MX2011002970A

MX2011002970A - Systems and methods for producing a crude product.

Info

Publication number: MX2011002970A
Application number: MX2011002970A
Authority: MX
Inventors: Shuwu Yang; Darush Farshid; Bruce Reynolds; Kaidong Chen; Julie Chabot; Bo Kou; Vivion Andrew Brennan; Erin Maris; Goutam Biswas
Original assignee: Chevron Usa Inc
Priority date: 2008-09-18
Filing date: 2009-09-15
Publication date: 2011-04-11
Also published as: JP2012503071A; CN102197116B; EP2331657B1; KR101700224B1; KR20110059881A; CA2737367A1; CA2737367C; CN102197116A; WO2010033480A3; EP2331657A4; EP2331657A2; WO2010033480A2; EA201170463A1; BRPI0918085A2; JP5661038B2; EA023427B1

Abstract

Systems and methods for hydroprocessing a heavy oil feedstock with reduced heavy oil deposits, the system employs a plurality of contacting zones and separation zones zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons, forming upgraded products, wherein water and / or steam being optionally injected into first contacting zone in an amount of 1 to 25 weight % on the weight of the heavy oil feedstock. In one embodiment, the first contacting zone is operated at a temperature of at least 10Â°F. lower than a next contacting zone. The contacting zones operate under hydrocracking conditions, employing a slurry catalyst for upgrading the heavy oil feedstock, forming upgraded products of lower boiling hydrocarbons. In the separation zones, upgraded products are removed overhead and optionally, further treated in an in-line hydrotreater. At least a portion of the non-volatile fractions recovered from at least one of the separation zones is recycled back to the first contacting zone in the system, in an amount ranging between 3 to 50 wt. % of the heavy oil feedstock. In one embodiment, at least some of the heavy oil feedstock is supplied to at least a contacting zone other than the first contacting zone and / or at least some of the fresh slurry catalyst is supplied to at least a contacting zone other than the first contacting zone. In one embodiment, at least a portion of the non-volatile fractions recovered from at least one of the separation zones is sent to the interstage solvent deasphalting unit, for separating unconverted heavy oil feedstock into deasphalted oil and asphaltenes. The deasphalted oil stream is sent to one of the contacting zones for further upgrade.

Description

SYSTEMS AND METHODS TO PRODUCE AN RAW PRODUCT Field of the Invention The invention relates to systems and methods for treating or improving heavy oil feeds, and raw products produced using such systems and methods.

Background of the Invention The oil industry is increasingly turning to heavy oil feeds such as heavy crudes, waste, coals, asphalt sands, etc., as sources for the feedstocks. These feedstocks are characterized by high concentrations of asphaltene-rich residues, and low API gravities, with some being as low as less than 0o API.

PCT Patent Publication No. WO2008 / 014947, U.S. Patent Publication No. 2008/0083650, U.S. Patent Publication No. 2005/0241993, U.S. Patent Publication No. 2007 / 0138057, and U.S. Patent No. 6,660,157 describe the processes, systems and catalysts for processing heavy oil feeds. The heavy oil feedstock typically contains large levels of heavy metals.

Ref. 218855 Some of the heavy metals such as nickel and vanadium tend to react rapidly, leading to sedimentation or entrapment of vanadium-rich solids in the equipment, such as reactors. Sedimentation of solids reduces the volume available for the reaction, shortening the running time.

There is still a need for improved systems and methods to improve / treat heavy process oil feeds with reduced heavy metal accumulation in the process equipment.

Brief Description of the Invention In one aspect, this invention relates to a process by which a heavy oil feedstock can be improved. The process employs a plurality of contact zones, separation zones and at least one solvent deasphalting unit, inter-stage (SDA). The process comprises: a) combining a feed of hydrogen-containing gas, a heavy oil feedstock, and a catalyst in suspension in a first contact zone under hydrodisintegration conditions to convert at least a portion of the petroleum feedstock heavy to improved products; c) sending a mixture of the improved products, the suspension catalyst, the hydrogen-containing gas, and the unconverted heavy oil feedstock to a separation zone; d) in the separation zone, the improved products are removed with the hydrogen-containing gas as an overhead stream, and the suspended catalyst and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; e) at least a portion of the non-volatile stream is sent to the SDA unit to separate the asphaltenes and suspension catalysts from the deasphalted petroleum; f) deasphalted oil and the remainder of the non-volatile stream from the pre-separation zone are sent to another contact zone, under hydro-disintegration conditions with additional hydrogen gas and additional suspension catalyst, to convert the deasphalted oil to products improved; f) improved products, suspended catalyst, hydrogen, and unconverted deasphalted oil are sent to a separation zone, whereby the improved products are removed with hydrogen as an overhead stream and the catalyst in suspension and the oil Unconverted de-asphalted are removed as a non-volatile stream; and g) at least a portion of the non-volatile stream containing the suspended catalyst and the unconverted deasphalted oil is recycled to at least one of the contact zones.

In still another aspect, a process is provided employing a plurality of contact zones, separation zones and at least one interstage solvent deasphalting unit (SDA) in which a heavy oil feedstock can be improved. , and wherein at least a portion of the non-volatile stream from at least one contact zone is sent to the SDA unit to separate the asphaltenes from the deasphalted oil.

In one aspect, this invention relates to a process by which a heavy oil feedstock can be improved with reduced deposits of heavy metals in the contact areas of the front end. The process employs a plurality of contact zones and separation zones, the process comprising: a) combining a gas supply containing hydrogen, a heavy oil feedstock, and a catalyst in suspension in a first contact zone, under hydrodegradation conditions for converting at least a portion of the heavy petroleum feedstock into improved products, wherein the water and / or the steam that is injected into the first contact zone in an amount of 1 to 25% by weight on the weight of the heavy oil feed material; b) sending a mixture of the improved products, the suspended catalyst, the hydrogen-containing gas, and the unconverted heavy oil feedstock to a separation zone; c) in the separation zone, the improved products are removed with the hydrogen-containing gas as an overhead stream, and the suspended catalyst and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; d) sending the non-volatile stream to another contact zone under hydrodisintegration conditions with additional hydrogen gas, unconverted heavy petroleum feedstock, and optionally, a fresh suspension catalyst to convert the unconverted heavy oil feedstock, in improved products; f) sending the improved products, suspended catalyst, hydrogen, and the unconverted heavy oil feedstock to a separation zone, whereby the improved products are removed with the hydrogen as an overhead stream, and the catalyst in suspension and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; and g) recycling at least one portion of the non-volatile stream to at least one of the contact zones.

In still another aspect, the invention relates to a method for improving a heavy oil feedstock, employing a plurality of contact zones and separation zones, in which water and / or steam are injected into the first contact area, and wherein at least a portion of the non-volatile stream coming from a separation zone different from the first separation zone, is recycled to the first contact zone, where the recycled stream is in the range between 3 to 50% by weight of the total heavy oil feed material to the process.

In one aspect, this invention relates to a process by which a heavy oil feedstock can be improved. The process employs a plurality of contact zones and separation zones, the process comprising: a) a heavy oil feedstock with at least a portion of the heavy oil feedstock that is fed into a contact zone other than the first contact area; b) combining a hydrogen-containing gas feed, a portion of the heavy petroleum feedstock, and a catalyst in suspension, in a first contact zone under hydrodisintegration conditions to convert at least a portion of the heavy petroleum feedstock in improved products; c) sending a mixture of the improved products, the suspension catalyst, the hydrogen-containing gas, and the heavy oil feed material not converted to a separation zone; d) in the separation zone, remove the improved products with the hydrogen-containing gas as an upper stream, and remove the suspended catalyst and the heavy oil feed material not converted as a non-volatile stream; e) sending the non-volatile stream to another contact zone under hydrodisintegration conditions with the additional hydrogen gas, at least a portion of the heavy petroleum feedstock, and optionally, fresh suspension catalyst to convert the heavy petroleum feedstock not converted to improved products; f) send the improved products, the suspended catalyst, the hydrogen, and the un-converted heavy petroleum feedstock to a separation zone, whereby the improved products are removed with the hydrogen as an overhead stream and the catalyst in suspension and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; and g) recycling to the first contact zone at least a portion of the non-volatile stream.

In yet another aspect, the process employs a plurality of contact zones and separation zones, the process comprising: a) providing a suspension catalyst containing a suspension catalyst used, and optionally a fresh suspension catalyst feed; b) combining a gas feed containing hydrogen, the heavy petroleum feedstock, and the catalyst in suspension in a contact zone under hydrodisintegration conditions to convert at least a portion of the heavy petroleum feedstock into improved products; c) sending a mixture comprising the improved products, the suspended catalyst, the hydrogen-containing gas, and the unconverted heavy petroleum feedstock to a separation zone; d) in the separation zone, the improved products are removed with the hydrogen-containing gas as an overhead stream, and the suspended catalyst and the heavy petroleum feedstock not converted as a non-volatile stream are removed; e) the non-volatile stream is sent to another contact zone under hydrodisintegration conditions with additional hydrogen gas and a fresh suspended catalyst, to convert the non-converted heavy petroleum feedstock into improved products; f) the improved products, the suspended catalyst, hydrogen, and the unconverted heavy oil feedstock are sent to a separation zone, with which the improved products are removed with the hydrogen as an overhead stream and the catalyst in suspension and the unconverted heavy petroleum feedstock are removed as a non-volatile stream; and g) recycling to the first contact zone, at least a portion of non-volatile current.

In yet another aspect, a process is provided employing a plurality of contact zones and separation zones in which a heavy oil feedstock can be improved, and where the fresh suspended catalyst is divided between the contact zones .

In one aspect, the process employs a plurality of contact zones and separation zones, the process comprising: a) combining a gas supply containing hydrogen, a heavy oil feedstock, and a catalyst in suspension in a first zone of contact under hydrodisintegration conditions to convert at least a portion of the heavy petroleum feedstock to improved products; c) sending a mixture of the improved products, the suspension catalyst, the hydrogen-containing gas, and the unconverted heavy oil feedstock to a separation zone; d) in the separation zone, the improved products are removed with the hydrogen-containing gas as an overhead stream, and the suspended catalyst and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; e) at least a portion of the non-volatile stream is sent to the SDA unit to separate the asphaltenes and suspension catalysts from the deasphalted petroleum; f) deasphalted oil and the remainder of the non-volatile stream from the pre-separation zone are sent to another contact zone, under hydro-disintegration conditions with additional hydrogen gas and additional suspension catalyst, to convert the deasphalted oil to products improved; f) improved products, suspended catalyst, hydrogen, and unconverted deasphalted oil are sent to a separation zone, whereby the improved products are removed with hydrogen as an overhead stream and the catalyst in suspension and the oil Unconverted de-asphalted are removed as a non-volatile stream; and g) at least one portion of the non-volatile stream containing the suspended catalyst and the unconverted deasphalted oil is recycled to at least one of the contact zones, and wherein the first contact zone operates at a temperature of at least 5.5. ° C (10 ° F), less than the next contact zone in the series.

In still another aspect, the invention relates to a process by which a heavy oil feedstock can be improved with reduced deposits of heavy metals in the contact areas of the front end. The process employs a plurality of contact zones and separation zones, comprising: a) combining a gas feed containing hydrogen, a heavy oil feedstock, and a catalyst in suspension in a first contact zone under conditions of hydrodisintegration to convert at least a portion of the heavy oil feedstock to improved products; c) sending a mixture of the improved products, the suspension catalyst, the hydrogen-containing gas, and the unconverted heavy oil feedstock to a separation zone; d) in the separation zone, the improved products are removed with the hydrogen-containing gas as an overhead stream, and the suspended catalyst and the non-converted heavy petroleum feedstock are removed as a non-volatile stream; e) at least a portion of the non-volatile stream is sent to the SDA unit to separate the asphaltenes and suspension catalysts from the deasphalted petroleum; f) deasphalted oil and the remainder of the non-volatile stream from the pre-separation zone are sent to another contact zone, under hydro-disintegration conditions with additional hydrogen gas and additional suspension catalyst, to convert the deasphalted oil to products improved; f) improved products, suspended catalyst, hydrogen, and unconverted deasphalted oil are sent to a separation zone, whereby the improved products are removed with hydrogen as an overhead stream and the catalyst in suspension and the oil Unconverted de-asphalted are removed as a non-volatile stream; and g) at least a portion of the non-volatile stream is recycled to at least one of the contact zones; and wherein the catalyst in suspension to the first separation zone comprises at least a portion of a non-volatile stream from one of the separation zones such as a stream of recycled catalyst, and wherein the stream of recycled catalyst is between 3 and 10. to 50% by weight of the heavy oil feedstock.

