtha fraction

54‧‧‧kerosene fraction

56‧‧‧ diesel fraction

58‧‧‧Light vacuum gas oil fraction

60‧‧‧Heavy gas fraction

62‧‧‧vacuum residue fraction

63‧‧‧Liquid flow

64‧‧‧Cutter Distillate

66‧‧‧Cutter Distillate

67‧‧‧Vapor flow

68‧‧‧Outflow logistics

72‧‧‧Vacuum fractionation system

81‧‧‧HP/HT V/L separator

86‧‧‧Fixed bed hydrotreating reactor

146‧‧‧Atmospheric fractionation system

147‧‧‧ fractionation system

163‧‧‧Liquid flow

167‧‧‧Vapor flow

168‧‧‧Outflow logistics

172‧‧‧Vacuum fractionation system

181‧‧‧HP/HT V/L separator

186‧‧‧Fixed bed hydrotreating reactor

1 is a simplified method flow diagram of a method for upgrading residual hydrocarbon feedstock in accordance with embodiments disclosed herein.

2 is a simplified method flow diagram of a method for upgrading residual hydrocarbon feedstock in accordance with embodiments disclosed herein.

3 is a simplified method flow diagram of a method for an integrated hydrotreating reactor system for use in a method for upgrading residual hydrocarbon feedstock in accordance with embodiments disclosed herein.

4 is a flow chart of another simplified method for a method for an integrated hydrotreating reactor system for use in a process for upgrading residual hydrocarbon feedstock in accordance with embodiments disclosed herein.

Detailed description

In one aspect, the examples herein are generally directed to a hydrogen conversion process comprising a process for hydrocracking a residue and other heavy hydrocarbon fractions. More particularly, the embodiments disclosed herein relate to solvent deasphalting-residual hydrocarbon feedstock, treating the formed deasphalted oil in a residue desulfurization unit and a residue hydrocracking unit, and The solvent deasphalted bitumen is treated in a separate residue hydrocracking unit.

The hydrogen conversion process disclosed herein can be used to react residual hydrocarbon feedstocks in the presence of hydrogen and one or more hydrogen conversion catalysts under conditions of elevated temperature and pressure to convert the feedstock to have reduced contaminants (such as sulfur and/or nitrogen). A lower molecular weight product. The hydrogen conversion process may include, for example, hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrocracking, hydrodemetallization, hydroDeCCR, or hydrogenated deasphaltenes, and the like.

As used herein, reference to a residual hydrocarbon fraction of a residual hydrocarbon or a similar term is defined as a hydrocarbon fraction having a boiling or boiling range above about 340 ° C, but may also include the entire heavy crude treatment. The residual hydrocarbon feedstock that can be used in the processes disclosed herein can comprise various refineries and other hydrocarbon fluids, such as petroleum atmospheric or vacuum residues, deasphalted oil, deasphalted asphalt, hydrocracked atmospheric distillation columns, or Vacuum distillation column bottom portion, straight-run vacuum gas oil, hydrocracked vacuum gas oil, fluid catalytic cracking (FCC) slurry oil, vacuum gas oil from fluidized bed hydrocracking method, shale derived Oil, coal derived oil, tar sand bitumen, tall oil, bio-derived crude oil, black oil, and other similar hydrocarbon fluids, or combinations thereof, each of which may be straight-run, treated, hydrogenated A fluid that is cracked, desulfurized, and/or partially demetallized. In certain embodiments, the residual hydrocarbon fraction may comprise a hydrocarbon having a normal boiling point of at least 480 ° C, at least 524 ° C, or at least 565 ° C.

Referring now to Figure 1, a residual hydrocarbon fraction (residue) 10 is supplied to a solvent deasphalting unit (SDA) 12. In SDA 12, the residual hydrocarbon is contacted with a solvent to selectively dissolve asphaltenes and similar hydrocarbons to produce a deasphalted oil (DAO) fraction 14 and a bitumen fraction 15.

Solvent deasphalting can be achieved by SDA 12, for example, by subjecting the residual hydrocarbon feedstock to a light hydrocarbon solvent at a temperature ranging from about 38 ° C to about 204 ° C and a pressure ranging from about 7 bar to about 70 bar. Implemented by contact. Solvents useful for SDA 12 may comprise C3, C4, C5, C6 and/or C7 hydrocarbons such as propane, butane, isobutylene, pentane, isopentane, hexane, heptane, or mixtures thereof. The use of light hydrocarbon solvents provides high lift (high DAO yield). In certain embodiments, the DAO fraction 14 recovered from the SDA unit 12 can contain 500 Asphaltene from wppm to 5000wppm (ie, heptane insoluble), 50 to 150wppm metal (such as Ni, V, and others), and 5% to 15% by weight of Conradson carbon residue .

The bitumen fraction 15 can then be combined with a diluent 17, such as SRVGO (straight-run vacuum gas oil), to produce a diluted bitumen (residue) fraction 19. The diluted bitumen fraction 19 and hydrogen 21 can then be supplied to an ebullated bed reactor system 42 which can include one or more ebullated bed reactors in which the hydrocarbon and hydrogen are contacted with a hydrogen conversion catalyst to at least A portion of the bitumen reacts with hydrogen to form a lighter hydrocarbon, demetallizing the bitumen hydrocarbon, removing the Conradson carbon residue, or converting the residue to a useful product.

