JP5661038B2 - System and method for producing a crude product - Google Patents

Description

  No. 12/233171, 12/233393, 12/233439, 12/212796, and 12/2008, all filed on Sep. 18, 2008. Insist on the priority of No. / 212737. This application claims the above priority and benefit, the disclosure of which is incorporated herein by reference.

  The present invention relates to systems and methods for treating or upgrading heavy oil feeds, and to crude products produced using such systems and methods.

  The oil industry increasingly relies on heavy oil feed streams such as heavy crude oil, residual oil, coal and tar sands as a source of feed. These feedstocks are characterized by high concentrations of asphaltene-rich residues and low API specific gravity (some are as low as 0 ° API).

  PCT Patent Application Publication No. WO 2008/014947, US Patent Application Publication No. 2008/0083650, US Patent Application Publication No. 2005/0241993, US Patent Application Publication No. 2007/0138057, and US Patent No. 6,660,157. Describes a process, system, and catalyst for processing a heavy oil feed stream. Heavy oil feedstocks typically contain high levels of heavy metals. Some heavy metals such as nickel and vanadium tend to react quickly, resulting in deposition or trapping of vanadium rich solids in equipment such as reactors. Solid deposition reduces the capacity available for reaction and shortens the operating time.

  There remains a need for improved systems and methods for upgrading / processing process heavy oil feed streams with reduced build-up of heavy metals in process equipment.

  According to one aspect, the present invention relates to a method by which a heavy oil feedstock can be upgraded. This method uses multiple contact zones, separation zones and at least one intermediate solvent deasphalting unit (SDA). The method comprises: a) combining a hydrogen-containing gas feed stream, a heavy oil feedstock, and a slurry catalyst in a first contact zone under hydrocracking conditions, wherein at least a portion of the heavy oil feedstock has been upgraded C) sending a mixture of the upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock to the separation zone; and d) upgrading in the separation zone The resulting product is withdrawn as an overhead stream with a hydrogen-containing gas, the slurry catalyst and unconverted heavy oil feed are withdrawn as a non-volatile stream, and e) at least a portion of the non-volatile stream is sent to the SDA unit. Separating asphaltene and slurry catalyst from deasphalted oil, and f) additional Under hydrocracking conditions with hydrogen gas and additional slurry catalyst, the deasphalted oil and the remainder of the non-volatile stream from the previous separation zone are sent to another contact zone to convert the deasphalted oil into an upgraded product. F) sending the upgraded product, slurry catalyst, hydrogen, and unconverted deasphalted oil to a separation zone, whereby the upgraded product is withdrawn as a head stream with hydrogen to produce a slurry catalyst And unconverted deasphalted oil is removed as a non-volatile stream; and g) recycling at least a portion of the non-volatile stream containing the slurry catalyst and unconverted deasphalted oil to at least one of the contact zones. Including.

  In another aspect, a method using a plurality of contact zones, separation zones and at least one intermediate solvent deasphalting unit (SDA) is provided, in which the heavy oil feed can be upgraded and at least one At least a portion of the non-volatile stream from the contact zone is sent to the SDA unit to separate the asphaltenes from the deasphalted oil.

  According to one aspect, the present invention relates to a method capable of upgrading a heavy oil feedstock with a reduction in heavy metal deposits in a front-end contact zone. The method uses a plurality of contact zones and separation zones, the method comprising: a) combining a hydrogen-containing gas feed stream, a heavy oil feedstock, and a slurry catalyst in a first contact zone under hydrocracking conditions. Converting at least a portion of the heavy oil feedstock into an upgraded product and injecting water and / or steam into the first contact zone in an amount of 1 to 25% by weight relative to the weight of the heavy oil feedstock. B) sending the mixture of upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock to the separation zone; and c) in the separation zone, the upgraded product is a hydrogen-containing gas. And the slurry catalyst and unconverted heavy oil feed are withdrawn as a non-volatile stream, and d) a non-volatile stream. Is sent to another contact zone under hydrocracking conditions along with additional hydrogen gas, unconverted heavy oil feedstock, and optionally fresh slurry catalyst, to convert the unconverted heavy oil feedstock into an upgraded product. And f) sending the upgraded product, slurry catalyst, hydrogen, and unconverted heavy oil feed to the separation zone so that the upgraded product is withdrawn as an overhead stream with hydrogen, and the slurry catalyst and Unconverted heavy oil feedstock is removed as a non-volatile stream and g) recycling at least a portion of the non-volatile stream to at least one of the contact zones.

  In another aspect, the invention relates to a method of upgrading heavy oil feedstock using a plurality of contact zones and separation zones, wherein water and / or steam is injected into the first contact zone, At least a portion of the non-volatile stream from the separation zone other than the separation zone is recycled to the first contact zone, the recycled stream ranging from 3 to 50% by weight of the total heavy oil feed to the process.

  According to one aspect, the present invention relates to a method by which a heavy oil feedstock can be upgraded. The method uses a plurality of contact zones and separation zones, the method comprising: a) a heavy oil feedstock having at least a portion of the heavy oil feedstock is fed to a contact zone other than the first contact zone; b) A product in which at least a portion of the heavy oil feedstock is upgraded by combining the hydrogen-containing gas feed stream, a portion of the heavy oil feedstock, and the slurry catalyst in the first contact zone under hydrocracking conditions. C) sending the mixture of upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock to the separation zone; and d) in the separation zone, the upgraded product, With the hydrogen-containing gas removed as a top stream, removing the slurry catalyst and unconverted heavy oil feed as a non-volatile stream, and e) the hydrogenated fraction Under conditions, the non-converted heavy oil feed to the upgraded product is sent to a separate contact zone with additional hydrogen gas, at least a portion of the heavy oil feed, and optionally a fresh slurry catalyst. F) sending the upgraded product, slurry catalyst, hydrogen, and unconverted heavy oil feed to the separation zone, whereby the upgraded product is withdrawn as a head stream with hydrogen to produce a slurry catalyst And unconverted heavy oil feedstock is removed as a non-volatile stream and g) recycling at least a portion of the non-volatile stream to the first contact zone.

  In another aspect, the method uses a plurality of contact zones and separation zones, the method comprising: a) providing a slurry catalyst containing a spent slurry catalyst and optionally a fresh catalyst slurry feed stream; b) combining a hydrogen-containing gas feed stream, a heavy oil feedstock, and a slurry catalyst in a contact zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock into an upgraded product; c) sending a mixture comprising the upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock to the separation zone; and d) in the separation zone, the upgraded product along with the hydrogen-containing gas. Removing as a top stream, removing the slurry catalyst and unconverted heavy oil feed as a non-volatile stream; and e) hydrogen. Under cracking conditions, sending a non-volatile stream with additional hydrogen gas and fresh slurry catalyst to another contact zone to convert the unconverted heavy oil feedstock into an upgraded product, and f) an upgraded product Product, slurry catalyst, hydrogen, and unconverted heavy oil feed are sent to the separation zone, whereby the upgraded product is withdrawn as overhead stream with hydrogen, and the slurry catalyst and unconverted heavy oil feed is non-volatile stream And g) recycling at least a portion of the non-volatile stream to the first contact zone.

  In yet another aspect, a method is provided that uses multiple contact zones and separation zones, in which the heavy oil feedstock can be upgraded and the fresh slurry catalyst is divided into contact zones.

  According to one aspect, the method uses a plurality of contact zones and separation zones, the method comprising: a) a hydrogen-containing gas feed stream, a heavy oil feedstock, in a first contact zone under hydrocracking conditions; And a slurry catalyst to convert at least a portion of the heavy oil feedstock into an upgraded product; and b) a mixture of the upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock. Sending to the separation zone, c) removing the upgraded product with the hydrogen-containing gas as an overhead stream in the separation zone, and removing the slurry catalyst and unconverted heavy oil feedstock as a non-volatile stream; d) Non-volatile with additional hydrogen gas, unconverted heavy oil feedstock, and optionally fresh slurry catalyst under hydrocracking conditions Sending a stream to another contact zone to convert the unconverted heavy oil feedstock into an upgraded product; and f) sending the upgraded product, slurry catalyst, hydrogen, and unconverted heavy oil feedstock to the separation zone. The upgraded product thereby is withdrawn as an overhead stream with hydrogen, and the slurry catalyst and unconverted heavy oil feedstock are withdrawn as a non-volatile stream, wherein the first contact zone is the next in series Operating at a temperature at least 10 ° F. below the contact zone.

  In yet another aspect, the present invention relates to a method capable of upgrading a heavy oil feedstock with a reduction in heavy metal deposits in the front contact zone. This method uses a plurality of contact zones and separation zones, and a) combining a hydrogen-containing gas feed stream, a heavy oil feedstock, and a slurry catalyst in a first contact zone under hydrocracking conditions, Converting at least a portion of the product into an upgraded product; b) sending a mixture of the upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock to the separation zone; and c) separation. In the zone, the upgraded product is withdrawn as an overhead stream with a hydrogen-containing gas, and the slurry catalyst and unconverted heavy oil feed are withdrawn as a non-volatile stream; and d) additional hydrogen under hydrocracking conditions. Non-volatile stream with gas, unconverted heavy oil feedstock, and optionally fresh slurry catalyst to separate contact zone F) converting the unconverted heavy oil feedstock into an upgraded product; and f) sending the upgraded product, slurry catalyst, hydrogen, and unconverted heavy oil feedstock to the separation zone, And the slurry catalyst and unconverted heavy oil feedstock are withdrawn as a non-volatile stream with hydrogen as a top stream, and the slurry catalyst to the first separation zone is recycled to the separation zone as a recycle catalyst stream. Including at least a portion of the non-volatile stream from one, the recycled catalyst stream is 3 to 50% by weight of the heavy oil feedstock.

FIG. 2 is a block diagram that schematically illustrates an embodiment of a hydroprocessing system for upgrading heavy oil feedstock having multiple contact zones and separation zones, wherein water and / or steam is injected into the front contact zone. To do. 2 is a flow diagram of a method for upgrading a heavy oil feed stream with water injection. 2 is a flow diagram of a method for upgrading a heavy oil feed stream with direct steam injection into the front contact zone. FIG. 4 is a flow diagram of another embodiment of a method for upgrading a heavy oil feed stream with a recycle catalyst stream at a rate sufficient to reduce heavy metal accumulation. A block diagram that schematically illustrates an embodiment of a hydroprocessing system for upgrading a heavy oil feedstock with a split fresh catalyst feed scheme, a split heavy oil feed scheme, and an additional intermediate hydrocarbon oil feedstock. It is. FIG. 3 is a block diagram that schematically illustrates another embodiment of a hydroprocessing system for upgrading heavy oil feedstock, with a solvent deasphalting unit for pretreating the heavy oil feedstock. 2 is a flow diagram of a method for upgrading a heavy oil feed stream with an embodiment of a catalyst split feed scheme, wherein a fresh catalyst feed stream is fed to all reactors in the process. FIG. 4 is a flow diagram of a method for upgrading a heavy oil feed stream, wherein a fresh catalyst feed stream is transferred from the first reactor to the other reactor in the method, with optional / additional hydrocarbon oil as feedstock Fed to the reactor. FIG. 5 is a flow diagram of another embodiment of a method for upgrading a heavy oil feed stream, wherein all of the fresh catalyst feed stream is sent to the last reactor in the method. 4 is a flow diagram of another embodiment of a method for upgrading a heavy oil feed stream, wherein some of the raw heavy oil feed stream is transferred from the first reactor to the other reactor in the method.

  The following terms are used throughout the specification and have the following meanings unless otherwise indicated.