Brief Description of the Figures Figure 1 is a block diagram schematically illustrating one embodiment of a hydroprocessing system for improving a heavy oil feedstock, with a plurality of contact zones and separation zones, wherein the water and / or vapor is injected into the contact area of the front end.

Figure 2 is a flow chart of a process for improving heavy oil feeds with water injection.

Figure 3 is a flowchart of a process for improving the feeds of heavy oil with steam injection directly into the front end contact zone.

Figure 4 is a flowchart of another embodiment of the process for improving heavy oil feeds with a stream of recycled catalyst at a rate sufficient to reduce heavy metal accumulation.

Figure 5 is a block diagram schematically illustrating one embodiment of a hydroprocessing system for improving a heavy oil feed material, having a fresh split catalyst feed scheme, a divided heavy oil feed scheme, and material Heavy oil feed inter-stage, additional.

Figure 6 is a block diagram schematically illustrating another embodiment of a hydroprocessing system for improving a heavy oil feedstock with a solvent de-escalation unit for pre-treating the heavy oil feedstock.

Figure 7 is a flow chart of a process for improving heavy oil feeds with a split catalyst feed scheme embodiment, wherein the fresh feed catalyst is fed into all the reactors in the process.

Figure 8 is a flow diagram of a process for improving heavy oil feeds, where the fresh catalyst feed is diverted from the first reactor to other reactors in the process, and where the hydrocarbon / additional oil is fed to the reactors as feedstock.

Figure 9 is a flow chart of yet another embodiment of a process for improving heavy oil feeds, where all fresh catalyst feed is sent to the last reactor in the process.

Figure 10 is a flow chart of yet another embodiment of a process for upgrading heavy oil feeds, where some of the untreated heavy oil feed is diverted from the first reactor and sent to other reactors in the process.

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

As used herein, "heavy oil" feedstock or feedstock refers to heavy and ultra-heavy crudes, including but not limited to waste, pellets, bitumen, shale oils, asphalt sands, etc. The heavy oil feedstock can be liquid, semi-solid and / or solid. Examples of heavy oil feedstock that can be improved as described herein include, but are not limited to, Canadian asphalt sands, reservoir vacuum residue and Santos and Campos de Brasil, the Gulf of Egypt, Chad, Zulia from Venezuela, Malaysia, and Sumatra in Indonesia. Other examples of the heavy oil feedstock include the bottom of the barrel and the residue left from the refinery processes including the "bottom of the barrel" and the "residue" (or "resid") - the bottoms of atmospheric towers - that have a boiling point of at least 343 ° C. (650 ° F.), Or the bottoms of the vacuum towers, which have a boiling point of at least 524 ° C. (975 ° F.), Or the "residual Batum" and "vacuum residue" - which have a boiling point of 524 ° C. (975 ° F.) Or greater.

The properties of the heavy oil feedstock may include, but are not limited to: TAN of at least 0.1, at least 0.3, or at least 1; viscosity of at least 10 cSt; API gravity of at most 15 in one modality, and at most 10 in another modality. One gram of the heavy oil feedstock typically contains at least 0.0001 grams of Ni / V / Fe; at least 0.005 grams of heteroatoms; at least 0.01 grams of residue; at least 0.04 grams of C5 asphaltenes; at least 0.002 grams of MCR; per gram of crude; at least 0.00001 grams of alkali metal salts of one or more organic acids; and at least 0.005 grams of sulfur. In one embodiment, the heavy oil feedstock has a sulfur content of at least 5% by weight and an API gravity of -6 to +6.

The terms "treatment", "treaty", "improve", "improve", "improvement" and "improved", when used in conjunction with a heavy oil feedstock, describe a heavy oil feedstock that is being or having been subjected to hydroprocessing, or a resulting material or crude product, having a reduction in the molecular weight of the heavy oil feedstock, a reduction in the boiling point range of the heavy oil feedstock, a reduction in the concentration of the asphaltenes, a reduction in the concentration of the hydrocarbon free radicals, and / or a reduction in the amount of impurities, such as sulfur, nitrogen, oxygen, halides and metals.

The improvement or treatment of heavy oil feeds is generally referred to herein as "hydroprocessing". Hydroprocessing is understood to be any process that is carried out in the presence of hydrogen, including, but not limited to, hydroconversion, hydrodisintegration, hydrogenation, hydrotreating, hydrodesulfurization, hydrodesnitrogenation, hydrodesmetalation, hydrodesaromatization, hydrodesisomerization, hydrodeparaffination, and hydrodisintegration including hydrodegradation selective Hydroprocessing products can show improved viscosities, viscosity indexes, saturates content, low temperature properties, volatilities and depolarization, etc.

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

SCF / BBL (or scf / bbl) refers to a standard cubic foot gas unit (N2, H2, etc.) per barrel of hydrocarbon feed.

Nm3 / m3 refers to the normal cubic meters of gas per cubic meter of heavy oil feed.

VGO or vacuum gas oil, refers to hydrocarbons with a boiling range distribution between 343 ° C (650 ° F) and 538 ° C (1000 ° F) at 0.101 mPa. "wppm" means parts in million by weight. As used herein, the term "catalyst precursor" refers to a compound that contains one or more catalytically active metals, from which compound, a catalyst is optionally formed. It should be noted that a catalyst precursor can be catalytically active as a hydroprocessing catalyst. As used herein, "catalyst precursor" can be referred to herein as "catalyst" when used in the context of a catalyst feed.

As used herein, the term "used catalyst" refers to a catalyst that has been used in at least one reactor in a hydroprocessing operation, and whose activity has already been decreased. For example, if a reaction rate constant of a fresh catalyst at a specific temperature is assumed to be 100%, the constant of the reaction rate for a used catalyst is 95% or less in one embodiment, 80% or less in another modality, and 70% or less in a third modality. The term "used catalyst" can be used interchangeably with "recycled catalyst", "used suspension catalyst" or "recycled suspension catalyst".

As used herein, the term "fresh catalyst" refers to a catalyst or a catalyst precursor that has not been used in a reactor in a hydroprocessing operation. The term "fresh catalyst" herein also includes "re-generated" or "rehabilitated" catalysts, for example, the catalyst that has been used in at least one reactor in a hydroprocessing operation ("used catalyst") but its activity catalytic has been restored or at least increased to a level well above the level of catalytic activity used. The term "fresh catalyst" can be used interchangeably with "fresh suspension catalyst".

As used herein, the term "suspended catalyst" (or sometimes referred to as "suspension," or "dispersed catalyst") refers to a liquid medium, for example, oil, water or mixtures thereof, in wherein the catalyst and / or the catalyst precursor particles (particles or crystallites) having very small average dimensions are dispersed within.

As used herein, the "catalyst feed" includes any catalyst suitable for improving heavy oil feed materials, for example, one or more bulk catalysts and / or one or more catalysts on a support. The catalyst feed may include at least one fresh catalyst, one used catalyst alone, or mixtures of at least one fresh catalyst and one used catalyst. In one embodiment, the catalyst feed is in the form of a suspension catalyst.

As used herein, the term "bulk catalyst" can be used interchangeably with "unsupported catalyst", w means that the catalyst composition is NOT of the optional catalyst form having, for example, a carrier support. formed, pre-formed catalyst, w is then charged with metals via the impregnation or the deposition catalyst. In one embodiment, the bulk catalyst is formed through precipitation. In yet another embodiment, the bulk catalyst has a binder incorporated within the catalyst composition. In yet another embodiment, the bulk catalyst is formed from metal compounds and without any binder. In a fourth embodiment, the bulk catalyst is a dispersed type catalyst for use as dispersed catalyst particles in liquid mixture (e.g., hydrocarbon oil). In one embodiment, the catalyst comprises one or more commercially known catalysts, for example, Microcat ™ from ExxonMobi1 Cor.

As used herein, the term "contact zone" refers to equipment in w the heavy oil feed is treated or improved by contact with a catalyst feed in suspension in the presence of hydrogen. In a contact zone, at least one property of the crude feed may be changed or improved. The contact zone may be a reactor, a portion of a reactor, multiple portions of a reactor, or a combination thereof. The term "contact zone" can be used interchangeably with "reaction zone".

As used herein, the term "separation zone" refers to equipment in w the improved heavy oil feed from a contact zone is fed either directly into, or subjected to, one or more intermediate processes, and then fed directly into the separation zone, for example, a sudden expansion drum or a high pressure separator, where gases and volatile liquids are separated from the non-volatile fraction. In one embodiment, the nonvolatile fraction stream comprises unconverted heavy oil feed, a small amount of heavier hydrodisintegrated liquid products (improved synthetic or less volatile / nonvolatile products), suspended catalyst and any entrained solids (asphaltenes , coke, etc.).

As used herein, the term "purge stream" refers to a stream that contains used (or recycled) catalyst, w is "purged" or diverted from the hydroprocessing system, helping to prevent or "jet wash" the metal sulfides that accumulate, and other impurities unwanted breeding system.

The present invention relates to an improved system for treating or improving heavy oil feeds, particularly heavy oil feedstock having high levels of heavy metals.

In a typical hydroprocessing system of the prior art, w has a plurality of contact zones (reactors) in series, it is observed that the feed stream to the second contact zone must be generally cleaner than the heavy oil feed towards the first contact zone in the system, for example, having less impurities such as nickel, vanadium, nitrogen, sulfur, etc., as the heavy oil has gone through a treatment process in the first contact zone. It is also noted that the first current to the first contact zone in the system should in general be cleaner than the supply current to the or previous contact zones in the system.

In a typical hydroprocessing system, it has further been observed that in the prior art catalyst feed scheme, the feed streams to the subsequent contact zones in the system, are typically more concentrated in terms of certain impurities, for example , MCR, the contents of asphaltenes of 5 and 7 carbon atoms, etc., thus promoting the formation of coke in the last contact zones in the system.

It has also been observed that the feed stream to the subsequent contact zones in the system has properties different from the properties of the heavy oil feed towards the contact zones present in the system, including: a) lower TAN; b) viscosity; c) lower waste content; d) lower API gravity; e) lower metal content in metallic salts of organic acids; and g) combinations thereof. However, it has also been found that it is generally more difficult to process the feed to the subsequent contact zones in the system, in terms of the speed of conversion and / or the properties of the resulting raw product. Furthermore, with the prior art feed scheme (fresh catalyst going to the first contact zone), it is observed that there is more coke formation in the subsequent contact areas than in the first contact zone. It is speculated that the coke formation may have something to do with the more difficult feed to process, towards the subsequent contact zones and / or the reduced activity of the fed catalyst towards the subsequent contact zones.

In one embodiment, the improvement process comprises a plurality of reactors for the contact zones, with the reactors that are in them or in different configurations. Examples of reactors that may be used herein include stacked bed reactors, fixed bed reactors, boiling bed reactors, continuous stirred tank reactors, fluidized bed reactors, spray reactors, liquid-liquid contactors, reactor reactors, suspension, liquid recirculation reactors, and combinations thereof. In one embodiment, the reactor is an upflow reactor. In yet another embodiment, this is a downflow reactor. In one embodiment, the contact zone refers to at least one suspension bed hydrodesylation reactor, in series in at least one fixed bed hydrotreating reactor. In yet another embodiment, at least one of the contact zones also comprises an in-line hydrotreater, capable of removing more than 70% of the sulfur, more than 90% of the nitrogen, and more than 90% of the heteroatoms in the crude product which It is processed.

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

Depending on the conditions and the position of the separation zone, in one embodiment, the amount of heavier hydrodisintegrated products in the nonvolatile fraction stream is less than 50% by weight (of the total weight of the non-volatile stream). . In a second embodiment, the amount of heavier hydrodisintegrated products in the non-volatile stream coming from the separation zone is less than 25% by weight. In a third embodiment, the amount of heavier hydro-disintegrated products in the non-volatile stream from the separation zone is less than 15% by weight. It should be noted that at least a portion of the catalyst in suspension remains with the improved feedstock, as the improved materials are removed from the contact zone, and fed into the separation zone, and the suspension catalyst continues to be available in the separation zone and leaves the separation zone with the non-volatile liquid fraction.

