EA023427B1 - Process for hydrocracking of a heavy oil feedstock - Google Patents

Abstract

Systems and methods for hydroprocessing a heavy oil feedstock with reduced heavy oil deposits, wherein 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 wt.% on the weight of the heavy oil feedstock. In one embodiment, the first contacting zone is operated at a temperature of at least 10 °F (5.56°C) 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

The application for this patent establishes the priority of US patent applications with registration numbers 12/233171, 12/233393, 12/233439, 12/212796 and 12/212737, filed September 18, 2008. This application establishes the priority and advantages of the above documents, the descriptions of which by references are included in this document.

The invention relates to systems and methods for processing or refinement of feed streams based on heavy oil and crude products obtained using such systems and methods.

State of the art

The oil industry is increasingly focusing on heavy oil-based flows, such as heavy crude oil, fuel oil, coal, tar sands, etc., as sources of feedstock. This feedstock is characterized by high concentrations of residues enriched in asphaltenes and low densities in degrees ANI, some of which are less than 0 ° by ANI.

PCT Patent Publication No. νθ 2008/014947, US Patent Publication No. 2008/0083650, US Patent Publication No. 2005/0241993, US Patent Publication No. 2007/0138057 and US Patent No. 6660157 describe methods, systems and catalysts for processing feed streams based on heavy oil. Heavy oil based feedstocks are typically characterized by high levels of heavy metals. Some of the heavy metals, such as nickel and vanadium, tend to react quickly, leading to the formation of deposits or trapping of vanadium enriched solids in equipment such as reactors. The formation of solid deposits reduces the available volume for the reaction, reducing the duration of continuous operation.

There is still a need to develop improved systems and methods for refinement / processing of process feed streams based on heavy oil with reduced accumulation of heavy metals in process equipment.

SUMMARY OF THE INVENTION

In one aspect, this invention relates to a method in which heavy oil feedstocks can be upgraded. The method uses a plurality of contact zones, separation zones and at least one interstage solvent deasphalting unit (DAP). The method includes a) combining a feed stream of a hydrogen-containing gas, a heavy oil feedstock and a suspended catalyst in a first contacting zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock to refined products; B) sending a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feedstock to the separation zone; c) in the separation zone, removing the refined products together with the hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feed in the form of a non-volatile product stream; g) sending at least a portion of the flow of non-volatile products to the DAR unit to separate asphaltenes and suspended catalyst from deasphalted oil; f) sending the deasphalted oil and the rest of the flow of non-volatile products from the previous separation zone to another contacting zone under hydrocracking conditions together with additional hydrogen gas and an additional suspended catalyst for converting the deasphalted oil to refined products; ί) sending the refined products, suspended catalyst, hydrogen and unreacted deasphalted oil to the separation zone, whereby the refined products are removed together with hydrogen in the form of an overhead stream, and the suspended catalyst and unreacted deasphalted oil are removed as a flow of non-volatile products; and §) recycling to at least one of the contacting zones of at least a portion of a non-volatile product stream containing a suspended catalyst and unreacted deasphalted oil.

In yet another aspect, a method is provided comprising a plurality of contacting zones, separation zones, and at least one multi-stage solvent deasphalting unit (DAP), wherein the heavy oil feedstock can be refined and wherein at least a portion of the non-volatile stream products from at least one contacting zone are sent to a DAR unit to separate asphaltenes from deasphalted oil.

In one aspect, this invention relates to a method in which heavy oil-based feedstocks can be upgraded with reduced deposition of heavy metals in the front contact zones. The method uses many contacting zones and separation zones, the method comprising a) combining a feed stream of a hydrogen-containing gas, a heavy oil feedstock and a suspended catalyst in a first contacting zone under hydrocracking conditions to convert at least a portion of the feedstock based on heavy oil in refined products, where water and / or water vapor is pumped into the first zone of introduction into the contact line in an amount of 1 to 25 wt.% in an amount of 1 to 25 wt.% based on the weight of the feedstock oil loy; B) sending a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feedstock to the separation zone; c) in the separation zone, removing the refined products together with the hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feed in the form of a non-volatile product stream; b) sending a flow of non-volatile products to another contacting zone under hydrocracking conditions together with additional hydrogen gas, unreacted heavy oil-based feedstocks and, optionally, a fresh suspended catalyst to convert unreacted heavy oil-based feedstocks to refined products; ί) sending refined products, suspended catalyst, hydrogen and unreacted heavy oil feed to the separation zone, whereby the refined products are removed together with hydrogen as an overhead stream, and suspended catalyst and unreacted heavy oil feed are removed to the flow of non-volatile products; and e) sending for recycling to at least one of the contacting zones of at least a portion of the non-volatile product stream.

In yet another aspect, the invention relates to a process for refining heavy oil-based feedstocks comprising a plurality of contacting zones and separation zones, wherein water and / or water vapor is injected into the first contacting zone, and wherein at least a portion of the flow is non-volatile products from the separation zone other than the first separation zone are recycled to the first contacting zone, where the flow sent for recycling is from 3 to 50 wt.% of the total heavy oil feedstock in the method.

In one aspect, this invention relates to a method in which heavy oil feedstocks can be upgraded. The method uses a plurality of contacting zones and separation zones, the method comprising: a) supplying a heavy oil-based feedstock together with at least a portion of the heavy oil-based feedstock to a contacting zone different from the first contacting zone; B) combining the feed stream of a hydrogen-containing gas, a portion of the heavy oil feedstock and a suspended catalyst in the first contacting zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock to refined products; c) sending a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feedstock to a separation zone; b) in the separation zone, removing the refined products together with a hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feedstock in the form of a flow of non-volatile products; f) sending a flow of non-volatile products to another contacting zone under hydrocracking conditions together with additional hydrogen gas, at least a portion of the heavy oil feedstock and, optionally, a fresh suspended catalyst to convert the unreacted heavy oil feedstock into ennobled products; ί) sending the refined products, suspended catalyst, hydrogen and unreacted heavy oil feed to the separation zone, whereby the refined products are removed together with hydrogen as an overhead stream, and the suspended catalyst and unreacted heavy oil feed are removed as flow of non-volatile products; and e) sending for recycling to the first contacting zone at least a portion of the non-volatile product stream.

In yet another aspect, the method utilizes a plurality of contacting and separation zones, the method comprising: a) supplying a suspended catalyst comprising a used suspended catalyst and an optionally supplied stream of a suspension of fresh catalyst; B) combining the feed stream of a hydrogen-containing gas, a heavy oil feedstock and a suspended catalyst in a contact zone under hydrocracking conditions to convert at least a portion of the heavy oil feedstock to refined products; c) sending the mixture containing the refined products, the suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feed to a separation zone; b) in the separation zone, removing the refined products together with a hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feedstock in the form of a flow of non-volatile products; f) sending a flow of non-volatile products to another contacting zone under hydrocracking conditions together with additional hydrogen gas and fresh suspended catalyst to convert unreacted heavy oil-based feedstocks to refined products; ί) sending the refined products, suspended catalyst, hydrogen and unreacted heavy oil feed to the separation zone, whereby the refined products are removed together with hydrogen as an overhead stream, and the suspended catalyst and unreacted heavy petroleum feed 2 023427 ty are removed as a stream of non-volatile products; and e) sending for recycling to the first contacting zone at least a portion of the non-volatile product stream.

In yet another aspect, a method is provided comprising a plurality of contacting zones and separation zones, wherein the heavy oil feed can be refined and where freshly suspended catalyst is divided between the contacting zones.

In one aspect, the method uses a plurality of contact zones and separation zones, the method comprising: a) combining a feed stream of a hydrogen-containing gas, a heavy oil feed and a suspended catalyst in a first contact zone under hydrocracking conditions to convert at least portions of heavy oil-based feedstocks in refined products; B) sending a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feedstock to the separation zone; c) in the separation zone, removing the refined products together with the hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feed in the form of a non-volatile product stream; ά) sending a flow of non-volatile products to another contacting zone under hydrocracking conditions together with additional hydrogen gas, unreacted heavy oil based feed and optionally fresh suspended catalyst to convert unreacted heavy oil based feed to refined products; £) sending the refined products, suspended catalyst, hydrogen and unreacted heavy oil feed to the separation zone, whereby the refined products are removed together with hydrogen as an overhead stream, and the suspended catalyst and unreacted heavy oil feed are removed to the flow of non-volatile products; and where the first contacting zone operates at a temperature of at least 10 ° P (5.56 ° C) lower than in the subsequent subsequent contacting zone.

In yet another aspect, the invention relates to a method in which heavy oil-based feedstocks can be upgraded with reduced formation of heavy metal deposits in the front contact zones. The method employs a plurality of contacting zones and separation zones, including a) combining a feed stream of a hydrogen-containing gas, a heavy oil feed and a suspended catalyst in a first contact zone under hydrocracking conditions to convert at least a portion of the heavy feed oil in refined products; B) sending a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feedstock to the separation zone; c) in the separation zone, removing the refined products together with the hydrogen-containing gas in the form of an overhead stream and removing the suspended catalyst and unreacted heavy oil-based feed in the form of a non-volatile product stream; ά) sending a flow of non-volatile products to another contacting zone under hydrocracking conditions together with additional hydrogen gas, unreacted heavy oil-based feedstocks and, optionally, a fresh suspended catalyst to convert unreacted heavy oil-based feedstocks to refined products; £) sending the refined products, suspended catalyst, hydrogen and unreacted heavy oil feed to the separation zone, whereby the refined products are removed together with hydrogen as an overhead stream, and the suspended catalyst and unreacted heavy oil feed are removed to the flow of non-volatile products; and where the suspended catalyst supplied to the first separation zone contains at least a portion of the non-volatile product stream from one of the separation zones as a catalyst stream sent for recycling, and where the catalyst stream sent for recycling is from 3 to 50% by weight of the total feed heavy oil based feedstocks.

Brief Description of the Drawings

FIG. 1 is a block diagram that schematically illustrates one embodiment of a hydrotreatment system for refining heavy oil feedstocks comprising a plurality of contacting and separation zones, where water and / or steam are injected into the front contacting zone.

FIG. 2 is a flowchart of a method for refining feed streams based on heavy oil, including pumping water.