The reactor in the bubbling bed reactor 42 can have a hydrogen partial pressure in the range of from about 380 ° C to about 450 ° C, a hydrogen partial pressure in the range of from about 70 bar to about 170 bar, and from about 0.2 h ^-1 to about 2.0 h. Liquid hourly space velocity (LHSV) operation over a range of ^-1 . In an ebullated-bed reactor, the catalyst can be counter-mixed and maintained in a random motion by recirculating the liquid product. This can be accomplished by first separating the recycled oil from the gas product. The oil is then recirculated by an external pump or, as exemplified, by a pump mounted to one of the bottom covers of the reactor having an impeller.

The target conversion in the bubbling bed reactor system 42 can range from about 40% by weight to about 75% by weight, depending on the starting material to be treated. In any event, the target conversion rate needs to be maintained below the extent to which the sludge forms an excess and thus hinders the continuity of the operation. In addition to converting residual hydrocarbons to lighter hydrocarbons, sulfur removal can range from about 40% to about 80% by weight, and metal removal can range from about 60% to 85% by weight, and Conrad Carbon residue The (CCR) removal can range from about 30% by weight to about 65% by weight.

After conversion in the bubbling bed reactor system 42, the partially converted hydrocarbons can be recovered via a flow line 44 as a mixed vapor/liquid effluent and supplied to a fractionation system 46 to recover one or more hydrocarbon fractions. As illustrated, the fractionation system 46 can be used to recover an exhaust gas 48 containing light hydrocarbon gas and hydrogen sulfide (H ₂ S), a light naphtha fraction 50, a heavy naphtha fraction 52, and a kerosene. Fraction 54, a diesel fraction 56, a light vacuum gas oil fraction 58, a heavy gas oil fraction 60, and a vacuum residue fraction 62. In certain embodiments, vacuum residue fraction 62 can be recycled for further processing, such as to SDA unit 12, ebullated bed reactor system 42, or other reaction units 16, 20 as discussed below. In other embodiments, vacuum residue fraction 62 can be blended with a cutter fraction 66 to produce a fuel oil.

Fractionation system 46 can include, for example, a high pressure high temperature (HP/HT) separator to separate effluent vapor from the effluent liquid. The separated vapor may be sent to a gas cooling, purification, and recycle gas compression, or may be combined via an integrated hydrogenation alone or in combination with an external distillate and/or a distillate produced in a hydrocracking process. The treatment reactor system (which may include one or more additional hydrogen conversion reactors) is treated and thereafter sent to a gas cooling, purification, and compression.

The separated liquid from the HP/HT separator can be flashed and sent to an atmospheric distillation system along with other distillate products recovered from the gas cooling and purification section. Then, the bottom portion of the atmospheric distillation column, such as a hydrocarbon having a starting boiling point of at least about 340 ° C, such as a starting boiling point ranging from about 340 ° C to about 427 ° C, may be further processed via a vacuum distillation system. The vacuum distillate is recovered.

The vacuum distillation column bottoms product, such as a hydrocarbon having a starting boiling point of at least about 480 ° C, such as a starting boiling point ranging from about 480 ° C to about 565 ° C, may be, for example, by direct heat exchange or A portion of the residual hydrocarbon feed is injected directly into the bottom of the vacuum distillation column and cooled to a container for storage.

In certain embodiments, the fuel oil fraction 62 recovered after treatment in the bubbling bed reactor system 42 and the fractionation system 46 may have a sulfur content of 2.25 wt% or less; 2.0 wt% or less in other embodiments; And in other embodiments, it is 1.75 wt% or less.

The deasphalted oil fraction 14 recovered from the SDA unit 12 is selectively heated, combined with a hydrogen rich gas 23, and supplied to a residue desulfurization (RDS) unit 16. RDS unit 16 can include one or more residue desulfurization reactors.

In certain embodiments, the RDS unit 16 can be included in one or more upflow reactors (UFR) upstream of the RDS reactor (not illustrated). The DAO can be mixed with a hydrogen rich gas 23 upstream of the reactor or with a feed entering the lower portion of the UFR, and in some embodiments with the effluent recovered from the UFR. The UFR can help increase the catalyst life of the downstream RDS catalyst bed and remove some of the sulfur, Conradson carbon residue, and asphaltenes in the feed.

Operating conditions for the RDS unit 16 comprising the UFR and/or RDS reactor can be included in a temperature ranging from about 360 ° C to about 400 ° C, and a hydrogen partial pressure ranging from about 70 bar to about 170 bar. The RDS can achieve at least 70% by weight in certain embodiments, at least 80% by weight in other embodiments, and in other The examples are desulfurization rates up to or higher than 92% by weight.

The effluent 18 recovered from the RDS unit 16 can then be further processed in a hydrocracking reactor system 20, which can comprise one or more hydrocracking reactors in series or in parallel.