In one embodiment, the contact zone and the separation zone are combined in one equipment, for example, a reactor having an internal separator, or a multi-stage reactor-separator. In this type of reactor-separator configuration, the vapor product leaves the top of the equipment, and the non-volatile fractions leave the side or the bottom of the equipment, with the catalyst in suspension and the solid fraction entrained, if there is.

In one embodiment, the catalyst stream in suspension contains a fresh catalyst. In yet another embodiment, the suspended catalyst stream contains a mixture of at least one fresh catalyst and one recycled (used) catalyst. In a third embodiment, the suspension catalyst stream comprises a used catalyst. In yet another embodiment, the suspension catalyst contains a well-dispersed catalyst precursor composition capable of forming an active catalyst in situ within the feed heaters and / or the contact zone. The catalyst particles can be introduced into the medium (diluent) as a powder in one embodiment, a precursor in another embodiment, or after a pre-treatment step in a third embodiment. In one embodiment, the medium (or diluent) is a hydrocarbon oil diluent. In yet another embodiment, the liquid medium is the same heavy oil feedstock. In yet another embodiment, the liquid medium is a hydrocarbon oil different from the heavy oil feedstock, for example, a VGO medium or diluent.

In one embodiment, the purge stream comprises non-volatile materials from a separation zone in the system, typically the last separation zone, comprising unconverted materials, the catalyst in suspension, a small amount of heavier hydrodisintegrated liquid products, small amounts of coke, asphaltenes, etc. In another embodiment, the purge current is the bottom current from a solvent deasphalting unit, inter-stage in the system. In embodiments where the purge stream is diverted from the lower stream of a separation zone, the purge stream is typically in the range of 1 to 35% by weight; 3-20% by weight; or 5-15% by weight of the total heavy oil feed material to the system. In the embodiments herein, the purge stream is diverted from the bottom of a deasphalting unit, the purge stream is in the range of 0.30 to 5% by weight; 1-30% by weight; or 0.5 to 10% by weight of the heavy oil feedstock.

In one embodiment, the purge stream contains between 3 to 30% by weight of catalyst in suspension. In yet another embodiment, the amount of the catalyst in suspension is in the range of 5 to 20% by weight. In yet another embodiment, the purge stream contains an amount of catalyst in suspension in the range of 1 to 15% by weight in concentration.

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

Also in some embodiments, instead of sending all the feed of the heavy oil to be improved, towards the first contact zone, at least a portion of the heavy oil feed is diverted to at least other of the contact zones in the system.

In other embodiments, a feed scheme in combination with a portion of the fresh catalyst feed and a portion of the heavy oil feed that is diverted to at least one of the different contact zones of the first contact zone is employed. in the heavy oil improvement system.

In one embodiment, the breeding system comprises at least two upflow reactors with at least two separators, with each separator being placed just after each reactor and with the inter-stage SDA unit being placed between at least one reactor in the system. In yet another embodiment, the breeding system comprises at least two upflow reactors and at least two separators in series, with each of the separators being placed just after each reactor, and the inter-stage SDA unit that is placed after the first separator in the series. In a fourth embodiment, the breeding system may comprise a combination of separate reactors and separators separated in series, with the multi-stage reactor separators, with the SDA being placed as an inter-stage treatment system between any two reactors in the Serie. Heavy oil feed: The non-converted heavy oil feed may comprise at present one or more different feeds of heavy oil from different sources such as a single feed stream, or as separate heavy oil feed streams. In some embodiments of the present invention, at least a portion of the heavy oil feed (to be improved) is "divided" or diverted to at least one of the other contact zones in the system (different from the first buffer zone). contact), or to the inter-stage SDA unit before being fed into a contact zone.

In one embodiment, "at least one portion" means at least 5% of the heavy oil feed to be improved, which is diverted to at least one of the contact zones in the system, different from the first contact zone . In another modality more, at least 10%. In a third modality, at least 20%. In a fourth embodiment, at least 30% of the heavy oil feed is diverted to at least one contact zone different from the first in the system. In one embodiment, the heavy oil feedstock is preheated before being mixed with the feed stream (s) of the feed suspension catalyst. In yet another embodiment, the mixture of the heavy oil feedstock and the suspension catalyst feedstock is preheated to create a feedstock that is sufficiently low in viscosity to allow good mixing of the catalyst within the feedstock. In one embodiment, preheating is conducted at a temperature that is at least about 100 ° C (180 ° F) lower than the hydrodisintegration temperature within the contact zone. In yet another embodiment, the preheating is at a temperature that is at least 50 ° C lower than the hydrodisintegration temperature within the contact zone.

Additional Hydrocarbon Feeding: In one embodiment, the supply of additional hydrocarbon oil, for example, VGO (vacuum gas oil), naphtha, MCO (medium cycle oil), solvent donor, or other aromatic solvents, etc., in an amount in the range of 2 to 40% by weight of the heavy oil feed, it can be optionally added as part of the heavy oil feed stream to any of the contact zones in the system. In one embodiment, the additional hydrocarbon feed functions as a diluent to lower the viscosity of the heavy oil feed.

Modes of the Heavy Oil Divided Feed Scheme: In some embodiments, at least a portion of the heavy oil feed (to be improved) is "split" or diverted to at least one of the contact zones in the system ( different from the first contact zone).

In one embodiment, "at least one portion" means that at least 5% of the heavy oil feed is going to be improved. In another modality, at least 10%. In a third modality, at least 20%. In a fourth embodiment, at least 30% of the heavy oil feed is diverted to at least one contact zone different from the first in the system.

In one embodiment, less than 90% of the non-converted heavy oil feed is fed into the first reactor in the system, with 10% or more of the feed of heavy oil not converted, which is diverted to another or other of the contact area in the system. In yet another embodiment, the heavy oil feed is equally divided between the contact zones in the system. In yet another embodiment, less than 80% of the non-converted heavy oil feed is fed to the first contact zone in the system, and the remaining heavy oil feed is diverted to the last contact zone in the system. In a fourth mode, less than 60% of the heavy oil feed is fed to the first contact zone in the system, and the rest of the non-converted heavy oil feed is equally divided between the other contact zones in the system .

The heavy oil feed not converted herein may comprise one or more different feeds of heavy oil from different sources such as a separate heavy feed stream or heavy oil feed stream. In one embodiment, a simple heavy oil pipe conduit goes to all contact zones. In yet another embodiment, multiple heavy oil pipes are used to supply the heavy oil feed to the different contact zones, with some heavy oil feed streams going to one or more contact zones, and some of the other or other feed streams of heavy oil not converted, which go towards one or more of different contact zones.

In one embodiment, the heavy oil feedstock is preheated before being mixed with the catalyst feed in suspension, and / or before being introduced into the hydrodisintegration reactors (contact zones). In another embodiment, the mixture of the heavy oil feedstock and the suspension catalyst feedstock is preheated to create a feedstock that is of sufficiently low viscosity to allow good mixing of the catalyst within the feedstock.

In one embodiment, preheating is conducted at a temperature that is approximately 100 ° C (180 ° F) lower than the hydrodisintegration temperature within the contact zone. In yet another embodiment, the preheating is at a temperature that is approximately 50 ° C lower than the hydrodisintegration temperature within the contact zone.

Hydrogen Feeding: In one embodiment, a gas containing hydrogen is provided to the process. Hydrogen can also be added to the heavy oil feed before entering the preheater, or after the preheater. In one embodiment, the hydrogen feed enters the contact zone concurrently with the heavy oil feed in the same conduit. In yet another embodiment, the hydrogen source may be added to the contact zone in a direction that is contrary to the flow of the crude feed. In a third embodiment, the hydrogen enters the contact zone via a gas conduit separately from the combined feed stream of heavy oil and catalyst in suspension. In a fourth embodiment, the hydrogen feed is introduced directly into the combined catalyst and heavy oil feed material, before being introduced into the contact zone. In yet another embodiment, the hydrogen gas and the combined feed of heavy oil and catalyst are introduced to the bottom of the reactor as separate streams. In still another embodiment, the hydrogen gas can be fed to the various sections of the contact zone.

In one embodiment, the hydrogen source is provided to the process at a rate (based on the ratio of the source of hydrogen gas to the raw feed), from 0.1 Nm3 / m3 to approximately 100,000 Nm3 / m3 (0.563 to 563.380 SCF / bbl), approximately 0.5 Nm3 / m3 to approximately 10,000 Nm3 / m3 (2.82 to 56.338 SCF / bbl), approximately 1 Nm3 / m3 to approximately 8,000 Nm3 / m3 (5.63 to 45.070 SCF / bbl), approximately 2 Nm3 / m3 to approximately 5,000 Nm3 / m3 (11.27 to 28.169 SCF / bbl), approximately 5 Nm3 / m3 to approximately 3,000 Nm3 / m3 (28.2 to 16,901 SCF / bbl), or approximately 10 Nm3 / m3 to approximately 800 Nm3 / m3 (56.3 to 4,507 SCF) / bbl). In one embodiment, some of the hydrogen (25-75%) is supplied to the first contact zone, and the rest is added as supplemental hydrogen to other contact zones in the system.

In one embodiment, the breeding system produces a volumetric yield of more than 100% (compared to the input of heavy oil) in improved products since the aggregate hydrogen expands the total volume of heavy oil. The improved productsFor example, low-boiling hydrocarbons, in one embodiment, include liquefied petroleum gas (LPG), gasoline, diesel, vacuum gas oil (VGO), and aircraft and fuel oils. In a second embodiment, the breeding system provides a volumetric yield of at least 110% in the form of LPG, naphtha, aircraft and fuel oils, and VGO. In a third modality, it is higher than 115%.

In one embodiment of the breeding system, at least 98% by weight of the heavy oil feed is converted to lighter products. In a second mode, at least 98.5% of the heavy oil feed is converted to lighter products. In a third embodiment, the conversion ratio is at least 99%. In a fourth embodiment, the conversion ratio is at least 95%. In a fifth mode, the conversion ratio is at least 80%. In a sixth mode, the conversion ratio is at least 60%. As used herein, the conversion ratio refers to the conversion of the heavy petroleum feedstock to materials with a boiling point of less than 538 ° C (1000 ° F.).

The source of hydrogen, in some embodiments, is combined with one or several carrier gases and re-circulated through the contact zone. The carrier gas can be, for example, nitrogen, helium and / or argon. The carrier gas can facilitate the flow of the raw feed and / or the flow of the hydrogen source in the contact zone (s). The carrier gas can also facilitate mixing in the contact zone (s). In some embodiments, the source of hydrogen (eg, hydrogen, methane or ethane) can be used as a carrier gas and re-circulated through the contact zone.

Catalyst feed: In one embodiment, all feed of the catalyst in suspension is provided to the first contact zone. In other embodiments, at least a portion of the catalyst feed is "split" or diverted to at least one other contact zone in the system (different from the first contact zone). In yet another embodiment, all contact zones in operation receive a suspension catalyst feed (together with a heavy oil feed). In yet another embodiment, the process is configured for a flexible catalyst feed scheme, such that the fresh catalyst can sometimes be fed completely to the last reactor in the system, for certain process conditions (for certain desired product characteristics) , or 50% of the first reactor in the system for some of the runs of the process, or equally divided or according to the predetermined proportions to all the reactors in the system, or divided according to the predetermined proportions for the same fresh catalyst that It will be fed to different reactors in different concentrations.

The suspension catalyst feed used herein may comprise one or more different suspension catalysts, such as a single catalyst feed stream or separate feed streams. In one embodiment, a fresh, simple catalyst feed stream is supplied to the contact zones. In yet another embodiment, the catalyst feed comprises multiple and different types of catalysts, with a certain type of catalyst going to one or more of the contact zones (e.g., the first contact zone in the system) as a current separate, and a different suspension catalyst going to one or more contact zones different from the first contact zone in the system, such as a different catalyst stream.

In one embodiment, "at least one portion" means at least 10% of the fresh catalyst. In another modality more, at least 20%. In a third modality, at least 40%. In a fourth embodiment, at least 50% of the fresh catalyst is diverted to at least one contact zone different from the first in the system. In a fifth mode, all fresh catalyst is diverted to a contact zone different from the first contact zone.