FIG. 3 is a flowchart of a process for upgrading heavy oil-based feed streams, comprising injecting water vapor directly into the front contacting zone.

FIG. 4 is a flowchart of yet another embodiment of a method for refining feed streams based on heavy oil, comprising a stream of catalyst sent for recycling at a rate sufficient to reduce the accumulation of heavy metals.

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FIG. 5 is a flowchart that schematically illustrates one embodiment of a hydroprocessing system for refining heavy oil feedstocks having a split feed stream of fresh catalyst, a split feed flow scheme based on heavy oil, and additional hydrocarbon oil based multistage feedstocks.

FIG. 6 is a flowchart that schematically illustrates another embodiment of a hydrotreatment system for refining heavy oil feedstocks, including a solvent deasphalting unit for pretreatment of heavy oil feedstocks.

FIG. 7 is a flow diagram of a process for refining heavy oil-based feed streams, including one embodiment of a split catalyst feed stream scheme, wherein the fresh catalyst feed stream is fed to all reactors in the process.

FIG. 8 is a flowchart of a process for upgrading heavy oil-based feed streams, where the fresh catalyst feed is diverted from the first reactor to other reactors in the process, and where optional / additional hydrocarbon oil is fed into the reactors.

FIG. 9 is a flowchart of yet another embodiment of a process for refining feed streams based on heavy oil, where the entire feed stream of fresh catalyst is sent to the last reactor in the process.

FIG. 10 is a flowchart of yet another embodiment of a method for refining heavy oil-based feed streams, where some of the untreated heavy oil-based feed stream is withdrawn from the first reactor and sent to other reactors in the method.

DETAILED DESCRIPTION OF THE INVENTION

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

As used herein, a heavy oil-based feed stream or feedstock refers to heavy and superheavy crude oils, including but not limited to the following: fuel oil, coal, bitumen, oil shale, tar sands, and the like. The heavy oil feedstocks may be liquid, semi-solid and / or solid. Examples of heavy oil-based feedstocks that can be upgraded as described herein include, but are not limited to: tar sands from Canada, vacuum distillation residues from the Brazilian basins of Santos and Campos, Egyptian Gulf of Suez, Chad, Venezuelan Zulia, Malaysia and Indonesian Sumatra. Other examples of heavy oil-based feedstocks include bottom sediments in a barrel and residues left over from processes at the refinery, including bottom sediments in a barrel and residue (or fuel oil) —residues from the bottom of the atmospheric distillation column that have a boiling point equal to at least 343 ° C (650 ° P), or bottoms of the vacuum distillation column that have a boiling point of at least 524 ° C (975 ° P), or solid bitumen pitch and tar, which have a boiling point 524 ° С (975 ° Р) or more.

The properties of heavy oil-based feedstocks may include, but are not limited to: a total acid number of at least 0.1, at least 0.3, or at least 1; a viscosity of at least 10 cSt; density in degrees ANI equal to maximum 15 in one embodiment and 10 in another embodiment. One gram of a heavy oil feedstock typically contains at least 0.0001 g Νί / ν / Pe; at least 0.005 g of heteroatoms; at least 0.01 g of residues; at least 0.04 g of C5 asphaltenes; at least 0.002 g of a micro carbon residue; per 1 g of crude oil; at least 0.00001 g of salts derived from alkali metals and one or more organic acids; and at least 0.005 g of sulfur. In one embodiment, the heavy oil feed is characterized by a sulfur content of at least 5 wt.% And a density in degrees of API in the range of -6 to 6.

The terms treatment, refinement, refinement, refinement and refinement, if used in connection with a heavy oil feedstock, describe a heavy oil feedstock that is or has been hydrotreated, or the resulting material or crude product, characterized by a reduction the molecular weight of the heavy oil-based feedstock, by reducing the boiling range of the heavy oil-based feedstock, by reducing the concentration of asphalt enes, decrease in the concentration of hydrocarbon free radicals, and / or decreasing the amount of impurities such as sulfur, nitrogen, oxygen, halides and metals.

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The refinement or processing of heavy oil-based feed streams is generally referred to herein as hydroprocessing. Hydroprocessing refers to any method that is implemented in the presence of hydrogen, including the following, but not limited to: hydroconversion, hydrocracking, hydrogenation, hydroprocessing, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodeparaffinization and hydrocracking, including selective. Hydro-processing products may have lower values of viscosity, viscosity index, levels of saturated compounds, low temperature properties, volatility and depolarization, etc.

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

Art. cube ft / b (or cc / ft) indicates the unit of measurement is the standard cubic foot of gas (Ν ₂ , H ₂ , etc.) per barrel of hydrocarbon feed stream.

Nm ³ / m ³ indicates normal cubic meters of gas per cubic meter of heavy oil-based feed stream.

The terms VGO or vacuum gas oil refer to hydrocarbons characterized by a distribution of the boiling range in the range from 343 ° C (650 ° P) to 538 ° C (1000 ° P) at 0.101 MPa.

ppm (wt.) denotes mass parts per million parts.

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

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 thereby been reduced. For example, assuming that the reaction rate constant for the fresh catalyst is equal at a particular temperature, 100%, the reaction rate constant for the used catalyst will be 95% or less in one embodiment, 80% or less in another embodiment, and 70% or less in the third embodiment . The term used catalyst can be used synonymously with the terms recycled catalyst, used suspended catalyst or recycled suspended catalyst.

As used herein, the term “fresh catalyst” means a catalyst or catalyst precursor that has not been used in the reactor in a hydroprocessing operation. The term fresh catalyst as used herein also includes regenerated or reduced catalysts, i.e. a catalyst that was used in at least one reactor at the hydroprocessing stage (used catalyst), but its catalytic activity was restored or at least increased to a level significantly higher than the level of activity of the used catalyst. The term fresh catalyst may be used synonymously with the term fresh suspended catalyst.

As used herein, the term “suspended catalyst” (or sometimes referred to as a suspension or dispersed catalyst) refers to a liquid medium, for example, oil, water, or mixtures thereof, in which particles of a catalyst and / or catalyst precursor are dispersed (dispersed inclusions or crystallites) having very small average sizes.

As used herein, the catalyst feed stream includes any catalyst suitable for upgrading heavy oil feedstocks, for example, one or more bulk catalysts and / or one or more supported catalysts. The catalyst feed stream may include at least only fresh catalyst, used catalyst, or mixtures of at least fresh catalyst and used catalyst. In one embodiment, the catalyst feed is in the form of a suspended catalyst.

As used herein, the term bulk catalyst may be used synonymously with the term “catalyst not supported” in the sense that the catalyst composition does not have a conventional catalyst form, which includes, for example, a preformed molded catalyst carrier, in which thereafter metals are impregnated or precipitated. In one embodiment, the bulk catalyst is obtained by precipitation. In yet another embodiment, the bulk catalyst comprises a binder incorporated into the catalyst composition. In yet another embodiment, the bulk catalyst is prepared from metal compounds and in the absence of any binder. In the fourth embodiment

- 5,023,427 implementation of the bulk catalyst is a dispersion type catalyst and is intended to be used as dispersed catalyst particles in a mixture with a liquid (eg, hydrocarbon oil). In one embodiment, the catalyst comprises one or more commercially known catalysts, for example Mygos! ™ from ExxoMoI Cogr.

As used herein, the term contact zone refers to equipment in which a heavy oil feed stream is treated or refined by contacting a suspended catalyst in contact with the feed stream in the presence of hydrogen. In the contacting zone, at least one property of the crude feed stream can be modified or refined. The contacting zone may be a reactor, part of a reactor, several parts of a reactor, or combinations thereof. The term contacting zone can be used synonymously with the term reaction zone.

As used herein, the term separation zone refers to equipment into which a refined heavy oil-based feed stream from the contacting zone is either supplied directly, or it is exposed to one or more intermediate methods therein, and then directly into a separation zone, for example, an evaporation drum or a high pressure separator, where gases and volatile liquids are separated from the non-volatile fraction. In one embodiment, the non-volatile fraction stream contains an unreacted heavy oil-based feed stream, a small amount of heavier hydrocracked liquid products (synthetic or less volatile / non-volatile products that have been upgraded), a suspended catalyst and any entrained solids (asphaltenes, coke, etc.) .P.).

As used herein, the term “bleed stream” or “by-stream” means a stream containing used (or recycled) catalyst that is bleed or removed from a hydroprocessing system, which helps to prevent the formation or washing away of accumulated metal sulfides and other undesirable impurities from the refining system .

The present invention relates to an improved system for processing or refining heavy oil-based feed streams, in particular heavy oil-based feedstocks characterized by high levels of heavy metals.

In one typical prior art hydroprocessing system, including a plurality of series-connected contact zones (reactors), it is observed that the feed stream to the second contact zone is generally cleaner than the heavy oil feed stream in the first the contact zone in the system, i.e. containing less impurities such as nickel, vanadium, nitrogen, sulfur, etc., since the heavy oil passed through the processing method in the first contacting zone. Also, according to observations, the feed stream to the last contacting zone in the system should generally be cleaner than the feed stream to the previous contacting zone (s) in the system.

In addition, in one typical hydroprocessing system, according to the observations in the prior art catalyst feed stream scheme, the feed flows to subsequent contact zones in the system are usually more concentrated in terms of certain impurities, for example, micro carbon residue, C ₅ and With ₇ asphaltenes and the like, which, thus, promotes coke formation in the last contact zones in the system.

Also, according to observations, the feed stream in the subsequent contact zones in the system has properties different from those of the heavy oil-based feed stream to the previous contact zone (s) in the system, including: a) a lower total acid number; B) viscosity; c) lower levels of residue; ά) lower density in degrees ANI; e) a lower level of metal content in metal salts of organic acids and e) their combination. However, it has also been observed that it is generally more difficult to process the feed stream to subsequent contacting zones with regard to the degree of conversion and / or properties of the resulting crude product. In addition, in the case of the prior art supply circuit (fresh catalyst entering the 1st contacting zone), it is observed that there is more significant coke formation in subsequent contacting zones than in the 1st contacting zone. As suggested, coke formation may have something to do with the more difficult to process feed stream to subsequent contact zones and / or reduced activity of the catalyst feed stream to subsequent contact zones.