  As used herein, “heavy oil” feed stream or feedstock means heavy crude oil and superheavy crude oil including but not limited to residual oil, coal, bitumen, shale oil, tar sands, and the like. . The heavy oil feedstock may be liquid, semi-solid, and / or solid. Examples of heavy oil feedstocks that can be upgraded as described herein include, but are not limited to, Canadian tar sands, Brazil's Santos and Campos basins, Egypt's Suez Bay, Chad, Venezuela's Suria, Includes vacuum residue from Malaysia and Sumatra, Indonesia. Other examples of heavy oil feedstocks include “barrel bottoms” and “residues” (or “residues”) (atmospheric tower bottoms (having a boiling point of at least 343 ° C. (650 ° F.)), or reduced pressure Refining process, including column bottoms (having a boiling point of at least 524 ° C. (975 ° F.)), or “residue pitch” and “vacuum residue” (having a boiling point of 524 ° C. (975 ° F.) or higher) Barrel bottoms and residual residues from

  Heavy oil feedstock properties include, but are not limited to, at least 0.1, at least 0.3, or at least 1 TAN; a viscosity of at least 10 cSt; up to 15 in one embodiment, up to 15 in another embodiment. Ten API specific gravity may be included. One gram of heavy oil feedstock is typically at least 0.0001 grams of Ni / V / Fe; at least 0.005 grams of heteroatoms; at least 0.01 grams of residue; at least 0.04 grams of C5 asphaltenes; At least 0.002 grams of MCR; (per gram of crude); one or more alkali metal salts of at least 0.00001 grams of organic acid; and at least 0.005 grams of sulfur. In one embodiment, the heavy oil feedstock has a sulfur content of at least 5% by weight and an API specific gravity of −6 to +6.

  The terms “treatment”, “treated”, “upgrade”, “upgrade” and “upgraded” are used in conjunction with heavy oil feedstocks to describe hydroprocessing. : Heavy oil feedstock that has been or has been subjected to hydroprocessing, or the material or crude product thus obtained (reduced molecular weight of heavy oil feedstock, reduced boiling point range of heavy oil feedstock, asphaltene concentration And / or a reduction in the concentration of hydrocarbon free radicals and / or a reduction in the amount of impurities such as sulfur, nitrogen, oxygen, halides, and metals).

  The upgrade or treatment of the heavy oil feed stream is generally referred to herein as “hydroprocessing”. Hydrotreating is not limited to these, but includes hydroconversion, hydrocracking, hydrogenation, hydrotreating, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodearomatization, hydrogen By any process carried out in the presence of hydrogen, including hydroisomerization, hydrodewaxing and hydrocracking (including selective hydrocracking). The hydroprocessing product may exhibit improved viscosity, viscosity index, saturate content, low temperature characteristics, volatility, depolarization, and the like.

  As used herein, hydrogen means hydrogen and / or the compound (s) that react to provide hydrogen when in the presence of a heavy oil feed stream and catalyst.

SCF / BBL (or scf / bbl) refers to a standard cubic foot unit of gas (N ₂ , H _2, etc.) per hydrocarbon feed stream of one barrel.

Nm ³ / m ³ means standard cubic meters of gas per heavy oil feed stream of 1 cubic meter.

  VGO or vacuum gas oil means a hydrocarbon having a boiling range distribution from 343 ° C. (650 ° F.) to 538 ° C. (1000 ° F.) at 0.101 MPa.

  “Wppm” means parts per million by weight.

  As used herein, the term “catalyst precursor” refers to a compound containing one or more catalytically active metals from which a catalyst is ultimately formed. It should be noted that the catalyst precursor may be catalytically active as a hydroprocessing catalyst. As used herein, a “catalyst precursor” can be referred to as a “catalyst” when used herein in the context of a catalyst feed stream.

  As used herein, the term “used catalyst” means a catalyst that has been used in at least one reactor in a hydroprocessing operation, thereby reducing its activity. For example, if the reaction rate constant of a fresh catalyst at a particular temperature is assumed to be 100%, the reaction rate constant for the spent catalyst is 95% or less in one embodiment and 80% or less in another embodiment. And in 3rd Embodiment, it is 70% or less. The term “spent catalyst” may be used interchangeably with “recycle catalyst”, “spent slurry catalyst” or “recycle slurry catalyst”.

  As used herein, the term “fresh catalyst” means a catalyst or catalyst precursor that has not been used in a reactor in a hydroprocessing operation. The term fresh catalyst is also used herein as a “regenerated” or “recovered” catalyst, ie used in at least one reactor in a hydroprocessing operation (“used catalyst”). A catalyst whose catalytic activity is restored or at least increased to a level well above the spent catalytic activity level. The term “fresh catalyst” may be used interchangeably with “fresh slurry catalyst”.

  As used herein, the term “slurry catalyst” (or sometimes referred to as “slurry” or “dispersed catalyst”) refers to a catalyst and / or catalyst precursor having a very small average dimension. Means a liquid medium in which body particles (fine particles or crystallites) are dispersed, for example, oil, water, or a mixture thereof.

  As used herein, “catalyst feed stream” refers to any catalyst suitable for upgrading heavy oil feed stream stock, such as one or more bulk catalysts and / or one or more supported catalysts. Is included. The catalyst feed stream may include at least one fresh catalyst, spent catalyst alone, or a mixture of at least one fresh catalyst and spent catalyst. In one embodiment, the catalyst feed stream is in the form of a slurry catalyst.

  As used herein, the term “bulk catalyst” may be used interchangeably with “unsupported catalyst” and the catalyst composition has a pre-prepared and shaped catalyst support. Mean that it is not in the form of a conventional catalyst, which is then filled with metal by an impregnation or deposition (deposition) catalyst. In one embodiment, the bulk catalyst is formed by precipitation. In another embodiment, the bulk catalyst has a binder incorporated into the catalyst composition. In yet another embodiment, the bulk catalyst is formed from a metal compound and does not include a binder. In a fourth embodiment, the bulk catalyst is a dispersion type catalyst for use as dispersed catalyst particles in a mixture of liquids (eg, hydrocarbon oils). In one embodiment, the catalyst comprises one or more commercially known catalysts, such as Microcat ™ from Exxon Mobil Corp.

  As used herein, the term “contacting zone” means an apparatus that is treated or upgraded by contacting a heavy oil feed stream with a slurry catalyst feed stream in the presence of hydrogen. In the contact zone, at least one characteristic of the coarse feed stream may be changed or upgraded. The contact zone may be a reactor, a portion of the reactor, multiple portions of the reactor, or a combination thereof. The term “contact zone” may be used interchangeably with “reaction zone”.

  As used herein, the term “separation zone” refers to an upgraded heavy oil feed stream from a contact zone that is fed directly to the separation zone or subjected to one or more intermediate processes. Then means a device that feeds directly into a separation zone, for example a flash drum or a high-pressure separator, where gas and volatile liquids are separated from non-volatile fractions. In one embodiment, the non-volatile fraction stream comprises an unconverted heavy oil feed stream, a small amount of heavier hydrocracked liquid product (synthetic or less volatile / non-volatile upgraded product), slurry catalyst And entrained solids (asphaltenes, coke, etc.).

  As used herein, the terms “bleed stream” or “bleed off stream” are “bleeded” or transferred from a hydroprocessing system and from an upgrade system. Means a stream containing spent (or recycled) catalyst that serves to prevent or “flush” the accumulation of metal sulfides and other undesirable impurities.

  The present invention relates to an improved system for treating or upgrading heavy oil feed streams, particularly heavy oil feedstocks having high levels of heavy metals.

  In a typical prior art hydroprocessing system having a plurality of contacting zones (reactors) in series, the feed stream to the second contacting zone is generally subject to heavy oil undergoing a treatment process in the first contacting zone. Thus, it is observed that it should be purified from the heavy oil feed stream to the first contact zone in the system, i.e., have less impurities such as nickel, vanadium, nitrogen, sulfur. It is also observed that the feed stream to the last contact zone in the system should generally be cleaner than the feed stream to the previous contact zone (s) in the system.

In a typical hydrotreating system, the catalyst feed scheme of the prior art, the supply flow stream to the contact zone after the system is typically specific impurity, for example, MCR, C ₅ and C ₇ asphaltenes content, such as It has further been observed that coke formation is promoted in the latter contact zone in the system.

  The feed stream to the later contact zone in the system is a) lower TAN; b) viscosity; c) lower residue content; d) lower API specific gravity; e) lower metal in the metal salt of the organic acid Content; and g) It has also been observed that, including these combinations, it has characteristics that differ from the characteristics of the heavy oil feed stream to the previous contact zone (s) in the system. However, in general, it is more difficult to process the feed stream to a later contact zone in the system with regard to the conversion and conversion characteristics of the crude product thus obtained. It was also observed. Furthermore, in the prior art feed scheme (fresh catalyst enters the first contact zone), it is observed that there is more coke formation in the later contact zone in the first contact zone. It is speculated that coke formation is probably related to the feed stream being more difficult to process into the subsequent contact zone and / or the reduced activity of the catalyst feed stream into the subsequent contact zone.

  In one embodiment, the upgrade method includes multiple reactors for the contact zone and the reactor configurations are the same or different. Examples of reactors that can be used herein include stacked bed reactors, fixed bed reactors, ebullated bed reactors, continuous stirred tank reactors, fluidized bed reactors, spray reactors, liquid / liquid Contactors, slurry reactors, liquid recycle reactors, and combinations thereof are included. In one embodiment, the reactor is an upflow reactor. In another embodiment, a downflow reactor. In one embodiment, contact zone refers to at least one slurry bed hydrocracking reactor in series with at least one fixed bed hydroprocessing reactor. In another embodiment, at least one of the contact zones is capable of removing more than 70% of the sulfur, more than 90% of the nitrogen, and more than 90% of the heteroatoms in the crude product being processed. Further included is an in-line hydrotreater.

  In one embodiment, the contact zone comprises a plurality of reactors in series to achieve a total residence time in the range of 0.1 to 15 hours. In the second embodiment, the residence time is in the range of 0.5 to 5 hours. In the third embodiment, the total residence time in the contact zone is in the range of 0.2 to 2 hours.

  In one embodiment, depending on the conditions and location of the separation zone, the amount of heavier hydrocracked product in the non-volatile fraction stream is less than 50% by weight (relative to the total weight of the non-volatile stream). . In a second embodiment, the amount of heavier hydrocracked product in the non-volatile stream from the separation zone is less than 25% by weight. In a third embodiment, the amount of heavier hydrocracked product in the non-volatile stream from the separation zone is less than 15% by weight. When the upgraded material is removed from the contact zone and fed into the separation zone, at least a portion of the slurry catalyst remains with the upgraded feedstock, and the slurry catalyst remains available in the separation zone and is non-volatile It should be noted that the liquid fraction is discharged from the separation zone.

  In one embodiment, both the contact zone and the separation zone are combined in one apparatus, for example, a reactor with an internal separator, or a multistage reactor-separator. In this type of reactor-separator configuration, the vapor product is discharged from the top of the apparatus, and the non-volatile fraction is transferred to the slurry catalyst and entrained solid fraction (if any) from the side or bottom of the apparatus. ).

  In one embodiment, the slurry catalyst stream contains fresh catalyst. In another embodiment, the slurry catalyst stream contains a mixture of at least one fresh catalyst and recycled (spent) catalyst. In a third embodiment, the slurry catalyst stream contains spent catalyst. In another embodiment, the slurry catalyst contains a well-dispersed catalyst precursor composition that can form an active catalyst in situ within a feed stream heater and / or contact zone. The catalyst particles can be introduced into the medium (diluent) as a powder in one embodiment, as a precursor in another embodiment, or after a pretreatment step in a third embodiment. In one embodiment, the medium (or diluent) is a hydrocarbon oil diluent. In another embodiment, the liquid medium is the heavy oil feedstock itself. In yet another embodiment, the liquid medium is a hydrocarbon oil other than heavy oil feedstock, such as a VGO medium or diluent.