In reactor system 20, the RDS effluent can be at a hydrogen partial pressure ranging from about 70 bar to about 170 bar, at a temperature ranging from about 380 ° C to about 450 ° C, and from about 0.2 h ^-1 The LHSV to a range of about 2.0 h ^-1 is hydrocracked in the presence of a catalyst. In certain embodiments, the operating conditions in the hydrocracking reactor system 20 can be similar to those described above for the bubbling bed reactor system 42. In other embodiments, such as where the hydrocracking reactor system 20 comprises one or more ebullated-bed reactors, the bubbling bed reactor can operate at a higher severity condition than in the reactor system 42, with a higher severity Refers to higher temperatures, higher pressures, lower space rates, or a combination of these.

Depending on the nature of the vacuum residual feedstock, the extent to which the metal and Conradson carbon residue are removed in the RDS unit 16, and the SDA solvent used, the recovered DAO can be as a fixed bed reaction system or as illustrated. Treatment in bed reactor system 20 can be similar to that described above for bubbling bed reactor system 42 with respect to gas/liquid separation and catalyst recycle. A fixed bed reactor system can be used, for example, where the metal and Conradson carbon residue content of DAO is less than 80 wppm and 10 wt%, respectively, such as 50 wppm and 7 wt% for individual systems. An ebullated bed reactor system can be used, for example, when the metal and Conradson carbon residue levels are higher than those described above for a fixed bed reactor system. For any hydrocracking reactor system, the number of reactors used can be based on feed rate, total target residue The degree of conversion of the material, and the amount of conversion achieved in the RDS unit 16 is determined by other variables. In certain embodiments, one or two hydrocracking reactors can be used in the hydrocracking reactor system 20.

After conversion in the hydrocracking reactor system 20, the partially converted hydrocarbons can be recovered via a flow line 22 as a mixed vapor/liquid effluent and supplied to a fractionation system 24 to recover one or more hydrocarbon fractions. As illustrated, the fractionation system 24 can be used to recover an exhaust gas 26, a light naphtha fraction 28, a heavy naphtha fraction 30, a kerosene fraction 32, a diesel fraction 34, a light vacuum gas. Oil fraction 36, a heavy vacuum gas oil fraction 38, and a vacuum residue fraction 40. In certain embodiments, the vacuum residue fraction 40 can be recycled for further processing. In other embodiments, vacuum residue fraction 40 can be blended with a cutter fraction 64 to produce a fuel oil.

Fractionation system 24 can include, for example, a high pressure high temperature (HP/HT) separator to separate effluent vapor from the effluent liquid. The separated vapor may be sent to a gas cooling, purification, and recycle gas compression, or may be combined via an integrated hydrogenation alone or in combination with an external distillate and/or a distillate produced in a hydrocracking process. The treatment reactor system (which may include one or more additional hydrogen conversion reactors) is treated and thereafter sent to a gas cooling, purification, and compression.

The separated liquid from the HP/HT separator can be flashed and sent to an atmospheric distillation system along with other distillate products recovered from the gas cooling and purification section. Then, the bottom portion of the atmospheric distillation column, such as a hydrocarbon having a starting boiling point of at least about 340 ° C, such as a starting boiling point ranging from about 340 ° C to about 427 ° C, may be further processed via a vacuum distillation system. The vacuum distillate is recovered.

The vacuum distillation column bottoms product, such as a hydrocarbon having a starting boiling point of at least about 480 ° C, such as a starting boiling point ranging from about 480 ° C to about 565 ° C, may be, for example, by direct heat exchange or A portion of the residual hydrocarbon feed is injected directly into the bottom of the vacuum distillation column and cooled to a container for storage.

The total conversion of the DAO fraction via RDS unit 16 and hydrocracking reaction system 20 can range from about 75% to about 95% by weight, such as from about 85% to about 90% by weight.

In certain embodiments, the fuel oil fraction 40 recovered after treatment in the RDS unit 16, the hydrocracking reactor system 20, and the fractionation 24 may have 1.25 wt% or less; in other embodiments 1.0 wt% or Less; and in other embodiments, a sulfur content of 0.75 wt% or less.

Catalysts useful in RDS reactors, URF, and bubbling bed reactors can comprise any catalyst useful for hydrotreating or hydrocracking a hydrocarbon feedstock. A hydrotreated catalyst, for example, can comprise any catalyst composition that can be used to catalyze the hydrogenation of a hydrocarbon feedstock to increase its hydrogen content and/or remove heteroatom contaminants. A hydrocracking catalyst, for example, can comprise any catalyst composition that can be used to catalyze the addition of hydrogen to large or complex hydrocarbon molecules and to cleave such molecules to obtain smaller, lower molecular weight molecules.

