KR20110059881A - Systems and methods for producing a crude product - Google Patents

Abstract

A system and method for hydroprocessing a heavy oil feedstock with reduced heavy oil deposits, wherein the system utilizes a plurality of contacting and separating zones under hydrocracking conditions to reduce at least some of the heavy oil feedstock to lower boiling hydrocarbons. By conversion to, a modified product is formed and water and / or steam are optionally introduced into the first contacting zone in an amount of 1 to 25% by weight relative to the weight of the heavy oil feedstock. In one embodiment the first contact region operates at a temperature at least 10 ° F. below the next contact region. The contacting zone operates under hydrocracking conditions, using a slurry catalyst to reform the heavy oil feedstock and forming a reformed product which is a lower boiling hydrocarbon. In the separation zone, the modified product is removed overhead and optionally further processed in an inline hydrotreater. At least some of the non-volatile fractions recovered from the at least one separation zone are recycled back to the first contacting zone of the system in an amount of 3-50% by weight of the heavy oil feedstock. In one embodiment, at least some of the heavy oil feedstock is supplied to at least one contacting zone other than the first contacting zone and / or at least some new slurry catalyst is supplied to at least one contacting zone other than the first contacting zone. . In one embodiment, at least some non-volatile fractions recovered from the at least one separation zone are sent to an interstage solvent deasphalting unit to separate the unconverted heavy oil feedstock into deasphalted oil and asphaltenes. A deasphalted oil stream is sent to one of the contacting zones for further modification.

Description

SYSTEM AND METHOD FOR PRODUCTION OF CRUDE PRODUCTS {SYSTEMS AND METHODS FOR PRODUCING A CRUDE PRODUCT}

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

The petroleum industry is increasingly becoming a source of feedstock for heavy crude oil, residues, coal and tar sands. These feedstocks are characterized by asphaltene rich residues, and low API specific gravity, some of which are lower than 0 ° API.

International Publication Nos. WO2008 / 014947, US Publication No. 2008/0083650 and US Publication No. 2005/0241993, US Publication No. 2007/0138057 and US Patent No. 6,660,157 for processing heavy oil feeds. Disclosed are processes, systems, and catalysts. Heavy oil feedstocks generally contain high levels of heavy metals. Some of these heavy metals, such as nickel and vanadium, tend to react rapidly, causing deposition or trapping of vanadium-rich solids in equipment such as reactors. Deposition of solids reduces the volume of reactions possible and reduces run time.

There remains a need for improved systems and methods for reforming / processing / processing heavy oil feeds that have reduced accumulation of heavy metals in process equipment.

Summary of the Invention

In one aspect, the present invention relates to a process capable of reforming a heavy oil feedstock. The process utilizes a plurality of contacting zones, separation zones and at least interstage solvent deasphalting units (SDAs). The process comprises: a) combining a hydrogen containing gas feed, a heavy oil feedstock and a slurry catalyst in a first contacting zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock into a reformed product; c) directing the mixture of the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to a separation zone; d) in the separation zone, removing the reformed product with the hydrogen containing gas as an overhead stream and removing the slurry catalyst and the unconverted heavy oil feedstock as a nonvolatile stream; e) sending at least a portion of the nonvolatile stream to the SDA unit to separate the asphaltene and slurry catalyst from the deasphalted oil; f) directing the deasphalted oil and the remaining nonvolatile stream from the previous separation zone to another contacting zone, converting the deasphalted oil to a reformed product under hydrocracking conditions with additional hydrogen gas and additional slurry catalyst; f) by sending the modified product, slurry catalyst, hydrogen and unconverted deasphalted oil to the separation zone, the modified product is removed with hydrogen as overhead stream and the slurry catalyst and unconverted deasphalted oil are removed as nonvolatile stream Becoming; And g) at least a portion of the nonvolatile stream comprising the slurry catalyst and unconverted deasphalted oil is recycled to at least one contacting zone.

In another aspect, a process using a plurality of contacting zones, separation zones and at least an interstage solvent deasphalting unit (SDA), wherein the heavy oil feedstock can be modified and at least a portion of the non-volatile stream from the contacting zone is SDA By being sent to the unit, a process for separating asphaltenes from the deasphalted oil is provided.

In one aspect, the present invention is directed to a process that can modify heavy oil feedstock by having reduced heavy metal deposition in the front-end contact area. The process utilizes a plurality of contacting zones and separation zones and a) combines a hydrogen containing gas feed, a heavy oil feedstock and a slurry catalyst under hydrocracking conditions in the first contacting zone, thereby modifying at least a portion of the heavy oil feedstock. Converting the product, wherein water and / or steam are introduced into the first contacting zone in an amount of 1 to 25% by weight based on the weight of the heavy oil feedstock; b) sending a mixture of the reformed product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone; c) in the separation zone, removing the modified product with hydrogen containing gas as overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream; d) directing the non-volatile stream to another contacting zone with additional hydrogen gas, unconverted heavy oil feedstock, and optionally a fresh slurry catalyst, under hydrocracking conditions to convert the unconverted heavy oil feedstock to the reformed product. ; f) sending the reformed product, slurry catalyst, hydrogen and unconverted heavy oil feedstock to the separation zone, whereby the reformed product is removed with hydrogen as an overhead stream and the slurry catalyst and unconverted heavy oil feedstock are removed as a nonvolatile stream. step; g) at least a portion of the nonvolatile stream is recycled to at least one of the contacting zones.

In another aspect, the present invention provides a method for reforming a heavy oil feedstock using a plurality of contacting zones and separation zones, wherein water and / or steam are introduced into the first contacting zone and are from a separation zone other than the first separation zone. At least a portion of the volatile stream is recycled to the first contacting zone, wherein the recycled stream is in the range of 3-50% by weight of the total heavy oil feedstock of the process.

In one aspect, the present invention relates to a process capable of reforming heavy oil feedstocks. The process uses a plurality of contacting zones and separation zones, the method comprising the steps of: a) supplying a heavy oil feedstock having at least a portion of the heavy oil feedstock to a contacting zone other than the first contacting zone; b) combining the hydrogen containing gas feed, a portion of the heavy oil feedstock and the slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to the modified product; c) sending a mixture of the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone; d) in the separation zone, removing the reformed product with a hydrogen containing gas as overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream; e) directing the non-volatile stream to another contacting zone with additional hydrogen gas, at least a portion of the heavy oil feedstock, and optionally a fresh slurry catalyst, under hydrocracking conditions to convert the unconverted heavy oil feedstock to the reformed product. step; f) sending the reformed product, slurry catalyst, hydrogen and unconverted heavy oil feedstock to the separation zone, whereby the reformed product is removed with hydrogen as an overhead stream and the slurry catalyst and unconverted heavy oil feedstock are removed as a nonvolatile stream. step; And g) recycling at least a portion of the nonvolatile stream to the first contacting zone.

In another aspect, the process utilizes a plurality of contacting and separating zones, a) providing a slurry catalyst comprising a slurry catalyst used and optionally a fresh catalyst slurry feed; b) combining the hydrogen containing gas feed, the heavy oil feedstock and the slurry catalyst under hydrocracking conditions in the contacting zone to convert at least a portion of the heavy oil feedstock to the modified product; c) sending a mixture comprising the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone; d) in the separation zone, removing the reformed product with the hydrogen containing gas as overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream; e) directing the nonvolatile stream to another contacting zone with additional hydrogen gas and fresh slurry catalyst under hydrocracking conditions to convert the unconverted heavy oil feedstock to the reformed product; f) sending the reformed product, slurry catalyst, hydrogen and unconverted heavy oil feedstock to the separation zone, thereby removing the reformed product with hydrogen as an overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream. Making; And g) recycling at least a portion of the nonvolatile stream to the first contacting zone.

In another aspect, a process using a plurality of contacting zones and separation zones is provided wherein a heavy oil feedstock can be modified and a fresh slurry catalyst is split between the contacting zones.

In one aspect, the process utilizes a plurality of contacting zones and separation zones, and a) combines a hydrogen containing gas feed, a heavy oil feedstock and a slurry catalyst under hydrocracking conditions in the first contacting zone to produce a heavy oil feedstock. Converting at least some of the modified products; b) sending a mixture of the reformed product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone; c) in the separation zone, removing the modified product with hydrogen containing gas as overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream; d) directing the nonvolatile stream to another contacting zone with additional hydrogen gas, unconverted heavy oil feedstock, and optionally a fresh slurry catalyst, under hydrocracking conditions to convert the unconverted heavy oil feedstock to the reformed product; f) sending the reformed product, slurry catalyst, hydrogen and unconverted heavy oil feedstock to the separation zone, thereby removing the reformed product with hydrogen as an overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream. Wherein the first contacting region is operated at a temperature at least 10 ° F. below the next subsequent contacting region.

In another aspect, the present invention is directed to a process capable of modifying heavy oil feedstocks with reduced heavy metal deposition in the front-end contact areas. The process utilizes a plurality of contacting zones and separation zones, and a) combines a hydrogen containing gas feed, a heavy oil feedstock and a slurry catalyst under hydrocracking conditions in a first contacting zone to reform at least a portion of the heavy oil feedstock. Converting to; b) sending a mixture of the reformed product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone; c) in the separation zone, removing the reformed product with a hydrogen containing gas as overhead stream and removing the slurry catalyst and unconverted heavy oil feedstock as a nonvolatile stream; d) directing the nonvolatile stream to another contacting zone with additional hydrogen gas, unconverted heavy oil feedstock, and optionally a fresh slurry catalyst, under hydrocracking conditions to convert the unconverted heavy oil feedstock to the reformed product; f) sending the reformed product, slurry catalyst, hydrogen and unconverted heavy oil feedstock to a separation zone, wherein the reformed product is removed with hydrogen as an overhead stream and the slurry catalyst and unconverted heavy oil feedstock are non-volatile The slurry catalyst removed as a stream, the slurry catalyst going to the first separation zone, is a recycled catalyst stream comprising at least a portion of the nonvolatile stream from one of the separation zones, wherein the recycled catalyst stream is 3-50% by weight of heavy oil feedstock .

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

As used herein, “heavy oil” feed or feedstock refers to heavy and ultra heavy crude oil including, but not limited to, residue oil, coal, bituminous coal, shale oil, tar sand, and the like. The heavy oil feedstock may be liquid, semi-solid, and / or solid. Examples of heavy oil feedstocks that can be modified as described herein include, but are not limited to, vacuum residues from Canadian tar sands, Brazilian Santos and Campos basins, Suezman, Chad, Venezuela Julia, Malaysia, and Sumatra, Indonesia. Include. Other examples of heavy oil feedstocks include "bottom of the barrel" and "residuum"-tower bottoms having a boiling point of at least 343 ° C (650 ° F), Or a refining tower reservoir having a boiling point of at least 524 ° C. (975 ° F.), or “resid pitch” and “reduced residue” having a boiling point of at least 524 ° C. (975 ° F.). The residues and residues of the barrels left from.

The characteristics of the heavy oil feedstock include a TAN of at least 0.1, at least 0.3, or at least 1; Viscosity of at least 10 cSt; In one embodiment, it may include, but is not limited to, an API gravity of at most 15 and in another embodiment at most 10. 1 g of heavy oil feedstock generally has at least 0.0001 g of Ni / V / Fe per gram of crude oil; At least 0.005 g heteroatoms; At least 0.01 g of residue; At least 0.04 g C5 asphaltenes; At least 0.002 g of MCR; At least 0.00001 g of alkali metal salt of at least one organic acid; And at least 0.005 g 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", "modified", "modified" and "modified", when used with heavy oil feedstocks, are used to reduce the molecular weight of the heavy oil feedstock that has been hydroprocessed or already coarse, or the heavy oil feedstock. Reduced, reduced boiling point range of feedstock, reduced concentration of asphaltenes, reduced concentration of hydrocarbon free radicals, and / or reduced amounts of impurities such as sulfur, nitrogen, oxygen, halides and metals Refers to a substance or crude oil product.

The reforming or treatment of the heavy oil feed is generally referred to as "hydroprocessing". Hydroprocessing includes but is not limited to hydrogenation, including hydroconversion, hydrocracking, hydrogenation, hydrotreating, hydrodesulfurization, hydrodenitrification, hydrodemetals, hydrodearomatics, hydroisomerization, hydrodewaxing, and selective hydrocracking. By any process carried out in the presence of hydrogen, including decomposition. Products of the hydroprocessing can exhibit improved viscosity, viscosity index, saturate content, low temperature properties, volatility and polarization.