  In one embodiment, the bleed-off stream is a non-volatile material (unconverted material, slurry catalyst, small amount of heavier hydrocracked liquid product, small amount from the separation zone in the system, typically the last separation zone. Including coke and asphaltene). In another embodiment, the bleed-off stream is the bottom stream from an intermediate solvent deasphalting unit in the system. In embodiments where the bleed-off stream is transferred from the stream at the bottom of the separation zone, the bleed stream is typically 1-35%, 3-20%, or 5-15% by weight of the total heavy oil feed to the system. % Range. In embodiments where the bleed-off stream is transferred from the bottom of the deasphalting unit, the bleed-off stream is 0.30-5%, 1-30%, or 0.5-10% by weight of the heavy oil feed stream stock. It is a range.

  In one embodiment, the bleed-off stream contains 3-30% by weight slurry catalyst. In another embodiment, the amount of slurry catalyst ranges from 5-20% by weight. In yet another embodiment, the bleed-off stream contains an amount of slurry catalyst in the concentration range of 1-15 wt%.

  In some embodiments, instead of sending all of the fresh catalyst to the first contact zone, as in the prior art process, at least a portion of the fresh catalyst is transferred to at least one other contact zone in the system. Transfer to (other than the first contact zone).

  Also, in some embodiments, instead of sending all of the upgraded heavy oil feed stream to the first contact zone, at least a portion of the heavy oil feed stream is transferred to at least one other contact zone in the system.

  In other embodiments, a combined feed scheme is used to transfer a portion of the fresh catalyst feed stream and a portion of the heavy oil feed stream to at least one other contact zone other than the first contact zone in the heavy oil upgrade system. To do.

  In one embodiment, the upgrade system includes at least two upflow reactors in series with at least two separators, each separator located immediately after each reactor, and an intermediate SDA unit (interstage SDA unit) , Located in front of at least one reactor in the system. In another embodiment, the upgrade system includes at least two upflow reactors in series and at least two separators, each of which is located immediately after each reactor, and an intermediate SDA unit is connected in series. Located after one separator. In a fourth embodiment, the upgrade system may include a combination of separate reactors and separate separators that are in series with a multistage reactor-separator, where the SDA is between any two reactors in series. Located as an intermediate processing system.

Heavy oil feed stream : The unconverted heavy oil feed stream herein may comprise one or more different heavy oil feed streams from different sources as a single feed stream or as separate heavy oil feed streams. In some embodiments of the invention, at least a portion of the (upgraded) heavy oil feed stream is fed to or into at least one other contact zone (other than the first contact zone) in the system. Previously “split” or transferred to an intermediate SDA unit.

  In one embodiment, “at least a portion” means that at least 5% of the upgrading heavy oil feed stream is transferred to at least one other contact zone other than the first contact zone in the system. In another embodiment, at least 10%. In the third embodiment, it is at least 20%. In a fourth embodiment, at least 30% of the heavy oil feed stream is transferred to at least one contact zone other than the first contact zone in the system. In one embodiment, the heavy oil feed is preheated before blending with the slurry catalyst feed stream (s). In another embodiment, a blend of heavy oil feedstock and slurry catalyst feedstream is preheated to produce a feedstock that is sufficiently low in viscosity to allow the catalyst to be well mixed into the feedstock. . In one embodiment, preheating is performed at a temperature that is at least about 100 ° C. (180 ° F.) below the hydrocracking temperature in the contact zone. In another embodiment, the preheating is at a temperature that is at least about 50 ° C. below the hydrocracking temperature in the contact zone.

Additional hydrocarbon feed stream : In one embodiment, an additional hydrocarbon oil feed stream in an amount ranging from 2 to 40% by weight of the heavy oil feed stream, such as VGO (vacuum gas oil), naphtha, MCO (medium cycle oil), A solvent donor, or other aromatic solvent, etc. can optionally be added to any of the contact zones in the system as part of the heavy oil feed stream. In one embodiment, the additional hydrocarbon feed stream functions as a diluent that reduces the viscosity of the heavy oil feed stream.

Embodiments of heavy oil split feed scheme : In some embodiments, at least a portion of the (upgraded) heavy oil feed stream is “split” into at least one other contact zone (other than the first contact zone) in the system. Or transferred.

  In one embodiment, “at least a portion” means at least 5% of the heavy oil feed stream to be upgraded. In another embodiment, at least 10%. In the third embodiment, it is at least 20%. In a fourth embodiment, at least 30% of the heavy oil feed stream is transferred to at least one contact zone other than the first contact zone in the system.

  In one embodiment, less than 90% of the unconverted heavy oil feed stream is fed to the first reactor in the system and 10% or more of the unconverted heavy oil feed stream is fed to the other contact zone (s) in the system. Forward. In another embodiment, the heavy oil feed stream is equally divided between contact zones in the system. In yet another embodiment, less than 80% of the unconverted heavy oil feed stream is fed to the first contact zone in the system and the remaining heavy oil feed stream is transferred to the last contact zone in the system. In a fourth embodiment, less than 60% of the heavy oil feed stream is fed to the first contact zone in the system and the remainder of the unconverted heavy oil feed stream is equally divided between the other contact zones in the system.

  The unconverted heavy oil feed streams herein may include one or more different heavy oil feed streams from different sources as a single feed stream or separate heavy oil feed streams. In one embodiment, a single heavy oil conduit pipe enters all contact zones. In another embodiment, multiple heavy oil conduits are used to feed heavy oil feed streams to different contact zones, with some heavy oil feed stream stream (s) entering one or more contact zones and others Some of the unconverted heavy oil feed stream (s) enter one or more different contact zones.

  In one embodiment, the heavy oil feed is preheated before blending with the slurry catalyst feed and / or prior to introduction into the hydrocracking reactor (contact zone). In another embodiment, a blend of heavy oil feedstock and slurry catalyst feedstream is preheated to produce a feedstock that is sufficiently low in viscosity to allow the catalyst to be well mixed into the feedstock. .

  In one embodiment, preheating is performed at a temperature about 100 ° C. (180 ° F.) below the hydrocracking temperature in the contact zone. In another embodiment, the preheating is at a temperature that is about 50 ° C. below the hydrocracking temperature in the contact zone.

Hydrogen feed stream : In one embodiment, a hydrogen-containing gas is provided to the process. Hydrogen can also be added to the heavy oil feed stream before entering the preheater or after the preheater. In one embodiment, the hydrogen feed stream enters the contact zone co-currently with the heavy oil feed stream in the same conduit. In another embodiment, the hydrogen source may be added to the contact zone in the opposite direction to the crude feed stream flow. In a third embodiment, hydrogen enters the contact zone via a gas conduit separate from the combined heavy oil and slurry catalyst feed stream. In a fourth embodiment, the hydrogen feed stream is introduced directly into the combined catalyst and heavy oil feed before being introduced into the contact zone. In yet another embodiment, the hydrogen gas and combined heavy oil and catalyst feed streams are introduced to the bottom of the reactor as separate streams. In yet another embodiment, hydrogen gas can be supplied to several sections of the contact zone.

In one embodiment, the hydrogen source is 0.1 Nm ³ / m ³ to about 100,000 Nm ³ / m ³ (0.563 to 563,380 SCF / bbl), about 0.5 Nm ³ / m ³ to about 10,000 Nm. ³ / m ³ (2.82-56,338 SCF / bbl), about 1 Nm ³ / m ³ to about 8,000 Nm ³ / m ³ (5.63 to 45,070 SCF / bbl), about 2 Nm ³ / m ³ to About 5,000 Nm ³ / m ³ (11.27 to 28,169 SCF / bbl), about 5 Nm ³ / m ³ to about 3,000 Nm ³ / m ³ (28.2 to 16,901 SCF / bbl), or about 10 Nm ^The process is provided to the process at a rate of ³ / m ³ to about 800 Nm ³ / m ³ (56.3-4,507 SCF / bbl) (based on the ratio of the gaseous hydrogen source to the crude feed stream). In one embodiment, some (25-75%) of hydrogen is fed to the first contact zone and the rest is added as supplemental hydrogen to other contact zones in the system.

  In one embodiment, the upgrade system produces a volumetric yield in the upgraded product of greater than 100% (compared to heavy oil dosage) because the added hydrogen increases the total volume of heavy oil. In one embodiment, upgraded products, ie lower boiling hydrocarbons, include liquefied petroleum gas (LPG), gasoline, diesel, vacuum gas oil (VGO), and jet and fuel oils. In a second embodiment, the upgrade system achieves a volume yield of at least 110% in the form of LPG, naphtha, jet and fuel oil, and VGO. In the third embodiment, it is over 115%.

  In one embodiment of the upgrade system, at least 98% by weight of the heavy oil feed stream is converted to a lighter product. In a second embodiment, at least 98.5% of the heavy oil feed stream is converted to a lighter product. In the third embodiment, the conversion rate is at least 99%. In the fourth embodiment, the conversion rate is at least 95%. In the fifth embodiment, the conversion rate is at least 80%. In the sixth embodiment, the conversion rate is at least 60%. As used herein, conversion means the conversion of a heavy oil feedstock to a material with a boiling point of less than 1000 ° F. (538 ° C.).

  In some embodiments, the hydrogen source is combined with the carrier gas (es) and recirculated through the contact zone. The carrier gas may be, for example, nitrogen, helium, and / or argon. The carrier gas may facilitate the flow of the crude feed stream and / or the flow of the hydrogen source in the contact zone (s). The carrier gas may also enhance mixing in the contact zone (s). In some embodiments, a hydrogen source (eg, hydrogen, methane or ethane) may be used as a carrier gas and recycled through the contact zone.

Catalyst feed stream : In one embodiment, all of the slurry catalyst feed stream is provided to the first contact zone. In other embodiments, at least a portion of the catalyst feed stream is “split” or transferred to at least one other contact zone (other than the first contact zone) in the system. In another embodiment, all operating contact zones receive a slurry catalyst feed stream (along with a heavy oil feed stream). In yet another embodiment, fresh catalyst can be fed entirely to the last reactor in the system for specific process conditions (for specific desired product characteristics) or for some operation of the process So that 50% can be fed to the first reactor in the system, or can be divided equally or by a predetermined percentage of all of the reactors in the system, or different reactors with different concentrations of the same fresh catalyst This process is configured for a flexible catalyst feed scheme so that it can be divided by a predetermined percentage to feed into.

  As used herein, a slurry catalyst feed stream may include one or more different slurry catalysts as a single catalyst feed stream or as separate feed stream streams. In one embodiment, a single fresh catalyst feed stream is fed to the contact zone. In another embodiment, the catalyst feed stream includes a plurality and different catalyst types, and a particular catalyst type enters one or more contact zones (eg, the first contact zone in the system) as separate streams, Different slurry catalysts enter as different catalyst streams in contact zone (s) other than the first contact zone in the system.

  In one embodiment, “at least a portion” means at least 10% of fresh catalyst. In another embodiment, at least 20%. In the third embodiment, it is at least 40%. In a fourth embodiment, at least 50% of the fresh catalyst is transferred to at least one contact zone other than the first contact zone in the system. In a fifth embodiment, all of the fresh catalyst is transferred to a contact zone other than the first contact zone.

  In one embodiment, less than 20% of the fresh catalyst is fed to the first reactor in the system and 80% or more of the fresh catalyst is transferred to the other contact zone (s) in the system. In another embodiment, fresh catalyst is equally divided between contact zones in the system. In one embodiment, at least a portion of the fresh catalyst feed stream is sent to at least one of the intermediate contact zone and / or the last contact zone in the system. In another embodiment, all of the fresh catalyst is sent to the last contact zone in the system, where the first contact zone in the system is from one or more of the processes in the system, eg, one of the separation zones in the system. Or from a solvent deasphalting unit.