In one embodiment, the refining process comprises a plurality of reactors used as contact zones, wherein the reactors have identical or different configurations. Examples of reactors that can be used in the present invention include reactors with a stacked catalyst bed, fixed bed reactors, fluidized bed reactors, mechanically agitated continuous reactors, fluidized bed reactors, spray reactors liquid / liquid contactors, suspended catalyst reactors, liquid recycling reactors, and combinations thereof. In one embodiment, the reactor is an upflow reactor. In yet another embodiment, the reactor is a downflow reactor. In one embodiment, the contacting zone denotes at least one suspended catalyst bed hydrocracking reactor in series with the at least one fixed bed hydrocracking reactor. In yet another embodiment, at least one of the contacting zones further includes an in-line hydrotreatment unit capable of removing more than 70% sulfur, more than 90% nitrogen, and more than 90% heteroatoms in the raw product being processed.

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

Depending on the conditions and location of the separation zone, in one embodiment, the amount of heavier hydrocracked products in the non-volatile fraction stream is less than 50 wt.% (Based on the total mass of the non-volatile product stream). In a second embodiment, the amount of heavier hydrocracked products in the non-volatile product stream from the separation zone is less than 25 wt.%. In a third embodiment, the amount of heavier hydrocracked products in the flow of non-volatile products from the separation zone is less than 15 wt.%. It should be noted that at least a portion of the suspended catalyst remains with the refined feedstock, since the refined materials are withdrawn from the contacting zone and fed into the separation zone, and the suspended catalyst continues to be available in the separation zone and leaves the separation zone together with non-volatile liquid fraction.

In one embodiment, both the contacting zone and the separation zone are combined in one piece of equipment, for example, a reactor including an internal separator, or a multi-stage reactor-separator. In this type of reactor-separator configuration, the vapor product exits through the top of the equipment, and the non-volatile fractions exit the equipment from the side or from the bottom, together with the suspended catalyst and entrained solid fraction, if any.

In one embodiment, the suspended catalyst stream comprises fresh catalyst. In yet another embodiment, the suspended catalyst stream comprises a mixture of at least fresh catalyst and recycled (used) catalyst. In a third embodiment, the suspended catalyst stream includes used catalyst. In yet another embodiment, the suspended catalyst comprises a well dispersed catalyst precursor composition capable of forming the active catalyst ίη 811 and in the feed flow heaters and / or contact zone. The catalyst particles can be introduced into the medium (diluent) in the form of a powder in one embodiment, a precursor in another embodiment, or after the pretreatment step in the third embodiment. In one embodiment, the medium (or diluent) is a hydrocarbon oil. In yet another embodiment, the liquid medium is the heavy oil feedstock itself. In yet another embodiment, the liquid medium is a hydrocarbon oil different from a heavy oil feedstock, such as a VGO medium or diluent.

In one embodiment, the by-pass contains non-volatile materials from the separation zone in the system, typically the last separation zone, containing unreacted materials, a suspended catalyst, a small amount of heavier cracked liquid products, small amounts of coke, asphaltenes, and the like. In yet another embodiment, the run-off stream is the bottom stream from the interstage solvent deasphalting unit in the system. In embodiments where the by-pass is diverted from the lower stream of the separation zone, the etched stream is typically 1 to 35 wt.%, 3-20 wt.%, Or 5-15 wt.% Of the total feedstock based on the heavy oil of the system. In embodiments, in this case, the bypass stream is diverted from the bottom of the deasphalting unit, the bypass stream is from 0.30 to 5 wt.%, 1-30 wt.% Or from 0.5 to 10 wt.% Of the heavy oil feedstock .

In one embodiment, the by-pass contains from 3 to 30% by weight of the suspended catalyst. In yet another embodiment, the amount of suspended catalyst is in the range from 5 to 20 wt.%. In yet another embodiment, the by-pass contains an amount of suspended catalyst 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 contacting zone, as in the prior art method, at least a portion of the fresh catalyst is diverted to at least one other contacting zone (other than the 1st contact zone contact) in the system.

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In addition, in some embodiments, instead of sending the entire heavy oil feed stream to be refined to the first contact zone, at least a portion of the heavy oil feed stream is diverted to at least one other contact zone in the system.

In other embodiments, a combined feed stream scheme is used to divert part of the fresh catalyst feed stream and part of the heavy oil feed stream to at least one other contact zone different from the first contact zone in the heavy oil refining system.

In one embodiment, the upgrading system includes at least two upflow reactors connected in series with at least two separators, with each separator immediately after each reactor, and a multi-stage DAR unit installed in front of at least one reactor in the system. In yet another embodiment, the upgrading system comprises at least two upstream reactors and at least two separators in series, each separator being located immediately after each reactor, and a DAP inter-stage unit is located after the first separator in series. In a fourth embodiment, the refinement system may include a combination of separate separators and separate separators connected in series with multi-stage reactor-separators, wherein the DAR unit is arranged as an inter-stage processing system between any two series-connected reactors.

Heavy Oil Based Feed

The unreacted heavy oil feed stream, as used herein, may include one or more different heavy oil feed flows from various sources 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 (refined) heavy oil-based feed stream is separated or diverted by directing at least one other contact zone in the system (other than the first zone) before being fed into the contacting zone contact) or in the interstage installation of DAR.

In one embodiment, at least a portion is a discharge of at least 5% of the refined heavy oil-based feed stream, leading to at least one other contact zone in the system other than the first contact zone. In yet another embodiment, at least 10%. In a third embodiment, at least 20%. In the fourth embodiment, at least 30% of the heavy oil-based feed stream is diverted to at least one contacting zone different from the first contacting zone in the system. In one embodiment, the heavy oil feed is preheated before being mixed with the feed stream (s) of the suspended catalyst. In yet another embodiment, the mixture of the heavy oil feedstock and the suspended catalyst feed stream is preheated to create a feedstock that has a viscosity low enough to ensure good mixing of the catalyst with the feedstock. In one embodiment, preheating is carried out at a temperature that is at least about 100 ° C (180 ° P) lower than the hydrocracking temperature in the contacting zone. In yet another embodiment, the preheating is carried out at a temperature that is approximately at least 50 ° C lower than the hydrocracking temperature in the contacting zone.

Additional hydrocarbon feed stream

In one embodiment, as part of the heavy oil-based feed stream to any of the contacting zones in the system, optionally an additional hydrocarbon oil feed stream may be added, for example, VGO (vacuum gas oil), naphtha, SRH (medium recycle gas oil), solvent donor or other aromatic solvents and the like, in an amount of from 2 to 40% by weight of the heavy oil-based feed stream. In one embodiment, the additional hydrocarbon feed stream serves as a diluent to reduce the viscosity of the heavy oil based feed stream.

Embodiments of a Heavy Oil Based Feed Split Scheme

In some embodiments, at least a portion of the (refined) heavy oil feed stream is separated or diverted to at least one other contact zone in the system (other than the first contact zone).

In one embodiment, at least a portion represents at least 5% of the heavy oil feed stream to be upgraded. In yet another embodiment, at least 10%. In a third embodiment, at least 20%. In a fourth embodiment, at least 30% of the heavy oil feed stream

- 8,023,427 is diverted by directing at least one contacting zone different from the first contacting zone in the system.

In one embodiment, less than 90% of the unreacted heavy oil based feed is fed to the first reactor in the system, with 10% or more of the unreacted heavy oil based feed is diverted to another contacting zone (s) in the system . In yet another embodiment, the heavy oil feed stream is equally divided between the contacting zones in the system. In yet another embodiment, less than 80% of the unreacted heavy oil feed is fed into 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 embodiment, less than 60% of the heavy oil feed stream is fed into the first contact zone in the system, and the remaining unreacted heavy oil feed stream is equally divided between the other contact zones in the system.

The unreacted heavy oil feed stream herein may include one or more different heavy oil feed flows from various sources as a single feed stream or separate heavy oil feed streams. In one embodiment, one heavy oil channel pipe extends into all contact zones. In yet another embodiment, several heavy oil channels are used to feed the heavy oil-based input stream to various contact zones, with a certain amount of heavy oil-based feed stream (stream) entering one or more contact zones, and some the amount of other unreacted feed streams (flow) based on heavy oil enters one or more other contact areas.

In one embodiment, the heavy oil feed is preheated before being mixed with the feed stream of the suspended catalyst and / or before being introduced into the hydrocracking reactors (contact zones). In yet another embodiment, the mixture of the heavy oil feedstock and the suspended catalyst feed stream is preheated to create a feedstock that has a viscosity low enough to ensure good mixing of the catalyst with the feedstock.

In one embodiment, preheating is carried out at a temperature that is approximately 100 ° C (180 ° P) lower than the hydrocracking temperature in the contacting zone. In yet another embodiment, the preheating is carried out at a temperature that is approximately 50 ° C lower than the hydrocracking temperature in the contacting zone.

Hydrogen Feed

In one embodiment, the method provides for the presence of a hydrogen-containing gas.

Hydrogen can also be added to the heavy oil feed stream before the latter enters the preheater or after the preheater. In one embodiment, the hydrogen feed stream enters the direct contact feed zone with respect to the heavy oil feed stream in the same channel. In yet another embodiment, a hydrogen source may be added to the countercurrent contact zone. In a third embodiment, hydrogen enters the contacting zone through the gas channel separately from the combined heavy oil and suspended catalyst feed stream. In a fourth embodiment, the hydrogen feed stream is introduced directly into the combined catalyst and heavy oil feedstock before being introduced into the contacting zone. In yet another embodiment, hydrogen gas and a combined heavy oil and catalyst feed stream are introduced into the bottom of the reactor as separate streams. In yet another embodiment, hydrogen gas may be supplied to several sections of the contacting zone.

In one embodiment, the hydrogen source in the method is provided with a flow rate (when calculated by the ratio between the amounts of the hydrogen gas source and the raw feed stream) in the range from 0.1 to about 100,000 nm ³ / m ³ (from 0.563 to 563380 cubic feet) / b.), from about 0.5 to about 10,000 nm ³ / m ³ (from 2.82 to 56338 st. cubic feet / b.), from about 1 to about 8000 nm ³ / m ³ (from 5, 63 to 45070 cubic feet / b.), From about 2 to about 5000 nm ³ / m ³ (11.27 to 28169 cubic feet / b.), From about 5 to approx. but 3,000 nm ³ / m ³ (from 28.2 to 16901 cubic feet / b.) or from about 10 to about 800 nm ³ / m ³ (56.3 to 4507 cubic feet / b. ) In one embodiment, some hydrogen (25-75%) is supplied to the first contacting zone, and the rest is added as additional hydrogen to other contacting zones in the system.