Hydrogen conversion catalyst compositions for use in accordance with the hydrogen conversion process disclosed herein are known to those skilled in the art, and several are commercially available from W.R. Grace & Co., Criterion Catalysts & Technologies, and Albemarle et al. Suitable hydrogen conversion catalysts may comprise one or more selected from the group Elements of Groups 4-12 of the Periodic Table of the Elements. In certain embodiments, the hydrogen conversion catalyst according to the disclosed embodiments may comprise nickel, cobalt, tungsten, molybdenum, and one or more of these combinations, thereby forming, or substantially The composition is unsupported or supported on a porous substrate such as cerium oxide, aluminum oxide, titanium oxide, or a combination thereof. The hydrogen conversion catalyst may be in the form of, for example, a metal oxide when supplied by a manufacturer or from a regeneration process. In certain embodiments, the hydrogen conversion catalyst can be presulfided and/or preconditioned prior to introduction to the hydrocracking reactor.

The distillate hydrotreating catalyst that can be used comprises a catalyst selected from the elements known to provide catalytic hydrogenation activity. At least one metal component selected from the group consisting of Group 8-10 elements and/or Group 6 elements is generally selected. The Group 6 element may comprise chromium, molybdenum, and tungsten. Group 8-10 elements may comprise iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The amount of the hydrogenation component in the catalyst is suitably in the range of from about 0.5% by weight to about 10% by weight of the Group 8-10 metal component, and from about 5% by weight to about 25% by weight of the Group 6 metal component, It is calculated as metal oxide per 100 parts by weight of the total catalyst, wherein the weight percentage is based on the weight of the catalyst before vulcanization. The hydrogenation component of the catalyst can be in the form of an oxide and/or a sulfide. If at least one of the compositions of the Group 6 and Group 8 metal components is present as a (mixed) oxide, it will undergo a sulfurization treatment prior to proper use in hydrocracking. In certain embodiments, the catalyst comprises one or more components of nickel and/or cobalt, and one or more components of molybdenum and/or tungsten, or one or more components of platinum and/or palladium. Catalysts containing nickel and molybdenum, nickel and tungsten, platinum and/or palladium are useful.

Hydrotreating catalysts which may be useful residues generally comprise a component selected from Group 6 (such as molybdenum and/or tungsten) and a Group 8-10 element (such as cobalt and/or nickel), or the like A catalyst consisting of a hydrogenated component of the mixture which can be supported on an alumina support. Phosphorus (Group 15) oxides are selectively present as an active ingredient. A typical catalyst may contain from 3 to 35% by weight of a hydrogenation component, and an alumina binder. The catalyst pellets may range in size from 1/32 inch to 1/8 inch and may have a spherical, extruded, trilobal or four-leaf shape. In certain embodiments, the feed to the catalyst zone is first contacted with a catalyst that is preselected for removal of the metal, even if some removal of sulfur, nitrogen, and aromatics can occur. The subsequent catalyst layer can be used to remove sulfur and nitrogen, even though such is also expected to catalyze the removal and/or cleavage of the metal. The catalyst layer for demetallization may comprise a catalyst having an average pore size ranging from 125 to 225 angstroms and a pore volume ranging from 0.5 to 1.1 cm ³ /g. The catalyst layer for denitrification/desulfurization may comprise a catalyst having an average pore size ranging from 100 to 190 angstroms and a pore volume of 0.5 to 1.1 cm ³ /g. U.S. Patent No. 4,990,243 describes a hydrotreating catalyst having a pore size of at least about 60 angstroms, and preferably from about 75 angstroms to about 120 angstroms. A demetallization catalyst that can be used in the present process is described, for example, in U.S. Patent No. 4,976,848, the entire disclosure of which is incorporated herein by reference. </ RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt; Catalysts useful for the desulfurization of the middle distillate, the vacuum gas oil fluid, and the naphtha fluid are described, for example, in U.S. Patent No. 4,990,243, the entire disclosure of which is incorporated herein by reference.

Useful residue hydrotreating catalysts comprise a catalyst having a porous refractory substrate comprised of alumina, ceria, phosphorus, or various combinations thereof. One or more catalysts may be used as a residue hydrotreating catalyst, and if two or more catalysts are used, such catalysts are present as a layer in the reactor zone. The catalyst in the lower layer can have good demetallization activity. These catalysts may also have hydrogenation and desulfurization activities, and it may be advantageous to use large pore size catalysts to maximize metal removal. Catalysts with these characteristics are not optimal for the removal of Conradson carbon residues and sulfur. The average pore size of the catalyst used for the lower or lower layers will typically be at least 60 Angstroms and will be quite large in many cases. The catalyst may contain a metal or metal composition such as nickel, molybdenum or cobalt. Catalysts which can be used in the lower or lower layers are described, for example, in U.S. Patent Nos. 5,071,805, 5,215,955, and 5,472,928. For example, a catalyst based on a nitrogen method as described in U.S. Patent No. 5,472,928 and having a pore size of at least 20% in the range of 130 to 170 angstroms can be used for the lower catalyst layer. The catalyst present in the upper layer or the upper layers of the catalyst zone is required to have a larger hydrogenation activity than the catalyst in the lower or lower layers. Thus, the catalysts that can be used in the upper or upper layers can be characterized by smaller pore sizes and larger Conradson carbon residue removal, denitrification, and desulfurization activities. Typically, the catalyst will contain metals such as nickel, tungsten and molybdenum to enhance hydrogenation activity. For example, a catalyst based on a nitrogen method as described in U.S. Patent No. 5,472,928 and having a pore size of at least 30% in the range of 95 to 135 angstroms can be used for the upper catalyst layer. The catalyst can be a shaped catalyst or a spherical catalyst. In addition, denser, less brittle catalysts can be used for upflow solidification. The catalyst zone is zoned to minimize catalyst particle rupture and entrainment of particles from the product recovered from the reactor.