  In one embodiment with an intermediate SDA unit, at least a portion of the fresh catalyst feed stream is sent to the contact zone immediately after the intermediate SDA unit. In another embodiment, all of the fresh catalyst is sent to contact zone (s) other than the first contact zone in the system, where the first contact zone sends only the SDA bottom from the SDA unit and the system Recycle catalyst is received from one or more of the processes in the process, eg, one of the separation zones in the system.

  In one embodiment, fresh catalyst is combined with a recycled catalyst stream from one of the processes in the system, eg, separation zone, distillation column, SDA unit, or flash tank, and the combined catalyst feed stream is subsequently contacted. Blend with heavy oil feed to feed into zone (s). In another embodiment, fresh catalyst and recycled catalyst streams are blended as separate streams into heavy oil feedstock.

  In one embodiment, the recycled catalyst stream from one of the processes in the system, eg, separation zone, SDA unit, etc., is combined with fresh slurry catalyst as a single catalyst feed stream. The combined catalyst feed stream is then blended with (treated or untreated) heavy oil feed stream (s) for feeding to the contact zone (s). In another embodiment, fresh catalyst and recycle catalyst streams are blended into heavy oil feed stream (s) as separate streams.

  In one embodiment, the catalyst feed stream is optionally fed to the first reactor in the system at a total rate (100% of the required catalyst rate) for a period of time and then to all of the reactors in the system for a predetermined time. This process is for a flexible catalyst feed scheme so that it can be split equally or by a predetermined ratio or by a predetermined ratio so that the catalyst feed streams are fed to different reactors at different concentrations. Composed.

  In one embodiment, sending different catalysts to the front end and back end contact zones may be useful in reducing vanadium trapping problems and sustaining overall upgrade performance. . In one embodiment, Ni-only or Ni-rich NiMo sulfide slurry catalyst is sent to the front reactor to help reduce vanadium trapping in the system, while in one embodiment a different catalyst, such as Mo, is used. Rich Mo sulfide or NiMo sulfide catalyst is injected into the rear reactor (s) to maintain high overall conversion, improve product quality and possibly reduce gas yield Can be made. As used herein, a Ni-rich slurry catalyst means that the Ni / Mo ratio is greater than 0.15 (as weight percent). Conversely, a Mo-rich slurry catalyst means that the Ni / Mo ratio is less than 0.05 (as weight percent).

  In one embodiment, the slurry catalyst feed stream is first preconditioned before entering one of the contact zones or before contacting the heavy oil feed stream before entering the contact zone. In one example, the catalyst is placed in the preconditioning unit at a rate of 500-7500 SCF / BBL with hydrogen (BBL means herein the total volume of heavy oil feed stream to the system). Instead of contacting the cold catalyst with the heavy oil feed stream, the preconditioning step is believed to help hydrogen adsorption to the active catalyst site and ultimately conversion. In one embodiment in the preconditioning unit, the slurry catalyst / hydrogen mixture is heated to a temperature of 300 ° F to 1000 ° F (149-538 ° C). In another embodiment, the catalyst is preconditioned in hydrogen at a temperature of 500-725 ° F. (260-385 ° C.). In yet another embodiment, the mixture is heated under a pressure of 300 to 3200 psi in one embodiment, 500 to 3000 psi in a second embodiment, and 600 to 2500 psi in a third embodiment.

Catalyst used : The slurry catalyst comprises an active catalyst in a hydrocarbon oil diluent. In one embodiment, the catalyst is a sulfided catalyst comprising at least one Group VIB metal, or at least one Group VIII metal, or at least one Group IIB metal, such as an iron sulfide catalyst, zinc sulfide, Nickel sulfide, molybdenum sulfide, or zinc iron sulfide catalyst. In another embodiment, the catalyst is a multimetallic catalyst comprising at least one Group VIB metal and at least one Group VIII metal (as promoter), wherein the metal is in elemental form. Alternatively, it may be in the form of a metal compound. In one example, the catalyst is a MoS ₂ catalyst promoted by at least one Group VIII metal compound.

In one embodiment, the catalyst is a bulk multimetal catalyst comprising at least one Group VIII non-noble metal and at least two Group VIB metals, wherein the at least two Group VIB metals and the Group VIII non-noble metal The ratio is about 10: 1 to about 1:10. In another embodiment, the catalyst is of the formula ( ^Mt ) _a ( ^Xu ) _b ( ^Sv ) _d ( ^Cw ) _e ( ^Hx ) _f ( ^Oy ) _g ( ^Nz ) _h ; Where M represents at least one Group VIB metal (such as Mo, W or a combination thereof), X functions as a promoter metal, Group VIII non-noble metals such as Ni, Co, Fe Represents at least one of a Group VIII metal such as Cr, a Group VIB metal such as Cr, a Group IVB metal such as Ti, a Group IIB metal such as Zn, and combinations thereof (X is a “promoter metal” hereinafter) "). In the equation, t, u, v, w, x, y, and z represent total charges for each of the components (respectively, M, X, S, C, H, O, and N), and ta + ub + vd + we + xf + yg + zh = 0. is there. The ratio of the subscripts of b and a has a value of 0-5, where (0 <= b / a <= 5). S represents sulfur, and the value of the subscript d is in the range of (a + 0.5b) to (5a + 2b). C represents carbon and the subscript e has a value of 0 to 11 (a + b). H is hydrogen, and the value of f ranges from 0 to 7 (a + b). O represents oxygen, the value of g ranges from 0 to 5 (a + b), N represents nitrogen, and h has a value of 0 to 0.5 (a + b). In one embodiment, the subscript b has a value of 0 for a single metal component catalyst, such as a Mo-only catalyst (without promoter).

  In one embodiment, the catalyst is prepared from a catalyst precursor composition that includes an organometallic complex or organometallic compound, such as an oil-soluble compound or complex of a transition metal and an organic acid. Examples of such compounds include group VIB and group VIII metal (Mo, Co, W, etc.) naphthenates, pentanediones, octanoates, and acetates (molybdenum naphthenate, vanadium naphthenate). , Vanadium octoate, molybdenum hexacarbonyl, and vanadium hexacarbonyl).

In one embodiment, the catalyst is a MoS ₂ catalyst promoted by at least one Group VIII metal compound. In another embodiment, the catalyst is a bulk multimetal catalyst, the bulk multimetal catalyst comprising at least one Group VIII non-noble metal and at least two Group VIB metals, wherein the at least two Group VB metals. The ratio of Group VIB metal to said at least one Group VIII non-noble metal is from about 10: 1 to about 1:10.

In one embodiment, the catalyst feed stream comprises a slurry catalyst having an average particle size of at least 1 micron in a hydrocarbon oil diluent. In another embodiment, the catalyst feed stream comprises a slurry catalyst having an average particle size in the range of 1-20 microns. In a third embodiment, the slurry catalyst has an average particle size in the range of 2 to 10 microns. In one embodiment, the feed stream comprises a slurry catalyst having an average particle size ranging from colloid (nanometer size) to about 1-2 microns. In another embodiment, the catalyst comprises catalyst molecules and / or very small particles of colloidal size (ie, less than 100 nm, less than about 10 nm, less than about 5 nm, and less than about 1 nm). During operation, the colloidal / nanometer sized particles agglomerate in the hydrocarbon diluent to form a slurry catalyst having an average particle size in the range of 1-20 microns. In yet another embodiment, the catalyst comprises a single layer of MoS ₂ clusters of nanometer size, eg, 5-10 nm at the ends.

  In one embodiment, a sufficient amount of fresh catalyst and spent catalyst is fed to the contact zone (s) such that each contact zone has a slurry (solid) catalyst concentration in the range of 2-30% by weight. To do. In a second embodiment, the (solid) catalyst concentration in the reactor is in the range of 3-20% by weight. In 3rd Embodiment, it is the range of 5 to 10 weight%.

  In one embodiment, the amount of fresh catalyst feed stream into the contact zone (s) is Mo in the range of 50-15000 wppm (concentration in heavy oil feed stream). In a second embodiment, the fresh catalyst feed stream concentration is Mo in the range of 150-2000 wppm. In 3rd Embodiment, it is Mo of the range of 250-5000 wppm. In a fourth embodiment, the concentration is less than 10,000 wppm Mo. The concentration of fresh catalyst in each contact zone may vary depending on the contact zone used in the system. This is because as the volatile fraction is removed from the non-volatile residue fraction, the catalyst becomes more concentrated and therefore adjustment of the catalyst concentration may be required.

Optional Processing System-SDA : In one embodiment of the present invention, a solvent deasphalting unit (SDA) is used before the first contact zone to pretreat heavy oil feedstock. In yet another embodiment, a solvent deasphalting unit is used as an intermediate unit located after one of the intermediate separation zones.

  SDA units are typically used in refiners to extract progressively lighter hydrocarbons from heavy hydrocarbon streams, and the oil extracted thereby is typically deasphalted oil (DAO) and While leaving behind a residue stream that is more concentrated in heavy molecules and heteroatoms, typically known as SDA tar, SDA bottoms, and the like. The SDA may be a separate unit or a unit that is integrated into the upgrade system.

  Depending on the desired level of deasphalting before feeding to the contact zone, various solvents ranging from propane to hexane may be used in the SDA. In one embodiment, the SDA produces deasphalted oil (DAO) for blending with the catalyst feed stream or for feeding directly into the contact zone instead of or in addition to the heavy oil feed stream. Configured as follows. Thus, the solvent type and operating conditions can be optimized so that a high volume and acceptable amount of DAO is produced and fed to the contact zone. In this embodiment, suitable solvents used include, but are not limited to, low volume SDA tar and hexane or similar C6 + solvent for high volume DAO. This scheme allows the bulk of the heavy oil feed stream to be upgraded in a later contact zone, while the heaviest that does not provide the economic aspect of favorable gradual conversion by requiring large amounts of hydrogen addition The barrel bottom is used in other ways.

  In one embodiment, all of the heavy oil feed stream is pretreated in the SDA, the DAO product is fed into the first contact zone, or fed by a split feed scheme, and at least a portion is fed into the first contact zone. Put in a series contact zone other than. In another embodiment, some of the heavy oil feed stream (by source) is first pretreated in SDA and some of the feedstock is fed directly into the contact zone (s) untreated. In yet another embodiment, DAO is combined with an untreated heavy oil feed as a single feed stream to the contact zone (s). In another embodiment, DAO and raw heavy oil feed are fed to the system in separate feed flow conduits, DAO enters one or more of the contact zones, and the raw heavy oil feed streams are the same or different contact zones. Enter one or more of

  In embodiments where SDA is used as an intermediate unit, a non-volatile fraction containing slurry catalyst from at least one of the separation zones, and optionally a minimum amount of coke / asphalten, etc. is sent to SDA for processing. . DAO is fed from the SDA unit as a feed stream with heavy oil feedstock or as a feed stream with a bottom stream from one of the separation zones and as such a feed stream to at least one of the contact zones send. DA bottoms containing asphaltenes are used to recover metals in carried slurry catalysts or for applications that require asphaltenes, such as blending with fuel oil, use in asphalt, or some other Sent for use in other applications.

  In one embodiment, the quality of DAO and DA bottoms is varied by adjusting the solvent used and the desired recovery of DAO for the heavy oil feed stream. As more DAO oil is recovered in an optional pretreatment unit such as SDA, the overall quality of DAO becomes poorer and the overall quality of DA bottoms becomes poorer. With respect to solvent selection, typically lighter solvents are used for SDA, resulting in less DAO but better quality. On the other hand, if a heavier solvent is used, more DAO is produced, but the quality is lower. This is due to the solubility of asphaltenes and other heavy molecules in the solvent, among other factors.