As used herein, hydrogen refers to a compound or compounds that react with hydrogen and / or in the presence of a heavy oil feed and a catalyst to provide hydrogen.

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

Nm ³ / m ³ refers to normal cubic meters per cubic meter of heavy oil feed.

VGO or reduced pressure gas oil refers to hydrocarbons having a boiling point range distribution from 343 ^o C (650 ^o F) to 538 ^o C (1000 ^o F) at 0.101 MPa.

"wppm" means ppm by weight.

As used herein, the term "catalyst precursor" refers to a compound containing at least one metal having catalytic activity, from which the catalyst is finally formed. It should be noted that the catalyst precursor may have catalytic activity as a hydroprocessing catalyst. As used herein, "catalyst precursor" may refer to "catalyst" when used in the context of a catalyst feed.

As used herein, the term “catalyst used” refers to a catalyst that is used at least in a reactor during hydroprocessing operation to reduce activity. For example, assuming that the reaction rate constant of the new catalyst at a certain temperature is 100%, the reaction rate constant of the catalyst used is no greater than 95% in one embodiment, or no greater than 80% in another embodiment, and the third Up to 70% in an embodiment. The term “used catalyst” may be used interchangeably with “recycled catalyst”, “slurry catalyst used” or “recycled slurry catalyst”.

As used herein, the term “new catalyst” refers to a catalyst or catalyst precursor that has never been used in a reactor during hydroprocessing operations. The term new catalyst is also used herein as a "regenerated" or "activated" catalyst, ie at least in the reactor during the hydroprocessing operation ("catalyst used"), but its catalytic activity is restored or at least used to the level of catalytic activity used. It includes increased catalyst to far exceeding levels. The term "fresh catalyst" can be used interchangeably with "fresh slurry catalyst".

As used herein, the term "slurry catalyst" (or sometimes "slurry" or "dispersed catalyst") refers to a liquid medium, such as oil, in which a catalyst and / or catalyst precursor particles (particulates or crystallites) with very small average values are dispersed. , Water or mixtures thereof.

As used herein, "catalyst feed" includes any catalyst suitable for reforming heavy oil feedstocks, such as one or more bulk catalysts and / or one or more catalysts on a support. The catalyst feed may comprise at least fresh catalyst, only used catalyst, or at least a mixture of fresh catalyst and used catalyst. In one embodiment the catalyst feed is in the form of a slurry catalyst.

As used herein, the term "bulk catalyst" can be used interchangeably with "non-supported catalyst", wherein the catalyst composition has a preformed and shaped catalyst support, and then the metal is loaded through the impregnation or deposition catalyst. It is not a conventional catalyst form. In one embodiment, the bulk catalyst is formed through precipitation. In another embodiment, the bulk catalyst has a binder embedded in the catalyst composition. In another embodiment, the bulk catalyst is formed from a metal compound without any binder. In a fourth embodiment, the bulk catalyst is a dispersed catalyst used as catalyst particles dispersed in a liquid mixture (eg, hydrocarbon oil). In one embodiment, the catalyst comprises one or more commercially known catalysts, such as MicroCat ^™ of ExxonMobil Corporation.

As used herein, the term “contacting zone” refers to an apparatus in which the heavy oil feed is treated or reformed by contacting the slurry catalyst feed in the presence of hydrogen. In the contacting zone, at least the characteristics of the crude oil feed are changed or modified. The contacting zone can be a reactor, part of a reactor, multiple parts of a reactor, or a combination thereof. The term "contact area" can be used interchangeably with "reaction zone."

As used herein, the term “separation zone” refers to a device in which a modified heavy oil feed from a contacting zone is fed directly or after being subjected to one or more intermediate processes to a direct separation zone, such as a flash drum or a high pressure separator, wherein the gas and volatile The liquid is separated from the nonvolatile fractions. In one embodiment, the nonvolatile fraction stream comprises an unconverted heavy oil feed, a smaller amount of heavier hydrocracked liquid product (synthetic or less volatile / nonvolatile modified product), slurry catalyst and any unentrained solid. (Asphaltene, coke, etc.).

As used herein, the term "bleed stream" or "bleed off stream" refers to a stream comprising a spent (or recycled) catalyst that has been leaked or bypassed from the hydroprocessing stream, and which has accumulated metal from the reforming system. It helps to prevent or wash away sulfides and other unwanted impurities.

The present invention relates to an improved system for processing or reforming heavy oil feeds, especially heavy oil feedstocks comprising high levels of heavy metals.

In a general prior art hydroprocessing system having a plurality of contacting zones (reactors) in series, the feed stream to the second contacting zone is generally cleaner than the heavy oil feed from the system to the first contacting zone, ie heavy oil It has been observed that when the substrate has been treated in the first contact region, it should contain less impurities such as nickel, vanadium, nitrogen, sulfur and the like. It is also observed that the feed stream going to the last contacting zone in the system should generally be cleaner than the feed stream to the previous contacting zone (s) in the system.

In a typical hydroprocessing system, in the prior art catalyst feed system, the feed stream to the subsequent contacting zone of the system is characterized by certain impurities such as MCR, C ₅ and C _7. It has been further observed that, in terms of asphaltene content and the like, it is generally more concentrated, promoting coke formation in the latter contact zones of the system.

Also, a) lower TAN; b) viscosity; c) lower residue content; d) lower API gravity; e) lower metal content in metal salts of organic acids; And combinations thereof, it has been observed that the feed stream destined for the subsequent contacting zone of the system has different characteristics than that of the heavy oil feed to the preceding contacting zone (s) of the system. However, it has also been observed that in terms of conversion and / or properties of the crude oil product obtained, it is generally more difficult to process the feed to the subsequent contacting zones of the system. In addition to the prior art feed system (new catalyst goes to the first contacting zone), it is observed that there is more coke formation in the subsequent contacting zone than the first contacting zone. Coke formation is probably associated with the fact that the feed to the subsequent contacting zone is more difficult to process and / or the reduced activity of the catalyst feed to the subsequent contacting zone.

In one embodiment, the reforming process includes a plurality of reactors for the contacting zone, where the reactors are the same or different in batch. Examples of reactors that may be used herein include stacked bed reactors, fixed bed reactors, ebullating bed reactors, continuous stirred tank reactors, fluidized bed reactors, spray reactors, liquid / liquid contactors, slurry reactors, liquids Recycle reactors and combinations thereof. In one embodiment, the reactor is an upward flow reactor. In another embodiment, the downflow reactor. In one embodiment, the contacting region refers to at least a slurry-bed hydrocracking reactor in series with at least a fixed bed hydrotreating reactor. In another embodiment, an in-line hydrotreater is capable of removing more than 70% sulfur, more than 90% nitrogen and more than 90% heteroatoms in the crude product being processed. Additionally included.

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

Depending on the conditions and location of the separation zone, in one embodiment, the amount of heavier hydrocracked product in the nonvolatile fraction stream is less than 50% by weight (of the total weight of the nonvolatile stream). In a second embodiment, the amount of heavier hydrocracked product in the nonvolatile stream from the separation zone is less than 25% by weight. In a third embodiment, the amount of heavier hydrocracked product in the nonvolatile stream from the separation zone is less than 15% by weight. As the modified material is withdrawn from the contacting zone and fed to the separation zone, at least a portion of the slurry catalyst remains with the modified feedstock such that the slurry catalyst remains available in the separation zone and exits the separation zone with the non-volatile liquid fraction. Points should be noted.

In one embodiment, both the contacting zone and the separation zone are combined into one device, such as, for example, a reactor with an internal separator, or a multistage reactor-separator. In this type of reactor-separator arrangement, the vapor product exits the top of the apparatus and the nonvolatile fraction exits the side or bottom of the apparatus together with the slurry catalyst and, if present, the entrained solid fraction.

In one embodiment, the slurry catalyst stream comprises a fresh catalyst. In another embodiment, the slurry catalyst stream comprises a mixture of at least fresh catalyst and recycled (used) catalyst. In a third embodiment, the slurry catalyst stream comprises the catalyst used. In another embodiment, the slurry catalyst comprises a well dispersed catalyst precursor composition capable of forming the active catalyst in situ within the feed heater and / or contacting zone. The catalyst particles may be introduced into the medium (diluent) after the pretreatment step as a powder in one embodiment, as a precursor in another embodiment, or 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 another embodiment, the liquid medium is a hydrocarbon oil other than a heavy oil feedstock, such as a VGO medium or diluent.

In one embodiment, the bleed off stream comprises an unconverted material, a slurry catalyst, a small amount of heavier hydrolyzed liquid product, a small amount of coke, asphaltenes, and the like, from the separation region of the system, in particular from the last separation region. Non-volatile materials. In another embodiment, the bleed off stream is a bottoms stream from the interphase solvent deasphalting unit of the system. In embodiments where the bleed off stream is diverted from the bottoms stream of the separation zone, the bleed stream is generally in the range of 1 to 35 weight percent, 3 to 20 weight percent, 5 to 15 weight percent of the total heavy oil feedstock of the system. In one embodiment where the bleed off stream is bypassed from the bottom of the deasphalted unit, the bleed off stream is in the range of 0.30 to 5%, 1 to 30%, or 0.5 to 10% by weight of the heavy oil feedstock.

In one embodiment, the bleed off stream comprises 3 to 30 weight percent slurry catalyst. In another embodiment, the amount of slurry catalyst is in the range of 5-20% by weight. In another embodiment, the bleed off stream comprises an amount of slurry catalyst in the range of 1 to 15 weight percent concentration.

In some embodiments, instead of sending all new catalyst to the first contacting region as in the prior art process, at least some new catalyst is diverted to at least one other contacting region (other than the first contacting region) of the system.

Further, in some embodiments, instead of sending all heavy oil feeds to be reformed to the first contacting zone, at least some heavy oil feeds are diverted to at least one other contacting zone of the system.

In another embodiment, a combined feed scheme is used to divert some fresh catalyst feed and some heavy oil feed to at least one other contact region other than the first contact region of the heavy oil reforming system.

In one embodiment, the reforming system comprises at least two consecutive upflow reactors having at least two separators, each separator located immediately after each reactor and the interstage SDA unit being at least one reactor of the system. Located in front In another embodiment, the modified system includes at least two upflow reactors and at least two separators in series, each separator being located immediately after each reactor, and the interstage SDA unit is continuously placed directly on the first separator. It is located next. In a fourth embodiment, the reforming system may comprise a combination of multistage reactor-separators and continuously separate reactors and separate separators, with the SDA located as an interstage treatment system between any two consecutive reactors.

Heavy oil Supply

The unconverted heavy oil feed herein can include one or more different heavy oil feeds from different sources as a single feed stream, or as separate heavy oil feed streams. In some embodiments of the present invention, at least one heavy oil feed (to be modified) is "split" or at least one other contacting area or interstage (other than the first contacting area) of the system before being fed to the contacting area. Bypassed to the unit.

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

Additional hydrocarbons Supply

In one embodiment, additional hydrocarbon oil feeds, such as VGO (reduced gas oil), naphtha, MGO (medium cycle oil), solvent donors, other aromatic solvents, etc., in amounts of 2-40% by weight of the heavy oil feed, etc. Any of the contacting zones of this system may optionally be added as part of the heavy oil feed stream. In one embodiment, the additional hydrocarbon feed serves as a diluent to lower the viscosity of the heavy oil feed.

Implementation Aspects of Heavy Oil Split Supply System

In some embodiments, at least a portion of the heavy oil feed (to be modified) is “split” or is diverted to at least one other contacting area of the system (other than the first contacting area).

In one embodiment, “at least a portion” means at least 5% of the heavy oil feed to be reformed. In another embodiment, at least 10%. In a third embodiment, at least 20%. In a fourth embodiment at least 30% of the heavy oil feed is diverted to at least one contact area other than the first of the system.