Those skilled in the art will appreciate that various catalyst layers may be composed not only of a single catalyst type but also of a mixture of different catalyst types to achieve optimum removal of metal or Conradson carbon residue and desulfurization of this layer. the amount. Although some hydrogenation will occur in the lower part of this zone, the removal of Conradon's carbon residue, nitrogen, and sulfur will occur primarily in the upper or upper layers. Obviously, another metal removal will also occur. The particular catalyst or catalyst mixture selected for each layer, the number of layers in the zone, the proportioned volume in the bed of each layer, and the particular hydrotreating conditions selected will depend on the material to be treated by the unit, In addition to the desired product, it is subject to commercial considerations such as catalyst cost. All of these parameters are within the skill of those engaged in the petroleum refining industry and need not be further elaborated herein.

Referring now to Figure 2, wherein like numerals indicate like parts, a simplified flow diagram of a method for upgrading residual hydrocarbon feedstock in accordance with the disclosed embodiments herein is illustrated. As described above with respect to Figure 1, residual hydrocarbon feedstock 10 is treated via SDA unit 12 and the formed bitumen fraction is processed in bubbling bed reactor system 42 and fractionation system 46. The deasphalted fraction 14 can be combined with a hydrogen rich gas 23 and supplied to the RDS unit 16, which can comprise one or more residue desulfurization reactors.

The effluent 18 recovered from the RDS unit 16 unit can then be processed in a fractionation system 24 to produce one or more hydrocarbon fractions 26, 28, and 38, and the like, and a vacuum residue fraction 40. The vacuum residue fraction 40 and optionally one or more additional heavier hydrocarbon fractions recovered from the fractionation system 24 can then be supplied to A hydrocracking reactor system 20 produces hydrocarbons in the range of additional distillates. After conversion in reaction system 20, effluent 22 can be fractionated to recover various distillate hydrocarbon fractions. In certain embodiments, the effluent 22 can be fractionated with the effluent 18 in a fractionation system 24 (as illustrated) or a combined fractionation system that treats the effluents 18 and 44.

By advantageously combining SDA and RDS with, for example, a bubbling bed hydrocracking reactor, the conversion of the DAO fraction can be increased to very high amounts, such as from 85% to 90% by weight, while still producing a weight percent Sulfur stabilized fuel oil, even when treated with high sulfur containing residues, such as sulfur having up to or greater than 6.5% by weight. Treatment of SDA bitumen in a separate reaction/separation reactor group produces a 2% by weight sulfur stabilized fuel oil while converting 40% to 65% by weight of the bitumen to atmospheric and vacuum distillate boiling range materials. The combined total conversion formed from the two treatment reactor groups can range from about 55% by weight or 60% by weight up to about 95% by weight or more, such as from about 65% by weight to about 85% by weight. . Moreover, such conversions can be advantageously achieved without the formation of sinks that can cause blockages and intermittent operations.

example

In the following example, a 40k BPSD Arabian Heavy vacuum residue was treated with 73% liters of lift prior to an SDA unit. The formation properties of DAO and SDA asphalt are summarized in Table 1. Then, DAO containing 4.27 wt% of stream, 10 wt% of CCR and 47 wppm of Ni+V was treated in an RDS unit to reduce the sulfur content of the feed by 85 to 87 wt%. At the same time, the residue fraction in the feed is converted to 35 to 45%. In this example, the RDS effluent is then reversed in a single ebullated bed coupled to the RDS reactor. The hydrocracking in the reactor increased the total conversion to 85% by volume and the total HDS to 91.8% by weight. It is estimated that the unconverted oil (UCO) formed individually has a sulfur content of about 1.0% by weight and 11.9° and an API gravity. It is expected that the UCO from this reaction system will meet the low sulfur fuel oil specifications without any additional cutter stock addition. The total space rate required to achieve this conversion and the amount of desulfurization was estimated to be about 0.2 hr-1.

Then, fifty-five (55) vol% of SDA bitumen was also converted in a separate ebullated bed reactor system containing a single reactor in parallel with the RDS and hydrocracking reactor to produce a medium containing 2.6 wt% sulfur. A vacuum residue of sulfur. After the cutter stock is added, the fuel oil formed will contain less than 2% by weight sulfur and more preferably less than 1.5% by weight sulfur, depending on the fuel oil blending component. The reactor space rate estimate for the bitumen conversion unit is about 0.25 h ^-1 , resulting in a total space velocity of 0.22 h ^-1 of RDS plus DAO hydrocracking reactor and bitumen conversion reactor.