Heavy metal deposit control-optional water injection : As used herein, the front contact zone (or first contact zone) is the first reaction in a system having three or less contact zones Means vessel. In another embodiment of a system having more than three contact zones, the first front contact zone may include both first and second reactors. In yet another embodiment, the first contact zone means only the first reactor.

  As used herein, the term “water” is used to indicate water and / or steam. In one embodiment of controlling heavy metal deposits, water is optionally injected into the system. In one embodiment, the injection is at a rate of about 1-25% by weight (relative to heavy oil feedstock). In one embodiment, a sufficient amount of water is injected at a concentration of water in the system ranging from 2 to 15% by weight. In a third embodiment, a sufficient amount is injected at a concentration of water in the range of 4-10% by weight.

  Water can be added to the heavy oil feed before or after preheating. In one embodiment, a substantial amount of water is added to the preheated heavy oil feed mixture and a substantial amount of water is added directly to the front contact zone (s). In another embodiment, water is added to the front contact zone (s) only through heavy oil feedstock. In yet another embodiment, at least 50% of the water is added to the heated heavy oil feed mixture and the remainder of the water is added directly to the front contact zone (s).

  In one embodiment, water is introduced into the system in the preheating stage (before preheating the heavy oil feedstock) in an amount of about 1 to about 25% by weight of the incoming heavy oil feedstock. In one embodiment, water is added to all of the contact zones as part of the heavy oil feed stream. In another embodiment, water is added only to the heavy oil feed stream to the first contact zone. In yet another embodiment, water is added only to the feed stream to the first two contact zones.

  In one embodiment, water is added directly into the contact zone at multiple points along the contact zone in a ratio of 1 to 25% by weight of the heavy oil feedstock. In yet another embodiment, water is added directly into the first few contact zones in the process most likely to cause heavy metal deposition.

  In one embodiment, some of the water is added to the process in the form of diluted steam. In one embodiment, at least 30% of the added water is in the form of steam. In embodiments where water is added as diluted steam, steam may be added at any point in the process. For example, steam may be added to the heavy oil feed, before or after preheating, to the catalyst / heavy oil mixture stream, and / or directly into the vapor phase of the contact zone, or at multiple points along the first contact zone. . The diluted steam stream may include process steam or purified steam. The steam can be heated or superheated in a furnace before being fed during the upgrade process.

  The presence of water in the process is thought to favorably change the equilibrium state of the metal compound and sulfur molecules, thus reducing heavy metal deposits. In one embodiment, the addition of water is also believed to help control / maintain the desired temperature profile in the contact zone. In yet another embodiment, the addition of water to the front contact zone (s) is believed to reduce the temperature of the reactor (s). As the reactor temperature decreases, the reaction rate of most reactive vanadium species decreases, vanadium deposition on the slurry catalyst proceeds in a more controlled manner, and the catalyst carries the vanadium deposit out of the reactor. And is thus believed to limit solid deposits in the reactor apparatus.

  In one embodiment, the addition of water reduces heavy metal deposits in the reactor apparatus for a comparable time during operation, e.g., for at least 2 months compared to operation without water addition. Reduce by at least 25%. In another embodiment, the addition of water reduces heavy metal deposits by at least 50% compared to operation without the addition of water. In a third embodiment, the addition of water reduces heavy metal deposits by at least 75% compared to operation without the addition of water.

Control of heavy metal deposits by reactor temperature : In one embodiment, instead of and / or in addition to adding water to the front contact zone (s), the front of the front most susceptible to heavy metal deposition. Reduce the temperature of the contact zone (s).

  In one embodiment, the temperature of the first reactor is set to be at least 10 ° F. (5.56 ° C.) lower than the next reactor in the series. In a second embodiment, the temperature of the first reactor is set to be at least 15 ° F. (8.33 ° C.) lower than the next reactor in series. In the third embodiment, the temperature is set to be at least 20 ° F. (11.11 ° C.) lower. In a fourth embodiment, the temperature is set to be at least 25 ° F. (13.89 ° C.) lower than the next reactor in series.

Control of heavy metal deposits by recycled catalyst stream : In one embodiment, at least a portion of the non-volatile stream from at least one of the separation zone and / or the intermediate deasphalting unit is in the front contact zone (s) Recycled to control heavy metal deposits.

  In one embodiment, this recycle stream ranges from 3 to 50% by weight of the total heavy oil feed to the process. In a second embodiment, the recycle stream is an amount in the range of 15-45% by weight of the total heavy oil feed to the system. In a fourth embodiment, the recycle stream is at least 10% by weight of the total heavy oil feed to the system. In a fifth embodiment, the recycle stream is 25-45% by weight of the total heavy oil feed stream. In a sixth embodiment, the recycle stream is at least 30% by weight. In a seventh embodiment, the recycle stream is in the range of 35-45% by weight. In an eighth embodiment, the recycle stream is in the range of 30-40% by weight.

  In one embodiment, the recycle stream contains non-volatile material from the last separation zone in the system that contains unconverted material, heavier hydrocracked liquid product, slurry catalyst, small amounts of coke, asphaltenes, and the like. Including. In one embodiment, the recycle stream contains 3-30% by weight slurry catalyst. In another embodiment, the amount of catalyst ranges from 5-20% by weight. In yet another embodiment, the recycle stream contains 1-15 wt% slurry catalyst.

  In some embodiments, with the additional recycle catalyst provided by the recycle stream, more catalyst surface area (due to the slurry catalyst in the recycle stream) is available to dissipate heavy metal deposits and thus on the equipment Less trapping or deposition. The additional catalyst surface area provided by the recycle stream helps to minimize overfilling of the catalyst surface with heavy metal deposits, resulting in deposition on process equipment (walls, internal structures, etc.).

Process conditions : In one embodiment, process conditions are controlled to be somewhat uniform across the contact zone. In another embodiment, the conditions differ between contact zones for an upgrade product having specific characteristics.

  In one embodiment, the upgrade system is maintained under hydrocracking conditions, for example at the lowest temperature that causes hydrocracking of the heavy oil feedstock. In one embodiment, the system operates at a temperature in the range of 400 ° C. (752 ° F.) to 600 ° C. (1112 ° F.) and a pressure in the range of 10 MPa (1450 psi) to 25 MPa (3625 psi). In one embodiment, the process conditions are controlled to be somewhat uniform across the contact zone. In another embodiment, the conditions differ between contact zones for an upgrade product having specific characteristics.

  In one embodiment, the process temperature of the contact zone ranges from about 400 ° C. (752 ° F.) to about 600 ° C. (1112 ° F.), and in another embodiment less than 500 ° C. (932 ° F.), In another embodiment, greater than 425 ° C. (797 ° F.). In one embodiment, the system operates with a temperature difference between the inlet and outlet of the contact zone in the range of 5-50 ° F. In the second embodiment, it is in the range of 10-40 ° F.

  The temperature of the separation zone is within ± 90 ° F. (about ± 50 ° C.) of the temperature of the contact zone in one embodiment, and within ± 70 ° F. (about ± 38.9 ° C.) in the second embodiment. Maintain within ± 15 ° F. (about ± 8.3 ° C.) in the third embodiment and within ± 5 ° F. (about ± 2.8 ° C.) in the fourth embodiment. In one embodiment, the temperature difference between the last separation zone and the immediately preceding contact zone is within ± 50 ° F. (about ± 28 ° C.).

  The process pressure in the contact zone ranges from about 10 MPa (1,450 psi) to about 25 MPa (3,625 psi) in one embodiment, and from about 15 MPa (2,175 psi) to about 20 MPa (2,900 psi) in the second embodiment. Range, less than 22 MPa (3,190 psi) in the third embodiment and greater than 14 MPa (2,030 psi) in the fourth embodiment. In certain embodiments, the pressure in the separation zone is maintained within ± 10 ± 50 psi of the previous contact zone in one embodiment and within ± 2 ± 10 psi in the second embodiment.

  In one embodiment, the upgrade system is configured for efficiency with optimal operation, e.g., with very little downtime due to device clogging compared to the prior art with a pressure drop of less than 100 psi. The In one embodiment, optimal efficiency is obtained with minimal pressure drop in the system, and the pressure in the separation zone is within ± 10 ± 100 psi of the previous contact zone in one embodiment, ± 20˜ in the second embodiment. Within ± 75 psi, and in the third embodiment within ± 50 to ± 100 psi. As used herein, pressure drop means the difference between the previous contact zone outlet pressure X and the separation zone inlet pressure Y, where (XY) is less than 100 psi.

  Optimal efficiency can also be obtained with a minimum pressure from one contact zone to the next for a system operating sequentially, with a pressure drop of 100 psi or less in one embodiment and 75 psi in a second embodiment. Below and in the third embodiment is maintained below 50 psi. The pressure drop in this specification means the difference between the outflow pressure of one contact zone and the inflow pressure of the next contact zone.

  In one embodiment, the contact zone is in direct fluid communication with the next separation zone or contact zone for minimal pressure drop. As used herein, direct fluid communication means that there is free flow from the contact zone to the next separation zone in series (or next contact zone) with no flow restrictions. In one embodiment, direct fluid communication is obtained without flow restrictions by the presence of valves, orifices (or similar devices), or changes in pipe diameter.

  In one embodiment, the minimum pressure drop from a contact zone to the next separation zone or contact zone (by entering the separation zone or contact zone) is reduced in piping elements, such as elbows, bends, T-tubes in the line, etc. This is not due to the use of a pressure reducing device such as a valve or a control valve for inducing a pressure drop as in the prior art. In the prior art, it is taught that the separation zone functions as an intermediate pressure differential separator.

  In one embodiment, the minimum pressure drop is induced by friction loss, wall drag, volume increase, and height change as the effluent flows from the contact zone to the next device in series. When the valve is used in an once through system, the valve is selected / configured such that the pressure drop from one device, eg, the contact zone, to the next device is maintained below 100 psi.

In one embodiment, a liquid hourly space velocity of the heavy oil feed stream (LHSV) is generally from about 0.025h ^-1 ~ about ^{10h -1,} about 0.5h ^-1 ~ about 7.5 h ^-1 to about 0.1 h ^{- 1} to about 5 h ⁻¹ , about 0.75 h ⁻¹ to about 1.5 h ⁻¹ , or about 0.2 h ⁻¹ to about 10 h ⁻¹ . In some embodiments, LHSV is at least 0.5h ^-1, at least ^{1h -1,} at least 1.5 h ^-1, or at least ^{2h -1.} In some embodiments, the LHSV ranges from 0.025 to 0.9 h- ¹ . In another embodiment, the LHSV ranges from 0.1-3 LHSV. In another embodiment, the LHSV is less than 0.5 h- ¹ .

  In one embodiment where all of the non-volatile fraction stream from at least one separation zone is sent to the SDA unit for deasphalting, the solid deposit in the last contact zone in the system is accompanied by deasphalting by the SDA unit. Compared to no prior art operation, it decreases by at least 10% (in terms of sediment volume) after a similar operating time. In a second embodiment, solid deposits are reduced by at least 20% compared to operation without an intermediate SDA unit. In a third embodiment, the solid deposit is reduced by at least 30%.