In one embodiment, the refining system provides a volumetric yield greater than 100% (compared to the amount of heavy oil added) of the refined products since the added hydrogen increases the total volume of the heavy

- 9,023,427 oil. Sublimated products, i.e. low boiling hydrocarbons, in one embodiment, include liquefied petroleum gas (LPG), gasoline, diesel, vacuum gas oil (VGO), and jet and fuel oils. In a second embodiment, the refinement system provides a volumetric yield of at least 110% in the form of LPG, naphtha, jet and fuel oils and VGO. In a third embodiment, the volumetric yield is over 115%.

In one embodiment, the refining systems at least 98% by weight of the heavy oil feed stream are converted to lighter products. In a second embodiment, at least 98.5% of the heavy oil feed stream is converted to lighter products. In a third embodiment, the conversion is at least 99%. In a fourth embodiment, the conversion is at least 95%. In the fifth embodiment, the conversion is at least 80%. In the sixth embodiment, the conversion is at least 60%. As used herein, the degree of conversion refers to the conversion of heavy oil feedstocks to materials having a boiling point of less than 1000 ° P (538 ° C).

A hydrogen source in some embodiments is combined with a gaseous carrier (s) and sent for recycling through the contacting zone. The gaseous carrier may be, for example, nitrogen, helium and / or argon. The gaseous carrier may facilitate the flow of the crude feed stream and / or the flow of a hydrogen source into the contact zone (s). A gaseous carrier can also improve mixing in the contact zone (s). In some embodiments, a hydrogen source (eg, hydrogen, methane or ethane) can be used as the gaseous carrier and sent for recycling through the contacting zone.

Catalyst Feed

In one embodiment, the entire suspended catalyst feed stream is fed to the first contacting zone. In other embodiments, at least a portion of the catalyst feed is separated or diverted to at least one other contact zone in the system (different from the first contact zone). In yet another embodiment, all functional contacting zones receive a suspended catalyst feed stream (together with a heavy oil feed stream). In yet another embodiment, the method is configured to provide a flexible catalyst feed stream such that fresh catalyst can sometimes be fully fed to the last reactor in the system to obtain certain process conditions (to obtain certain desired product characteristics) or 50% the first reactor in the system for some of the technological runs, or is divided equally or in accordance with predetermined ratios between all reactors in the system , or separated in accordance with predetermined ratios for supplying the same fresh catalyst to different reactors at different concentrations.

The suspended catalyst feed stream used herein may contain one or more different suspended catalysts in the form of a single catalyst feed stream or separate feed streams. In one embodiment, one fresh catalyst feed stream is supplied to the contact zones. In yet another embodiment, the catalyst feed stream contains several different types of catalyst, with a particular type of catalyst entering one or more contacting zones (e.g., the first contacting zone) as a separate stream, and another suspended catalyst entering the zone ( zone) contacting, different from the 1st zone of contacting in the system, in the form of a different catalyst stream.

In one embodiment, at least a portion is at least 10% of the fresh catalyst. In yet another embodiment, at least 20%. In a third embodiment, at least 40%. In a fourth embodiment, at least 50% of the fresh catalyst is diverted to at least one contacting zone different from the first contacting zone in the system. In the fifth embodiment, all of the fresh catalyst is withdrawn, directing to the contacting zone different from the 1st contacting zone.

In one embodiment, less than 20% of the fresh catalyst is supplied to the first reactor in the system, with 80% or more of the fresh catalyst being diverted to a different contacting zone (s) in the system. In yet another embodiment, the fresh catalyst is equally divided between the contacting zones in the system. In one embodiment, at least a portion of the fresh catalyst feed stream is sent to at least one of the intermediate contacting zones and / or the last contacting zone in the system. In yet another embodiment, all of the fresh catalyst is sent to the last contacting zone in the system, with the first contacting zone in the system receiving only the recycled catalyst from one or more methods in the system, for example, from one of the separation zones in the system or from installation

- 10,023,427 deasphalting solvent.

In one embodiment, including an inter-stage DAR unit, at least a portion of the fresh catalyst feed stream is sent to the contacting zone immediately after the inter-stage DAR unit. In yet another embodiment, the entire fresh catalyst is sent to a contacting zone (s) other than the first contacting zone in the system, with the first contacting zone receiving only bottoms of DAR from the DAR unit and the catalyst sent for recycling from one or more methods in the system, for example, from one of the separation zones in the system.

In one embodiment, the fresh catalyst is combined with a stream of recycled catalyst from one of the methods in the system, for example, a separation zone, a distillation column, a DAP unit or an evaporation tank, and the feed stream of the combined catalyst is then mixed with the heavy oil feedstock into the contact zone (s). In yet another embodiment, streams of fresh catalyst and recycled catalyst are mixed into the heavy oil feed as separate streams.

In one embodiment, the catalyst stream sent for recycling from one of the methods in the system, such as a separation zone, a DAP unit, and the like, is combined with freshly suspended catalyst in the form of a single catalyst feed stream. The combined catalyst feed stream is then mixed with the heavy oil feed stream (s) (treated or not) to feed into the contact zone (s). In yet another embodiment, streams of fresh catalyst and recycled catalyst are mixed into the heavy oil feed stream (s) as separate streams.

In one embodiment, the method is configured to provide a flexible catalyst feed stream scheme such that the catalyst feed stream can sometimes be delivered in full (100% of the required catalyst flow) to the first reactor in the system for a certain period of time, then split equal in a manner or in accordance with predetermined ratios between all reactors in the system for a predetermined amount of time, or divided in accordance with a predetermined edelennymi ratios for feeding the feed stream of the catalyst in different reactors at different concentrations.

In one embodiment, dispatching the various catalysts to the front and rear contacting zones may be suitable to alleviate the problem of vanadium capture and maintain the overall performance of the refinement. In one embodiment, to help reduce vanadium uptake in the system, only Νί or suspended сульфο sulphide catalyst поο enriched in Νί is sent to the front reactor while another catalyst, such as Mo sulphide or Mo enriched sulphide catalyst ,ο, can be pumped into the rear reactor (s) to withstand an aggregate high degree of conversion, improve product quality and possibly reduce gas yield in one embodiment. As used herein, в enriched suspended catalyst means that the соотношение / Μο ratio is greater than 0.15 (in wt.%). Conversely, a suspended Mo-rich catalyst indicates that the Νί / Μο ratio is less than 0.05 (in wt.%).

In one embodiment, the suspended catalyst feed stream is first preconditioned before it enters the contact zone or before it is brought into contact with the heavy oil feed stream before it enters the contact zone. In one example, the catalyst enters the pre-conditioning unit together with hydrogen at a flow rate in the range of 500 to 7500 st. cube ft / b (b. in this case denotes the total volume of the feed stream based on heavy oil into the system) (from 88.8 to 1243 nm ³ / m ³ ). It appears that instead of bringing the cold catalyst into contact with the heavy oil-based feed stream, the preconditioning step facilitates the adsorption of hydrogen at the active sites of the catalyst and ultimately provides the desired degree of conversion. In one embodiment, in a preconditioner, the suspended catalyst / hydrogen mixture is heated to a temperature in the range of 300 ° P to 1000 ° P (149 to 538 ° C). In yet another embodiment, the catalyst is preconditioned in hydrogen at a temperature in the range of 500 to 725 ° C. (260 to 385 ° C.). In yet another embodiment, the mixture is heated under pressure in the range of 300 to 3200 lbs / in ² (from 2070 to 22100 kPa) in one embodiment; 500-3000 lb / ⁱⁿ² (3450-20700 kPa), in the second embodiment and 600-2500 lb / ⁱⁿ² (4140-17200 kPa) in the third embodiment.

- 11 023427

Used catalysts.

The suspended catalyst contains an active catalyst in a hydrocarbon oil. In one embodiment, the catalyst is a sulfonated catalyst containing at least a metal from group νίΒ or at least a metal from group VIII or at least a metal from group ΙΙΒ, for example a catalyst based on ferric sulfide, a catalyst based on zinc sulfide, nickel sulfide , molybdenum sulfide or iron-zinc sulfide. In yet another embodiment, the catalyst is a polymetallic catalyst containing at least a metal from group νίΒ and at least a metal from group VIII (as a promoter), where the metals may be present in elemental form or in the form of a metal compound. In one example, the catalyst is a Mo8 ₂ -based catalyst promoted with at least a Group VIII metal compound.

In one embodiment, the catalyst is a bulk polymetallic catalyst containing at least one base metal from group VIII and at least two metals from group U1B, and wherein the ratio of the amounts of at least two metals from group UTV and the base metal from group VIII is in a range of from about 10: 1 to about 1:10. In yet another embodiment, the catalyst is described by the formula (M ') _a (X ^u ) b (8 ^¥ ) a (C ”) _e (H ^x ) £ (O ^y ) 6 (M ² ) _b , where M represents at least at least one metal from the group ^ B, such as Mo, A, etc. or a combination thereof; and X performs the function of a promoter metal, representing at least one representative of: a base metal from group VIII, such as Νί, Co; a metal from group VIII, such as Fe; a metal from group VIΒ, such as Cr; a metal from group IVΒ, such as Tg; metal from the group of IV, such as Ζη, and combinations thereof (X in this document denotes a promoter metal). In addition, in equation 1, ν, ν,,, x, y, ζ represent the total charge for each of the components (M, X, 8, C, H, O, and Ν, respectively); Ια + ιι6 + νύ + \\ Ό + χΓ + \ β + ζ1ι = 0. The ratio between subscripts b and a has a value in the range from 0 to 5 and (0 <b / a <5). 8 represents sulfur with a subscript value ά ranging from (a + 0.5b) to (5a + 2b). C is carbon with an interline index e ranging from 0 to 11 (a + b). H represents hydrogen with a value of Γ in the range from 0 to 7 (a + b). O represents oxygen with a value of q in the range from 0 to 5 (a + b); and N represents nitrogen with a value of d in the range from 0 to 0.5 (a + b). In one embodiment, subscript b has a value of 0 for a catalyst based on a single metal component, for example, a catalyst based on only Mo (no promoter).