This configuration resulted in a total conversion of 75% by volume, producing about 12,096 BPSD diesel, 12,332 BPSD hydrocrack or FCC feed, 4,056 BPSD LS fuel oil, 4,760 BPSD moderate sulfur vacuum residue. The overall yield and product properties of this treatment configuration are provided in Table 2.

Figures 3 and 4 illustrate an embodiment of IHRS and are described below, but other embodiments may be apparent to those skilled in the art. image 3 An embodiment in which the IHRS system is installed downstream of the bubbling bed reactor system 42 is described. 4 illustrates an embodiment in which an IHRS system is installed downstream of a hydrocracking reactor system 20.

As shown in Figure 3, the effluent stream 44 from the fluidized bed hydrotreating reactor 42 can be cooled in a heat exchanger (not shown) and supplied to an HP/HT V/L separator 81 where A vapor stream comprising a light product and a distillate having a boiling point below about 1000 °F and a liquid stream comprising unconverted residue can be separated and processed separately in downstream equipment. A vapor stream 67 can be supplied to a fixed bed hydrotreating reactor 86 for completion of hydrotreating, hydrocracking, or a combination thereof. An effluent stream 68 from the IHRS fixed bed reactor system 86 is supplied to a fractionation system 147 which recovers one of the exhaust streams 48 as described above, a light hydrotreated or hydrocracked naphtha stream 50, heavy The hydrotreated or hydrocracked naphtha stream 52, the hydrotreated or hydrocracked kerosene stream 54, the hydrotreated or hydrocracked diesel sulfur 56. The liquid stream 63 can be cooled in a heat exchanger (not shown) and depressurized in a pressure drop system (not shown), after which it is supplied to a vacuum fractionation system 72 which recovers a light hydrogenation. The treated or hydrocracked VGO stream 58, a heavier hydrotreated or hydrocracked VGO stream 60, and an unconverted vacuum residue stream 62. In certain embodiments, the vacuum distillation column bottoms product stream, such as a hydrocarbon having a starting boiling point of at least about 480 ° C, such as a starting boiling point in the range of from about 480 ° C to about 565 ° C, may be, for example, The product is directly stored by direct heat exchange or by injecting a portion of the residual hydrocarbon feed directly into the bottom of the vacuum distillation column for storage.

As shown in Figure 4, in another IHRS flow chart, from the bubbling bed The effluent stream 22 of the reactor system 20 can be cooled in a heat exchanger (not shown) and supplied to an HP/HT V/L separator 181 where one contains light products and has a boiling point below about 1000 °F. The vapor stream of the normal boiling distillate and a liquid stream containing the unconverted residue can be separated and processed separately in downstream equipment. A vapor stream 167 is supplied to a fixed bed hydrotreating reactor 186 for completion of hydrotreating, hydrocracking, or a combination thereof. An effluent stream 168 from the IHRS fixed bed reactor system 166 can be supplied to an atmospheric fractionation system 146 that recovers an exhaust stream 26, a light hydrotreated or hydrocracked naphtha stream 28, and a heavy Hydrotreated or hydrocracked naphtha stream 30, hydrotreated or hydrocracked kerosene stream 32, hydrogen hydrotreated or hydrocracked diesel stream 34. A liquid stream 163 is cooled in a heat exchanger (not shown) and depressurized in a pressure drop system (not shown) and supplied to a vacuum fractionation system 172 which recovers a light hydrogenation. The treated or hydrocracked VGO stream 36, a heavier hydrotreated or hydrocracked VGO stream 38, and an unconverted vacuum residue stream 40. In certain embodiments, then, the vacuum distillation column bottoms product stream, such as a hydrocarbon having a starting boiling point of at least about 480 ° C, such as a starting boiling point in the range of from about 480 ° C to about 565 ° C, may, For example, by direct heat exchange or by injecting a portion of the residual hydrocarbon feed directly into the bottom of the vacuum distillation column, it is cooled and sent to a vessel for storage.

Although the above description is directed to two separate fractionation systems 24, 46, the embodiments disclosed herein also contemplate the fractionation of the effluent 22, 44 in a common fractionation system. For example, the effluent may be supplied to a common gas cooling, purification, and compression circuit prior to further processing in an atmospheric distillation column and a vacuum distillation column as described above. If you want, use a combined separation The approach may provide a reduced capital investment, but will result in a single fuel oil fraction having a stream content intermediate between the individual treatments. This combined separation can also be used with IHRS installed downstream of the bubbling bed reactor system 42 and the hydrocracking reactor system 20 and supplied by the combined effluent 22,44.

As noted above, the embodiments disclosed herein effectively integrate SDA and RDS with residue hydrocracking to extend the residue conversion limit above that achieved by hydrocracking alone. Again, higher conversion rates can be achieved with less catalytic reactor volume than would otherwise be the case with similar conversion rates. Thus, the embodiments disclosed herein can provide comparable or higher conversion rates, but require lower capital investment. Furthermore, the embodiments disclosed herein can be used to provide a fuel oil having less than 1% by weight sulfur from a high sulfur containing feed while maximizing the overall conversion.