  In various embodiments, by transferring some if not all of the fresh catalyst to contact zone (s) other than the first contact zone in the system, the overall cracking efficiency of the heavy oil feedstock is reduced. It can be seen that all of the fresh catalyst was not noticeable or not affected at all compared to the prior art feed scheme entering the first contact zone. In one embodiment, the change in fresh catalyst injection location results in a significant increase in overall catalyst activity, with respect to API, viscosity, MCR level, nickel, hydrogen / carbon ratio, and hot heptane asphaltene (HHA) levels. , With an improvement in the quality of the non-volatile stream (bleed stream, “Stripper Bottoms” or STB) from the last separation zone in the system. In some other embodiments, less catalyst bleed is also observed with an overall improvement in catalyst activity.

  In one embodiment, the STB product improvement includes a nickel reduction of at least 10%, and in a second embodiment, a nickel reduction of at least 20%. In the third embodiment, the Ni level is less than 10 ppm.

  In one embodiment, the reduction in MCR in STB is at least 5%. In another embodiment, the reduction in MCR is at least 10%. In a third embodiment, the MCR level is less than 13% by weight.

  In one embodiment, the STB exhibits an API viscosity improvement of at least 15%. In a second embodiment, an improvement in API viscosity of at least 30%. In a third embodiment, the API viscosity is at least 50% and is between 2.7 and 4.5. In some embodiments, it is observed that the improvement in API is due to the overall improved catalytic activity, thus resulting in a higher H / C ratio.

  In an embodiment involving a heavy oil split feed scheme, the overall coke formation is achieved by transferring a portion of the heavy oil feedstock from the first contact zone to at least one other contact zone in series. Is found to be substantially reduced compared to prior art feeding schemes that enter the first contact zone. Furthermore, when at least a portion of the heavy oil feedstock is transferred to contact zones other than the first contact zone in the system, some liquid dilution occurs in these contact zones (which did not occur in the prior art schemes). Liquid dilution allows a more uniform catalyst concentration profile across all reactors in the system, thus protecting the last reactor from solid level excursions that can lead to operational problems.

  In some embodiments of the heavy oil split feed scheme, as the conversion level in the reactor (contact zone) increases, the overall system efficiency improves, further oil evaporation, corresponding reduction in liquid throughput, and catalyst. It is also observed that an increase in concentration is possible. This essentially enhances the efficiency of the system with lower liquid throughput (or higher liquid residence time) and higher catalyst concentration. In addition, the second stable heavy oil feed flow goes directly into the last reactor to protect the last reactor from abnormal conditions that can cause liquid flow to be lost from this vessel. Thus, the heavy oil split feed scheme reduces or eliminates the “excess conversion conditions” or “dry” conditions often observed in hydroprocessing reactors. In an upgrade system operating under "dry" conditions, there is insufficient liquid flow, thus solid accumulation / coking, flow pattern and / or hydrodynamic degradation, temperature measurement degradation, reaction volume There is a compromise between loss, ultimately performance, stability and lifetime of operation.

Drawings Illustrating Embodiments : Reference is made to the drawings that further illustrate embodiments of the invention.

  FIG. 1 is a block diagram that schematically illustrates a system for upgrading heavy oil feedstock with reduced heavy metal deposition. Initially, a heavy oil feed is introduced into the first contact zone in the system along with a slurry catalyst feed stream. In the figure, the slurry catalyst feed stream comprises a combination of fresh catalyst and recycled catalyst slurry as separate streams. Hydrogen can be introduced along with the feed stream in the same conduit, or optionally as a separate feed stream. Water and / or steam can be introduced into the same conduit or separate feed stream along with the feed stream and slurry catalyst. Although not shown, the mixture of water, heavy oil feed stream, and slurry catalyst can be preheated with a heating device prior to feeding to the contact zone. Although not shown, an additional hydrocarbon oil feed stream, eg, VGO, naphtha, in an amount ranging from 2 to 30% by weight of the heavy oil feed stream, can be used as part of the feed stream in any of the contact zones in the system Can be optionally added.

  Although not shown in the figure, the system uses reactants in the contact zone, particularly with high circulation flow rates to the first contact zone, to cause turbulent mixing in the reactor and thereby reduce heavy metal deposition. Recycle / recycle channels and pumps to facilitate dispersion of the catalyst, and heavy oil feedstock. In one embodiment, the recirculation pump circulates in the loop reactor and maintains a temperature difference between the reactor feed and outlet points in the range of 1 to 50 ° F., preferably between 2 and 25 ° F. Be drunk.

  In the contact zone under hydrocracking conditions, at least a portion of the heavy oil feedstock (higher boiling hydrocarbons) is converted to lower boiling hydrocarbons to form an upgraded product. Water / steam in the first contact zone is expected to reduce heavy oil deposition on the device. Although not shown, the temperature of the first contact zone can be kept at least 5-25 degrees (Fahrenheit) lower than the temperature of the next contact zone in series.

  The upgraded feed is withdrawn from the first contact zone and sent to a separation zone, such as a hot separator, that operates at high temperatures and pressures similar to the contact zone. The upgraded feed may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further upgrade before going to the hot separator. The separation zone causes or enables separation of gases and volatile liquids from non-volatile fractions. Gaseous and volatile liquid fractions are withdrawn from the top of the separation zone for further processing. A non-volatile (or less volatile) fraction is withdrawn from the bottom. Slurry catalyst and entrained solids, coke, hydrocarbons newly produced in the hot separator, etc. are withdrawn from the bottom of the separator and fed to the next contact zone in series. In one embodiment (not shown), a portion of the non-volatile stream is recycled to one of the contact zones prior to the separation zone to provide a recycle catalyst for use in the hydroconversion reaction. .

  In one embodiment (as indicated by the dashed line), a fresh catalyst feed stream and a portion of the heavy oil feed is fed directly to a contact zone (reactor) other than the first contact zone in the system. In one embodiment where a portion of the heavy oil feedstock is fed directly to a contact zone other than the first contact zone, water and / or steam is also provided to the contact zone as a separate feed stream or within the same conduit Together with the feed stream and slurry catalyst.

  The liquid stream from the previous separation zone is used as a feed stream for the next contact zone in series, such as an optional fresh catalyst, an optional additional heavy oil feed stream, an optional VGO (vacuum gas oil), etc. Combined with a hydrocarbon oil feed, and optionally a recycle catalyst (not shown). Hydrogen can also be introduced into the same conduit along with the feed stream, or optionally as a separate feed stream. The upgraded feed flows along with the slurry catalyst to the next separation zone in series for separation of gas and volatile liquid from the non-volatile fraction. Gaseous and volatile liquid fractions are withdrawn from the top of the separation zone and combined with gaseous and volatile liquid fractions from the previous separation zone for further processing. The non-volatile (or less volatile) fraction stream is withdrawn and sent to the next contact zone in series so that the unconverted heavy oil feedstock is upgraded.

  In the final contact zone, hydrogen is added along with the unconverted heavy oil feedstock, optional additional heavy oil feedstock, optional VGO feed stream, and optional fresh catalyst. The upgraded feed flows along with the slurry catalyst to the next separation zone where the upgraded product is removed and some non-volatile feed is recycled. In one embodiment, the recycled stream is sent to the first contact zone to provide some of the recycled catalyst for use in the hydroconversion reaction. In a second embodiment, the recirculated stream is divided between the contact zones before the last contact zone in series.

  In one embodiment, the system may optionally include an in-line hydroprocessor (not shown) for processing gaseous and volatile liquid fractions from the separation zone. The in-line hydrotreater in one embodiment using a conventional hydrotreating catalyst is operated at high pressure (within 10 psig) similar to other upgrade systems and removes sulfur, Ni, V, and other impurities from the upgraded product. Can be removed. In another embodiment, the inline hydrotreater operates at a temperature within 100 ° F. of the temperature of the contact zone.

  FIG. 2 is a flow diagram of a heavy oil upgrade method using water injection. As shown, water 81 is injected into the system along with heavy oil feedstock, and this mixture is preheated in a furnace before being introduced into the contact zone. Water / steam can also optionally be injected into the system as stream 82 after the preheater. In this embodiment, the fresh catalyst feed stream is divided between the contact zones. A recycle catalyst stream 17, a water / heavy oil feed mixture, and hydrogen gas 2 are fed as feed stream 3 to the first contact zone.

  Stream 4 containing the upgraded heavy oil feedstock exits contact zone R-10 and flows to separation zone 40, where the upgraded product in the form of gas (including hydrogen) and volatile liquid is It is separated from the non-volatile liquid fraction 7 and taken up as stream 6. The non-volatile stream 7 is sent to the next contact zone 20 in series for further upgrade. The non-volatile stream 7 includes, in some embodiments, a slurry catalyst together with unconverted oil and small amounts of coke and asphaltenes.

  The upgrade method continues with other contact zones as shown, where the feed stream to contact zone 20 is a non-volatile fraction, a hydrogen feed stream, an optional VGO feed stream, and a fresh catalyst feed. Contains stream 32. From contact zone 20, stream 8 containing the upgraded heavy oil feedstock flows to separation zone 50, where the upgraded product is combined with hydrogen and removed as overhead product 9. A bottoms stream 11 comprising non-volatile fractions, for example unconverted oil comprising catalyst slurry, coke and asphaltenes, flows to the next contact zone 30 in series.

  In contact zone 30, an additional hydrogen-containing gas 16, fresh catalyst 33, an optional hydrocarbon feed stream such as VGO (not shown), an optional raw heavy oil feed stream (not shown), Added to the non-volatile stream from the previous separation zone. From the contact zone 30, upgraded product, unconverted heavy oil, slurry catalyst, hydrogen, etc. are withdrawn as stream 12 and sent to the next separation zone 60. From the separator, the overhead stream 13 containing hydrogen and the upgraded product is combined with the overhead stream from the previous separation zone, for subsequent processing in another part of the system, for example, a high pressure separator. And / or delivered to a lean oil contactor and / or an in-line hydrotreater (not shown). A part of the non-volatile stream 17 is extracted as a bleed-off stream 18. The remainder is recycled as a recycled catalyst stream to at least one of the contact zones (first contact zone 10 shown).

  FIG. 3 is a flow diagram of another embodiment of a heavy oil upgrade method using a steam injection 91 instead of / in addition to the water injection stream 81.

  FIG. 4 is a flow diagram of another embodiment of a heavy oil upgrade method using a recycle catalyst stream 19 ranging between 3 and 50% by weight of the total heavy oil feed to the process.

  FIG. 5 is a block diagram that schematically illustrates another embodiment for upgrading heavy oil feedstock. Initially, the heavy oil feed is introduced into the first contact zone of the system along with the slurry catalyst feed stream. The hydrogen can be introduced along with the feed stream in the same conduit or optionally as a separate feed stream. In one embodiment (not shown), VGO (vacuum gas oil), naphtha, MCO (medium cycle oil), solvent donor, or other aromatic solvent in an amount ranging from 2 to 30% by weight of the heavy oil feed stream Optional hydrocarbon oil feedstocks are used. Additional hydrocarbon feedstock can be used to alter the concentration of metals and impurities in the system. In the contact zone under hydrocracking conditions, at least a portion of the heavy oil feed (high boiling hydrocarbons) is converted to low boiling hydrocarbons to form an upgraded product.

  The upgraded raw material is withdrawn from the first contact zone and sent to a separation zone, such as a hot separator. The upgraded feed may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further upgrade before going to the hot separator. The separation zone causes or enables separation of gases and volatile liquids from non-volatile fractions. Gaseous and volatile liquid fractions are withdrawn from the top of the separation zone for further processing. A non-volatile (or less volatile) fraction is withdrawn from the bottom. Slurry catalyst, a small amount of heavier hydrocracked liquid product, and entrained solids, coke, newly produced hydrocarbons in the hot separator, etc. are withdrawn from the bottom of the separator and sent to the next contact zone in series. In one embodiment (not shown), a portion of the non-volatile stream is recycled to the contact zone located in front of the separation zone in an amount corresponding to 2 to 40% by weight of the total heavy oil feed stream.