In one embodiment, less than 20% of the fresh catalyst is fed to the first reactor in the system, with 80% or more of the fresh catalyst being diverted to the other or other contact zones in the system. In another modality more, the fresh catalyst is also being divided between the contact zones in the system. In one embodiment, at least a portion of the fresh catalyst feed is sent to at least one of the intermediate contact zones and / or to the last contact zone in the system. In yet another embodiment, all fresh catalyst is sent to the last contact zone in the system, with the first contact zone in the system obtaining only recycled catalyst from one or more of the processes in the system, for example, from one of the separation zones in the system, or from the solvent de-escalation unit.

In one embodiment, with an inter-stage SDA unit, at least a portion of the fresh catalyst feed is sent to the contact zone immediately after the inter-stage SDA unit. In yet another embodiment, all the fresh catalyst is sent to the contact zone (s) different from the first in the system, with the first contact zone that obtains only the SDA funds from the SDA unit and the recycled catalyst originating from the SDA unit. of one or more of the processes in the system, for example, from one of the separation zones in the system.

In one embodiment, the fresh catalyst is combined with the recycled catalyst stream from one of the processes in the system, for example, a separation zone, a distillation column, an SDA unit, or a flash expansion tank, and the combined catalyst feed is thereafter mixed with the heavy oil feedstock to be fed into the contact zone (s). In yet another embodiment, the fresh catalyst and the recycled catalyst streams are mixed in the heavy petroleum feedstock as separate streams.

In one embodiment, the recycled catalyst stream from the processes in the system, for example, a separation zone, the SDA unit, etc., is combined with the fresh suspension catalyst, as a simple catalyst feed stream. The combined catalyst feed is thereafter mixed with the heavy oil feed stream (s) (treated or untreated) to be fed into the contact zone (s). In yet another embodiment, the fresh catalyst and the recycled catalyst streams are mixed in the stream (s) of the heavy petroleum feedstock as separate streams.

In one embodiment, the process is configured for a flexible catalyst feed scheme, such that the catalyst feed can sometimes be fed at full speed (100% of the required catalyst speed) to the first reactor in the system by a certain period of time, then divided equally or according to the predetermined proportions to all the reactors in the system for a predetermined amount of time, or divided according to the predetermined proportions for the feed of catalyst to be fed to the Different reactors at different concentrations.

In one embodiment, the delivery of different catalysts to the contact areas of the front end and the trailing end may be useful in mitigating vanadium entrapment production and sustain overall breeding performance. In one embodiment, a nickel-only or nickel-containing NiMo sulphide catalyst is sent to the front end reactor to help reduce the entrapment of vanadium in the system, while a different catalyst, for example, the molybdenum sulphide or a NiMo sulphide catalyst rich in molybdenum can be injected into or from the rear end reactors to maintain a high overall conversion rate, to improve product quality and possibly to reduce gas performance in a modality. As used herein, a nickel-rich suspension catalyst means that the nickel / molybdenum ratio is greater than 0.15 (as% by weight). Conversely, a suspension catalyst rich in molybdenum means that the nickel / molybdenum ratio is less than 0.05 (as% by weight).

In one embodiment, the suspension catalyst feed is first preconditioned before entering one of the contact zones, or before being put in contact with the heavy oil feed before entering the contact zones. In one example, the catalyst enters a pre-conditioning unit together with the hydrogen at a rate of 500 to 7500 SCF / BBL (BBL here refers to the total volume of the heavy oil feed to the system). It is believed that instead of putting a cold catalyst in contact with the heavy oil feed, the pre-conditioning step helps with the adsorption of hydrogen to the active catalyst sites, and ultimately at the conversion rate. In one embodiment in the pre-conditioning unit, the suspension / hydrogen catalyst mixture is heated to a temperature between 149 to 538 ° C (300 ° F to 1000 ° F). In yet another embodiment, the catalyst is pre-conditioned in hydrogen at a temperature of 260 to 385 ° C (500 to 725 ° F). In yet another embodiment, the mixture is heated under a pressure of 2.06 to 22.06 mPa (300 to 3200 psi) in a; 3.44 to 20.69 mPa (500-3000 psi) in a second mode; and 4.14-17.24 mPa (600-2500 psi) in a third mode.

Catalysts Used: The suspension catalyst comprises an active catalyst in a hydrocarbon oil diluent. In one embodiment, the catalyst is a sulfided catalyst comprising at least one Group VIB metal, or at least one Group VIII metal, or at least one Group IIB metal, for example, a ferric sulphide catalyst, zinc sulfide. , nickel sulphide, molybdenum sulphide, or an iron and zinc sulfide catalyst. In yet another embodiment, the catalyst is a multi-metal catalyst comprising at least one Group VIB metal and at least one Group VIII metal (as a promoter), wherein the metals may be in elemental form or in the form of a metal compound. In one example, the catalyst is an MoS2 catalyst promoted with at least one Group VIII metal compound.

In one embodiment, the catalyst is a bulk multi-metal catalyst comprising at least one non-noble metal of Group VIII and at least two metals of Groups VIB, and wherein the proportion of at least two metals of Group VIB to the metal does not noble of Group VIII is from about 10: 1 to about 1:10. In still another embodiment, the catalyst is of the formula (Mc) a (Xu) b (Sv) d (Cw) e (Hx) f (0y) g (Nz) h, wherein M represents at least one metal of the Group VIB metal, such as molybdenum, tungsten, etc., or a combination thereof; and X functions as a metallic promoter, which represents at least one of: a non-noble metal of Group VIII such as nickel, cobalt; a Group VIII metal such as iron; a metal of Group VIB such as chromium; a Group IVB metal such as titanium; a metal of Group IIB such as zinc, and combinations thereof (X is hereinafter referred to as "Metal Promoter"). Also in the equation, t, u, v, w, x, y, z represent the total charge for each of the components (M, X, S, C, H, 0 and N, respectively); ta + ub + vd + we + xf + yg + xh = 0. The proportion of the subscripts from b to a has a value from 0 to 5, and (0 < = b / a < = 5). S represents sulfur with the value of the subscript d in the range from (a + 0.5b) to (5a + 2b). C represents the carbon with the subscript e that has a value of 0 to 1 1 (a + b). H is hydrogen has the value of f with the interval from 0 to 7 (a + b). 0 represents oxygen has the value of g with the range from 0 to 5 (a + b); and N represents nitrogen with h having a value from 0 to 0.5 (a + b). In one embodiment, the subscript b has a value of 0, for a catalyst of a single metal component, for example, only molybdenum catalyst (without promoter).

In one embodiment, the catalyst is prepared from catalyst precursor compositions that include complexes or organometallic compounds, for example, oil soluble compounds or complexes of the transition metals and organic acids. Examples of such compounds include naphthenates, pentanediones, octoates, and acetates of Group VIB and Group VIII metals such as molybdenum, cobalt, tungsten, etc., such as molybdenum naphthanate, vanadium naphthanate, vanadium octoate, hexacarbonyl molybdenum, and vanadium hexacarbonyl.

In one embodiment, the catalyst is an MoS2 catalyst, promoted with at least one Group VIII metal compound. In yet another embodiment, the catalyst is a bulk multi-metal catalyst, wherein the bulk multi-metal catalyst comprises at least one non-noble metal of a Group VIII and at least two metals of Group VIB and wherein the proportion of at least two metals of Group VIB at least one non-noble metal of Group VIII is from about 10: 1 to about 1:10.

In one embodiment, the catalyst feed comprises the suspension catalyst having a particle size of at least 1 micrometer in a hydrocarbon oil diluent. In yet another embodiment, the catalyst feed comprises the suspension catalyst having an average particle size in the range of 1-20. In a third modality, the suspension catalyst has an average particle size in the range of 2-10 microns. In one embodiment, the feed comprises a suspension catalyst having an average particle size in the colloidal range (nanometric size) up to about 1-2 microns. In yet another embodiment, the catalyst comprises catalyst molecules and / or extremely small particles that are colloidal in size (eg, less than 100 nm, less than approximately 10 nm, less than approximately 5 nm, and less than about 1 nm). In operations, the colloidal / nanometric size particles are added in a hydrocarbon diluent, forming a suspension catalyst with an average particle size in the range of 1-20 microns. In yet another embodiment, the catalyst groups of single layer MoS2 of nanometric sizes, for example, 5-10 nm on the edge.

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

In one embodiment, the amount of the fresh catalyst feed to the contact zone (s) is in the range of 50 to 15,000 wppm molybdenum (concentration in the heavy oil feed). In a second embodiment, the concentration of fresh catalyst feed is in the range of 150 to 2000 wppm molybdenum. In a third mode, from 250 to 5000 wppm of molybdenum. In a fourth embodiment, the concentration is less than 10,000 wppm molybdenum. The concentration of the fresh catalyst within each contact zone can vary, depending on the contact zone used in the system, since the catalyst can become more concentrated as the volatile fractions are removed from a non-volatile waste fraction, requiring this adjustment of the catalyst concentration.

Optional Treatment System-SDA: In one embodiment of the invention, a solvent de-escalation unit (SDA) is employed before the first contact zone to pre-treat the heavy oil feedstock. In yet another embodiment, a solvent de-escalation unit is employed as an intermediate unit located after one of the intermediate separation zones.

SDA units are typically used in refineries to extract lighter hydrocarbons in increments, from a heavy hydrocarbon stream, whereby the extracted oil is typically called deasphalting oil (DAO), while a residual stream is left behind. it is more concentrated in molecules and heavy heteroatoms, typically known as SDA tar, SDA funds, etc. The SDA can be a separate unit or an integrated unit within the improvement system.

Various solvents can be used in the SDA, ranging from propane to hexanes, depending on the desired level of deasphalting before feeding the contact area. In one embodiment, the SDA is configured to produce a deasphalted oil (DAO) to mix with the catalyst feed or feed directly into the contact zones instead of, or in addition to the heavy oil feed. As such, the type of solvent and operating conditions can be optimized such that DAO is produced in high volume and in acceptable quality and fed into the contact zone. In this embodiment, a suitable solvent to be used includes, but is not limited to hexane or a similar solvent of more than 6 carbon atoms for a low volume SDA tar and high volume DAO. This scheme could allow the vast majority of the heavy oil feed to be improved in the subsequent contact zone, while the heavier bottom of the barrel does not produce favorable conversion economy in increments, due to the massive requirement of addition of oil. hydrogen, be used in some other way.

In one embodiment, all of the heavy oil feed is pre-treated in the SDA and the DAO product is fed into the first contact zone, or fed according to a split feed scheme with at least one portion going towards a contact area different from the first in the series. In yet another mode, some of the heavy oil feed (depending on the source) is the first to be pre-treated in the SDA and some of the feed material is fed directly to the untreated contact zone or zones. In yet another embodiment, the DAO is combined with the untreated heavy oil feedstock as a feed stream to the contact zone (s). In yet another embodiment, the DAO and the untreated heavy oil feedstock are fed into the system as in separate feed conduits, with the DAO going to one or more of the contact areas and feeding the untreated heavy oil. which goes to one or more of the same or different contact zones.

In an embodiment where the SDA is employed as an intermediate unit, the non-volatile fraction containing the catalyst in suspension and optionally minimum amounts of coke / asphaltenes, etc., from at least one of the separation zones, is sent to the SDA for treatment. From the SDA unit, the DAO is sent to at least one of the contact zones as a feed stream by itself, in combination with a heavy oil feed material as a feed, or in combination with the feed stream. bottom coming from one of the separation zones as a feed. DA funds containing asphaltenes are shipped away for the recovery of metals in any remaining slurry catalyst, or for applications that require asphaltenes, for example, mixed with fuel oil, used in asphalt, or used in some other applications.

In one embodiment, the quality of the DAO and the DA funds is varied by adjusting the solvent used and the desired recovery of the DAO in relation to the heavy oil feed. In an optional pretreatment unit such as the SDA, the more DAO oil is recovered, the poorer the overall quality of the DAO, and the poorer the overall quality of the DA funds. With respect to solvent selection, typically, since 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, but the quality will be lower. This is due to, among other factors, the solubility of asphaltenes and other heavy molecules in the solvent.