In one embodiment, less than 90% of the unconverted heavy oil feed is fed to the first reactor of the system and at least 10% of the unconverted heavy oil feed is bypassed to the remaining contacting zone (s) of the system. In another embodiment, the heavy oil feed is equally divided between the contacting zones in the system. In another embodiment, less than 80% of the unconverted heavy oil feed is fed to the first contacting zone of the system and the remaining heavy oil feed is bypassed to the last contacting zone of the system. In a fourth embodiment, less than 60% of the heavy oil feed is fed to the first contacting zone of the system and the remaining unconverted heavy oil feed is divided equally between the remaining contacting zones of the system.

The unconverted heavy oil feed herein can include one or more different heavy oil feeds from different sources as a single feed stream or as separate heavy oil feed streams. In one embodiment, a single heavy oil conduit pipe goes to all contact areas. In another embodiment, multiple heavy oil conduits are used to feed the heavy oil feed to different contacting zones so that some heavy oil feed stream (s) go to one or more contacting zones and the remaining unconverted heavy oil feed stream (s). Some go to one or more different contact areas.

In one embodiment, the heavy oil feedstock is preheated before blending with the slurry catalyst feed and / or before being introduced into the hydrocracking reactor (contacting zone). In another embodiment, the blend of heavy oil feedstock and slurry catalyst feed is preheated to produce a feedstock with a sufficiently low viscosity so that the catalyst mixes well with the feedstock.

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

Hydrogen Supply

In one embodiment, a hydrogen containing gas is supplied to the process. Hydrogen may also be added to the heavy oil feed before entering the preheater or after the preheater. In one embodiment, the hydrogen feed enters the contacting zone in co-current with the heavy oil feed in the same conduit. In another embodiment, a hydrogen source can be applied to the contacting zone in a direction opposite to the flow of the crude oil feed. In a third embodiment, hydrogen enters the contacting zone through the gas conduit separately from the combined heavy oil and slurry catalyst feed streams. In a fourth embodiment, the hydrogen feed is introduced directly into the combined catalyst and heavy oil feedstock before being introduced into the contacting zone. In another embodiment, hydrogen gas and combined heavy oil and catalyst feeds are introduced to the bottom of the reactor as separate streams. In another embodiment, hydrogen gas may be supplied to some sections of the contacting region.

In one embodiment, the hydrogen source is 0.1 Nm ³ / m ^{3 (} based on the ratio of gaseous hydrogen source to crude oil feed) 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 to 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 ³ / m ³ to about 800 Nm ³ / m ³ (56.3 to 4,507 SCF / bbl). In one embodiment, a portion (25-75%) of hydrogen is supplied to the first contacting zone and the remainder is added as additional hydrogen to the other contacting zones of the system.

In one embodiment, the added hydrogen expands the total volume of heavy oil, thus producing over 100% volume yield in the modified product (compared to heavy oil input). Modified products, ie in one embodiment, lower boiling hydrocarbons include liquefied petroleum gas (LPG), gasoline, diesel, reduced pressure gas oil (VGO), and jet and fuel oils. In a second embodiment, the reforming system provides a volume yield of at least 110% in the form of LPG, naphtha, jet and fuel oils, and VGO. In a third embodiment, a volume yield of at least 115% is provided.

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

In some embodiments, the hydrogen source is combined with the carrier gas (s) and recycled through the contacting zone. The carrier gas can be, for example, nitrogen, helium and / or argon. The carrier gas may promote the flow of crude oil feed and / or the flow of hydrogen source in the contacting zone (s). The carrier gas can also promote mixing in the contacting zone (s). In some embodiments, a hydrogen source (eg, hydrogen, metal or ethane) is used as the carrier gas and can be recycled through the contacting zone.

catalyst Supply

In one embodiment, all slurry catalyst feed is fed to the first contacting zone. In other embodiments, at least a portion of the catalyst feed is "split" or bypassed to at least one other contacting zone of the system (other than the first contacting zone). In another embodiment, all the contacting zones in operation receive the slurry catalyst feed (along with the heavy oil feed). In another embodiment, the process is set up for a flexible catalyst feed system so that new catalyst is sometimes supplied entirely to the last reactor in the system (for certain desired product characteristics) for certain process conditions, or 50% of the process runs May be fed to the first reactor of the system, or split to all reactors of the system equally or according to a predetermined ratio, or the same new catalyst may be divided according to a predetermined ratio to feed different reactors at different concentrations.

As used herein, the slurry catalyst feed may include one or more different slurry catalysts as a single catalyst feed stream or as separate catalyst streams. In one embodiment, a single fresh catalyst feed stream is fed to the contacting zone. In another embodiment, the catalyst feed comprises a number of different catalyst types, with the particular catalyst type going to one or more contacting zones (eg, the first contacting zone of the system) as separate streams, and the different slurry catalysts having different catalyst streams. As part of the contact area (s) other than the first contact area of the system.

In one embodiment, "at least some" means at least 10% of fresh catalyst. In another embodiment, at least 20%. In a third embodiment, at least 40%. In a fourth embodiment, at least 50% of fresh catalyst is diverted to at least one contact area other than the first of the system. In a fifth embodiment, all fresh catalyst is diverted to contacting areas other than the first contacting area.

In one embodiment, less than 20% of the fresh catalyst is fed to the first reactor of the system and at least 80% of the fresh catalyst is bypassed to the remaining contacting zone (s) of the system. In another embodiment, the new catalyst is equally divided between the contacting zones of the system. In one embodiment, at least some fresh catalyst feed is directed to at least one intermediate and / or last contacting zone of the system. In another embodiment, all new catalyst is sent to the last contacting zone of the system and the first contacting zone of the system is obtained from one or more processes in the system, such as from one of the separation zones of the system or from a solvent deasphalting unit. Only the recycled catalyst obtained is obtained.

In one embodiment of an interstage SDA unit, at least some fresh catalyst feed is directed to the contacting area immediately after the interstage SDA unit. In another embodiment, all new catalyst is sent to contacting zone (s) other than the first one of the system, the first contacting zone being obtained from SDA retentate from the SDA unit, and one or more processes of the system, such as Only the recycled catalyst obtained from one of the separation zones of the system is obtained.

In one embodiment, the fresh catalyst is combined with a recycled catalyst stream obtained from one of the processes of the system, such as a separation zone, a distillation column, an SDA unit or a flash tank, and the combined catalyst feed is then contacted ( Is blended with the heavy oil feedstock for feed. In another embodiment, the fresh catalyst and recycled catalyst stream are blended into the heavy oil feedstock as separate streams.

In one embodiment, the recycled catalyst stream obtained from one of the processes of the system, such as separation zone, SDA unit, etc., is combined with the fresh slurry catalyst as one single catalyst feed stream. The combined catalyst feed is then blended with the heavy oil feedstock stream (s) (treated or untreated) to be fed to the contacting zone (s). In another embodiment, the fresh catalyst and recycled catalyst stream are blended into the heavy oil feedstock stream (s) as separate streams.

In one embodiment, the process is set up for a flexible catalyst feed system so that the catalyst feed is sometimes fed to the first reactor of the system for a certain time at a total rate (100% of the required catalyst rate), and then a predetermined time May be split equally or according to a predetermined ratio to all reactors of the system, or according to a predetermined ratio such that the catalyst feed is fed to different reactors at different concentrations.

In one embodiment, sending different catalysts to the front-end and back-end contacting zones may be useful to alleviate vanadium trapping problems and maintain overall reforming performance. In one embodiment, Ni-rich Ni-alone or NiMo sulfide slurry catalyst is sent to the front-end reactor to help reduce vanadium trapping in the system and different catalysts, such as Mo-rich Mo sulfides or NiMo sulfide catalysts Can be added to the back-end reactor (s) to maintain overall high conversion, thereby improving product quality and, in one embodiment, reducing gas yield. As used herein, a Ni-rich slurry catalyst means that the Ni / Mo ratio is greater than 0.15 (as weight percent). In contrast, a Mo rich slurry catalyst means that the Ni / Mo ratio is below 0.05 (by weight).

In one embodiment, the slurry catalyst feed is first preconditioned prior to contacting the heavy oil feed prior to entering one of the contacting zones or before entering the contacting zone. In one example, the catalyst enters the preconditioning unit with hydrogen at a rate of 500 to 7500 SCF / BBL, where BBL refers to the total volume of heavy oil feed to the system. Instead of contacting the cold catalyst with the heavy oil feed, the preconditioning step is believed to assist in the adsorption of hydrogen to the active catalyst site, and ultimately in the conversion rate. In one embodiment of the preconditioning unit, the slurry catalyst / hydrogen mixture is heated to a temperature between 300 ° F and 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 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.

Used catalyst

The slurry catalyst comprises the active catalyst in a hydrocarbon oil diluent. In one embodiment, the catalyst is a sulfiding catalyst comprising at least a Group VIB metal, at least a Group VIII metal or at least a Group IIB metal such as an iron sulfide catalyst, zinc sulfide, nickel sulfide, molybdenum sulfide or iron zinc sulfide catalyst. In another embodiment, the catalyst is a multimetal catalyst comprising at least a Group VIB metal and at least a Group VIII metal (as a promoter), wherein the metals may be in elemental or metal compound form. As one example, the catalyst is a MoS ₂ catalyst promoted with at least a Group VIII metal compound.

의 화학식을 갖고, 여기서 M은 적어도 하나의 VIB족 금속, 예컨대, Mo, W 등과 이들의 조합을 나타내며; X는 프로모터 금속으로서 기능하고, Ni, Co와 같은 비-귀금속 VIII족 금속, Fe와 같은 VIII족 금속, Cr과 같은 VIB족 금속, Ti와 같은 IVB족 금속, Zn과 같은 IIB족 금속 및 이들의 조합 중 적어도 하나를 나타낸다(이후, X는 "프로모터 금속"을 가리킴). 또한 방정식에서, t, u, v, w, x, y, z는 각 성분(M, X, S, C, H, O 및 N 각각)의 전체 전하를 나타내며, ta+ub+vd+we+xf+yg+zh=0이다. b와 a의 아래 첨자 비율은 0 내지 5의 값이고, 0≤b/a≤5이다. S는 (a+0.5b) 내지 (5a+2b) 범위의 아래 첨자 d의 값을 갖는 황을 나타낸다. C는 0 내지 11(a+b)의 값을 갖는 아래 첨자 e를 갖는 탄소를 나타낸다. H는 0 내지 7(a+b)의 f 값을 갖는 수소이다. O는 0 내지 5(a+b)의 g 값을 갖는 산소를 나타내고, N은 0 내지 0.5(a+b)의 값을 갖는 h를 갖는 질소를 나타낸다. 하나의 실시 태양에서, 아래 첨자 b는 0의 값을 가지며, 단일 금속 성분 촉매, 예컨대, (프로모터 없는) Mo 단독의 촉매를 나타낸다.In one embodiment, the catalyst is a bulk multimetallic catalyst comprising at least one Group VIII non-noble metal metal and at least two Group VIB metals, wherein the catalyst is a non-noble metal metal of the at least two Group VIB metals and the Group VIII metal The ratio of is from about 10: 1 to about 1:10. In another embodiment, the catalyst is

Wherein M represents at least one group VIB metal such as Mo, W, and the like; X functions as a promoter metal and includes non-noble metals Group VIII metals such as Ni and Co, group VIII metals such as Fe, group VIB metals such as Cr, group IVB metals such as Ti, group IIB metals such as Zn and their At least one of the combinations (hereinafter, X refers to “promoter metal”). Also in the equation, t, u, v, w, x, y, z represent the total charge of each component (M, X, S, C, H, O and N respectively), ta + ub + vd + we + xf + yg + zh = 0. The subscript ratio of b and a is a value of 0-5, and 0 <= b / a <5. S represents sulfur having a value of the subscript d in the range (a + 0.5b) to (5a + 2b). C represents carbon with subscript e having a value from 0 to 11 (a + b). H is hydrogen with an f value of 0 to 7 (a + b). O represents oxygen having a g value of 0 to 5 (a + b), and N represents nitrogen having h having a value of 0 to 0.5 (a + b). In one embodiment, the subscript b has a value of zero and represents a single metal component catalyst, such as a catalyst of Mo alone (without promoter).

In one embodiment, the catalyst is prepared from a catalyst precursor composition comprising an organometallic complex or compound, such as a fat soluble compound or complex of a transition metal and an organic acid. Examples of such compounds are group VIB and group VIII metals, such as naphthenates such as Mo, Co, W, pentanedionate, octoate and acetates such as molybdenum naphtanate, vanadium naphtanate, vanadium octoate, molybdenum hexa Carbonyl and vanadium hexacarbonyl.