  The non-volatile stream from the previous separation zone, containing unconverted feed, is supplied as an additional fresh catalyst, an optional additional heavy oil feed stream, and optionally as a feed stream for the next contact zone in series. Combined with a recycle catalyst (not shown).

  In the next contact zone, under hydrocracking conditions, more heavy oil feedstock is upgraded to lower boiling hydrocarbons. The upgraded feed flows along with the slurry catalyst to the next separation zone in series for separation of gas and volatile liquid from the non-volatile fraction. A non-volatile (or less volatile) stream is withdrawn from the bottom. Gaseous and volatile liquid fractions can be used as "upgraded" products for further processing or blending for final blend products and / or transport carriers that meet specifications specified by refineries, for example. , Drawn from the top of the separation zone (and combined with the gaseous and volatile liquid fractions from the previous separation zone).

  In one embodiment (not shown), the non-volatile feed containing unconverted feed is sent to the next contact zone in series. In another illustrated embodiment, the non-volatile feed is recycled to one of the contact zones in the system and a portion of the feed is withdrawn for further processing, eg, solvent deasphalting equipment, catalytic deoiling. Go to equipment and subsequent metal recovery system. The recycled non-volatile feed in one embodiment is an amount corresponding to 2 to 50% by weight of the heavy oil feed to the system and provides a recycle catalyst for use in the hydroconversion reaction.

  Depending on the operating conditions, the type of catalyst fed to the contact zone and the concentration of slurry catalyst in one embodiment, the outlet stream from the contact zone is 20:80 to 60 for the unconverted heavy oil feed stream of the upgraded product. : The ratio of 40 is included. In one embodiment, the amount of upgraded product from the first contact zone ranges from 30-35% for 65-70% unconverted heavy oil product.

  Although not shown in the figure, the system can optionally include a recirculation / recycle channel and pump to facilitate the dispersion of reactants, catalyst, and heavy oil feedstock in the contact zone. In one embodiment, the recirculation pump circulates through the loop reactor with a volume recirculation ratio (recycle ratio to heavy oil feed stream) of 5: 1 to 15: 1, thereby in the range of 10 to 50 ° F. Preferably, the temperature difference between the reactor feed point and the outlet point between 20 and 40 ° F. is maintained.

  In one embodiment, the system may optionally include an in-line hydroprocessor (not shown) for processing gaseous and volatile liquid fractions from the separation zone. In-line hydrotreaters in one embodiment using conventional hydrotreating catalysts are operated and upgraded at high pressures (within 10 psig in one embodiment and within 50 psig in the second embodiment) similar to other upgrade systems. Sulfur, Ni, V, and other impurities can be removed from the resulting product.

  FIG. 6 is a block diagram that schematically illustrates another embodiment of the upgrade system, where the solvent deasphalting device pre-treats some if not all of the heavy oil feed stream to the system. Used for. Deasphalted oil (DAO) can be fed directly to the contact zone (s) or combined with a heavy oil feed stream as a feed. In some embodiments, other hydrocarbon feeds, such as VGO, can also be combined with heavy oil feed streams and / or DAOs as feeds for some of the contact zone (s). All of the fresh catalyst can be fed directly to the first contact zone in the system or can be redirected to other contact zone (s) in series.

  FIG. 7 is a flow diagram of a heavy oil upgrade process using a fresh catalyst split feed stream scheme, where some of the fresh catalyst feed stream is directed from the first reactor to the other reactors in the process. . As shown, the fresh catalyst feed stream is divided between the various contact zones as feed stream streams 31, 32, and 33. Fresh catalyst feed stream 31 is combined with recycled catalyst feed stream 17 and fed to the first contact zone as slurry catalyst feed stream 3. Hydrogen gas 2 and heavy oil feedstock 1 are combined with the slurry catalyst 3 as a feed stream to the first contact zone 10. In this embodiment, the heavy oil feed is preheated in a furnace 80 before being introduced into the contact zone as a heated oil feed stream 4.

  The stream 5 containing the upgraded heavy oil feedstock exits the contact zone 10 and flows to the separation zone 40, where the gas (including hydrogen) and volatile upgraded product are non-volatile fraction 7. And is taken up as stream 6. The non-volatile fraction stream 7 is sent to the next contact zone 20 in series for further upgrade. Stream 7 includes, in some embodiments, a slurry catalyst together with unconverted oil and small amounts of coke and asphaltenes.

  This upgrade process continues with other contact zones as shown, where stream 7 is combined with hydrogen feed stream 15 and fresh catalyst 32 as a feed stream to contact zone 20. Although not shown, the stream can also be supplied to the contact zone by a separate conduit. Stream 8 containing the upgraded heavy oil feedstock flows to separation zone 50, where the upgraded product is combined with hydrogen and removed as overhead product 9. A bottoms stream 11 comprising catalyst slurry, unconverted oil (and in some embodiments small amounts of coke and asphaltene) is fed as fresh feed stream 33 and fresh hydrogen as feed stream to the next contact zone 30. Combined with supply 16. Stream 12 exits the contact zone and flows to separation zone 60, where upgraded product and hydrogen are withdrawn as stream 13. In some embodiments, some of the bottom stream 17 from the separation zone, including catalyst slurry, unconverted oil plus small amounts of coke and asphaltenes, is recycled to the first contact zone 10 as a recycle stream 19. . The remainder of the bottom stream 17 is withdrawn as a bleed-off stream 18 and sent to other processes in the system for catalytic deoiling, metal recovery, and the like. Although not shown, the vapor stream 14 containing the upgraded product and hydrogen in one embodiment is subsequently processed in another part of the system, for example, in a high pressure separator and / or lean oil contactor. Is done.

  FIG. 8 illustrates another embodiment of the present invention, where a reactor with an internal separator is used, so a separate hot separator / flash drum is not required for phase separation. In this upgrade system, a reactor differential pressure control system (not shown) is used to regulate the product stream from the top of each reactor-separator. An external pump (not shown) can be used to help disperse the slurry catalyst in the system and help control the temperature in the system.

  In the illustrated embodiment of FIG. 8, all of the fresh catalyst is directed to the second and third contact zones in the system. The recycled catalyst stream 19 provides a slurry catalyst feed stream to the first contact zone and optionally to other contact zone (s) in the system. Also, as shown, an additional hydrocarbon oil feed stream, eg, VGO, naphtha, in an amount ranging from 2 to 30% by weight of the heavy oil feed stream, can be fed into any of the contact zones in the system. As part, it can optionally be added.

  FIG. 9 shows that all of the fresh catalyst feed stream 99 is fed directly to the final contact zone in the upgrade system and the other contact zone (s) in the system simply receives a portion of the recycled catalyst stream 19. 1 illustrates one embodiment of the invention.

  FIG. 10 illustrates one embodiment of a heavy oil split feed stream scheme. As shown, some of the heavy oil feed stream is diverted from the first reactor as a heavy oil feed stream 42 and fed directly to the second contact zone in the system. Also, as shown, the recycled catalyst is optionally sent as a stream 32 along with a portion of fresh catalyst to the second contact zone in the system.

  The following examples are given as non-limiting illustrations of aspects of the present invention.

Comparative Example 1
Heavy oil upgrade experiments were performed in a pilot system with three gas-liquid slurry phase reactors connected in series, each with three hot separators connected in series with the reactor. The upgrade system was operated continuously for about 50 days.

  The new slurry catalyst used was prepared according to the teachings of US Patent Application No. 2006/0058174, ie, the Mo compound is first mixed with aqueous ammonia to form an aqueous Mo compound mixture and sulfidized with a hydrogen compound. Sulfied and promoted with Ni compounds, then converted in hydrocarbon oil (other than heavy oil feedstock) at a temperature of at least 350 ° F. and a pressure of at least 200 psig, the first reaction An active slurry catalyst is formed for delivery to the vessel.

The hydrotreating conditions are as follows. Reactor temperature of about 825 ° F. (in 3 reactors); total pressure in the range of 2400 to 2600 psig; fresh Mo / fresh heavy oil feed flow ratio (wt%) 0.20-0.40; fresh Mo Catalyst / total Mo catalyst ratio 0.125 to 0.250; total feed LHSV about 0.070 to 0.15; and 7500 to 20000 H ₂ gas ratio (SCF / bbl).

  The effluent taken from each reactor was sent to a separator (connected in series) and separated into a hot vapor stream and a non-volatile stream. The vapor stream was removed from the top of the high pressure separator and collected for further analysis ("HPO" or high pressure overhead stream). A non-volatile stream containing the slurry catalyst and unconverted heavy oil feed was removed from the separator and sent to the next reactor in series.

  A portion of the non-volatile stream from the final separator in an amount of 30% by weight of the heavy oil feed was recycled (STB) and the remainder was removed as a bleed stream (amount about 15% by weight of the heavy oil feed). The STB stream contains about 10 to 15 wt% slurry catalyst.

The feed stream blend to the system was a heavy metal with high metal content having the properties shown in Table 1.

  The operation was stopped after 50 days of operation. The reactor, distributor and internal thermowell were visually inspected. All three parts showed significant deposition of deposits, and about 28.5% of the front (first) reactor volume was lost due to heavy metal deposits. Analysis of the slurry catalyst used in the bleed stream in the 50-day range showed an increasing depletion of vanadium, and deposits deposited inside the front reactor were not only generated, but also during operation. Suggested that it was actually getting worse. The performance of the process was also damaged by the reduction of the reaction volume.

Example 2
Decrease the temperature of the first reactor by 20 ° F. (from about 825 ° F. to about 805 ° F.) and increase the recycle catalyst rate from 30% by weight of heavy oil feed flow rate (in Example 1) to about 40% by weight Example 1 was repeated, except that water was added to the front reactor at a rate corresponding to 5% by weight of the heavy oil feed flow rate. The system was stopped after 54 days of operation.

  Water injection was performed by adding water to the fresh catalyst, and then the water and catalyst mixture was preheated to a temperature of about 350 ° F. and added to the autoclave along with the heavy oil feed stream and hydrogen.

  Analysis of the slurry catalyst used in the bleed stream in the 54 day range showed a fairly close agreement between the amount of vanadium expected to exit the process and the amount of vanadium in the catalyst in the bleed stream, Capture significantly reduced, thus suggesting that heavy metal deposition in the device was significantly reduced.

  The analytical results were further confirmed by visual inspection of the reactor interior, distributor, and internal thermowell. The apparatus was remarkably clean in Example 2, with only 6.6% of the front end reactor volume lost due to heavy metal deposits.

Comparative Example 3
The heavy oil upgrade experiment was performed in a pilot system having three gas-liquid slurry phase reactors connected in series with two hot separators. The hot separator was connected in series with the first and third reactors respectively, and there was no hot separator after the second reactor. The gas-liquid slurry phase reactor is a continuously stirred reactor. The upgrade system operated continuously for about 70 days.

  The fresh slurry catalyst used was prepared according to the teachings of US Patent Application No. 2006/0058174, i.e., the Mo compound is first mixed with aqueous ammonia to form an aqueous Mo compound mixture to form a hydrogen / sulfur compound. Sulfidated with, promoted with Ni compounds and then converted in hydrocarbon oil (other than heavy oil feedstock) at a temperature of at least 350 ° F. and a pressure of at least 200 psig to form an active slurry catalyst .

In Comparative Example 3, all of the fresh catalyst slurry was sent to the first reactor in the system, and the concentration of fresh slurry catalyst in heavy oil expressed as the weight of metal (molybdenum) relative to the weight of the heavy oil feed stream, It ranged from 2,000 to 5,000 ppm. The hydrotreating conditions were as follows. Reactor temperature of 815 to 825 ° F; total pressure in the range of 2400 to 2600 psig; fresh Mo / fresh heavy oil feed stream ratio (wt%) 0.20 to 0.40; fresh Mo catalyst / total Mo catalyst ratio 0.1; total feed stream LHSV 0.10 to 0.15; and H ₂ gas ratio (SCF / bbl) of 10,000 to 15000.