Heavy Metal Tank Control - Optional Water Injection: As used herein, the front end contact zone (or the first contact zone) means the first reactor in a system with three or less contact zones. In yet another embodiment of a system with more than three contact zones, the first contact area of the front end may include the first and second reactors. In yet another embodiment, the first contact zone means the first reactor only.

As used herein, the term "water" is used to indicate either water and / or steam. In one embodiment, to control the deposit of heavy metals, the water is optionally injected into the system. In one embodiment, the injection is a ratio of about 1 to 25% by weight (relative to the heavy petroleum feedstock). In one embodiment, a sufficient amount of water is injected for a water concentration in the system in the range of 2 to 15% by weight. In a third embodiment, an amount sufficient for a water concentration in the range of 4 to 10% by weight is injected.

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

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

In one embodiment, the water is added directly into the contact zone at multiple points along the contact zone, in proportion of 1 to 25% by weight of the heavy oil feed material. In another modality, water is added directly into the first few contact zones in the process, which are the most prone to heavy metal deposits.

In one embodiment, some of the water is added to the process in the form of dilution vapor. In one embodiment, at least 30% of the added water is in the vapor form. In the modalities where the water is added as the dilution vapor, the steam can be added at any point in the process. For example, it can be added to the heavy oil feedstock before or after preheating, the steam mixed with catalyst / heavy oil and / or directly into the vapor phase of the contact zones, or at multiple points to along the first contact zone. The dilution vapor stream may comprise process steam or clean steam. The steam can be heated overheated in an oven before being fed into the brewing process.

It is believed that the presence of water in the process favorably alters the molecular balance of the sulfur of the metal compound, thereby reducing the deposition of heavy metals. In one embodiment, it is believed that the addition of water also helps control / maintain a desired temperature profile in the contact zones. In yet another embodiment, it is believed that the addition of water to the contact zone (s) of the front end decreases the temperature of the reactor (s). Since the temperature of the reactor is lowered, it is believed that the reaction rate of the more reactive vanadium species decreases, allowing the deposition of vanadium on the suspended catalyst to proceed in a more controlled manner and for the catalyst to carry the deposits of vanadium outside the reactor, and thus limiting the deposit of solids in the reactor equipment.

In one embodiment, the addition of water reduces the heavy metal deposits in the reactor equipment by at least 25% compared to an operation without the addition of water, for a comparable period of time in operation, for example, by at least 2 months In yet another embodiment, the addition of water reduces heavy metal deposits of at least 50% compared to an operation without the addition of water. In a third embodiment, the addition of water reduces the heavy metal deposits by at least 75% compared to an operation without the addition of water.

Control of the Heavy Metal Tank with the Reactor Temperature: In one mode, instead of and / or in addition to the addition of the water to the contact zone (s) of the front end, the temperature of the end contact zone (s) frontal, more prone to heavy metal deposits, is diminished.

In one embodiment, the temperature of the first reactor is adjusted to be at least 5.56 ° C (10 ° F) lower than the next reactor in the series. In a second embodiment, the first reactor temperature is adjusted to be at least 8.33 ° C (15 ° F) lower than the next reactor in the series. In a third embodiment, the temperature is adjusted to be at least 11.11 ° C (20 ° F) lower. In a fourth embodiment, the temperature is adjusted to be at least 12.89 ° C (25 ° F) lower than the next reactor in the series.

Control of the Deposit of Heavy Metals with the Recycled Catalyst Current: In one embodiment, at least a portion of the non-volatile stream from at least one of the separation zones and / or an intra-stage de-asphalting unit is recycled back to the area or contact zones of the front end to control heavy metal deposits.

In one embodiment, this recycled stream is in the range of 3 to 50% by weight of the total heavy oil feed material to the process. In a second embodiment, the recycled stream is an amount in the range of 15 to 45% by weight of the total heavy oil feed material to the system. In a fourth embodiment, the recycled stream is at least 10% by weight of the total heavy oil feed material to the system. In a fifth embodiment, the recycled stream is 25 to 45% by weight 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 non-volatile materials from the last separation zone in the system, which contains unconverted materials, hydrody-disintegrated liquid products, heavier ones, suspended catalyst, small amounts of coke, asphaltenes, etc. In one embodiment, the recycled stream contains between 3 to 30% by weight of catalyst in suspension. In yet another embodiment, the amount of catalyst is in the range of 5 to 20% by weight. In yet another embodiment, the recycled stream contains 1 to 15% by weight of the catalyst in suspension.

In some embodiments, it is believed that with the additional recycle catalyst, provided by the recycled stream, more catalytic surface area (via the catalyst in suspension in the recycled stream), it is available to disperse the deposition of heavy metals, and thus exists less entrapment or deposition on the equipment. The additional surface areas of catalyst, provided by the recycled stream, help to minimize the overload of the catalyst surface with the deposit of heavy metals, driving the deposition on the process equipment (walls, internal, etc.).

Process Conditions: In one modality, the process condition is controlled to be more or less uniform through the contact zones. In another modality, the condition varies between the contact zones for the improved products, with specific properties.

In one embodiment, the breeding system is maintained under hydrodisintegration conditions, for example, at a minimum temperature to effect the hydrodisintegration of a heavy oil feedstock. In one embodiment, the system operates at a temperature in the range of 400 ° C (752 ° F) to 600 ° C (1112 ° F), and a pressure in the range of 10 mPa (1450 psi) to 25 mPa (3625) psi). In one embodiment, the process conditions are controlled to be more or less uniform through the contact zones. In another modality, the condition varies between the contact zones for improved products, with specific properties.

In one embodiment, the process temperature of the contact zone is in the range of about 400 ° C (752 ° F) to about 600 ° C (1112 ° F), less than 500 ° C (932 ° F) in another modality, and greater than 425 ° C. (797 ° F) in another mode. In one embodiment, the system operates with a temperature difference between the input and output of a contact zone in the range of 2.75 to 27.7 ° C (5 to 50 ° F). In a second mode, from 5.55 to 22.2 ° C (10 to 40 ° F).

The temperature of the separation zone is maintained within approximately + 50 ° C (± 90 ° F) of the contact zone temperature in one mode, within approximately 38.9 ° C (± 70 ° F) in a second mode, within of about ± 8.3 ° C (± 15 ° F) in a third mode, and within about + 2.8 ° C (± 5 ° F) in a fourth mode. In one embodiment, the temperature difference between the last separation zone and the immediately preceding contact zone is within ± 28 ° C (± 0 ° F).

The process pressure in the contact zones is in the range of about 10 mPa (1,450 psi) to about 25 mPa (3.625 psi) in one embodiment, about 15 mPa (2,175 psi) to about 20 mPa (2,900 psi) in one embodiment. second mode, less than 22 mPa (3,190 psi) in a third mode, and more than 14 mPa (2,030 psi) in a fourth mode. In one embodiment, the pressure of the separation zone is maintained within ± 0.069 mPa to ± 0.344 mPa (± 10 to ± 50 psi) of the preceding contact zone in one embodiment, and within ± 0.014 mPa to + 0.069 mPa (+ 2 to + 10 psi) in a second mode.

In one embodiment, the improvement system is configured for optimal operation, for example, efficiency with much less time lost due to plugging of the equipment compared to the prior art with a pressure drop of less than 0.689 mPa (100 psi). The optimum efficiency is obtained in a mode with minimum pressure drop in the system, where the pressure of the separation zone is maintained within ± 0.069 to ± 0.689 mPa) ± 10 to ± 100 psi) of the preceding contact zone in one mode, within ± 0.138 to ± 0.517 mPa (± 20 to ± 75 psi) in a second mode, and within ± 0.344 to + 0.689 mPa (± 50 to ± 100 psi) in a third mode. As used herein, the pressure drop refers to the difference between the outlet pressure of the preceding contact zone X and the inlet pressure of the separation Y, with (XY) being less than 0.689 mPa (100 psi) .

The optimum efficiency can also be obtained with minimum pressure from one contact zone to the next contact zone for a system operating sequentially, with the pressure drop being maintained as 0.689 mPa (100 psi) or less in one mode, and 0.517 mPa (75 psi) or less in a second mode, and less than 0.344 mPa (50 psi) in a third mode. The pressure drop in the present refers to the difference between the outlet pressure of a contact zone and the inlet pressure of the next contact zone.

In one embodiment, the contact zone is in direct fluid communication with the next separation zone or the contact zone for a minimum pressure drop. As used herein, direct fluid communication means that there is free flow from the contact zone to the next separation zone (or the next contact zone) in series, without flow restriction. In one embodiment, direct fluid communication is obtained without flow restriction due to the presence of valves, orifices (or a similar device), or changes in the diameter of the tube.

In one embodiment, the minimum pressure drop from the contact zone to the next separation zone or the contact zone (after entering the separation zone or the contact zone) is due to the components of the pipeline , for example, elbows, turns, tees on the line, etc., and not due to the use of the pressure reducing device, such as valves, control valves, etc., to induce pressure drop as in the prior art. In the prior art, it was thought that the separation zone functions as an interstage pressure differential separator.

In one embodiment, the minimum pressure drop is induced by friction loss, wall drag, volume increase, and changes in height as the effluent flows from the contact zone to the next equipment in the series. If valves are used in the system from side to side, the valves are selected / configured such that the pressure drop of one piece of equipment, for example, the contact area, towards the next piece of equipment, is maintained to be 0.689 mPa (100 psi) or less.

In one embodiment, the liquid space velocity per hour (LHSV) of the heavy oil feed in general will be in the range of about 0.025 h "1 to about 10 h" 1, about 0.5 h "1 to about 7.5 h" 1, approximately 0.1 h-1 to approximately 5 h "1, approximately 0.75 h'1 to approximately 1.5 h" 1, or approximately 0.2 h "1 to approximately 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- \ or at least 2 h" 1. In some modalities, 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 to 3 LHSV. In another modality, the LHSV is less than 0.5 h "1.

In a modality in which all the currents of the non-volatile fractions coming from at least one separation zone are sent to the SDA unit for deasphalting, the deposit of solid in the last contact zone in the system decreases by at least 10% (in terms of the volume of the deposit) after a similar running time compared to a prior art operation without de-asphalting with the SDA unit. In a second embodiment, the solid deposit decreases by at least 20% compared to an operation without the use of the inter-stage SDA unit. In a third embodiment, the deposit of solid decreases at least 30%.

In various modalities, it was found that by deviation from something, if not all the fresh catalyst towards the contact zone or zones different from the first in the system, the overall disintegration efficiency of the heavy oil feed material was not noticeably completely impacted, in comparison to the feeding scheme of the prior art with all the fresh catalyst going to the first contact zone. In one embodiment, the displacement of the injection position of the fresh catalyst produces a significant reinforcement in the overall catalytic activity, with the improved quality of the nonvolatile current of the last separation zone in the system (purge stream, "Funds"). of the Debugger "or STB) in terms of API, viscosity, MCR level, nickel, hydrogen / carbon ratio, and hot asphaltene heptane (HHA) level. In some other embodiments, less purging of the catalyst is also observed with general improvement in catalytic activity.

In one embodiment, the STB product improvements include a nickel reduction of at least 10%, in a second mode, a nickel reduction of at least 20%. In a third embodiment, a nickel level of less than 10 ppm.

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

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

In embodiments with a heavy oil split feed scheme, it is found that by diverting a portion of the heavy oil feed material from the first contact zone into at least one other contact zone in the series, the total coke formation is substantially reduced compared to the prior art feed scheme, with all the heavy oil feed material going to the first contact zone. Furthermore, with at least a portion of the heavy oil feedstock being diverted to the contact zones different from the first in the system, there is some dilution of the liquid in these contact zones (which may not have been present in the scheme). of the prior art). The dilution with liquid allows a more uniform concentration profile of the catalyst through all the reactors in the system, thus protecting the last reactor against the excursion of the solids level, which could lead to operational problems.

In some modalities with a split heavy oil feed scheme, it is also observed that the total efficiency of the system improves as the conversion level in the reactors (contact zones) increases, allowing the additional vaporization of the oil and the corresponding decrease in the liquid yield and the increase in the catalyst concentration. This could essentially reinforce the efficiency of the system with lower liquid performance (or a higher residence time of liquid) and higher catalyst concentration. In addition, with a second feed rate of heavy oil at rest, directly within the last reactor, the last reactor is protected against conditions of upset that could deprive this vessel of liquid flow. Therefore, the heavy oil split feed scheme reduces or eliminates the "overconversion events" or "dry" conditions often observed in hydroprocessing reactors. In the breeding system that runs under "dry" conditions, it presents insufficient liquid flow, thus leading to solids accumulation / coking, degrading flow patterns and / or hydrodynamics, degrading thermometry, loss of volume reaction, operation, stability and longevity of the operation eventually compromised.