In one embodiment, the catalyst is a MoS ₂ catalyst, promoted with 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 VIB metals and the at least The proportion of one Group VIII non-noble metal is from about 10: 1 to 1:10.

In one embodiment, the catalyst feed 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 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 2-10 microns. In one embodiment, the feed comprises a slurry catalyst having an average particle size ranging from colloidal size (nanometer size) to about 1 to 2 microns. In another embodiment, the catalyst comprises extremely small particles of catalyst molecule and / or colloid size (ie, less than 100 nm, less than about 10 nm, less than about 5 nm, and less than about 1 nm). In operation, colloidal / nanometer sized particles aggregate in a hydrocarbon diluent to form a slurry catalyst having an average particle size in the range of 1 to 20 microns. In another embodiment, the catalyst comprises a single layer MoS2 cluster of nanometer size, eg, 5-10 nm at the edge.

In one embodiment, a sufficient amount of fresh catalyst and used catalyst is fed to the contacting zone (s) such that each contacting zone has a slurry (solid) catalyst concentration in the range of 2 to 30% by weight. In a second embodiment, the (solid) catalyst concentration in the reactor ranges from 3 to 20 weight percent. In a third embodiment, from 5 to 10% by weight.

In one embodiment, the amount of fresh catalyst feed to the contacting zone (s) is in the Mo range of 50 to 15000 wppm (as concentration in heavy oil feed). In a second embodiment, the concentration of fresh catalyst feed is in the range of 150-2000 wppm Mo. In a third embodiment, 250 to 5000 wppm Mo. In a fourth embodiment, the concentration is less than 10,000 wppm Mo. As the volatile fraction is removed from the non-volatile residue fraction, the catalyst may be more concentrated, and therefore, the concentration of the catalyst may need to be adjusted, so the concentration of fresh catalyst going to each contacting zone may vary depending on the contacting zone used in the system. have.

Optional treatment system SDA

In one embodiment of the present invention, a solvent deasphalting unit (SDA) is used before the first contacting zone to pretreat the heavy oil feedstock. In another embodiment, a solvent deasphalting unit is used as the intermediate unit located after one of the intermediate separation zones.

SDA units are generally used in refiners to extract incrementally lighter hydrocarbons from a heavy hydrocarbon stream, so that the extracted oil is generally referred to as deasphalted oil (DAO), and is commonly referred to as SDA tar, SDA retentate, etc. Known heavy molecules and heteroatoms leave a more concentrated residue stream. The SDA may be a separate unit or unit integrated into the reforming system.

Depending on the desired level of deasphalted before being fed to the contacting zone, various solvents from propane to hexane can be used for SDA. In one embodiment, the SDA is set to produce deasphalted oil (DAO) for blending with the catalyst feed or in addition to, or instead of, the heavy oil feed directly to the contacting zone. In this way, solvent type and operating conditions are optimized so that a solid and acceptable quality DAO is produced and fed to the contacting zone. In such embodiments, suitable solvents used include, but are not limited to, hexane or similar C6 + solvents for low volume SDA tar and solid DAO. This scheme allows the vast majority of heavy oil feeds to be reformed in subsequent contact zones, and the bottoms of the barrel reservoirs, which do not achieve the desired incremental conversion economics due to the heaviest, heavy hydrogenation requirements, are used in some other way. something to do.

In one embodiment, all heavy oil feeds are pretreated in SDA and the DAO product is supplied to the first contacting zone, or at least a portion of the heavy oil feed goes to the non-continuous first contacting zone, depending on the split feed regime. In another embodiment, a portion of the heavy oil feed (depending on the source) is first pretreated in SDA, and a portion of the feedstock is supplied to the direct contacting zone (s) untreated. In another embodiment, the DAO is combined with the untreated heavy oil feedstock as one feed stream to the contacting zone (s). In another embodiment, the DAO and untreated heavy oil feedstock are fed to the system as separate feed conduits so that the DAO goes to one or more contacting zones and the untreated heavy oil feed goes to one or more identical or different contacting zones.

In an embodiment in which SDA is used as an intermediate unit, a nonvolatile fraction comprising slurry catalyst from at least one separation zone and optionally a minimum amount of coke / asphalten and the like is sent to the SDA for processing. From the SDA unit, the DAO is sent alone to the at least one contacting zone as a feed stream, combined with the heavy oil feedstock as feed, or with the bottoms stream from one of the separation zones as feed. DA deposits containing asphaltenes may be used to recover metals in any residual slurry catalyst, or for applications requiring asphaltenes, for example, blended with fuel oil, used in asphalt, or used in some other applications. Are sent separately.

In one embodiment, the amount of DAO and DA deposits is varied by adjusting the desired recovery of DAO for the solvent and heavy oil feed used. In an optional pretreatment unit such as SDA, the more DAO oil is recovered, the worse the overall quality of the DAO and the poorer the overall quality of the DA deposits. For solvent selection, generally, if a lighter solvent is used for SDA, less DAO will be produced, but the quality will be better, whereas if a heavier solvent is used, more DAO will be produced. The quality will be lower. This is due to, among other factors, the solubility of asphaltenes and other heavy molecules in the solvent.

Control of Heavy Metal Deposition-Selective Water Input

As used herein, the front-end contacting region (or first contacting region) means the first reactor in a system having up to three contacting regions. In another embodiment of a system having more than three contact regions, the first front-end contact region may comprise first and second reactors. In another embodiment, the first contacting zone means only the first reactor.

As used herein, the term "water" is used to refer to water and / or steam. In one embodiment for controlling heavy metal deposition, water is optionally introduced into the system. In one embodiment, the input is at a rate of about 1 to 25 weight percent (relative to the heavy oil feedstock). In one embodiment, a sufficient amount of water is added so that the water concentration of the system is in the range of 2-15% by weight. In a third embodiment, a sufficient amount is added so that the water concentration is 4 to 10% by weight.

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

In one embodiment, the water introduced to the system in the preheating step (prior to the preheating of the heavy oil feedstock) is in an amount of about 1 to about 25 weight percent of the incoming heavy oil feedstock. In one embodiment, water is added as part of the heavy oil feed to all contacting zones. In another embodiment, water is added only to the heavy oil feed to the first contacting zone. In another embodiment, water is added only to the feed going to the first two contacting zones.

In one embodiment, water is added to the direct contacting zone at a number of points along the contacting zone at a rate of 1 to 25% by weight of the heavy oil feedstock. In another embodiment, water is added directly to the first two contact areas of the process, where the most heavy metals are most likely to deposit.

In one embodiment, a portion of the water is added to the process in the form of dilution steam. In one embodiment, at least 30% of water is added in the form of steam. In embodiments where water is added as dilution steam, steam may be added at any point in the process. For example, it may be added to the heavy oil feedstock before or after preheating, to the catalyst / heavy oil mixture stream and / or to the vapor of the direct contacting zone, or at multiple points along the first contacting zone. The dilution vapor stream may comprise process steam or clean steam. The steam may be heated or superheated in the furnace before it is fed to the reforming process.

The presence of water in the process is believed to advantageously alter the metal compound sulfur molecular equilibrium to reduce heavy metal deposition. In one embodiment, the addition of water is also believed to help control / maintain the desired temperature profile in the contact zone. In another embodiment, the addition of water to the front-end contacting zone (s) is believed to lower the temperature of the reactor (s). When the reactor temperature is lowered, the reaction rates of the most reactive vanadium species are slowed down so that the vanadium deposition into the slurry catalyst proceeds in a more controlled manner, and the catalyst carries the vanadium deposits out of the reactor, thus allowing solid deposition in the reactor apparatus. It is thought to limit.

In one embodiment, the addition of water reduces at least 25% of the heavy metal deposits in the reactor apparatus compared to when operated without significant addition of water for a significant period of operation, such as for at least two months. In another embodiment, the addition of water reduces at least 50% of heavy metal deposits as compared to when operated without the addition of water. In a third embodiment, the addition of water reduces at least 75% of heavy metal deposits as compared to when operated without the addition of water.

Reactor Temperature Controls Heavy Metal Deposition

In one embodiment, instead of and / or in addition to the addition of water to the front-end contacting area (s), the temperature of the front-end contacting area (s) where heavy metal deposits are most likely to occur is reduced.

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

Recycled Catalyst As a stream  Control heavy metal deposition

In one embodiment, at least a portion of the nonvolatile stream from at least one of the separation zone and / or the interphase deasphalting unit is recycled back to the front-end contacting zone (s) to control heavy metal deposits.

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

In one embodiment, the recycled stream comprises a nonvolatile material from the last separation zone of the system, including unconverted material, heavier hydrocracked liquid product, slurry catalyst, small amount of coke, asphaltenes, and the like. . In one embodiment, the recycled stream comprises 3 to 30 weight percent slurry catalyst. In another embodiment, the amount of catalyst is in the range of 5-20% by weight. In another embodiment, the recycled stream comprises 1 to 15 weight percent slurry catalyst.

In some embodiments, with the additional recycled catalyst provided by the recycled stream, more catalyst surface area is available (through the slurry catalyst in the recycled stream) to diffuse heavy metal deposition, thus trapping or It is thought that deposition occurs less. The additional catalyst surface area provided by the recycled stream helps to minimize overloading by heavy metal deposits on the catalyst surface, causing deposition on process equipment (walls, interiors, etc.).

Process conditions

In one embodiment, the process conditions are controlled somewhat uniformly over the contact area. In another embodiment, for modified products having specific properties, the conditions vary between contact areas.

In one embodiment, the reforming system is maintained at hydrocracking conditions such as the minimum temperature to effect hydrocracking of the heavy oil feedstock. In one embodiment, the system operates at temperatures ranging from 400 ° C. (725 ° F.) to 600 ° C. (1112 ° F.), and pressures from 10 MPa (1450 psi) to 25 MPa (3625 psi). In one embodiment, the process conditions are controlled somewhat uniformly over the contact area. In another embodiment, for modified products having specific properties, the conditions vary between the contacting regions.

In one embodiment, the contact zone process temperature is about 400 ° C. (725 ° F.) to about 600 ° C. (1112 ° F.), in another embodiment less than 500 ° C. (932 ° F.), and in another embodiment 425 ° C. (797 ° F.) The range exceeds In one embodiment, the system operates with a temperature difference between the inlet and outlet of the contact area in the range of 5-50 ° F. 10 to 40 ° F. in a second embodiment.

The temperature of the separation zone is the + of the contact zone temperature in one embodiment. 90 ^o F (about + 50 ^o C), + 70 ^o F (about + 38.9 ^o C) in the second embodiment, + 15 ^o F (about + 8.3 ^o C) in the third embodiment, and 4 In the embodiment it is maintained within + 5 ^o F (about + 2.8 ^o C). In one embodiment, the temperature difference between the last separation region and the immediately preceding contact region is + 50 ^o F (about + 28 ^o C).

The process pressure of the contact region may range from about 10 MPa (1,450 psi) to about 25 MPa (3,625 psi) in one embodiment, from about 15 MPa (2,175 psi) to about 20 MPa (2,900 psi) in a second embodiment, In a third embodiment, less than 22 MPa (3,190 psi), and in a fourth embodiment, more than 14 MPa (2,030 psi). In one embodiment, the pressure in the separation zone is maintained within the ± 10 to + 50 psi, in the second exemplary aspect of + 2 to + 10 psi in the contact zone prior to in one embodiment.

In one embodiment, the reforming system is set for efficiency with much lower downtime due to clogging of the device as compared to the prior art, with optimal operation, eg, a pressure drop of less than 100 psi. Optimum efficiency is obtained in one embodiment with minimal pressure drop in the system, the pressure in the separation zone ± In one embodiment 10 to + 100 psi, the second embodiment in solar + 20 to + 75 psi, and in the embodiment of the three and is held within + 50 to + 100 psi. Here, the pressure drop refers to the difference between the discharge pressure X of the preceding contacting region and the inlet pressure Y of the separation, where (XY) is less than 100 psi.