In one embodiment, the catalyst is prepared from catalyst precursor compositions comprising organometallic complexes or compounds, for example, oil-soluble compounds or complexes of transition metals and organic acids. Examples of such compounds include naphthenates, pentanedionates, octanoates and acetates of metals from group ΫΤΕ and group VIII, such as Mo, Co, A and the like, such as molybdenum naphthenate, vanadium naphthenate, vanadium octanoate, molybdenum hexacarbonyl and vanadium hexacarbonyl.

In one embodiment, the catalyst is a Mo8 ₂ -based catalyst promoted with at least a Group VIII metal compound. In yet another embodiment, the catalyst is a bulk polymetallic catalyst, wherein said bulk polymetallic catalyst contains at least one base metal from group VIII and at least two metals from group и, and where the ratio of the amounts of said at least two metals from group VIΒ and said at least one base metal of group VIII is in the range from about 10: 1 to about 1:10.

In one embodiment, the catalyst feed stream comprises a suspended catalyst having an average particle size of at least 1 μm in a diluting hydrocarbon oil. In yet another embodiment, the catalyst feed stream comprises a suspended catalyst characterized by an average particle size in the range of 1-20 microns. In a third embodiment, the suspended catalyst is characterized by an average particle size in the range of 2-10 μm. In one embodiment, the feed stream comprises a suspended catalyst characterized by an average particle size in the range from colloidal (nanometer size) to about 1-20 microns. In yet another embodiment, the catalyst includes molecules and / or extremely small catalyst particles that are colloidal in size (e.g., smaller than 100 nm, less than about 10 nm, less than about 5 nm, and less than about 1 nm). In operation, colloidal / nanometer-sized particles aggregate in a hydrocarbon diluent to form a suspended catalyst, characterized by an average particle size in the range of 1-20 μm. In yet another embodiment, the catalyst comprises monolayer Mo8 clusters of ₂ nanometer sizes, for example 5-10 nm in width.

In one embodiment, a sufficient amount of fresh catalyst and used catalyst are fed into the contact zone (s) to provide a suspended (solid) catalyst concentration in the range of 2 to 30 wt.% In each contact zone. In a second embodiment, the concentration of (solid) catalyst in the reactor is in the range of from 20 wt.%. In the third embodiment, from 5 to 10 wt.%.

In one embodiment, the amount of fresh catalyst feed to the contact zone (s) is in the range of 50 to 15,000 ppm (wt) Mo (concentration in the heavy oil feed). In a second embodiment, the concentration of the fresh catalyst feed stream is in the range of 150 to 2000 ppm (wt.) Mo. In a third embodiment, from 250 to 5000 ppm (wt.) Of Mo. In a fourth embodiment, the concentration is less than 10,000 ppm (wt.) Mo. The concentration of fresh catalyst in each contacting zone may vary depending on the contacting zone used in the system, since the catalyst may become more concentrated as volatile fractions are removed from the non-volatile fraction of the fuel oil, which therefore requires adjusting the concentration of the catalyst.

Optional Processing System - GIFT.

In one embodiment, a solvent deasphalting unit (DAP) is used to pretreat the heavy oil feedstock prior to the first contacting zone. In yet another embodiment, the solvent deasphalting unit is used as an intermediate unit located after one of the intermediate separation zones.

DAR units are typically used in refineries to extract additional lighter hydrocarbons from a heavy hydrocarbon stream, while the extracted oil is usually called deasphalted oil (DAN), leaving a stream of residue that is more concentrated in heavy molecules and heteroatoms, commonly known as VAR DAR, vat precipitation DAR, etc. A DAR unit can be a standalone unit or a unit built into the upgrading system.

Various solvents ranging from propanes to hexanes can be used in the DAR unit, depending on the required level of deasphalting before being fed into the contact zone. In one embodiment, a DAR unit is configured to produce deasphalted oil (DAN) to mix with the feed stream of the catalyst or to feed directly into the contacting zones instead of or in addition to the heavy oil feed stream. As such, the type of solvent and operating conditions can be optimized in such a way as to obtain DAN in large volumes and with acceptable quality and submit it to the contact zone. In this embodiment, a suitable solvent used includes, but is not limited to: hexane or the like C6 + solvent for var DAR in small volumes and DAN in large volumes. This scheme makes it possible to refine in the subsequent zone of contacting the vast majority of heavy oil-based feed streams, while the heaviest bottoms from bottom sediments in the barrel do not lead to favorable economic parameters for additional conversion due to the need for industrial hydrogen addition must be used in some other way.

In one embodiment, the entire heavy oil-based feed stream is pretreated in a DAR unit, and the DAN product is fed into the first contacting zone or fed in accordance with a dividing pattern of the feed stream when at least a portion enters the contacting zone, excellent from the first zone in serial connection. In yet another embodiment, a certain amount of the heavy oil-based feed stream (depending on the source) is first pretreated in a DAR unit, and a certain amount of feed is fed directly to the untreated contact zone (s). In yet another embodiment, the DAN is combined with an untreated heavy oil feedstock in the form of a single feed stream to the contact zone (s). In yet another embodiment, DAN and an untreated heavy oil based feed are fed into the system in separate feed channels, with the DAN entering one or more contact zones, and the untreated heavy oil based feed is fed to one or more of the same or different contacting zones.

In one embodiment, where a DAR unit is used as an intermediate unit, a non-volatile fraction containing a suspended catalyst and optionally minimal amounts of coke / asphaltenes and the like is sent to the DAR unit for processing. at least one of the separation zones. From the DAR DAN installation, at least one of the contacting zones is sent as a feed stream per se, as a feed stream in combination with a heavy oil feedstock, or as a feed stream in combination with a bottom stream from one of the zones separation. DAN bottoms containing asphaltenes are sent to the side to recover the metal in any entrained suspended catalyst or for applications requiring the use of asphaltenes, for example, mixed with fuel oil, used in asphalt, or used in some other applications.

- 13 023427

In one embodiment, the quality of the DAN and bottoms of the DAN varies as a result of adjusting the solvent used and the desired recovery of the DAN relative to the heavy oil feed stream. In an optional pre-treatment unit, such as a DAR unit, the more DAN oil that is recovered, the worse the overall quality of the DAN will be, and the worse the overall quality of the bottoms of the DAN will be. Regarding the choice of solvent, when a lighter solvent is used for the DAR installation, less DAN will usually be obtained, but the quality will be better, while if a heavier solvent is used, more DAN will be obtained, but the quality will be worse. Among other factors, this is due to the solubility of asphaltenes and other heavy molecules in the solvent.

The fight against the formation of deposits of heavy metals is an optional injection of water.

As used herein, the front contacting zone (or first contacting zone) refers to the 1st reactor in a system comprising three or less contacting zones. In yet another embodiment of a system comprising more than three contacting zones, the first front contacting zone may include both the first and second reactors. In yet another embodiment, the first contacting zone denotes only the 1st reactor.

As used herein, the term water is used to refer to either water and / or water vapor. In one embodiment of controlling the deposition of heavy metals, water is optionally injected into the system. In one embodiment, the injection is carried out at a fraction in the range of from about 1 to 25 wt.% (In comparison with the heavy oil feedstock). In one embodiment, a sufficient amount of water is injected to obtain a water concentration in the system in the range of 2 to 15% by weight. In a third embodiment, a sufficient amount is injected to obtain a water concentration in the range of 4 to 10% by weight.

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

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

In one embodiment, water is added directly to the contacting zone at several positions along the length of the contacting zone with a fraction in the range of 1 to 25% by weight of the heavy oil feedstock. In yet another embodiment, water in the process is added directly to the first few contact zones that are most susceptible to heavy metal deposits.

In one embodiment, some water is added to the process in the form of diluting water vapor. In one embodiment, at least 30% of the water is added in the form of water vapor. In embodiments where water is added as diluting water vapor, water vapor may be added to the process at any position. For example, it can be added to heavy oil feedstocks before or after preheating, to the catalyst / heavy oil mixture stream and / or directly to the vapor phase of the contacting zones or at several positions along the length of the first contacting zone. The dilution water vapor stream may include process water vapor and pure water vapor. Before serving, the steam may be heated or overheated in a furnace.

It appears that the presence of water in the process favorably alters the molar equilibrium of the metal compound — sulfur, thereby reducing the formation of heavy metal deposits. In one embodiment, the addition of water also appears to contribute to controlling / maintaining the desired temperature profile in the contacting zones. In yet another embodiment, it appears that the addition of water to the front contact zone (s) reduces the temperature of the reactor (s). It seems that as the reactor temperature decreases, the reaction rate of the most reactive vanadium compounds slows down, which makes it possible to form vanadium deposits on the suspended catalyst more

- 14 023427 in a controlled manner and removal of vanadium deposits from the reactor by the catalyst, which thus limits the formation of solid deposits in the reactor equipment.

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

Combating the formation of heavy metal deposits using reactor temperature.

In one embodiment, instead of adding water and / or in addition to adding water to the front contact zone (s), the temperature of the contact front zone (s) most susceptible to heavy metal deposits is reduced.

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

The fight against the formation of deposits of heavy metals when using the stream sent for recycling of the catalyst /

In one embodiment, to combat the formation of heavy metal deposits, at least a portion of the non-volatile product stream from at least one of the separation zones and / or the inter-stage deasphalting unit is recycled back to the front contact zone (s).

In one embodiment, the recycled stream comprises from 3 to 50% by weight of the total heavy oil feed in the process. In a second embodiment, the stream sent for recycling is present in an amount in the range of 15 to 45% by weight of the total heavy oil feedstock in the system. In a fourth embodiment, the recycled stream comprises at least 10% by weight of the total heavy oil feedstock in the system. In a fifth embodiment, the recycle stream comprises from 25 to 45% by weight of the total heavy oil based feed stream. In a sixth embodiment, the stream sent for recycling is at least 30% by weight. In the seventh embodiment, the stream sent for recycling is from 35 to 45 wt.%. In the eighth embodiment, the stream sent for recycling is from 30 to 40 wt.%.