  The effluent taken from the first and third reactors was introduced into a hot separator connected in series with the reactor and separated into a hot vapor stream and a non-volatile stream. The vapor stream was removed and collected from the top of the high pressure separator ("HPO" or high pressure overhead stream) for further analysis. A non-volatile stream containing the slurry catalyst and unconverted heavy oil feed was removed from the bottom of the first separator and sent to the second reactor in series. The effluent from the second reactor was sent directly to the third reactor as a raw material.

  A portion of the non-volatile stream from the final separator in an amount of 5 to 15% by weight of the heavy oil feed is withdrawn as a bleed-off stream and a total conversion of 98 to 98.5% of the heavy oil feed to distillate product. Met. The “stripper bottom product” or STB, which is the remainder of the non-volatile stream, containing the bulk of the catalyst (in an amount of 80% to 95% of the total slurry catalyst entering the system) maintains the catalyst flow in the upgrade system To be recycled to the first reactor. The STB stream contains about 7 to 20 weight percent slurry catalyst. The STB was also analyzed to evaluate the overall performance of the system.

The feed stream blend to the system was a heavy oil feed stream having the properties shown in Table 2.

Example 4
After all of the fresh catalyst was fed to the first reactor for 70 days (Comparative Example 3), the fresh catalyst feed position was moved from the first to the third reactor, and the first and second reactors were 28 Dependent on the fully recycled catalyst feed stream for days. All other process conditions remained the same. HPO and STB products were collected, analyzed and compared with the results of Comparative Example 3. There was no significant change in the quality of the HPO product. For the STB product, the results are as follows.

  The results show that diverting fresh catalyst to the final contact zone in the system did not change the product nitrogen concentration. However, there is a change in the sulfur concentration, which may be due to the unusually low sulfur concentration in the heavy oil feed stream to the system and the high sulfur concentration in the VGO oil used in the slurry catalyst feed stream. Thus, by injecting fresh catalyst into the final reactor, the VGO oil carrier (in the slurry catalyst) has little time to react, resulting in a higher product sulfur concentration, resulting in product sulfur. May have been disadvantaged. Further note that diverting fresh catalyst to the final reactor resulted in STB products with improved properties, including API, viscosity, MCR, HHA, nickel, and H / C ratio. I want to be. The improvement of the STB product API was not related to the improvement of the STB product distillation. In other words, the STB product API was not improved by additional cracking in the lighter product distillation, but improved by improved catalytic activity, resulting in higher H / C ratios.

  For the 28-day system operation, there was no evidence of pressure drop accumulation or blockage around the front reactor suggesting coking or solid accumulation. There was no measurable negative impact on overall conversion rate. The results suggest that the catalyst used retains sufficient hydrogenation activity to prevent coking even in the presence of fresh / untreated heavy oil feedstock, and the fresh catalyst splitting scheme is It shows that coking is still sufficiently suppressed.

Example 5
Comparative Example 3 is repeated with the other process conditions remaining the same except that 20% of the heavy oil feedstock is directed from the first reactor to the third reactor.

  In a comparison of process stability, reactor performance, and reactor conditions between the above examples, in Comparative Example 3, the third reactor has a lower liquid throughput (no throughput) and more With high catalyst concentrations, these are considered directionally beneficial for conversion purposes. However, these conditions also tend to make the final reactor more prone to malfunctions, resulting in insufficient liquid flow, and consequently more solids accumulation, decomposition temperature measurements and reduced process run times.

  In Example 5, where a portion of the heavy oil feed is fed directly to the final reactor, the previous reactor (first and second) reduced liquid throughput (because a portion of the heavy oil feed is diverted) and responds With increasing catalyst concentration, it is expected to operate more efficiently and at higher conversion rates. Furthermore, due to dilution with more liquid in the third reactor, there is a more uniform catalyst concentration profile across all three reactors.

  It is further expected that drying conditions associated with insufficient liquid flow will be avoided because the final reactor in series obtains part of the heavy oil feed stream. Since the final reactor is protected from overconversion conditions or drying conditions, there is less solid accumulation or coke deposition. The final reactor is also expected to be less susceptible to operational fluctuations such as wide variations in temperature, pressure, flow, and the like.

  For purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing amounts, percentages or proportions, and other numerical values used in this specification and claims are all In the case of the term “about”. Accordingly, unless indicated otherwise, the numerical parameters set forth in the following specification and attached claims are dependent on the accuracy of the apparatus for measuring the desired property and / or value to be obtained. Approximations that may vary, including the standard deviation of the instrument or method error used to determine the value. The use of the term “or” in the claims expressly indicates that this disclosure supports a definition that only means an alternative and “and / or”, but that only the alternative or the alternatives are incompatible with each other. Unless used, it is used to mean “and / or”. The use of the term “a” or “an” when used in conjunction with the term “comprising” in the claims and / or the specification is “one”. Is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”. Further, all ranges disclosed herein include endpoints and can be combined independently. In general, unless otherwise indicated, singular elements may be plural and vice versa without loss of generality. As used herein, the term “include” and grammatical variations thereof are intended to be non-limiting, and thus a list of items in a table may replace the listed items or It is not an exclusion of other similar items that may be added to the listed items.

  It is contemplated that any aspect of the invention described in connection with one embodiment of the invention may be implemented or applied with respect to any other embodiment of the invention. Similarly, any composition of the invention is a result of the invention or may be used in any method or process of the invention. This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are those where they have structural elements that do not differ from the literal words in the claims, or equivalent structures that have insubstantial differences from the literal words in the claims. Including elements is intended to be included within the scope of the claims. All citations referred to herein are expressly incorporated herein by reference.

Claims (17)

Using multiple contact zones and separation zones,
Providing a heavy oil feedstock, a hydrogen-containing gas, and a slurry catalyst;
In the first contact zone under hydrocracking conditions, the heavy oil feedstock, hydrogen-containing gas, and slurry catalyst are combined to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons that are upgraded. Forming a product,
A mixture comprising the upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock is sent to the first separation zone so that the upgraded product is removed from the first separation zone along with the hydrogen-containing gas. Removing the slurry catalyst, heavier hydrocracked liquid product and unconverted heavy oil feedstock as a first non-volatile stream from the first separation zone, withdrawn as a first overhead stream;
The first non-volatile stream is sent to a contact zone other than the first contact zone that is maintained under hydrocracking conditions, with an additional hydrogen-containing gas feed stream, and at least a portion of the heavy oil feedstock has a lower boiling point. Converting to hydrocarbons to form additional upgraded products;
A mixture comprising additional upgraded product, slurry catalyst, hydrogen-containing gas, and unconverted heavy oil feedstock is sent to a separation zone other than the first separation zone so that the upgraded product is combined with the hydrogen-containing gas. Withdrawn as a top stream, and the slurry catalyst and unconverted heavy oil feedstock are withdrawn as a second non-volatile stream;
The slurry catalyst to the first contacting zone, at least a portion of from one of the nonvolatile stream separation zone comprises a recyclable catalyst stream, recycle catalyst stream, Ri 3-50 wt% der heavy oil feedstock A method for hydrotreating a heavy oil feedstock, wherein water is added to the first contact zone at 1-25% by weight of the heavy oil feedstock.   A sufficient amount of a hydrogen-containing gas feed stream so that the process has a volume yield of over 100% in upgraded products including liquefied petroleum gas, gasoline, diesel, vacuum gas oil, and jet and fuel oils. The method according to claim 1, which is provided.   The process according to any one of claims 1 to 2, wherein the recycled catalyst stream is at least 10% by weight of the total heavy oil feedstock.   3. At least a portion of the second non-volatile stream is recycled to at least one of the contact zones as a recycle stream, and the remainder of the second non-volatile stream is removed from the method as a bleed-off stream. The method as described in any one of.   The method of claim 4, wherein the recycle stream is sent to the first contact zone.   5. The method of claim 4, wherein a sufficient amount of bleed-off stream is taken such that the method has a conversion of at least 98%. The contact zone is maintained under hydrocracking conditions at a temperature of 410 ° C. to 600 ° C. and a pressure of 10 MPa to 25 MPa, and the first contact zone is at least 10 ° F. (5.56 ° C.) lower than the next contact zone. The method of claim 1, wherein the method is operated at temperature.   The method according to any one of claims 1 to 2 and 7, wherein a part of the slurry catalyst is for supplying to a contact zone other than the first contact zone. Providing a fresh slurry catalyst feed stream, wherein at least a portion of the fresh slurry catalyst feed stream is for feeding to a contact zone other than the first contact zone;
Providing a slurry catalyst comprising a used slurry catalyst and optionally a portion of a fresh catalyst slurry feed stream;
The first non-volatile stream being sent to a contact zone other than the first contact zone, wherein the contact zone other than the first contact zone is with an additional hydrogen-containing gas feed stream and at least a portion of the fresh slurry catalyst. Maintained under hydrocracking conditions, converting at least a portion of the unconverted heavy oil feedstock to lower boiling hydrocarbons to form additional upgraded products;
The method of claim 1.   10. A method according to any one of claims 1, 2, 7 and 9, wherein at least a portion of the heavy oil feedstock is for feeding to a contact zone other than the first contact zone. The method of claim 1, wherein at least a portion of the water is added to the first contact zone as a steam injection. Sending at least a portion of the first non-volatile stream to a solvent deasphalting unit;
Obtaining two streams from the solvent deasphalting unit, one stream containing deasphalted oil, one stream containing asphaltene and slurry catalyst,
The deasphalted oil is sent to a contact zone other than the first contact zone maintained under hydrocracking conditions, along with an additional hydrogen-containing gas feed stream and an additional slurry catalyst feed stream, so that at least one of the deasphalted oil Converting parts to lower boiling hydrocarbons to form additional upgraded products;
A mixture of additional upgraded product, slurry catalyst, additional hydrogen-containing gas, and unconverted deasphalted oil is sent to the second separation zone for additional volatile upgraded product and additional hydrogen-containing gas Is removed as a second overhead stream and the slurry catalyst, additional non-volatile upgraded product and unconverted deasphalted oil are withdrawn as a second non-volatile stream;
a) a portion of a stream containing asphaltenes and a slurry catalyst, b) a portion of a first non-volatile stream, c) a portion of a second non-volatile stream, and d) at least one of a mixture thereof. Recycling the recycle stream to at least one of the contact zones;
The method of claim 1, further comprising: The first contact zone has an outlet pressure of X, the first separation zone has an inlet pressure of Y, the outlet pressure X of the first contact zone and the inlet pressure Y of the first separation zone, 13. The method according to any one of claims 1 to 2, 7, 9, and 12, wherein the pressure drop Z is between 100 psi (0.69 MPa). 13. A process according to any one of claims 1 to 2, 7, 9, and 12, wherein the slurry catalyst has an average particle size in the range of 1 to 20 microns. 13. The slurry catalyst according to any one of claims 1, 2, 7, 9, and 12, wherein the slurry catalyst comprises clusters of colloidal sized particles having a particle size of less than 100 nm, the clusters having an average particle size in the range of 1-20 microns. The method according to one item. An additional hydrocarbon oil feed stream other than the heavy oil feedstock in an amount ranging from 2 to 30% by volume of the heavy oil feedstock is added to any of the contact zones. 13. The method according to any one of 12. 13. The method of any one of claims 1-2, 7, 9, and 12, further comprising recycling at least a portion of the non-volatile stream to at least one of the contact zones.

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