Optimal efficiency can also be achieved with minimal pressure from one contact area to the next in a sequentially operating system, with pressure drops of 100 psi or less in one embodiment and 75 in a second embodiment. psi or less, and is maintained at less than 50 psi in a third embodiment. Here, the pressure drop refers to the difference between the discharge pressure of one contact area and the inlet pressure of the next contact area.

In one embodiment, for minimal pressure drop, the contacting zone may be in direct fluid communication with the next separation zone or contacting zone. In this context, direct fluid communication means that there is a free flow, without restriction of flow, from the contacting region to the subsequent next separation region (or next contacting region). In one embodiment, direct fluid communication is accomplished without the restriction of flow due to the presence of valves, holes (or similar devices), or pipe diameter changes.

In one embodiment, the minimum pressure drop from the contact area to the next separation area or contact area (when entering into the separation area or contact area) is an L-shaped portion, such as a line, a U-shaped portion, T By the magnetic part and not by the use of pressure reducing devices such as valves, control valves, etc., which induce a pressure drop as in the prior art. In the prior art, it is taught that the separation zone functions as a pressure differential separator between stages.

In one embodiment, the minimum pressure drop is induced by frictional losses, wall drag, volume increase, and height change as the effluent flows into the next continuous device in the contact area. If a valve is used in a single pass system, the valve is selected / set so that the pressure drop from one device, such as the contact area, to the next device part can be maintained below 100 psi.

In one embodiment, the liquid hourly space velocity (LHSV) of the heavy oil feed is generally from about 0.025 h ⁻¹ to about 10 h ⁻¹ , about 0.5 h ⁻¹ to about 7.5 h ⁻¹ , 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, the LHSV is at least 0.5 h ⁻¹ , at least 1 h ⁻¹ , at least 1.5 h ⁻¹ , or at least 2 h ⁻¹ . In some embodiments, the LHSV is in the range of 0.025 to 0.9 h ⁻¹ . In another embodiment, the LHSV is in the range of 0.1-3 LHSV. In another embodiment the LHSV is less than 0.5 h ⁻¹ .

In one embodiment, where at least all of the non-volatile fraction stream from the separation zone is sent to the SDA unit for deasphalting, after a similar run time (composition volume) compared to the prior art operation of not deasphalting the SDA unit. In terms of) solid deposition at the last contact area of the system is reduced by at least 10%. In a first embodiment, solid deposition is reduced by at least 20% compared to operation without using an interstage SDA unit. In a third embodiment, solid deposition is reduced by at least 30%.

In various embodiments, heavy oil, as compared to conventional feed schemes, where all new catalysts go to the first contacting zone by bypassing some, if not all, of the new catalysts to the contacting zone (s) other than the first of the system. The overall degradation efficiency of the feedstock was not noticeable or was not affected at all. In one embodiment, the change in position of the new catalyst input resulted in a significant increase in overall catalyst activity and in terms of API, viscosity, MCR level, nickel, hydrogen / carbon ratio, and hot heptane asphaltene (HHA) level. It has resulted in an improvement in the quality of the non-volatile streams (bleed streams, “striper deposits” or STBs) from the last separation zone of the system. In some other embodiments, less catalyst bleeding is observed with an overall improvement in catalyst activity.

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

In one embodiment, the reduction in MCR in the 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 wt%.

In one embodiment, the STB shows an API viscosity improvement of at least 15%. In a second embodiment, the API viscosity improvement is at least 30%. In a third embodiment, the API viscosity of at least 50% is improved from 2.7 to 4.5. In some embodiments, the improvement of the API is observed due to the overall improved catalytic activity resulting in higher H / C ratios.

In an embodiment of the heavy oil split feed scheme, a portion of the heavy oil feedstock is diverted from the first contacting zone to at least one successive other contacting zone, thereby comparing all heavy oil feedstocks to the prior art feeding scheme that goes to the first contacting zone. In time, the overall coke formation appears to be substantially reduced. In addition, if at least some heavy oil feedstock is diverted to a contact area other than the first of the system, there is some liquid dilution in these contact areas (which would not be present in the prior art system). Liquid dilution allows for a more uniform catalyst concentration profile across the entire reactor of the system, thus making it possible to protect the last reactor from solid level deviations that can cause operational problems.

In one embodiment of the heavy oil split feed system, the increase in the level of conversion in the reactor (contact area) also improves the overall system efficiency, permitting further oil evaporation and correspondingly reduced liquid throughput and increased catalyst concentration. Is observed. This will essentially increase the efficiency of the system with lower liquid throughput (or higher liquid residence time) and higher catalyst concentrations. Also, as a secondary steady heavy oil feed rate fed directly to the last reactor, the last reactor is protected from upset conditions that may deprive the liquid flow from this vessel. Thus, the heavy oil split feed system reduces or eliminates the "over-conversion occurrence" or "dry" conditions often observed in hydroprocessing reactors. In reforming systems operating under “dry” conditions, insufficient liquid flow is present, resulting in solid buildup / coking, loss of flow patterns and / or hydrodynamics, loss of temperature measurements, loss of reaction volume, and finally deterioration. Resulting in performance, stability and operating life.

Figures Showing an Embodiment

Reference will be made to the drawings, which further illustrate embodiments of the present invention.

1 is a schematic block diagram of a system for reforming a heavy oil feedstock with reduced heavy metal deposits. First, the heavy oil feedstock is introduced into the first contacting zone of the system along with the slurry catalyst feed. In the figure, the slurry catalyst feed comprises a combination of fresh catalyst and recycled catalyst slurry as a separate stream. Hydrogen may be introduced together with the feed into the same conduit, or optionally as a separate feed stream. Water and / or steam may be introduced together with the feed and slurry catalyst in the same conduit or in separate feed streams. Although not shown, the mixture of water, heavy oil feed and slurry catalyst may be preheated in the heater before being fed to the contacting zone. Although not shown, additional hydrocarbon oil feeds, such as VGO, naphtha, may optionally be added to any of the contacting zones of the system as part of the feed stream in an amount of from 2 to 30% by weight of the heavy oil feed.

Although not shown in the figures, the system facilitates the dispersion of reactants, catalysts and heavy oil feedstock in the contacting zone, especially with a high recycle flow rate to the first contacting zone which reduces heavy metal deposits by inducing fluctuating mixing in the reactor. Recycling / recycling channels and pumps for the purpose of In one embodiment, the recycle pump circulates through the loop reactor to maintain a temperature difference between 1 and 50 ° F., preferably 2 to 25 ° F., between the reactor feed point and the discharge point.

In the contacting area under hydrocracking conditions, at least some of the heavy oil feedstock (higher boiling hydrocarbons) is converted to lower boiling hydrocarbons to form a modified product. Water / vapor in the first contact area is expected to reduce heavy metal deposits on the device. Although not shown, the temperature of the first contact region can be maintained at least 5-25 degrees Fahrenheit below the temperature of the next subsequent contact region.

The modified material is withdrawn from the first contacting zone and sent to a separation zone, such as a hot separator, operated at a high temperature and high pressure similar to the contacting zone. The modified material may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further modification before going to the hot separator. The separation zone causes or permits separation of gas and volatile liquids from the nonvolatile fractions. Gas phase and volatile liquid fractions are withdrawn from the top of the separation zone for further processing. Nonvolatile (or less volatile) fractions are withdrawn from the bottom. Slurry catalyst and newly produced hydrocarbons and the like in entrained solids, coke, hot separators and the like are withdrawn from the bottom of the separator and fed to the next subsequent contacting zone. In one embodiment (not shown), a portion of the nonvolatile stream is recycled back to one of the contacting zones preceding the separation zone, providing a recycling catalyst for use in the hydrogen conversion reaction.

In one embodiment (as indicated by dashed lines), a portion of the fresh catalyst feed and the heavy oil feedstock are fed directly to the contacting zones (reactors) other than the first contacting zone in the system. In one embodiment where a portion of the heavy oil feedstock is fed directly to the contacting zone other than the first contacting zone, water and / or vapor are also provided to the contacting zone as a separate feed stream, or feed and slurry in the same conduit Is introduced together with the catalyst.

The liquid stream from the preceding separation zone is optionally fed as a feed stream for the next contacting zone, optional new catalyst, optional additional heavy oil feed, optional hydrocarbon oil feedstock such as VGO (reduced gas oil), and Combined with an optional recycled catalyst (not shown). Hydrogen may be introduced with the feed in the same conduit or optionally as a separate feed stream. The material modified with the slurry catalyst flows into the next subsequent separation zone for separation of gas and volatile liquid from the nonvolatile fractions. The gaseous and volatile liquid fractions are withdrawn from the top of the separation zone and combined with the gaseous and volatile liquid fractions from the preceding separation zone for further processing. A nonvolatile (or less volatile) fraction stream is withdrawn and sent to the next subsequent contacting zone to reform the unconverted heavy oil feedstock.

In the last contacting zone, hydrogen is added with the unconverted heavy oil feedstock, optional additional heavy oil feedstock, optional VGO feed, and optional fresh catalyst. The modified material flows with the slurry catalyst to the next separation zone, the modified product is overhead removed, and a portion of the nonvolatile material is recycled. In one embodiment, the recycled stream is sent to the first contacting zone to provide a portion of the recycled catalyst for use in the hydrogen conversion reaction. In a second embodiment, the recycled stream is split between the contact regions preceding the continuous last contact region.

In one embodiment, the system can optionally include an inline hydrotreater (not shown) for treating gaseous and volatile liquid fractions from the separation zone. In one embodiment, the inline hydrotreater uses a conventional hydrotreating catalyst, operates at high pressure (within 10 psig) similar to the rest of the reforming system, and removes sulfur, Ni, V and other impurities from the reformed product. Can be removed In another embodiment, the inline hydrotreater operates at a temperature within 100 ° F., the contact zone temperature.

2 is a flow chart of a heavy oil reforming process with water input. As shown, water 81 is introduced into the system with the heavy oil feedstock and preheated in the furnace before the mixture is introduced into the contacting zone. Water / steam may also optionally be introduced into the system after the preheater as stream 82. In this embodiment, the fresh catalyst feed is split between the contacting zones. Recycled catalyst stream 17, a water / heavy oil feedstock mixture, and hydrogen gas 2 are supplied as feed 3 to the first contacting zone.

Stream 4 comprising the reformed heavy oil feedstock exits contacting zone R-10 and flows to separation zone 40 where the reformed product in the form of a gaseous volatile liquid (containing hydrogen) is a non-volatile liquid fraction. Separated from (7) and removed overhead as stream (6). The nonvolatile stream 7 is sent to the next subsequent contact region 20 for further modification. Nonvolatile stream 7 comprises unconverted oil, and in some embodiments a slurry catalyst combined with a small amount of coke and asphaltenes.

The reforming process continues to the remaining contacting zone as shown and the feed stream to the contacting zone 20 comprises a nonvolatile fraction, a hydrogen feed, an optional VGO feed and a fresh catalyst feed 32. From the contacting zone 20, a stream 8 containing the reformed heavy oil feedstock flows into the separation zone 50, where the modified product is combined with hydrogen and removed as overhead product 9. Storage stream 11 containing unvolatile fractions, such as unconverted oil, including catalyst slurry, coke and asphaltenes, flows into a subsequent next contacting zone 30.

In the contacting zone 30, an additional hydrogen containing gas 16, a fresh catalyst 33, an optional hydrocarbon feed (not shown) such as VGO, and an optional untreated heavy oil feed (not shown) are separated from the preceding separation zone. It is added to the nonvolatile stream. From the contacting zone 3, the reformed product, unconverted heavy oil, slurry catalyst, hydrogen and the like are removed overhead as stream 12 and sent to the next separation zone 60. From the separator, the overhead stream 13 containing hydrogen and the modified product is combined with the overhead streams from the preceding separation zones and, for example, a high pressure separator and / or for subsequent processing in another part of the system. It is sent separately to a lean oil contactor and / or an inline hydrotreater (not shown). Part of the nonvolatile stream 17 is removed as a bleed-off stream 18. The remainder is recycled back to at least one of the contacting zones (first contacting zone 10 as shown) as a recycled catalyst stream.

3 is a flow diagram of another embodiment of a heavy oil reforming process with steam input 91 in place of or in addition to water input stream 81.

FIG. 4 is a flow chart of another embodiment of a heavy oil refinement process with recycled catalyst stream 19 in the range of 3 to 50 weight percent of the total heavy oil feedstock of the process.