Figures illustrating the modalities: Reference will now be made to the figures to further illustrate the embodiments of the invention.

Figure 1 is a block diagram schematically illustrating a system for improving heavy petroleum feedstock with reduced heavy metal deposits. First, a heavy oil feedstock is introduced into the first contact zone in the system, along with a suspension catalyst feed. In the Figure, the suspension catalyst feed comprises a combination of fresh catalyst and recycled catalyst in suspension, as separate streams. The hydrogen can be introduced together with the feed into the same conduit, or optionally, as a separate feed stream. Water and / or steam can be introduced together with the feed and the catalyst in suspension in the same conduit, or in a separate feed stream. Although not shown, the water mixture, the heavy oil feed, and the suspension catalyst can be preheated in a heater before feeding into the contact zone. Although not shown, the additional feed of hydrocarbon oil, eg, VGO, naphtha, in an amount in the range of 2 to 30% by weight of the heavy oil feed, can optionally be added as part of the feed stream to any of the contact zones in the system.

Although not shown in the Figures, the system may comprise recirculation / recycling channels and pumps to promote the dispersion of reactants, catalyst and heavy oil feedstock in the contact zones, particularly with a high flow rate of recirculation to the first contact zone, to induce turbulent mixing in the reactor, thereby reducing the heavy metal deposits. In one embodiment, a recirculation pump circulates through the loop reactor, thereby maintaining a temperature difference between the feed point of the reactor to the exit point in the range of 0.55 to 27.77 ° C (1 to 50 °). F), and preferably between 1.11 and 13.88 ° C (2 to 25 ° F).

In the contact zones under hydrodisintegration conditions, at least a portion of the heavy oil feed material (hydrocarbons of higher boiling point) is converted to lower boiling hydrocarbons, forming an improved product. It is expected that the water / vapor in the first contact zone reduces the heavy metal deposits on the equipment. Although not illustrated, the temperature of the first contact zone can be maintained at least 2.77 to 13.88 degrees Centigrade (5 to 25 degrees (Fahrenheit) less than the temperature of the next contact zone in the series.

The improved material is removed from the first contact zone and sent to a separation zone, for example, a hot separator, operated at a high temperature and high pressure, similar to the contact zone. The improved material can alternatively be introduced into one or more additional hydroprocessing reactors (not shown) to further improve before going to the hot separator. The separation zone causes or allows separation of the gas and volatile liquids from the non-volatile fractions. The gaseous and volatile liquid fractions are removed from the upper part of the separation zone for further processing. The nonvolatile fraction (or less volatile) is removed from the bottom.

The catalyst in suspension and the entrained solids, the coke, the newly generated hydrocarbons in the hot separator, etc., are removed from the bottom of the separator and fed to the next contact zone with the series. In one embodiment (not shown), a portion of the non-volatile stream is recycled back to one of the contact zones preceding the separation zone, providing recycled catalyst for use in the hydroconversion reactions.

In one embodiment (as indicated by dashed lines), portions of the fresh catalyst feed and the heavy oil feed material are directly fed into the contact zones (reactors), different from the first contact zone in the system. In one embodiment, wherein portions of the heavy oil feedstock are fed directly into the contact zones, other than the first contact zone, water and / or steam is also provided to the contact zones as a current of separate feeding, or introduced together with the feeding and the catalyst in suspension in the same conduit.

The liquid stream from the preceding separation zone is combined with optional fresh catalyst, optional additional heavy oil feed, optional hydrocarbon oil feed such as VGO (vacuum gas oil), and optionally recycled catalyst (not shown) as the feed current for the next contact zone in the series. The hydrogen can be introduced together with the feed into the same conduit, or optionally as a separate feed stream. The improved materials together with the suspended catalysts flow into the next separation zone in the series, for the separation of the gas and volatile liquids from the non-volatile fractions. The gaseous and volatile liquid fractions are removed from the upper part of the separation zone and combined with the gaseous and volatile liquid fractions from a preceding separation zone, for further processing. The current of the non-volatile (or less volatile) fraction is removed and sent to the next contact zone in the series, so that the heavy, non-converted petroleum feedstock is improved.

In the last contact zone, the hydrogen is added together with the unconverted heavy oil feedstock, the additional, optional heavy oil feedstock, optional VGO feedstock, and optional fresh catalyst. The improved materials flow to the next separation zone along with the suspension catalyst, where the improved products are removed at the top, and a portion of the non-volatile materials is recycled. In one embodiment, the recycled stream is sent to the first contact zone, providing some recycled catalyst for use in the hydroconversion reactions. In a second mode, the recycled stream is divided between the contact zones that precede the last contact zone in the series.

In one embodiment, the system may optionally comprise an in-line hydrotreater (not shown) for treating gaseous and volatile liquid fractions from the separation zone. The in-line hydrotreater, in one embodiment, employs conventional hydrotreating catalysts, and is operated at a similarly high pressure (within 0.069 Mpa (10 psig)) as the rest of the breeding system, and capable of eliminating sulfur, nickel, vanadium and other impurities of the improved products. In yet another embodiment, the online hydrotreater operates at a temperature within 55.5 ° C (100 ° F) of the contact zone temperature.

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

The stream 4 comprising the improved heavy petroleum feedstock leaves the contact zone R-10 and flows to a separation zone 40, where the gases (including hydrogen) and the improved products in the form of volatile liquids , they are separated from the non-volatile liquid fraction 7 and withdrawn at the top as the current 6. The non-volatile stream 7 is sent to the next contact zone 20 in the series for further improvement. The non-volatile stream 7 contains catalyst in suspension in combination with unconverted oil together with unconverted oil, and small amounts of coke and asphaltenes in some embodiments.

The improvement process continues with the other contact zones as shown, wherein the feed stream to the contact zone 20 comprises non-volatile fractions, hydrogen feed, optional VGO feed, and fresh catalyst feed 32. From from the contact zone 20 the stream 8 comprising the improved heavy petroleum feed material flows into the separation zone 50, where the improved products are combined with hydrogen and withdrawn as product 9 from the top. The bottom stream 11 containing the non-volatile fractions, for example the catalyst suspension, the unconverted petroleum containing coke and the asphaltenes, flows to the next contact zone in the series 30.

In the contact zone 30, the gas 16 containing additional hydrogen, the fresh catalyst 33, the optional hydrocarbon feed, such as VGO (not shown), the untreated, optional heavy oil feed (not shown), are added. to the non-volatile current from the preceding separation zone. From the contact zone 30, the improved products, the unconverted heavy oil, the suspended catalyst, the hydrogen, etc., are removed from the top as the stream 12, and sent to the next separation zone 60. From the separator, the upper stream 13 containing hydrogen and improved products, is combined with the higher streams from the preceding separation zones, and sent away for subsequent processing in another part of the system, for example, to a separator. high pressure and / or a thin oil contactor and / or an online hydrotreater (not shown). A portion of the non-volatile stream 17 is removed as the purge stream 18. The remainder is recycled back to at least one of the contact zones (first contact zone 10 as shown) as a stream of recycled catalyst.

Figure 3 is a flow chart of yet another embodiment of the heavy oil upgrading process, but with steam injection 91 instead of / or in addition to the water injection stream 81.

Figure 4 is a flow chart of yet another embodiment of the heavy oil upgrading process, with a stream of recycled catalyst 19 in the range of 3 to 50% by weight of the total heavy oil feedstock for the process.

Figure 5 is a block diagram schematically illustrating yet another embodiment for improving the heavy oil feedstock. First, a heavy oil feedstock is introduced into the first contact zone in the system, along with a suspension catalyst feed. The hydrogen can be introduced together with the feed into the same conduit, or optionally, as a separate feed stream. In one embodiment (not shown), the optional hydrocarbon oil feedstock, such as VGO (vacuum gas oil), naphtha, MCO (middle cycle oil), solvent donor, or other aromatic solvents etc., in an amount in the range of 2 to 30% by weight of the heavy oil feed. The additional heavy oil feedstock can be used to modify the concentration of metals and impurities in the system. In the contact zones under hydrodisintegration conditions, at least a portion of the heavy oil feed material (hydrocarbons of higher boiling point) is converted to lower boiling hydrocarbons, forming an improved product.

The improved material is removed from the first contact zone and sent to a separation zone, for example, a hot separator. The improved material may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further improvement before going to the hot separator. The separation zone causes or allows separation of the gas and volatile liquids from the non-volatile fractions. The liquid and volatile fractions are removed from the upper part of the separation zone for further processing. The nonvolatile fraction (or less volatile) is removed from the bottom. The catalyst in suspension, small quantities of liquid, hydrodisintegrated, heavier products, and entrained solids, coke, newly generated hydrocarbons in the hot separator, etc., are removed from the bottom of the separator and fed to the next contact zone in the Serie. In one embodiment (not shown), a portion of the non-volatile stream is recycled back to the contact zone 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 combined with the additional fresh catalyst, the optional additional heavy oil feed, and optionally the recycled catalyst (not shown) as the feed stream for the next contact zone in the series.

In the next contact zone and under hydrodresintegration conditions, more of the heavy oil feed material is upgraded to lower boiling hydrocarbons. The improved materials together with the suspended catalyst flow to the next separation zone in the series, for the separation of the gas and the volatile liquids from the non-volatile fractions. The non-volatile (or less volatile) current is removed from the bottom. Gaseous and volatile liquid fractions are removed from the upper part of the separation zone (and combined with gaseous and volatile liquid fractions from a preceding separation zone) as "improved" products for further processing and mixing, for example, for final mixed products that meet the specifications designated by the refineries and / or transportation carriers.

In one embodiment (not shown), non-volatile material containing unconverted materials is sent to the next contact zone in the series. In yet another embodiment as shown, the non-volatile material is recycled back to one of the contact zones in the system, with a portion of the material being purged for further processing, for example, going to a de-asphalting unit with solvent, a catalyst de-oiling unit and subsequently a metal recovery system. The non-volatile material recycled in one embodiment is an amount equivalent to 2 to 50% by weight of the heavy oil feedstock to the system, providing recycled catalyst, for use in the hydroconversion reactions.

Depending on the operating conditions, the type of catalyst fed into the contact zone and the concentration of the catalyst in suspension, in one embodiment, the output current from the contact zone comprises a ratio of 20:80 to 60: 40 of the products improved to the feeding of heavy oil not converted. In one embodiment, the amount of the improved products from the first contact zone is in the range of 30-35% to the non-converted heavy oil product of 65-70%.

Although not shown in the figures, the system can optionally comprise recirculation / recycling channels and puto promote the dispersion of the reagents, the catalyst and the heavy oil feed material in the contact zones. In one embodiment, a recirculation pump circulates through a loop reactor, a volumetric flow ratio of 5: 1 to 15: 1 (ratio amount recirculated to heavy oil feed), thereby maintaining a temperature difference between the point of feed of the reactor to the point of exit in the range of 5.5 to 27.7 ° C (10 to 50 ° F), and preferably between 11.1 to 22.2 ° C (20-40 ° F).

In one embodiment, the system may optionally comprise an inline hydrotreater (not shown) for treating gaseous and volatile liquid fractions from the separation zone. The online hydrotreator, in one mode, uses conventional hydrotreating catalysts, is operated at a similarly high pressure (within 0.069 MPa (10 psig) in one mode, and 0.34 MPa (50 psig) in a second mode) as the rest of the improvement system, and capable of eliminating the sulfur, nickel, vanadium and other impurities of the improved products.

Figure 6 is a block diagram schematically illustrating yet another embodiment of an improvement system, wherein a solvent deasphalting unit is employed to pretreat something, if not all of the heavy oil feed into the system. The deasphalted oil (DAO) can be fed directly to the contact zone (s), and combined with a heavy oil feed stream as a feedstock. In some embodiments, other hydrocarbon materials, for example VGO, may also be combined with the heavy oil feed, and / or the DAO as the feed material for some of the contact zones. All fresh catalyst can be fed directly to the first contact zone in the system, or diverted to another or other contact zones in the series.