Advantageously, the initial SDA allows hydrocracking of the bitumen to be operated at relatively high temperatures and air rates by limiting conversion and without the tendency to form excessive sinking. Hydrocracking of DAO can also be carried out at relatively high temperatures and space rates because DAO can have a very low asphaltene content. Thus, the overall treatment disclosed herein can be carried out using a low reactor volume while still achieving high conversions. Similarly, other advantages may include: reduced catalyst consumption due to unacceptable metals in the bitumen from the SDA unit; reduced capital investment; and the need to remove or significantly reduce the injection of slurry oil upstream of the bubbling bed reactor Sex, and other advantages.

Although this disclosure contains a limited number of embodiments, it has Other embodiments of the present disclosure will be apparent to those skilled in the art. Therefore, the scope is limited by the scope of the appended patent application.

10‧‧‧Residual hydrocarbon fractions

12‧‧‧Solvent deasphalting unit

14‧‧‧Deasphalted oil fraction

15‧‧‧Asphalt fraction

16‧‧‧Residue desulfurization unit

17‧‧‧ Thinner

18‧‧‧ effluent

19‧‧‧Diluted bitumen fraction

20‧‧‧ Hydrocracking Reactor System

21‧‧‧ hydrogen

22‧‧‧Flow pipeline

23‧‧‧Gas-rich gas

24‧‧‧ fractionation system

26‧‧‧Exhaust

28‧‧‧Light naphtha fraction

30‧‧‧Heavy naphtha fraction

32‧‧‧kerosene fraction

34‧‧‧ diesel fraction

36‧‧‧Light vacuum gas oil fraction

38‧‧‧ Heavy vacuum gas oil fraction

40‧‧‧vacuum residue

42‧‧‧Boiled bed reactor system

44‧‧‧Flow pipeline

46‧‧‧ fractionation system

48‧‧‧Exhaust

50‧‧‧Light naphtha fraction

52‧‧‧Heavy naphtha fraction

54‧‧‧kerosene fraction

56‧‧‧ diesel fraction

58‧‧‧Light vacuum gas oil fraction

60‧‧‧Heavy gas fraction

62‧‧‧vacuum residue fraction

64‧‧‧Cutter Distillate

66‧‧‧Cutter Distillate

Claims (22)