5 is a block diagram schematically illustrating another embodiment for reforming a heavy oil feedstock. First, the heavy oil feedstock is introduced into the first contacting zone of the system along with the slurry catalyst feed. Hydrogen may be introduced with the feed in the same conduit, or optionally as a separate feed stream. In one embodiment (not shown), an optional hydrocarbon oil feedstock, such as VGO (reduced gas oil), naphtha, MCO (medium cycle oil), solvent donor or other aromatic solvent, and the like, are from 2 to 30 weight of the heavy oil feed. Is the amount of%. Additional hydrocarbon feedstocks can be used to alter the concentration of metals and impurities in the system. In the contacting zone under hydrocracking conditions, at least a portion of the heavy oil feedstock (hydrocarbons with higher boiling points) is converted to hydrocarbons with lower boiling points, forming a modified product.

The modified material is withdrawn from the first contacting zone and sent to a separation zone, such as a hot separator. As an alternative, the modified material may be sent to one or more additional hydroprocessing reactors (not shown) for further modification before going to the hot separator. The separation zone causes or permits separation of gas and volatile liquids from the nonvolatile fractions. Gas phase and volatile liquid fractions are withdrawn from the top of the separation zone for further processing. Nonvolatile (or less volatile) fractions are withdrawn from the bottom. Slurry catalyst, a smaller amount of heavier hydrocracked liquid product, and hydrocarbons newly produced in entrained solids, coke, hot separators and the like are withdrawn from the bottom of the separator and fed to the next subsequent contacting zone. In one embodiment (not shown), a portion of the nonvolatile stream is recycled back to one of the contacting zones directly preceding the separation zone in an amount equivalent to 2 to 40% by weight of the total heavy oil feed.

The non- volatile stream from the preceding separation zone containing the unconverted feedstock is the feed stream for subsequent next contacting zones, with additional new catalyst, optional additional heavy oil feed, and optionally recycled catalyst ( (Not shown).

In the next contacting zone under hydrocracking conditions, more heavy oil feedstock is reformed to lower boiling hydrocarbons. The modified material along the slurry catalyst flows to the next subsequent separation zone for separation of gas and volatile liquid from the nonvolatile fraction. A nonvolatile (or less volatile) stream is withdrawn from the bottom. The gaseous and volatile liquid fractions are withdrawn from the top of the separation zone, for example as "modified" products for further processing or blending, for the final blended product that meets specifications specified by the purifier and / or transport carrier. do. (And, combined with gaseous and volatile liquid fractions from the preceding separation zone.)

In one embodiment (not shown), a nonvolatile material comprising an unconverted material is sent to the next subsequent contact area. In another embodiment shown, the nonvolatile material is recycled back to one of the contacting regions of the system, and a portion of the material is bleed-off for further processing, such as solvent deasphalting units, catalytic deoiling units and subsequently metal recovery. Go to the system. In one embodiment, the recycled nonvolatile material provides a recycled catalyst for use in the hydrogen conversion reaction, in an amount corresponding to 2 to 50 weight percent of the heavy oil feedstock of the system.

Depending on the operating conditions, the type of catalyst supplied to the contacting zone and the concentration of the slurry catalyst, in one embodiment, the output stream from the contacting zone is modified product and unconverted heavy oil feed in a ratio of 20:80 to 60:40. It includes. In one embodiment, the amount of modified product in the first contacting region is in the range of 30-35% for 65-70% unconverted heavy oil product.

Although not shown in the figures, the system may optionally include a recycle / recycle channel and a pump to facilitate dispersion of the reactants, catalyst and heavy oil feedstock in the contacting zone. In one embodiment, the recycle pump circulates through the loop reactor at a volume recycle ratio (ratio of recycled amount to heavy oil feed) of 5: 1 to 15: 1, and thus the temperature difference between the reactor feed point and the discharge point. Is maintained at 10 to 50 ° F., preferably 20 to 40 ° F.

In one embodiment, the system may further include an inline hydrotreater (not shown) for treating gaseous and volatile liquid fractions from the separation zone. In one embodiment, the inline hydrotreater uses a conventional hydrotreating catalyst and operates at similar high pressures (within 10 psig in one embodiment and within 50 psig in a second embodiment) as the remainder of the modified system. Sulfur, Ni, V and other impurities can be removed from the modified product.

FIG. 6 is a block diagram diagrammatically showing another embodiment of a reforming system that is used for some pretreatment if the solvent deasphalting unit is not all of the heavy oil feed of the system. Deasphalted oil (DAO) may be fed to the direct contacting zone (s) or combined with the heavy oil feed stream as feedstock. In some embodiments, other hydrocarbon materials, such as VGO, may also be combined with heavy oil feed and / or DAO as feedstock for some contacting zone (s). All of the fresh catalyst may be fed directly to the first contacting zone of the system or bypassed to another successive contacting zone (s).

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

Stream 5 comprising the reformed heavy oil feedstock exits contacting zone 10 and flows to separation zone 40 where gas and volatile modified products (including hydrogen) are removed from non-volatile fraction 7. Separated and removed overhead as stream (6). The nonvolatile fraction stream 7 is sent to the next subsequent contact zone 20 for further modification. Stream 7 comprises unconverted oil, and in some embodiments a slurry catalyst combined with a small amount of coke and asphaltenes.

The reforming process continues with the other contacting zones shown, where stream 7 is combined with hydrogen feed 15 and fresh catalyst 32 as feed stream to contacting zone 20. Although not shown, the streams can also be fed to the contacting zone in separate conduits. Stream 8 containing the reformed heavy oil feedstock flows into separation zone 50 and the reforming product is combined with hydrogen to remove as overhead product 9. Reservoir stream 11 comprising catalyst slurry, unconverted oil (and in some embodiments, small amounts of coke and asphaltenes) is a feed stream to the next contacting zone 3 as fresh feed stream 33 and Combined with fresh hydrogen feed 16. Stream 12 exits the contacting zone and flows to separation zone 60 where the modified product and hydrogen are removed overhead as stream 13. The catalyst slurry, unconverted oil, and in some embodiments, are recycled back to the first contacting zone 10 as a partially recycled stream 19 of the storage stream 17 from the separation zone, comprising a small amount of coke and asphaltenes. do. The remainder of the reservoir stream 17 is removed as bleed-off stream 18 and sent to other processes in the system for catalytic deoiling, metal recovery, and the like. Although not shown, in one embodiment, the vapor stream 14 comprising the modified product and hydrogen is processed sequentially in other parts of the system, such as a high pressure separator and / or a lean oil contactor.

Figure 8 illustrates another embodiment of the present invention in which a reactor with an internal separator is used so that no separate hot separator / flash drum is needed for phase separation. In this reforming system, a reactor differential pressure control system (not shown) is used to regulate the product stream coming from the top of each reactor-separator. An external pump (not shown) can be used to assist in the dispersion of the slurry catalyst in the system and to help control the temperature in the system.

In the embodiment of FIG. 8 as shown, all fresh catalyst bypasses the second and third contacting zones of the system. The recycled catalyst stream 19 provides a slurry catalyst feed to the first contacting zone, and optionally to other contacting zone (s) of the system. As also shown, in amounts ranging from 2 to 30% by weight of the heavy oil feed, additional hydrocarbon oil feeds, such as VGO, naphtha, may optionally be added as part of the feed stream to any contacting zone of the system. .

9 shows an embodiment of the present invention in which all new catalyst feed 99 is fed directly to the last contacting zone of the reforming system, and the other contacting zone (s) of the system obtain only a portion of the recycled catalyst stream 19. To show.

10 illustrates an embodiment of a heavy oil split feed system. As shown, a portion of the heavy oil feed is bypassed from the first reactor and fed directly to the second contacting zone of the system as the heavy oil feed stream 42. As also shown, the recycled catalyst is optionally sent to the second contacting zone of the system along with a portion of the fresh catalyst as stream 32.

1 is a schematic block diagram of an embodiment of a hydroprocessing system for reforming a heavy oil feedstock having a plurality of contacting zones and separation zones, into which water and / or steam is introduced into the front-end contacting zone.
2 is a flow chart of a process for reforming a heavy oil feed with water input.
3 is a flow chart of a process for reforming a heavy oil feed by direct steam injection to the front-end contacting area.
4 is a flow chart of another embodiment of a process for reforming a heavy oil feed with a recycled catalyst stream in a proportion sufficient to reduce accumulation of heavy metals.
5 is a schematic block diagram of an embodiment of a hydroprocessing system for reforming a heavy oil feedstock having a split fresh catalyst feed system, a split heavy oil feed system, and an additional interstage hydrocarbon oil feedstock. .
6 is a block diagram schematically illustrating another embodiment of a hydroprocessing system for reforming a heavy oil feedstock having a solvent deasphalting unit for pre-treating the heavy oil feedstock.
FIG. 7 is a flow chart of a process for reforming a heavy oil feed with one embodiment of a catalyst split feed scheme where fresh catalyst feed is supplied to all reactors in the process.
8 is a flow diagram of a process for reforming a heavy oil feed where fresh catalyst feed is diverted from the first reactor to other reactors in the process and optional / additional hydrocarbon oil is fed to the reactor as feedstock.
FIG. 9 is a flow diagram of another embodiment of a process for reforming a heavy oil feed where all fresh catalyst feed is sent to the last reactor of the process.
10 is a flow diagram of another embodiment of a process for reforming a heavy oil feed where a portion of the crude heavy oil feed is diverted from the first reactor to other reactors in the process.

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

compare Example  One

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

The new slurry catalyst used was prepared according to the disclosure of U.S. Patent No. 2006/0058174, ie, the Mo compound was first mixed with aqueous ammonia to form an aqueous Mo compound mixture, sulfided with hydrogen compound, and promo with Ni compound. And then transformed 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 to be sent to the first reactor.

Hydroprocessing conditions were as follows: reactor temperature (of three reactors) of about 825 ° F .; Overall pressure in the range of 2400 to 2600 psig; Fresh Mo / new heavy oil feed ratio by weight 0.20-0.40; Fresh Mo catalyst / total Mo catalyst ratio 0.125-0.250; Total feed LHSV about 0.070 to 0.15; And hydrogen gas ratio (SCF / bbl) 7500 to 20000.

The discharge taken from each reactor was sent to a (continuously connected) separator and separated into a hot vapor stream and a nonvolatile stream. The vapor stream was separated from the top of the high pressure separator and collected for further analysis (“HPO” or high pressure overhead stream). The nonvolatile stream comprising the slurry catalyst and unconverted heavy oil feedstock was removed from the separator and sent to the next subsequent reactor.

A portion of the nonvolatile stream from the last separator in the 30 wt% amount of heavy oil feedstock was recycled (STB) and the remainder was removed (in an amount of about 15 wt% of the heavy oil feedstock) as a bleed stream. The STB stream comprises about 10 to 15 weight percent slurry catalyst.

The feed blend to the system was a heavy metal heavy crude with the properties specified in Table 1.

VR feed API weight at 60/60 - importance 1.0760 Sulfur (% by weight) 5.27015 Nitrogen (ppm) 7750 Nickel (ppm) 135.25 Vanadium (ppm) 682.15 Carbon (wt%) 83.69 Hydrogen (% by weight) 9.12 H / C ratio 0.109

After operation for 50 days, operation was stopped. The reactor, distributor and internal thermowell were visually inspected. As all three parts showed significant deposit accumulation, about 28.5% of the volume of the front-end (first) reactor was lost due to the deposition of heavy metals. Analysis of the slurry catalyst used in the bleed stream over 50 days revealed increased deficiency of vanadium, suggesting that not only did accumulation of deposits occur inside the front-end reactor, but also actually worsened as the run progressed. . The performance of the process was also impaired due to the loss of reaction volume.

Example  2

Reduce the temperature of the first reactor to 20 ° F. (from about 825 ° F. to about 805 ° F.), increase the recycled catalyst proportion from 30% by weight (of Example 1) to about 40% of the heavy oil feed rate, and add water to the heavy oil Example 1 was repeated except that it was added to the front-end reactor at a rate corresponding to 5% by weight of the feed rate. It was run for 54 days before stopping the system.