Figure 7 is a flowchart of a heavy oil upgrading process with a split feed scheme of fresh catalyst, where some of the fresh catalyst feed is diverted from the first reactor to another reactor in the process. As shown, the fresh catalyst feed is divided among the various contact zones as feed streams 31, 32, and 33. The fresh catalyst feed 31 is combined with the recycle catalyst stream 17 and fed into the first zone. of contact as feed 3 of catalyst in suspension. The hydrogen gas 2 and the heavy oil feed material 1 are combined with the suspended catalyst 3 as the feed into the first contact zone 10. In this embodiment, the heavy oil feed material is preheated in the furnace 80 before being introduced into the contact zone as hot oil feed 4.

The stream 5 comprising the improved heavy oil feedstock leaves the contact zone 10 and flows into a separation zone 40, where the gases (including hydrogen) and the volatile improved products are separated from the non-volatile fractions. 7 and removed from the top as the current 6. The stream 7 of non-volatile fractions is sent to the next contact zone 20 in the series, for further improvement. Stream 7 contains catalyst in suspension in combination with unconverted petroleum, and small amounts of coke and asphaltenes in some embodiments.

The improvement process continues with the other contact zones as shown, where the stream 7 is combined with the hydrogen feed 15 and the fresh catalyst 32, as the feed stream to the contact zone 20. Although not shown , the currents can also be fed to the contact area in separate conduits. The stream 8 comprising the improved heavy oil feedstock flows into the separation zone 50, where the improved products are combined with the hydrogen and removed as product 9 from the top. The bottom stream 11 containing catalyst in suspension, unconverted oil (smaller amounts of coke and asphaltenes in some embodiments) is combined with a stream 33 of fresh catalyst and a fresh supply of hydrogen 16 as the feed stream to the next contact zone 30. Current 12 leaves the contact zone and flows into the separation zone 60, where the improved products and hydrogen are removed at the top as the stream 13. Some of the lower stream 17 coming from the separation zone, containing the catalyst suspension, unconverted oil, smaller amounts of coke and Asphaltenes in some embodiments, it is recycled back to the first contact zone 10 as the recycled stream 19. The rest of the bottom stream 17 is withdrawn as the purge stream 18 and sent to other processes in the system for catalyst de-aeration , the recovery of metals etc. Although not shown, the vapor stream 14 containing the improved products and hydrogen in one embodiment is subsequently processed in another part of the system, for example, in a high pressure separator and / or thin oil contactor.

Figure 8 illustrates yet another embodiment of the invention, where reactors having internal spacers are employed, thus hot spacers / sudden expansion drums are not necessary for phase separation. In this improvement system, a reactor differential pressure control system (not shown) is used, which regulates the product stream from the top of each reactor-separator. External pumps (not shown) can be employed to assist in the dispersion of the catalyst in suspension in the system, and help control the temperature in the system.

In the embodiment of Figure 8 as shown, all fresh catalyst is diverted to the second and third contact zones in the system. The recycle catalyst stream 19 provides the catalyst feed in suspension to the first contact zone, and optionally, to another or other contact zones in the system. Also as shown, the supply of additional hydrocarbon oil, for example VGO, naphtha, in an amount in the range of 2 to 30% by weight of the heavy oil feed, can be optionally added as part of the feed stream to any of the contact zones in the system.

Figure 9 illustrates an embodiment of the invention wherein all the feed 99 of the fresh catalyst is fed directly to the last contact zone in the breeding system, with another or other contact zones in the system that simply obtain a portion of the 19 stream of recycled catalyst.

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

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

Comparative Example 1: Heavy oil upgrading experiments were carried out in a pilot system having three gas-liquid suspension phase reactors connected in series with three hot separators, each being connected in series with the reactors.

The breeding system was run continuously for approximately 50 days.

A fresh suspension catalyst, used, was prepared according to the teaching of United States Patent No. 2006/0058174, for example a molybdenum compound was first mixed with aqueous ammonia to form an aqueous mixture of the sulfur-containing molybdenum compound with the hydrogen compound, promoted with a nickel compound, and then transformed into a hydrocarbon oil (different from the heavy oil feed material) at a temperature of at least 176.6 ° C (350 ° F) and a pressure of at least 1.38 MPa (200 psig), forming an active suspension catalyst to send to the first reactor.

The hydroprocessing conditions were as follows: a reactor temperature (in three reactors) of approximately 440.5 ° C (825 ° F); a total pressure in the range of 16.55 to 17.93 MPa (2400 to 2600 psig); a proportion of fresh molybdenum feed / fresh heavy oil (% by weight) 0.20 - 0.40; proportion of fresh molybdenum catalyst / total molybdenum catalyst of 0.125 - 0.250; LHSV of total feed of approximately 0.070 to 0.15; and H2 gas ratio (SCF / bbl) from 7500 to 20000.

The effluent taken from each reactor was sent to the separator (connected in series), and separated into a stream of hot steam and a non-volatile stream. The vapor streams were removed from the top of the high pressure separators and collected for further analysis ("HPO" or higher high pressure streams). The non-volatile stream containing the catalyst in suspension and the unconverted heavy petroleum feedstock was removed from the separator and sent to the next reactor in the series.

A portion of the non-volatile stream from the last separator in an amount of 30% by weight of the heavy oil feedstock was recycled (STB), and the remainder was removed as a purge stream (in an amount of about 15% by weight of the heavy oil feedstock). The STB stream contains about 10 to 15% by weight of catalyst in suspension.

The feed mix to the system was heavy crude, high in metals, with the properties specified in Table 1.

Table 1 VR power Gravity API to 60/60 Specific gravity 1.0760 Sulfur (% by weight) 5.27015 Nitrogen (ppm) 7750 Nickel (ppm) 135.25 Vanadium (ppm) 682.15 Carbon (% by weight) 83.69 Hydrogen (% by weight) 9.12 H / C ratio 0.109 After 50 days of operation, the operation was stopped. The reactor, the distributor and the internal thermowell were visually inspected. The three pieces show significant accumulation of deposits, with approximately 28.5% of the volume of the (Io) front end reactor that is lost due to heavy metal deposits. Analysis of the suspension catalyst used in the purge stream over the 50 day period showed an increased deficit in vanadium, suggesting that the accumulation of the deposit within the front end reactor was not only happening, but was actually getting worse in the course of the corrida. The operation of the process also suffered due to the loss in the reaction volume.

Example 2: Example 1 was repeated, except that the temperature of the first reactor was decreased 11.1 ° C (20 ° F), (from about 440.5 ° C (825 ° F) to about 429.4 ° C (805 ° F)), the proportion of the recycled catalyst was increased from 30% by weight (in Example 1) to about 40% by weight of the heavy oil feed ratio, and water was added to the front end reactor at a rate equivalent to 5% in weight of the proportion of heavy oil feed. The system ran for 54 days before stopping.

The water injection was carried out by the addition of water to the fresh catalyst, then the mixture of water and catalyst was added to an autoclave together with the heavy oil and hydrogen feed, with the mixture being preheated to a temperature of about 176.6 ° C (350 ° F.) The analysis of the spent suspension catalyst in the purge stream over the period of 54 days showed a clearly close match between the amount of vanadium expected to come out of the process and the amount of vanadium in the catalyst in the purge stream , suggesting that the entrapment of vanadium has thus significantly reduced the deposit of heavy metal in the equipment.

The analytical results were also confirmed by visual inspections of the internal parts of the reactor, the distributor and the internal thermowell. The equipment was significantly cleaner than in Example 2, with only 6.6% of the front end reactor volume lost due to heavy metal deposits.

Comparative Example 3: Heavy oil improvement experiments were carried out in a pilot system having three reactors in the gas-liquid suspension phase, connected in series with two hot separators. The hot separators are connected in series with the first and third reactors respectively, without the hot separator after the second reactor. The reactors in the gas-liquid suspension phase were continuously stirred reactors. The breeding system was run continuously for approximately 70 days.

A fresh suspension catalyst was prepared according to the teaching of United States Patent No. 2006/0058174, for example, a molybdenum compound was first mixed with aqueous ammonia to form an aqueous mixture of the molybdenum compound, sulfided with the hydrogen / sulfur compound, promoted with a nickel compound, then transformed into a hydrocarbon oil (different from heavy petroleum feed material) at a temperature of at least 176.6 ° C (350 ° F) and a pressure of at least 1.38 MPa (200 psig), forming an active suspension catalyst.

In Comparative Example 3, all of the suspension of the fresh catalyst was sent to the first reactor in the system, for a concentration of catalyst in fresh suspension in the heavy oil in the range of 2,000 to 5,000 ppm, expressed as weight of metal (molybdenum) to the weight of the heavy oil feed. The hydroprocessing conditions were as follows: reactor temperature of 435 ° C - 440.5 ° C (815 - 825 ° F); a total pressure in the range of 16.55 mPa and 17.93 mPa (2400 to 2600 psig); a fresh molybdenum / fresh heavy oil (wt%) feed ratio of 0.20 - 0.40; proportion of fresh molybdenum catalyst / total molybdenum catalyst of 0.1; LHSV total feeding from 0.10 to 0.15; and H2 gas ratio (SCF / bbl) from 10,000 to 15,000.

The effluent taken from the first and third reactors was introduced into the hot separators connected in series with the reactors, and separated into a stream of hot steam and a non-volatile stream. The vapor streams were removed from the top of the high pressure separators and collected for further analysis ("HPO" or higher high pressure streams). The non-volatile stream containing the catalyst in suspension and the unconverted heavy petroleum feedstock was removed from the bottom of the first separator and sent to the second reactor in series. The effluent from the second reactor was sent directly to the third reactor as feed material.

A portion of the non-volatile stream from the last separator in an amount of 5 -15% by weight of the heavy oil feedstock was removed as the purge stream, for a total conversion ratio of 98 to 98.5% of the feeding heavy oil to distilled products. The rest of the non-volatile stream, the "bottom of purification product" or STB, which contained the largest volume of the catalyst (in an amount of 80 to 95% of the catalyst in total suspension entering the system) was recycled back to the first reactor to maintain the flow of the catalyst through the improvement system. The STB stream contains about 7 to 20% by weight of the catalyst in suspension. The STB was also analyzed to evaluate the general functioning of the system.

The feed mixture into the system was a heavy oil feed with the properties specified in Table 2.

Table 2 Properties VR Gravity API to 60/60 4.6 Specific gravity 1.04 Sulfur (% by weight) 1.48 Nitrogen (ppm) 11069 Nickel (ppm) 118.8 Vanadium (ppm) 108.7 Carbon (% by weight) 83.57 Hydrogen (% by weight) 10.04 MCR (% by weight) 20.7 Viscosity at 100 ° C. (cSt) 20796 Pentane asphaltenes (% by weight) 13.9 Fraction that boils above 537. 7 ° C (1000 ° F) (% by weight) 100% Example 4: After 70 days with all the fresh catalyst towards the first reactor (in Comparative Example 3), the fresh catalyst supply position was moved from the first to the third reactor, with the first two reactors completely relying on the current of recycled catalyst feed, for 28 days. All the other conditions of the process remained the same. The HPO and STB products were collected, analyzed and compared with the results of Comparative Example 3. There was no significant change in the quality of the HPO product. With respect to the STB product, results are as follows: Table 3 Example Properties Example 4 Comparative STB Product 3 % by weight of VR (PE 15.9 15.3 537 ° C (1000 ° F)) % by weight HVGO (PE 49.8 48.6 426. 6 ° C 800 ° F)) % by weight VGO (PE 79.8 80.0 343. 3 ° C 650 ° F)) API 2.7 4.5 Sulfur (% by weight) 0.12 0.16 Nitrogen (ppm) 12711 12335 MCR (% by weight) 14.7 12.4 Proportion 0.098 0.102 Hydrogen / Carbon Ni (ppm) 10.8 7.9 Asfáltenos of 174255 119713 hot heptane, ppm Viscosity at 70 ° C, 68.4 47.3 cSt The results show that the deviation of the fresh catalyst towards the last contact zone in the system, did not trigger changes in the nitrogen levels of the product. However, there was a change in the sulfur level, which could be due to the unusually low level of sulfur in the heavy oil feed to the system, and the high level of sulfur in the VGO oil used in the feed of the catalyst in suspension. It is therefore possible that the injection of the fresh catalyst into the last reactor penalized the sulfur produced by providing less time for the VGO oil carrier (in the suspension catalyst) to react, resulting in a higher level of sulfur produced. It is further noted that by diverting the fresh catalyst to the last reactor an STB product with improved properties was produced, including API, viscosity, MC, HHA, nickel, and H / C ratio. The improvement in the API of the STB product did not correlate with an improvement in the distillation of the STB product. In other words, the API of the STB product did not improve due to the additional disintegration in a lighter product distillation, but due to the improved catalytic activity, resulting in a higher H / C ratio.