In one embodiment, the recycled stream contains non-volatile materials from the last separation zone in the system, containing unreacted materials, heavier hydrocracked liquid products, suspended catalyst, small amounts of coke, asphaltenes, and the like. In one embodiment, the stream sent for recycling contains from 3 to 30 wt.% Suspended catalyst. In yet another embodiment, the amount of catalyst is in the range of 5 to 20 wt.%. In yet another embodiment, the stream sent for recycling contains from 1 to 15 wt.% Suspended catalyst.

It seems that in some embodiments, thanks to the additional catalyst sent for recycling supplied in the stream sent for recycling, more of the catalytic surface area (due to the suspended catalyst in the stream sent for recycling) becomes available for the distribution of heavy metal deposits, thus, less grip or deposits in equipment. Additional areas of the catalytic surface provided by the stream sent for recycling contribute to minimizing the overload of the catalyst surface with heavy metal deposits, which leads to the formation of deposits on technological equipment (walls, internal equipment, etc.).

Technological conditions

In one embodiment, the process conditions are controlled to withstand more or less constant across all areas of contact. In yet another embodiment, the conditions vary between the contacting zones for the refined products having specific properties.

In one embodiment, the refining system is maintained under conditions of hydrocracking, for example, at a minimum temperature of hydrocracking of the feedstock based on heavy oil. In one embodiment, the system operates at a temperature ranging from 400 ° C (752 ° F) to 600 ° C (1112 ° F) and a pressure in the range of 10 MPa (1450 lb / ⁱⁿ²⁾ to 25 MPa (3625 lb / inch ² ). In one embodiment, the process conditions are controlled to withstand more or less constant across all contact areas. In yet another embodiment, the conditions vary between contacting zones for refinement products having specific properties.

In one embodiment, the process temperature of the contact zone is in the range of from about 400 ° C (752 ° P) to about 600 ° C (1112 ° P), less than 500 ° C (932 ° P) in yet another embodiment and greater than 425 ° C (797 ° P) in yet another embodiment. In one embodiment, the system operates at a temperature difference between the inlet and the outlet of the contacting zone in the range of 5 to 50 ° P (2.8 to 28 ° C). In the second embodiment, from 10 to 40 ° P (from 5.56 to 22.2 ° C).

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

Technological pressure in the zones contacting is in the range from about 10 MPa (1450 lb / ⁱⁿ²⁾ to about 25 MPa (3625 lbs / ⁱⁿ²⁾ in one embodiment, between about 15 MPa (2175 lb / ⁱⁿ²⁾ to about 20 MPa (2900 lbs / ⁱⁿ²⁾ in the second embodiment is less than 22 MPa (3190 lbs / ⁱⁿ²⁾ in the third embodiment, and greater than 14 MPa (2030 lbs / ⁱⁿ²⁾ in the fourth embodiment. In one embodiment, the separation zone pressure is maintained within the range of ± 10 to ± 50 lb / in ² (from 68.9 ± to ± 345 kPa) pressure in the prior introduction zone into contact, in one embodiment, and in the range of up to ± 2 ± 10 lb / in ² (from 13.8 ± to ± 68.9 kPa) in the second embodiment.

In one embodiment, the system upgrading configured for optimal operation, e.g. to achieve efficiency at much lower unproductive losses of time due to clogging of equipment as compared with that occurred in the prior art with a pressure drop of less than 100 lb / ⁱⁿ² (689 kPa). Optimum efficiency in one embodiment is prepared with a minimum pressure drop in the system, where the pressure in the separation zone is maintained within the range of ± 10 to ± 100 lb / ⁱⁿ² (from 68.9 ± to ± 689 kPa) pressure in the prior administration district contact in one embodiment in the range from ± 20 to ± 75 lb / ⁱⁿ² (from ± 138 to ± 517 kPa) in the second embodiment, and in the range of ± 50 to ± 100 lb / ⁱⁿ² (from ± 345 to ± 689 kPa) in the third embodiment. In accordance with the use, in this case, the pressure drop represents the difference between the pressure at the outlet prior introduction zone into contact X and the inlet pressure separation zone Υ, wherein the value (X-Υ) is less than 100 lb / ⁱⁿ² (689 kPa) .

Optimum efficiency can also be achieved with a minimum pressure difference when moving from one contacting zone to a subsequent contacting zone for a sequential system, with a pressure drop of 100 lb / in ² (689 kPa) or less in one embodiment and 75 lb / ⁱⁿ² (517 kPa) and less in the second embodiment, and less than 50 lb / ⁱⁿ² (345 kPa) in the third embodiment. The pressure drop in this case denotes the difference between the pressure at the outlet of one contacting zone and the pressure at the inlet of the subsequent contacting zone.

In one embodiment, to ensure a minimum pressure drop, the contacting zone is directly in fluid communication with the subsequent separation zone or contacting zone. As used herein, direct fluid communication means there is free flow from the contacting zone to the subsequent subsequent separation zone (or subsequent contacting zone) without any flow restriction. In one embodiment, direct fluid communication is obtained without any flow restriction due to the presence of valves, diaphragms (or the like), or changes in pipe diameter.

In one embodiment, the minimum pressure drop during the transition from the contacting zone to the subsequent separation zone or contacting zone (when entering the separation zone or contacting zone) is due to the presence of pipeline components, for example elbows, bends, tees in a line, etc. .p., but not using a pressure reducing device, such as valves, control valves, etc., which caused a pressure drop in the prior art. As suggested in the prior art, the separation zone performs the function of an inter-stage separator using a pressure differential.

- 16 023427

In one embodiment, the minimum pressure drop is caused by the loss of pressure on the friction of the flow, friction against the wall, increase in volume, and a change in height as the waste products flow from the contact zone to subsequent connected equipment. In the case of using valves in a one-way system, the valves are selected / configured so that the pressure drop during the transition from one equipment, for example, the contacting zone, to the next piece of equipment is maintained at 100 lb / in ² (689 kPa) or less.

In one embodiment, the hourly volumetric fluid velocity (LSS) for the heavy oil-based feed stream will generally be in the range of from about 0.025 to about 10 h ⁻¹ , from about 0.5 to about 7.5 h ⁻¹ , from from about 0.1 to about 5 h ^-1 , from about 0.75 to about 1.5 h ^-1, or from about 0.2 to about 10 h ^-1 . In some embodiments, the LHSV is at least 0.5 h ⁻¹ , at least 1 h ⁻¹ , at least 1.5 h ^−1, or at least 2 h ⁻¹ .

In some embodiments, the LHSV value is in the range of 0.025 to 0.9 h ⁻¹ . In yet another embodiment, the LHSV value is in the range of 0.1 to 3. In yet another embodiment, the LHSV value is less than 0.5 h ⁻¹ .

In one embodiment, where the entire flow of non-volatile fractions from at least one separation zone is sent to a DAP unit for deasphalting, the formation of solid deposits in the last contacting zone in the system is reduced by at least 10% (when expressed through the volume of deposits) after a similar duration of continuous operation in comparison with the operation of the prior art in the absence of deasphalting when using the DAR installation. In the second embodiment, the formation of solid deposits is reduced by at least 20% in comparison with the operation without the use of an inter-stage DAR unit. In a third embodiment, solid deposits are reduced by at least 30%.

It was found that in various embodiments, when some, if not all, of the amount of fresh catalyst is withdrawn to the contacting zone (s) other than the first contacting zone in the system, the overall cracking efficiency of the feedstock based on tangible heavy oil or in general, at least there is no effect if compared with the prior art feed flow scheme, including the receipt of all fresh catalyst in the first contact zone. In one embodiment, a shift in the injection position of fresh catalyst leads to a significant increase in total catalytic activity with improved quality of the flow of non-volatile products from the last separation zone in the system (bleed stream, stripping residue in the stripper or OROK), in terms of density in degrees ANI viscosity, the level of micro carbon residue, nickel, the ratio of hydrogen / carbon and the level of asphaltenes recovered in hot heptane (AGG). In some other embodiments, less catalyst bleeding is also observed with a combined improvement in catalytic activity.

In one embodiment, improving the OROC product includes reducing the nickel level by at least 10%, in a second embodiment, reducing the nickel level by at least 20%. In a third embodiment, the content of Νί is less than 10 ppm.

In one embodiment, the reduction in the level of microcarbon residue in the OROC is at least 5%. In yet another embodiment, the reduction in the level of micro carbon residue is at least 10%. In a third embodiment, the level of micro carbon residue is less than 13 wt.%.

In one embodiment, the OROK demonstrates an increase in API viscosity of at least 15%. In a second embodiment, an API viscosity improvement of at least 30%. In a third embodiment, an API viscosity improvement of at least 50%, with a transition from 2.7 to 4.5. According to observations in some embodiments, the improvement in ANI is due to the cumulative improved catalytic activity, which thus results in an increased H / C ratio.

As was established in embodiments comprising a heavy oil-based feed flow splitting scheme, as a result of withdrawing a portion of the heavy oil-based feedstock from the first contacting zone with at least one other series-connected contacting zone, the total coke formation is significantly reduced in comparison with what occurs in the flow pattern of the prior art upon receipt of all the feedstock based on heavy oil in the 1st zone of introduction into the con act. In addition, as a result of the withdrawal of at least a portion of the heavy oil feedstock to contact zones other than the 1st in the system, in these contact zones there is some dilution with liquid (which would not be present in the previous prior art). Dilution with a liquid makes it possible to obtain a more uniform catalyst concentration profile for all reactors in the system, which thus protects the latter reactor from a sharp increase in the level of solids, which could lead to operational problems.

In some embodiments, including a heavy oil-based feed flow dividing scheme, it has been observed that the overall efficiency of the system also improves with the degree of conversion in the reactors (contact zones), which allows additional evaporation of the oil and a corresponding decrease in liquid throughput and increase in catalyst concentration. This would in particular increase the efficiency of the system with less liquid throughput (or longer liquid residence time) and higher catalyst concentration. In addition, in the case of a stationary flow rate of the secondary feed stream based on heavy oil when fed directly to the last reactor, the latter reactor will be protected from abnormal conditions that could deprive this fluid flow capacity. Thus, a heavy oil-based feed flow dividing scheme reduces or eliminates the likelihood of occurrence of excessive conversion events or dry conditions, often observed in hydroprocessing reactors. In a refining system operating in dry conditions, there is insufficient fluid flow, which thus leads to the accumulation of solids / coking, disruption of flow patterns and / or hydrodynamics, violation of thermometry, loss of reaction volume, and, ultimately, deterioration of operational characteristics, stability and durability of functioning.