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

Analysis of the slurry catalyst used in the bleed stream over 54 days showed a very close agreement between the amount of vanadium expected to exit the process and the amount of vanadium in the catalyst in the bleed stream, which was trapped in vanadium trapping. Thus, it was suggested that heavy metal deposition in the device was significantly reduced.

The inside of the reactor, the distributor and the inner protective tube were visually inspected to further confirm the results of the analysis. The apparatus was significantly cleaner in Example 2, with only 6.6% of the front-end reactor volume lost due to heavy metal deposits.

compare Example  3

In a pilot system with three gas-liquid slurry phase reactors connected in series with two hot separators, heavy oil reforming experiments were performed. The hot separators are connected in series with the first and third reactors respectively, and there is no hot separator following the second reactor. The gas-liquid slurry phase reactor was a continuously stirred reactor. The reforming system was operated continuously for about 70 days.

The new slurry catalyst used was prepared according to the disclosure of U.S. Patent No. 2006/0058174, that is, the Mo compound was first mixed with aqueous ammonia to form an aqueous Mo compound mixture, sulfided with hydrogen / sulfur compounds, and Ni compounds And then modified 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 fresh catalyst slurries are sent to the first reactor of the system, expressed as the weight of the metal (molybdenum) relative to the weight of the heavy oil feed, at a fresh slurry catalyst concentration in heavy oil ranging from 2,000 to 5,000 ppm. Hydroprocessing conditions are as follows: reactor temperature of 815-825 ° F .; Overall pressure in the range of 2400 to 2600 psig; Fresh Mo / new heavy oil feed ratio by weight 0.20-0.40; Fresh Mo catalyst / total Mo catalyst ratio 0.1; Total feed LHSV 0.10 to 0.15; And H ₂ gas ratio (SCF / bbl) 10000 to 15000

The discharge taken from the first and third reactors was introduced into a hot separator connected in series with the reactors, and separated into a hot vapor stream and a nonvolatile stream. The vapor stream was separated from the top of the high pressure separator and collected for further analysis (“HPO” or high pressure overhead stream). The nonvolatile stream comprising the slurry catalyst and unconverted heavy oil feedstock was removed from the bottom of the first separator and sent to a second continuous reactor. Effluent from the second reactor was sent directly to the third reactor as feedstock.

A portion of the nonvolatile stream from the last separator in the amount of 5-15% by weight of the heavy oil feedstock was removed as a bleed-off stream so that the overall conversion of the heavy oil feed to the distillation product was 98-98.5%.

The remainder of the non- volatile stream, the “striper underflow product” or STB, containing the catalyst bulk (in an amount of 80 to 95% of the total slurry catalyst entering the system) is subjected to a first reactor to maintain catalyst flow through the reforming system. Was recycled again. The STB stream contains about 7-20 wt% slurry catalyst. The STB was also analyzed to evaluate the overall performance of the system.

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

VR characteristics API weight at 60/60 4.6 importance 1.04 Sulfur (% by weight) 1.48 Nitrogen (ppm) 11069 Nickel (ppm) 118.8 Vanadium (ppm) 108.7 Carbon (wt%) 83.57 Hydrogen (% by weight) 10.04 MCR (wt%) 20.7 Viscosity at 100 ^o C (cSt) 20796 Pentane asphaltenes (wt%) 13.9 Fractions with a boiling point above 1000 ^o F (% by weight) 100%

Example  4

Send all new catalyst to the first reactor (in Comparative Example 3) and after 70 days, position the new catalyst feed in the first reactor in the first reactor, allowing the first two reactors to rely entirely on the recycled catalyst for 28 days. Changed to reactor. 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 difference in the quality of the HPO product. The results for the STB product were as follows:

STB product properties Comparative Example 3 Example 4 VR weight% (BP 1000 ℉) 15.9 15.3 HVGO Weight% (BP 800 ℉) 49.8 48.6 VGO weight% (BP 650 ℉) 79.8 80.0 API 2.7 4.5 Sulfur (% by weight) 0.12 0.16 Nitrogen (ppm) 12711 12335 MCR (% by weight) 14.7 12.4 Hydrogen / carbon ratio 0.098 0.102 Ni (ppm) 10.8 7.9 Hot heptane asphaltenes (ppm) 174255 119713 Viscosity at 70 ^o C (cSt) 68.4 47.3

The results show that bypassing the fresh catalyst to the last contacting zone in the system did not result in a change in product nitrogen level. However, there has been a change in sulfur levels, which may be due to the unusually low sulfur levels in the heavy oil feed to the system and the high sulfur levels in the VGO oil used in the slurry catalyst feed. Therefore, it is possible to introduce fresh catalyst into the last reactor (in slurry catalyst) by providing less time for the VGO oil carrier to react, thereby providing an adverse environment for product sulfur, resulting in higher product sulfur levels. It is also noted that by bypassing the new catalyst to the last reactor, an STB product with improved properties, including API, viscosity, MCR, HHA, nickel and H / C ratio, was produced. The improvement of the STB product API was not related to the improvement of the distillation of the STB product. In other words, the STB product API is not improved due to further decomposition in lighter product distillation, but due to improved catalytic activity, leading to higher H / C ratios.

With regard to system operation during 28 days of operation, there was no evidence of pressure-drop buildup or clogging around the front-end reactor, suggesting any coke formation or solid buildup. There was no measurable negative effect on overall conversion. The results suggest that the catalyst used had sufficient hydrogenation activity to inhibit coke formation even in the presence of fresh / untreated heavy oil feedstocks, indicating that the new catalyst splitting system still adequately inhibits coke formation. .

Example  5

Comparative Example 3 was repeated except that 20% of the heavy oil feedstock was diverted from the first reactor to the third reactor while maintaining the same process conditions.

Comparing process stability, reactor performance and reactor conditions between the examples, in Comparative Example 3, the third reactor yields lower liquid throughput (no heavy oil feed) and higher catalyst concentrations, which is a beneficial direction for conversion purposes. It is thought to have. However, these conditions also tend to make the last reactor more susceptible to operational disturbances, resulting in insufficient liquid flow and, consequently, more solid accumulation, impairing temperature measurements and shortening process uptime.

In Example 5, where some heavy oil feedstock is fed directly to the last reactor, (first and second) preceding reactors in which liquid throughput is reduced and correspondingly increased catalyst concentrations (as some of the heavy oil feedstock is bypassed) It is expected to operate more efficiently and have a higher conversion rate. In addition, there is more liquid dilution in the third reactor, so that there is a more uniform catalyst concentration profile across all three reactors.

In addition, it is expected that as the last continuous reactor gets a portion of the heavy oil feed, drying conditions associated with insufficient liquid flow are avoided. As the last reactor is protected from over-conversion occurrence or drying conditions, there is less solid accumulation or coke deposition. It is also expected that the last reactor will be less susceptible to large fluctuations in operating disturbances such as temperature, pressure, flow and the like.

For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers indicating quantities, percentages, or ratios, and other numerical values, as used herein and in the claims, may be changed in all instances by the term "about". It should be understood that there is. Thus, unless indicated to the contrary, the numerical variables set forth herein and in the appended claims are approximations that may vary depending upon the accuracy of the device for measuring the desired characteristics and / or values to be achieved, and therefore, measuring the values. Standard deviation of the device or method used for the purpose. Although the disclosure in the specification supports a substitute and only a definition of “and / or”, the use of the term “or” in the claims is directed to expressly referring only to the alternative or “and / or” unless the alternative is mutually exclusive. It is used to mean. When used in conjunction with the term "comprising" in this specification and in the claims, the use of the word "a" or "an" may mean "one" but also "one or more", "at least one" and "one or" Goes with more than one ". In addition, all ranges disclosed herein include the ends and may be combined independently. In general, unless otherwise indicated, the singular elements may be in the plural, and vice versa, without compromising generality. As used herein, the term “comprises” and grammatical variations thereof is intended to be non-limiting, so that the description of an item in a list is not intended to exclude other similar items that may replace or be added to the listed item.

It is contemplated that any aspect of the invention discussed in the context of one embodiment of the invention may be practiced or applied to any other embodiment of the invention. Likewise, any composition of the present invention may result in or be used in any method or process of the present invention. The description herein discloses the invention, including the best mode, and uses examples for those skilled in the art to produce and use the invention. The patentable scope is specified by the claims, and may include other examples that occur to those skilled in the art. These other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal description of the claims, or if they have structural elements with an insubstantial difference from the literal description of the claims. All citations referred to herein are expressly incorporated herein by reference.

Claims (47)