A method for upgrading residual hydrocarbons, the method comprising: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; converting the bitumen fraction and hydrogen with a first hydrogen The catalyst is contacted in a first bubbling bed hydrogen shift reactor system; an effluent from the first ebullated bed hydrogen shift reactor system is recovered; and the effluent from the first ebullated bed hydrogen shift reactor system is fractionated One or more hydrocarbon fractions are recovered. The method of claim 1 further comprising mixing the bitumen fraction with a diluent prior to the contacting to form a diluted bitumen fraction. The method of claim 2, wherein the diluent comprises at least one of FCC cycle oil, slurry oil, aromatic compound extract, and straight-run vacuum gas oil. The method of claim 1, further comprising: contacting the deasphalted oil fraction and hydrogen with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; recovering a hydrodesulfurization from the residue An effluent of the unit; contacting the residue hydrodesulfurization unit effluent or a portion thereof with a third hydrogen conversion catalyst in a hydrocracking reactor system; recovering a system from the hydrocracking reactor An effluent; fractionating the effluent from the hydrocracking reactor system to recover one Or a plurality of hydrocarbon fractions. The method of claim 4, wherein the hydrocracking reactor system comprises a second bubbling bed hydrogen shift reactor system comprising one or more ebullated bed reactors. The method of claim 5, wherein the deasphalted oil fraction has a metal content greater than about 80 wppm and a Conradson carbon residue (CCR) content greater than about 10 wt%. The method of claim 4, wherein the effluent from the first bubbling bed hydrogen conversion reactor system and the hydrocracking reactor system is fractionated in a common fractionation system. The method of claim 4, wherein the one or more hydrocarbon fractions produced by fractionating the effluent from the one or two of the first bubbling bed hydrogenation reactor system and the hydrocracking reactor system comprises A vacuum residual hydrocarbon fraction. The method of claim 7, further comprising recycling the vacuum residual hydrocarbon fraction to at least one of the solvent deasphalting, the first bubbling bed hydrogen conversion reactor system, and the hydrocracking reactor system. The method of claim 1, wherein the residual hydrocarbon fraction comprises at least one of petroleum atmospheric or vacuum residual oil, deasphalted oil, deasphalted asphalt, atmospheric distillation column for hydrogen hydrocracking, or vacuum distillation. Tower bottom, straight-run vacuum gas oil, hydrocracked vacuum gas oil, fluid catalytic cracking (FCC) slurry oil, vacuum gas oil from a fluidized bed process, shale derived oil, coal derived Oil, biologically derived crude oil, tar sand asphalt, tall oil, black oil. The method of claim 1, wherein the contacting in the first bubbling bed hydrogen shift reactor system results in a hydrocarbon conversion ranging from about 40% by weight to about 75% by weight, the sulfur removal being from about 40 weights From about 100% by weight to about 80% by weight, the metal removal is in the range of from about 60% by weight to about 85% by weight, and the Conradson Carbon Residue (CCR) removal is from about 30% by weight to about 65% by weight. The range of %. The method of claim 4, wherein the total conversion of the deasphalted oil fraction via both the residue desulfurization unit and the hydrocracking reactor system is from about 75% by weight to about 95% by weight. The range of %. The method of claim 4, wherein the fuel oil is produced by the fractionation of the hydrocracking reaction system effluent to have a sulfur content of 1% by weight or less. The method of claim 1, wherein the fuel oil produced by the fractional distillation of the ebullating reaction system effluent has a sulfur content of less than 2% by weight or less. The method of claim 4, wherein the total conversion of the residual hydrocarbon fraction is in the range of from about 60% by weight to about 95% by weight. The method of claim 1, wherein the solvent used in the solvent deasphalting unit contains a light hydrocarbon having from 3 to 7 carbon atoms. The method of claim 1, further comprising converting the effluent from the first bubbling bed hydrogen conversion reactor with a second hydrogen prior to fractionating the effluent from the first bubbling bed hydrogen conversion reactor system Catalyst contact. The method of claim 4, further comprising reacting from the hydrocracking The effluent from the hydrocracking reactor system is contacted with a second hydrogen conversion catalyst prior to fractionation of the effluent of the reactor system. A method for upgrading residual hydrocarbons, the method comprising: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; converting the bitumen fraction and hydrogen with a first hydrogen The catalyst is contacted in a first bubbling bed hydrogen shift reactor system; an effluent from the first ebullated bed hydrogen shift reactor system is recovered; and the effluent from the first ebullated bed hydrogen shift reactor system is fractionated Retrieving one or more hydrocarbon fractions; contacting the deasphalted oil fraction and hydrogen with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; recovering a hydrodesulfurization unit from the residue An effluent; contacting the residue hydrodesulfurization unit effluent with a third hydrogen conversion catalyst in a hydrocracking reactor system; recovering an effluent from the hydrocracking reactor system; The effluent of the hydrocracking reactor system is fractionated to recover one or more hydrocarbon fractions. A method for upgrading residual hydrocarbons, the method comprising: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; converting the bitumen fraction with hydrogen and a first hydrogen The catalyst is contacted in a first bubbling bed hydrogen conversion reactor system; Recovering an effluent from the first ebullated bed hydrogen shift reactor system; fractionating the effluent from the first ebullated bed hydrogen shift reactor system to recover one or more hydrocarbon fractions; and deasphalting the oil The fraction and hydrogen are contacted with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; an effluent from the residue hydrodesulfurization unit is recovered; the effluent from the hydrocracking reactor system is passed Fractionating to recover one or more hydrocarbon fractions comprising a vacuum residual hydrocarbon fraction; contacting the vacuum residual hydrocarbon fraction with a third hydrogen conversion catalyst in a hydrocracking reactor system; recovering one from the addition The effluent of the hydrogen cracking reactor system; and fractionating the effluent from the hydrocracking reactor system to recover one or more hydrocarbon fractions. A method for upgrading residual hydrocarbons, the method comprising: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; converting the bitumen fraction with hydrogen and a first hydrogen The catalyst is contacted in a first ebullated-bed hydrogen shift reactor system; an effluent from the first ebullated-bed hydrogen shift reactor system is recovered; and the effluent from the first ebullated-bed hydrogen shift reactor system is fractionated And recovering the effluent from the first bubbling bed hydrogen conversion reactor with a second hydrogen conversion catalyst before recovering the one or more hydrocarbon fractions Contacting the deasphalted oil fraction and hydrogen with a third hydrogen conversion catalyst in a residue hydrodesulfurization unit; recovering an effluent from the residue hydrodesulfurization unit; The hydrodesulfurization unit effluent is contacted with a fourth hydrogen conversion catalyst in a hydrocracking reactor system; an effluent from the hydrocracking reactor system is recovered; and the hydrocracking reactor system is derived from the hydrocracking reactor system The effluent is fractionated to recover one or more hydrocarbon fractions. A method for upgrading residual hydrocarbons, the method comprising: solvent deasphalting a residual hydrocarbon fraction to produce a deasphalted oil fraction and a bitumen fraction; converting the bitumen fraction with hydrogen and a first hydrogen The catalyst is contacted in a first bubbling bed hydrogen shift reactor system; an effluent from the first ebullated bed hydrogen shift reactor system is recovered; and the effluent from the first ebullated bed hydrogen shift reactor system is fractionated Retrieving one or more hydrocarbon fractions; contacting the deasphalted oil fraction and hydrogen with a second hydrogen conversion catalyst in a residue hydrodesulfurization unit; recovering a hydrodesulfurization unit from the residue An effluent; contacting the residue hydrodesulfurization unit effluent or a portion thereof with a third hydrogen conversion catalyst in a hydrocracking reactor system; recovering an effluent from the hydrocracking reactor system ;and The effluent from the hydrocracking reactor system is contacted with a fourth hydrogen conversion catalyst prior to fractionating the effluent from the hydrocracking reactor system to recover one or more hydrocarbon fractions.