Figures illustrating embodiments

To further illustrate embodiments of the invention, reference will be made to the figures.

FIG. 1 is a block diagram schematically illustrating a system for refining heavy oil-based feedstocks with reduced deposition of heavy metals. First, heavy oil-based feedstocks are introduced into the first contacting zone in the system together with the feed stream of the suspended catalyst. In the figure, the suspended catalyst feed stream includes a combination of fresh catalyst and a suspension of recycled catalyst in separate streams. Hydrogen can be introduced together with the feed stream in the same channel or, optionally, as a separate feed stream. Together with the feed stream and the suspended catalyst in the same channel or a separate feed stream, water and / or water vapor may be introduced. Although not shown, a mixture of water, a heavy oil based feed stream and a suspended catalyst may be preheated in a heater before being fed to the contacting zone. Although not shown, as part of the feed stream to any of the contact zones in the system, an optional feed stream based on hydrocarbon oil, for example, VGO, naphtha, in an amount of 2 to 30% by weight of the feed stream per heavy oil base.

Although not shown in the figures, the system may include recirculation / recycling channels and pumps to promote dispersion of the heavy oil based reagents, catalyst, and feedstocks in the contact zones, in particular at high flow rates when recycled to the first zone contacting to induce turbulent mixing in the reactor, thereby reducing the formation of heavy metal deposits. In one embodiment, the recirculation pump circulates through the loop reactor, which thus maintains the temperature difference between the position of the feed into the reactor and the position of the release from it in the range from 1 to 50 ° P (from 0.6 to 28 ° C), and preferably 2-25 ° P (1.1-14 ° C).

In the contacting zones under conditions of hydrocracking, at least a portion of the heavy oil feed (higher boiling hydrocarbons) is converted to lower boiling hydrocarbons to obtain an ennobled product. Water / water vapor in the first contacting zone is believed to reduce the formation of heavy metal deposits on the equipment. Although not illustrated, the temperature of the first contacting zone can be maintained at least 5-25 ° P (2.78-13.89 ° C) lower than the temperature of the subsequent subsequent contacting zone.

The material to be upgraded is taken from the 1st contacting zone and sent to a separation zone, for example a hot separator operating at high temperature and high pressure, similar to those in the contacting zone. The refined material before being sent to the hot separator may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further refining. The separation zone causes or makes it possible to separate gas and volatile liquids from non-volatile fractions. Gaseous and volatile liquid fractions are taken from the top of the separation zone for further processing. Non-volatile (or less volatile) fraction is taken from below. Suspended catalyst and entrained solids, coke, hydrocarbons newly recovered in a hot separator, and the like. taken from the bottom of the separator and served in a series-connected subsequent zone of introduction into contact. In one embodiment (not shown), a portion of the non-volatile product stream is sent to

- 18 023427 recycling to one of the contacting zones preceding the separation zone, which ensures the use of the catalyst sent for recycling in hydroconversion reactions.

In one embodiment (indicated by dashed lines), portions of the fresh catalyst feed stream and heavy oil feed are fed directly to the contact zones (reactors) other than the first contact zone in the system. In one embodiment, where portions of the heavy oil feed are fed directly to the contacting zones other than the 1st contacting zone, water and / or steam are also supplied to the contacting zones as a separate feed stream. or they are introduced together with the feed stream and the suspended catalyst in the same channel.

The liquid stream from the preceding separation zone is combined with an optional fresh catalyst, an optional additional heavy oil based feed stream, an optional hydrocarbon oil based feedstock such as VGO (vacuum gas oil), and an optionally recycled catalyst (not shown) as a feed flow for a series connected subsequent zone of contact. Hydrogen may be introduced along with the feed stream into the same channel or, optionally, as a separate feed stream. Sublimated materials, together with the suspended catalyst, flow into a subsequently connected subsequent separation zone to separate gas and volatile liquids from non-volatile fractions. Gaseous and volatile liquid fractions are taken from the top of the separation zone and combined with gaseous and volatile liquid fractions from the previous separation zone for further processing. The flow of non-volatile (or less volatile) fractions is taken and sent to the subsequent connected contact zone in order to refine the unreacted heavy oil-based feedstock.

In the last contacting zone, hydrogen is added together with unreacted heavy oil feedstock, an optional heavy oil feedstock, an optional HGO feed, and an optional fresh catalyst. Treated materials flow into the subsequent separation zone together with the suspended catalyst, where the treated products are removed from above, and some non-volatile materials are recycled. In one embodiment, the recycled stream is sent to the first contacting zone, allowing for the use of some recycled catalyst in hydroconversion reactions. In a second embodiment, the recycled stream is divided between the contacting zones preceding the last contacting zone connected in series.

In one embodiment, the system may optionally include an in-line hydroprocessing unit (not shown) for treating gaseous and volatile liquid fractions from separation zones. Built-in-line installation in a hydrotreating embodiment employs conventional hydrotreating catalysts and operated at such a high pressure (within 10 lb / ⁱⁿ² (g.) (68.9 kPa (g.))), As well as the rest of the refining system, and is capable of removing sulfur, Νί, V and other impurities from refined products. In yet another embodiment, the in-line hydroprocessing unit operates at a temperature within 100 ° P (55.6 ° C) of the temperature of the contacting zones.

FIG. 2 is a flowchart of a process for upgrading heavy oil, including pumping water. As demonstrated, water 81 is injected into the system along with a heavy oil feedstock, the mixture being preheated in a furnace before being introduced into the contacting zone. Water / water vapor is also optionally injected into the system after pre-heating as stream 82. In this embodiment, the fresh catalyst feed stream is divided between the contacting zones. The stream of catalyst sent for recycling 17, the water / heavy oil-based feed mixture and hydrogen gas 2 are supplied to the first contacting zone as a feed stream 3.

Stream 4, containing the refined heavy oil-based feedstock, leaves the K-10 contact zone and flows into separation zone 40, where gases (including hydrogen) and refined products in the form of volatile liquids are separated from the non-volatile liquid fraction 7 and removed from the top in the form of stream 6. The flow of non-volatile products 7 is sent to the subsequent subsequent introduction zone into contact 20 for further refinement. The non-volatile product stream 7 comprises a suspended catalyst in combination with unreacted oil and small amounts of coke and asphaltenes in some embodiments.

The refinement process continues in the other contact areas shown, where the feed to contact 20 includes non-volatile fractions, a hydrogen feed, an optional VGO feed, and fresh catalyst feed 32. From the contact 20 contact 20, a stream 8 containing heavy oil feedstock flows to separation zone 50, where the treated products are combined with hydrogen and removed as top product 9. Bottom stream 1 1, containing non-volatile fractions, for example, a catalyst suspension, unreacted oil containing coke and asphaltene, flows into a successively connected subsequent contact introduction zone 30.

In the contact introduction zone 30, additional hydrogen-containing gas 16, fresh catalyst 33, an optional hydrocarbon feed stream such as VGO (not shown), an optional untreated heavy oil feed stream (not shown) are added to the non-volatility product stream from the previous separation zone 16 ) Refined products, unreacted heavy oil, suspended catalyst, hydrogen, and the like are from the contacting zone 30. removed from the top in the form of stream 12 and sent to the subsequent separation zone 60. From the separator, the upper stream 13 containing hydrogen and processed products is combined with the upper flows from the previous separation zones and sent to the side for further processing in another part of the system, for example, a high pressure separator and / or a topped oil contactor and / or an in-line hydroprocessing unit (not shown). A portion of the non-volatile product stream 17 is removed as a bleed stream 18. The remainder is recycled to at least one of the contacting zones (the first contacting zone 10 shown) as a recycled catalyst stream.

FIG. 3 is a flowchart of yet another embodiment of a process for refining heavy oil by injecting water vapor 91 instead of and / or in addition to the water injection stream 81.

FIG. 4 is a flowchart of yet another embodiment of a method for refining heavy oil, wherein the stream of catalyst 19 sent for recycling is from 3 to 50% by weight of the total heavy oil feedstock in the method.

FIG. 5 is a block diagram schematically illustrating yet another embodiment of a refinement of heavy oil feedstocks. First, heavy oil-based feedstocks are introduced into the first contacting zone in the system together with the feed stream of the suspended catalyst. Hydrogen may be introduced in conjunction with the feed stream in the same channel or, optionally, as a separate feed stream. In one embodiment (not shown) in an amount in the range of 2 to 30% by weight of the heavy oil-based feed stream, optional hydrocarbon oil-based feedstocks such as VGO (vacuum gas oil), naphtha, SRH (medium recycle gas oil) are present ), a solvent donor or other aromatic solvents and the like. Additional hydrocarbon feedstocks can be used to modify the concentration of metals and impurities in the system. In the contacting zones under hydrocracking conditions, at least a portion of the heavy oil feedstock (higher boiling hydrocarbons) is converted to lower boiling hydrocarbons to obtain a refined product.

Sublimated material is taken from the 1st contacting zone and sent to a separation zone, for example a hot separator. Sublimated material before entering the hot separator may alternatively be introduced into one or more additional hydroprocessing reactors (not shown) for further refinement. The separation zone causes or makes it possible to separate gas and volatile liquids from non-volatile fractions. Gaseous and volatile liquid fractions are taken from the top of the separation zone for further processing. Non-volatile (or less volatile) fraction is taken from below. Suspended catalyst, small amounts of heavier hydrocracked liquid products and entrained solid, coke, hydrocarbons newly obtained in a hot separator, and the like. taken from the bottom of the separator and served in a series-connected subsequent zone of introduction into contact. In one embodiment (not shown), a portion of the non-volatile product stream is recycled to the contacting zone immediately preceding the separation zone in an amount equivalent to a range of 2 to 40% by weight of the total heavy oil feed stream.

A non-volatile product stream from the preceding separation zone containing unreacted feedstock is combined with an additional fresh catalyst, an optional additional heavy oil feed stream, and an optionally recycled catalyst (not shown) as a feed stream for the subsequent subsequent contact zone.