A method of hydroprocessing a heavy oil feedstock, the method employing a plurality of contacting and separating zones,
Providing a heavy oil feedstock, a hydrogen containing gas and a slurry catalyst;
Combining the heavy oil feedstock, the hydrogen containing gas and the slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a modified product;
By sending a mixture comprising the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the first separation zone, the modified product is removed from the first separation zone to the hydrogen containing gas as a first overhead stream. The slurry catalyst, heavier hydrocracked liquid product and unconverted heavy oil feedstock are removed from the first separation zone as a first non- volatile stream;
By sending the first non-volatile stream to a contacting zone other than the first contacting zone and maintaining under hydrocracking conditions with an additional hydrogen containing gas feed to convert at least a portion of the heavy oil feedstock to a lower boiling hydrocarbon Forming a modified product; And
By sending a mixture comprising additional modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to a separation zone other than the first separation zone, the modified product is removed as hydrogen overhead gas as overhead stream, The slurry catalyst and unconverted heavy oil feedstock are removed as a second non-volatile stream,
Wherein the slurry catalyst going to the first separation zone comprises at least a portion of the nonvolatile stream from one of the separation zones as recycled catalyst stream, wherein the recycled catalyst stream is from 3 to 50% by weight of heavy oil feedstock, Process for hydroprocessing heavy oil feedstock. The method of claim 1, wherein a sufficient amount of hydrogen-containing gas feed is provided such that the process has a volume yield of greater than 100% in modified products comprising liquefied petroleum gas, gasoline, diesel, reduced pressure gas oil and jet and fuel oil. A process for hydroprocessing a heavy oil feedstock, characterized in that provided. 3. Process according to claim 1 or 2, characterized in that the recycled catalyst stream is at least 10% by weight of the total heavy oil feedstock. 4. The process of claim 3, wherein the recycled catalyst stream ranges from 35 to 50 weight percent of the heavy oil feedstock. 5. The process of claim 4, wherein the recycled stream ranges from 5 to 35 weight percent of the heavy oil feedstock brought to the process. The process of claim 1 or 2, wherein at least a portion of the second nonvolatile stream is recycled to at least one of the contacting zones as a recycled stream and the remainder of the second nonvolatile stream is removed from the process as a bleed-off stream. A method for hydroprocessing heavy oil feedstock. 7. The process of claim 6, wherein the recycled stream is sent to the first contacting zone. 7. The process of claim 6, wherein the bleed-off stream contains 3 to 25 weight percent solids as slurry catalyst. 9. The process of claim 8, wherein the bleed-off stream contains 3 to 10 weight percent solids as slurry catalyst. 7. The process of claim 6, wherein a sufficient amount of bleed-off stream is removed so that the process has a conversion of at least 98%. 3. The process of claim 1, wherein the first contacting zone is operated at a temperature at least 10 ° F. below the next contacting zone. 4. A method of hydroprocessing a heavy oil feedstock, the method employing a plurality of contacting and separating zones,
Combining the heavy oil feedstock, the hydrogen containing gas and the slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a modified product;
By sending a mixture of the modified product, slurry catalyst, hydrogen containing gas, and unconverted heavy oil feedstock to the first separation zone, the modified product is removed from the first separation zone as hydrogen containing gas as the first overhead stream and slurry The catalyst, heavier hydrocracked liquid product, and unconverted heavy oil feedstock are removed from the first separation zone as a first non- volatile stream;
Directing the first non-volatile stream to a contacting region other than the first contacting region and maintaining the contacting region under hydrocracking conditions with an additional hydrogen containing gas to convert at least a portion of the heavy oil feedstock to a lower boiling hydrocarbon, Forming a further modified product; And
By sending a mixture comprising additional reformed product, slurry catalyst, additional hydrogen containing gas and unconverted heavy oil feedstock to a separation zone other than the first separation zone, the additional reformed product is further hydrogen as an overhead stream. Removing with the containing gas and removing the slurry catalyst and the unconverted heavy oil feedstock as a second non-volatile stream,
Hydrogenating the heavy oil feedstock, wherein the contacting 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 contacting zone is operated at a temperature at least 10 ° F. below the next contacting zone. How to process. 13. The process of any of claims 1, 2 and 12, wherein the first contacting zone is operated at a temperature at least 15 ° F. below the next contacting zone. 13. The process of any of claims 1, 2 and 12, wherein the first contacting zone is operated at a temperature at least 20 [deg.] F. below the next contacting zone. 13. The process of any one of claims 1, 2 and 12, characterized in that a portion of the slurry catalyst is fed to a contacting zone other than the first contacting zone. 13. The process of any of claims 1, 2 and 12, wherein the slurry catalyst comprises a fresh slurry catalyst feed. A method for hydroprocessing a heavy oil feedstock, the method employs a plurality of contacting zones and separation zones including a first contacting zone and a contacting zone other than the first contacting zone, the method comprising:
Providing a hydrogen containing gas feed;
Providing a fresh slurry catalyst feed, wherein at least a portion of the fresh slurry catalyst feed is fed to a contacting zone other than the first contacting zone;
Providing a slurry catalyst comprising the slurry catalyst used and optionally a portion of the fresh catalyst slurry feed;
Combining the portion of the hydrogen-containing gas feed, the heavy oil feedstock, and the slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a modified product;
By sending a mixture of the reformed product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the first separation zone, the volatile modified product is removed from the first separation zone to the hydrogen containing gas as a first overhead stream. The slurry catalyst, heavier hydrocracked liquid product and unconverted heavy oil feedstock are removed from the first separation zone as a first non- volatile stream;
Directing the first non-volatile stream to a contacting zone other than the first contacting zone and maintaining the contacting zone under hydrocracking conditions with an additional hydrogen-containing gas feed and at least some fresh slurry catalyst to ensure that at least a portion of the unconverted heavy oil feedstock Converting some to lower boiling hydrocarbons to form additional modified products; And
By sending a mixture of additional reformed product, slurry catalyst, additional hydrogen containing gas and unconverted heavy oil feedstock to a separation zone other than the first separation zone, the modified product is further hydrogen containing gas as a second overhead stream. Removing the slurry catalyst and the unconverted heavy oil feedstock as a second non- volatile stream, wherein the heavy oil feedstock is hydroprocessed. 18. The process of claim 17, wherein the fresh slurry catalyst is equally divided and fed to the contacting zone of the process. 18. The process of claim 17, wherein all fresh slurry catalyst is to be supplied to at least one contacting zone other than the first contacting zone. 18. The process of claim 17, wherein at least 50% of the fresh slurry catalyst is for feeding to at least one contacting zone other than the first contacting zone. 18. The process of claim 17, wherein the process utilizes three contact zones and all of the fresh catalyst feed is fed to the third contact zone. 18. The heavy oil feedstock according to any one of claims 1, 2, 12 and 17, characterized in that at least a portion of the heavy oil feedstock is supplied to a contacting region other than the first contacting region. Hydroprocessing. A method for hydroprocessing a heavy oil feedstock, the method employs a plurality of contacting zones and separation zones including a first contacting zone and a contacting zone other than the first contacting zone, the method comprising:
Providing a hydrogen containing gas feed and a slurry catalyst feed;
Providing a heavy oil feedstock and supplying at least a portion of the heavy oil feedstock to a contact region other than the first contact region;
Combining a portion of the hydrogen-containing gas feed, a portion of the heavy oil feedstock and a slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a modified product. step;
By sending a mixture of the reformed product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the first separation zone, the volatile modified product is removed from the first separation zone to the hydrogen containing gas as a first overhead stream. The slurry catalyst, heavier hydrocracked liquid product and unconverted heavy oil feedstock are removed from the first separation zone as a first non- volatile stream;
At least a portion of the heavy oil feedstock and the first non-volatile stream are sent to a contacting zone other than the first contacting zone, and the contacting zone is maintained under hydrocracking conditions with an additional hydrogen containing gas feed to provide at least a portion of the heavy oil feedstock. Converting to a lower boiling hydrocarbon, thereby forming additional modified products; And
By sending a mixture comprising additional modified product, slurry catalyst, additional hydrogen containing gas and unconverted heavy oil feedstock to a separation zone other than the first separation zone, the additional volatile modified product is added as an overhead stream. Removing the hydrogen-containing gas and removing the slurry catalyst and the unconverted heavy oil feedstock as a second non- volatile stream. 24. The process of any one of claims 1, 2 and 23, characterized in that at least 5% of the heavy oil feedstock is fed to a contacting zone other than the first contacting zone. Way. 24. The process of any one of claims 1, 2 and 23, wherein at least 30% of the heavy oil feedstock is fed to a contacting zone other than the first contacting zone. Way. 24. The method of any one of claims 1, 2 and 23, wherein less than 80% of the heavy oil feedstock is for feeding to the first contacting zone, and the remainder of the heavy oil feedstock is at least one other than the first contacting zone. A process for hydroprocessing a heavy oil feedstock, characterized in that it is supplied to a contacting zone of the oil. 24. The method of any one of claims 1, 2, 12, 17 and 23, wherein water is added to the first contacting zone in an amount of 1 to 25% by weight relative to the weight of the heavy oil feedstock. And hydroprocessing the heavy oil feedstock, characterized in that it further comprises the step of. A method for hydroprocessing a heavy oil feedstock, the method employing a plurality of contacting zones and separation zones,
Combining the heavy oil feedstock, the hydrogen containing gas, the slurry catalyst and water under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a reformed product, the water being Present in an amount of 1 to 25% by weight relative to the weight of the heavy oil feedstock;
By sending a mixture comprising the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the first separation zone, the modified product is removed from the first separation zone to the hydrogen containing gas as a first overhead stream. The slurry catalyst, heavier hydrocracked liquid product and unconverted heavy oil feedstock are removed from the first separation zone as a first non- volatile stream;
Sending the first non-volatile stream to a contacting zone other than the first contacting zone and maintaining under hydrocracking conditions with an additional hydrogen containing gas feed to convert at least a portion of the unconverted heavy oil feedstock to a lower boiling hydrocarbon, Forming a further modified product; And
By sending a mixture comprising additional modified product, slurry catalyst, additional hydrogen containing gas, and unconverted heavy oil feedstock to a separation zone other than the first separation zone, the volatile additional modified product is added as an overhead stream. Removing the hydrogen-containing gas and removing the slurry catalyst and the unconverted heavy oil feedstock as a second non- volatile stream. 29. The process of claim 28, wherein at least some of the water is added directly to the heavy oil feedstock that forms the mixture prior to being fed to the first contacting zone. 29. The process of claim 28, wherein the mixture of water and heavy oil feedstock is preheated at a temperature at least 50 [deg.] C. below the hydrocracking temperature. 29. The process of claim 28, wherein water is added directly to the contacting zone at a plurality of points along the first contacting zone. 29. The process of claim 28, wherein at least some water is added to the first contacting zone as steam input. 33. The method of claim 32, wherein steam is introduced into the plurality of feed points in the first contacting zone. A method for hydroprocessing a heavy oil feedstock, the method employing a plurality of contacting zones and separation zones,
Combining the heavy oil feedstock, the hydrogen containing gas and the slurry catalyst under hydrocracking conditions in the first contacting zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to form a modified product;
By sending a mixture of the modified product, slurry catalyst, hydrogen containing gas and unconverted heavy oil feedstock to the separation zone, the volatile modified product is removed from the separation zone as hydrogen containing gas as the first overhead stream, slurry catalyst, Removing the nonvolatile modified product and unconverted heavy oil feedstock from the separation zone as a first nonvolatile stream;
Directing at least some of the first nonvolatile stream to a solvent deasphalting unit;
Obtaining from the solvent deasphalting unit two streams, one comprising deasphalted oil and one comprising asphaltene and a slurry catalyst;
The deasphalted oil is sent to a contacting zone other than the first contacting zone, and the contacting zone is maintained under hydrocracking conditions with an additional hydrogen containing gas feed and an additional slurry catalyst feed so that at least a portion of the deasphalted oil is lowered. Conversion to the boiling boiling hydrocarbons to form additional modified products; And
By sending a mixture of further modified product, slurry catalyst, additional hydrogen containing gas and unconverted deasphalted oil to the second separation zone, the volatile additional modified product and additional hydrogen containing gas are passed as the second overhead stream. Removed, and the slurry catalyst and the nonvolatile further modified product and unconverted deasphalted oil are removed as a second nonvolatile stream; And
a) a portion of the stream comprising asphaltene and a slurry catalyst, b) a portion of the first non- volatile stream; c) recycling a recycled stream comprising at least one of a portion of the second non- volatile stream, and d) a mixture thereof to at least one contacting zone. 35. The method of any of claims 1, 2, 17, 23, and 34, wherein the contacting zone is maintained under hydrocracking conditions at a temperature of 410 ° C to 600 ° C and a pressure of 10 MPa to 25 MPa. A method of hydroprocessing a heavy oil feedstock, characterized in that. 35. The heavy oil feedstock of any one of claims 1, 2, 17, 23 and 34, wherein the separation zone is maintained at a temperature within 90 ° F of the contact zone temperature. Hydroprocessing. 35. The method of any one of claims 1, 2, 17, 23 and 34, wherein the first contacting region has an outlet pressure X, the first separating region has an inlet pressure Y, and the first A process for hydroprocessing a heavy oil feedstock, characterized in that the pressure drop Z between the discharge pressure X in the contact zone and the inlet pressure Y in the first separation zone is less than 100 psi. 35. The process of any one of claims 1, 2, 17, 23, and 34, wherein the slurry catalyst has an average particle diameter in the range of 1 to 20 microns. How to. 35. The method of any one of claims 1, 2, 17, 23, and 34, wherein the slurry catalyst comprises a cluster of colloidal particles having a size of less than 100 nm, wherein the cluster is from 1 to 1. A process for hydroprocessing a heavy oil feedstock, characterized in that it has an average particle diameter in the range of 20 microns. 35. The process of any one of claims 1, 2, 17, 23 and 34, wherein the process utilizes a plurality of contact regions and separation regions, and at least one contact region and at least one separation region. A process for hydroprocessing a heavy oil feedstock, characterized in that it is combined in one apparatus as a reactor having this internal separator. 35. The method of any one of claims 1, 2, 17, 23 and 34, wherein the additional hydrocarbon oil feed other than the heavy oil feedstock is present in an amount of from 2 to 30% by volume of the heavy oil feedstock. Process for hydroprocessing heavy oil feedstock, characterized in that it is added to any contacting zone. 42. The process of claim 41, wherein the additional hydrocarbon oil feed is selected from the group consisting of reduced pressure gas oil, naphtha, medium cycle oil, solvent donors, and aromatic solvents. 35. The process of any one of claims 1, 2, 17, 23 and 34, wherein the hydrotreating catalyst is used and at least 70% sulfur, at least 90% nitrogen in the modified product, and Further comprising an in-line hydrotreater operating at a pressure within 10 psig of the contacting zone to remove at least 90% of heteroatoms. 35. The method of any one of claims 1, 2, 17, 23, and 34, further comprising: a TAN of at least 0.1; Viscosity of at least 10 cSt; API share at most 15; At least 0.0001 g of Ni / V / Fe; At least 0.005 g heteroatoms; At least 0.01 g of residue; At least 0.04 g C5 asphaltenes; A method for hydroprocessing a heavy oil feedstock, characterized in that for processing a heavy oil feedstock comprising at least 0.002 g of MCR. 35. The process of any one of claims 1, 2, 17, 23 and 34, further comprising a plurality of recycle pumps for promoting the dispersion of the heavy oil feedstock and the slurry catalyst in the contacting zone. A method of hydroprocessing a heavy oil feedstock, characterized in that. 35. A recycle pump as claimed in any one of claims 1, 2, 17, 23 and 34, wherein the first contacting zone facilitates the dispersion of the heavy oil feedstock and the slurry catalyst in the contacting zone. A method for hydroprocessing a heavy oil feedstock, characterized in that it comprises a. 35. The method of any one of claims 1, 2, 17, 23 and 34, further comprising recycling at least a portion of the nonvolatile stream into at least one contact region. , Hydroprocessing heavy oil feedstock.

Images