With respect to the operation of the system in the 28-day run, there was no evidence of constitution of pressure drop or clogging around the reactors at the front end, suggesting some coking or accumulation of solids. There was no measurable negative impact on the overall conversion speed. The results suggest that the used catalyst has retained sufficient hydrogenation activity to prevent coking, even in the presence of heavy / untreated heavy oil feedstock, indicating that a fresh catalyst splitting scheme still adequately suppresses coking.

Example 5: Comparative Example 3 was repeated except that 20% of the heavy oil feed material is diverted from the first reactor to the third reactor, while other process conditions remain the same.

By comparing the stability of the process, the operation of the reactor and the reactor conditions between the examples, it is believed that in Comparative Example 3, the third reactor has a lower liquid yield (without the heavy oil feed) and the concentration Higher catalyst that are directionally beneficial for conversion purposes. However, these conditions also tend to make the last reactor more susceptible to operational adjustments that lead to insufficient liquid performance, and consequently, more solid accumulation, degrading thermometry and shortening the run time of the process.

In Example 5, with a portion of the heavy petroleum feedstock that is fed directly to the last reactor, it is anticipated that the preceding reactors (1 ° and 2 °) with a decrease in the liquid yield (as a portion of the material heavy oil feed that is diverted) and a corresponding increase in catalyst concentration, will operate more efficiently and with a higher conversion ratio. Additionally, with more liquid dilution in the third reactor, there is a more uniform catalyst concentration profile through all three reactors.

It is further anticipated that as the last reactor in the series obtains a portion of the heavy oil feed, the dry conditions associated with insufficient liquid flow are avoided. Since the last reactor is protected from overconversion events or dry conditions, there is less accumulation of solid or coke deposition. It is also expected that the last reactor will be less susceptible to operational adjustments, for example, wide oscillations in temperature, pressure, flows, etc.

For the purpose of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all cases by the term "approximately".

Accordingly, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired properties sought and / or the accuracy of an instrument for measure the value, which includes in this way the standard deviation of the error for the device or the method that is used to determine the value. The use of the term "or" in the claims, is used to imply "and / or" unless explicitly indicated to refer to alternatives only or the alternative are mutually exclusive, although the description supports a definition that refers only to alternatives and "and / or." The use of the word "a", "an" or "an" when used in conjunction with the term "comprising" in the claims and / or in the specification, may mean "one", but is also consistent with the meaning "one or more," "at least one," and "one or more than one." In addition, all the ranges described herein are inclusive of the endpoints and are independently combinable. In general, unless indicated otherwise, the singular elements may be in the plural and vice versa, without loss of generality. As used herein, the term "includes" and its grammatical variants, is intended to be non-limiting, such that the indication of items in a list is not to the exclusion of the other items that may be substituted or added to the items listed.

It is contemplated that any aspect of the invention discussed in the context of one embodiment of the invention may be implemented or applied with respect to any other embodiment of the invention. Likewise, any composition of the invention may be the result or may be used in any method or process of the invention. This described description uses examples to describe the invention, including the best mode, and also to make it possible for any person skilled in the art to make or use the invention. The patentable scope is defined by the claims, and may include other examples that occur to those skilled in the art. Other such examples are intended to be within the scope of the claims and these have structural elements that do not differ from the literal language of the claims, and if they include equivalent structural elements with insubstantial differences from the literal legals of the claims. All citations referred to herein are expressly incorporated by reference herein.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A process for hydroprocessing a heavy oil feedstock, the process employs a plurality of contact zones and separation zones, characterized in that it comprises: provide a heavy oil feedstock, a gas containing hydrogen and a catalyst in suspension; combining the heavy oil feedstock, the hydrogen-containing gas, and a catalyst in suspension in a first contact zone under hydrodisintegration conditions, to convert at least a portion of the heavy oil feedstock to low-point hydrocarbons boiling, forming improved products; sending a mixture comprising improved products, the suspended catalyst, the hydrogen-containing gas, and the heavy oil feed material not converted to a first separation zone, whereby the improved products are removed with the hydrogen-containing gas of the first separation zone as a first top stream, and the suspension catalyst, the heavier hydrodisintegrated liquid products and the un-converted heavy petroleum feedstock are removed from the first separation zone as a first non-volatile stream; sending the first non-volatile stream to a contact zone other than the first contact zone, which is maintained under hydrodisintegration conditions with gas containing additional hydrogen, to convert at least a portion of the heavy oil feedstock into hydrocarbons of low boiling point, forming additional improved products; send a mixture comprising the additional improved products, the suspension catalyst, the hydrogen-containing gas, and the heavy oil feed material without converting to a separation zone different from the first separation zone, whereby the products improved with the hydrogen-containing gas as an overhead stream, and the catalyst in suspension and the unconverted heavy petroleum feedstock are removed as a second non-volatile stream, and wherein the catalyst in suspension to the first separation zone comprises at least a portion of the non-volatile stream of one of the separation zones as a stream of recycled catalyst, and wherein the recycled catalyst stream is from 3 to 50% in weight of the heavy oil feed material.

2. The process according to claim 1, characterized in that a sufficient amount of hydrogen-containing gas feed is provided so that the process has a volumetric yield of more than 100% in the improved products comprising liquefied petroleum gas, gasoline, diesel, vacuum gas oil, and fuel oil and turbosine.

3. The process according to claim 1, characterized in that the recycled catalyst stream is at least 10% by weight of the total, heavy petroleum feedstock.

4. The process according to claim 1, characterized in that at least a portion of the second non-volatile stream is recycled to at least one of the contact zones as a recycled stream, and the remainder of the second non-volatile stream is removed from the recycle stream. process as a purge current.

5. The process according to claim 4, characterized in that the recycled stream is sent to the first contact zone.

6. The process according to claim 4, characterized in that a sufficient amount of the purge stream is removed so that the process has a conversion ratio of at least 98%.

7. The process according to claim 1, characterized in that the contact zones are maintained under hydrodisintegration conditions at a temperature of 410 ° C to 600 ° C and at a pressure of 10 MPa to 25 MPa, and the first contact zone is operated at a temperature at least 5.5 ° C (10 ° F) below a subsequent contact zone.

8. The process according to claim 7, characterized in that a portion of the catalyst in suspension is for feeding a contact zone different from the first contact zone.

9. The process according to claim 1, characterized in that it comprises: providing a fresh suspension catalyst feed, wherein at least a portion of the catalyst in fresh suspension is to feed a contact zone different from the first contact zone; providing a suspension catalyst comprising a used suspension catalyst and, optionally, a fresh, suspension portion of the catalyst feed; and wherein, in the stage in which the first non-volatile stream is sent to the contact zone different from the first contact zone, the other contact zone is maintained under hydrodisintegration conditions with additional feed of hydrogen-containing gas and at least a portion of the catalyst in fresh suspension to convert at least a portion of the unconverted heavy petroleum feedstock to low boiling hydrocarbons, forming other improved products.

10. The process according to claim 1, characterized in that at least a portion of the heavy oil feedstock is for feeding a contact zone other than the first contact zone.

11. The process according to claim 10, characterized in that at least 5% of the heavy oil feedstock is for feeding a contact zone other than the first contact zone.

12. The process according to claim 1, characterized in that it further comprises the addition of water to the first contact zone in an amount of 1 to 25% by weight on the weight of the heavy petroleum feedstock.

13. The process according to claim 12, characterized in that at least a portion of the water is added to the first contact zone as steam injection.

1 . The process according to claim 1, characterized in that the first contact zone has an outlet pressure of X, the first separation zone has an inlet pressure of Y, and a pressure drop Z between the outlet pressure X of the first contact zone and the inlet pressure Y of the first separation zone is less than 0.689 MPa (100 psi).

15. The process according to claim 1, characterized in that the suspension catalyst has an average particle size in the range of 1 to 20 micrometers.

16. The process according to claim 1, characterized in that the suspension catalyst comprises groups of colloidal particles of size less than 100 nm, wherein the groups have an average particle size in the range of 1 to 20 microns.

17. The process according to claim 1, characterized in that the additional feed of hydrocarbon oil different from the heavy oil feed material, in an amount ranging from 2 to 30% by volume of the heavy oil feed material, is added to any of the contact zones.

18. The process according to claim 1, characterized in that it comprises recycling at least one portion of the non-volatile current to at least one of the contact areas.

19. A process for hydroprocessing a heavy oil feedstock, the process employs a plurality of contact zones and separation zones, characterized in that it comprises: combining the heavy petroleum feedstock, a gas containing hydrogen, and a catalyst in suspension in a first contact zone under hydrodisintegration conditions, to convert at least a portion of the heavy petroleum feedstock into low point hydrocarbons boiling, forming improved products; send a mixture of the improved products, the suspended catalyst, the hydrogen-containing gas, and the non-converted heavy petroleum feedstock to a separation zone, whereby the volatile improved products are removed with the hydrogen-containing gas from the separation zone, as a first top stream, and the suspension catalyst, the improved non-volatile products and the un-converted heavy petroleum feedstock are removed from the first separation zone as a first non-volatile stream; sending at least a portion of the first nonvolatile stream to a solvent deasphalting unit; obtaining from the solvent deasphalting unit two streams, a stream comprising deasphalted oil, and a stream comprising asphaltenes and the catalyst in suspension; send the deasphalted oil to a contact zone other than the first contact zone, whose contact zone is maintained under hydrodisintegration conditions with hydrogen-containing gas feed and the additional feed of the catalyst in suspension to convert at least a portion of deasphalted oil in low boiling point hydrocarbons, forming other improved products; send a mixture of the additional improved products, the suspended catalyst, the additional hydrogen-containing gas, and the unconverted deasphalted oil, to a second separation zone, wherein the additional volatile improved products and the additional hydrogen-containing gas are withdrawn as a second top stream, and the catalyst in suspension, the additional non-volatile enhanced products and the unconverted deasphalted oil are removed as a second non-volatile stream, and recycle to at least one of the contact zones, a recycled stream comprising at least one of: a) a portion of the stream containing asphaltenes and the catalyst in suspension, b) a portion of the first nonvolatile stream, c) a portion of the second non-volatile stream, and d) mixtures thereof.

20. The process according to claim 19, characterized in that it further comprises recycling to at least one of the contact zones, at least a portion of the non-volatile stream. SUMMARY OF THE INVENTION Systems and methods for hydroprocessing a heavy oil feedstock with reduced heavy oil deposits are described, the system employs a plurality of contact zones and separation zones under hydrodisintegration conditions to convert at least a portion of the feedstock of heavy oil in hydrocarbons of lower boiling point, forming improved products, wherein the water and / or the steam is optionally injected into the first contact zone in an amount of 1 to 25% by weight on the weight of the material of heavy oil feed. In one embodiment, the first contact zone is operated at a temperature at least 5.5 ° C (10 ° F) lower than a next contact zone. The contact zones operate under hydrodisintegration conditions, using a suspension catalyst to improve the heavy oil feed material, forming improved products of lower boiling hydrocarbons. In the separation zones, the improved products are removed at the top, and optionally, additionally treated in an online hydrotreater. At least a portion of the non-volatile fractions recovered from at least one of the separation zones is recycled back to the first contact zone in the system, in an amount in the range of 3 to 50% by weight of the feedstock of heavy oil. In one embodiment, at least some of the heavy oil feedstock is supplied to at least one contact zone different from the first contact zone, and / or at least some of the catalyst in fresh suspension is supplied to at least one contact zone different from the first contact zone. In one embodiment, at least a portion of the nonvolatile fractions recovered from at least one of the separation zones is sent to the deasphalting unit with interstage solvent, to separate the heavy oil feed material not converted to deasphalted oil. and asphalt us. The deasphalted oil stream is sent to one of the contact zones for further improvement.