In the subsequent contacting zone and under conditions of hydrocracking, a greater amount of heavy oil-based feedstock is subjected to refinement to obtain lower boiling hydrocarbons. The materials to be upgraded together with the suspended catalyst flow into the subsequent separation zone connected in series to separate gas and volatile liquids from non-volatile fractions. The flow of non-volatile (or less volatile) products is taken from below. Gaseous and volatile liquid fractions are taken from the top of the separation zone (and combined with gaseous and volatile liquid fractions from the previous separation zone) in the form of refined products for further processing or mixing, for example, to ensure that the final mixed products meet the technical characteristics developed by oil refineries and / or transport carriers.

- 20 023427

In one embodiment (not shown), non-volatile material containing unreacted materials is sent to a subsequent connected contact zone in series. In yet another embodiment, as demonstrated, non-volatile material is recycled to one of the contacting zones in the system when a portion of the material is drained for further processing, for example, entering a deasphalting unit with a solvent, a catalyst de-oiling unit, and subsequently a metal recovery system. The non-volatile material sent for recycling in one embodiment forms an amount equivalent to a value in the range from 2 to 50 wt.% Of the heavy oil feedstock in the system, which ensures the use of the catalyst sent for recycling in hydroconversion reactions.

Depending on the operating conditions, the type of catalyst fed to the contacting zone, and the concentration of the suspended catalyst, in one embodiment, the stream leaving the contacting zones is characterized by the ratio of the amount of refined products to the unreacted heavy oil-based feed stream in the range of about 20 : 80 to 60:40. In one embodiment, the amount of the refined products from the first contact zone is in the range of 30-35%, and the unreacted heavy oil product is in the range of 65-70%.

Although not shown in the figures, the system may include recirculation / recycling channels and pumps to promote dispersion of the reagents, catalyst, and heavy oil feed in the contact zones. In one embodiment, the recirculation pump circulates through the loop reactor at a volume ratio of recirculation in the range of 5: 1 to 15: 1 (the ratio of the amount sent to recirculation and the amount of the supplied flow based on heavy oil), which thus allows to withstand the temperature difference between the position of the feed into the reactor and the position of the release from it in the range from 10 to 50 ° P (from 5.56 to 27.8 ° C), and preferably 20-40 ° P (11.1-22.2 ° C )

In one embodiment, the system may optionally include an in-line hydroprocessing unit (not shown) for treating gaseous and volatile liquid fractions from separation zones. Built-in-line installation in a hydrotreating embodiment employs conventional hydrotreating catalysts and operated at such a high pressure (within 10 lb / ⁱⁿ² (g.) (68.9 kPa (g.)) In one embodiment, and 50 lb / in ² (g) (345 kPa (g)) in the second embodiment), like the rest of the refinement system, and is capable of removing sulfur, Νί, V and other impurities from the treated products.

FIG. 6 is a block diagram schematically illustrating yet another embodiment of a refinement system where a solvent deasphalting unit is used to pretreat some, if not all, amount of heavy oil-based feed stream in the system. Deasphalted oil (DAN) can be fed directly to the contacting zone (s) or combined with a heavy oil feed stream as a feedstock. In one embodiment, with the feed stream based on heavy oil and / or DAN as the feedstock for some of the contact zones (zones), other hydrocarbon materials, such as VGO, can also be combined. All fresh catalyst can be fed directly to the first contacting zone in the system or diverted to another contacting zone (s) connected in series.

FIG. 7 is a flowchart of a process for upgrading heavy oil, comprising a dividing feed stream of fresh catalyst, wherein a certain amount of feed of fresh catalyst is diverted from the first reactor to other reactors in the process. As demonstrated, the fresh catalyst feed stream is divided between the various contacting zones as feed streams 31, 32 and 33. The fresh catalyst feed stream 31 is combined with the recycled catalyst stream 17 and fed into the first contact zone as a feed stream suspended catalyst 3. Hydrogen gas 2 and heavy oil-based feedstock 1 are combined with suspended catalyst 3 as a feed stream to the first contacting zone 10. In this embodiment, Ante the implementation of the heavy oil-based feedstock is preheated in furnace 80 before being introduced into the contacting zone as a heated oil-based feed stream 4.

Stream 5 containing the refined heavy oil-based feedstock leaves the contacting zone 10 and flows into separation zone 40, where the gases (including hydrogen) and the volatile refined products are separated from the non-volatile fractions 7 and removed from above as a stream 6. The flow of non-volatile fractions 7 is sent to the subsequent subsequent introduction zone to the contact 20 in series for further refinement. Stream 7 contains a suspended catalyst in combination with unreacted oil and small amounts of coke and asphaltenes in some embodiments.

- 21 023427

The refinement process continues in the other contacting areas shown, where stream 7 is combined with a feed stream of hydrogen 15 and fresh catalyst 32 as a feed stream to a contact introduction zone 20. Although not shown, streams can also be fed into a contact zone contact in separate channels. Stream 8 containing the refined heavy oil-based feedstock flows to separation zone 50, where the refined products are combined with hydrogen and removed as top product 9. Bottom stream 11, containing a catalyst suspension, unreacted oil (plus small amounts of coke and asphaltenes in some embodiments) are combined with a fresh catalyst stream 33 and a fresh hydrogen supply 16 as a feed stream to a subsequent contacting zone 30. Leaving stream 12 comes into contact zone and flows into separation zone 60, where the refined products and hydrogen are removed from above as stream 13. A certain amount of bottom stream 17 from the separation zone, which contains a catalyst suspension, unreacted oil, plus small amounts of coke and asphaltenes in some embodiments implementation, sent for recycling in the 1st zone of the introduction into contact 10 in the form sent to the recycling stream 19. The remaining portion of the lower stream 17 is removed as a bypass stream 18 and sent to other ways I am in a system for deoiling catalyst metals recovery, etc. Although not shown, the steam stream 14 containing the refined products and hydrogen in one embodiment is then processed in another part of the system, for example in a high pressure separator and / or topped oil contactor.

FIG. 8 illustrates yet another embodiment of the invention where reactors comprising internal separators are used, so that separate hot separators / evaporation drums are not required for phase separation. In this refinement system, a reactor pressure control system (pressure difference (not shown)) is used to control the flow of products from the top of each separator reactor. External pumps (not shown) may be used to facilitate dispersion of the suspended catalyst in the system and to facilitate temperature control in the system.

In the illustrated embodiment of FIG. 8, all fresh catalyst is withdrawn, directing to the 2nd and 3rd contacting zones in the system. The stream of catalyst sent for recycling 19 forms a feed stream of suspended catalyst in the first contacting zone and, optionally, in the other contacting zones (zone) in the system. As also demonstrated, as part of the feed stream to any of the contacting zones in the system, an optional feed stream of hydrocarbon oil, for example, VGO, naphtha, in an amount of 2 to 30 wt.% Of the feed stream based on heavy oil may optionally be supplied .

FIG. 9 illustrates one embodiment of the invention where the entire fresh catalyst feed stream 99 is fed directly to the last contacting zone in the refining system, while the other contacting zones (zone) in the system simply receive a portion of the recycled catalyst stream 19.

FIG. 10 illustrates one embodiment of a heavy oil based feed flow division scheme. As demonstrated, a certain amount of the heavy oil-based feed stream is withdrawn from the 1st reactor and fed directly to the 2nd contact zone in the system as a heavy oil-based feed stream 42. The catalyst sent for recycling is optionally sent to the 2- th contact zone in the system together with parts of the fresh catalyst in the form of stream 32.

The following examples are presented by way of non-limiting illustration of aspects of the present invention.

Comparative Example 1. The heavy oil refinement experiments were carried out in a semi-industrial system comprising three gas-liquid reactors with a suspension phase, connected in series with three hot separators, each of which was connected in series with the reactors. The upgrading system has been continuously operating for approximately 50 days.

Used fresh suspended catalyst was obtained in accordance with the provisions of US patent No. 2006/0058174, i.e. Mo compound was first mixed with aqueous ammonia to obtain an aqueous mixture of Mo compound, sulfidized with a hydrogen compound, promoted with compound Νί, then transferred to hydrocarbon oil (different from the heavy oil feedstock) at a temperature of at least 350 ° P (177 ° C) and a pressure of at least 200 lb / ⁱⁿ² (g.) (1380 kPa (g.)), to obtain active catalyst suspended and sending it into the first reactor.

The hydroprocessing conditions were as follows: reactor temperature (in three reactors) equal to approximately 825 ° P (440.6 ° C); the total pressure in the range from 2400 to 2600 lb / ⁱⁿ² (g.) (from 16500 to 17900 kPa (g).); the ratio of the quantities of fresh Mo / fresh feed stream based on heavy oil (wt.%) 0.20-0.40; fresh catalyst ratio

- 22 023427 based on Mo / total catalyst based on Mo 0.125-0.250; the COSG value for the total feed stream in the range of about 0.070 to 0.15 and gaseous H ₂ flow rate (cc / ft) in the range of 7500 to 20,000 ((nm ³ / m ³ ) in the range of 1330 to 3550 )

Waste products taken from each reactor were sent to a (series connected) separator and separated into a hot steam stream and a non-volatile product stream. Vapor flows were removed from the top of the high pressure separators and collected for subsequent analysis (HPW or upper high pressure flows). A non-volatile product stream containing a suspended catalyst and unreacted heavy oil feed was removed from the separator and sent to a subsequent downstream reactor.

Part of the flow of non-volatile products from the last separator was recycled in an amount of 30 wt.% Of the heavy oil-based feedstock (OROC), and the rest was removed as a etched stream (in an amount of approximately 15 wt.% Of the heavy-based feedstock oil). The OROC stream contains about 10 to 15% by weight of the suspended catalyst.

The mixture of the feed stream into the system was a heavy crude oil, characterized by a high level of metal content and having the properties shown in table. one.

Table 1

ORP feed stream Density in degrees ANI at 60/60 - Relative density 1,0760 Sulfur (% (mass.)) 5.27015 Nitrogen (ppm) 7750 Nickel (ppm) 135.25 Vanadium (ppm) 682.15 Carbon {% (mass.)) 83, 69 Hydrogen (% (mass.)) 9.12 The ratio of the quantities N / C 0.109

After 50 days, the functioning was stopped. The reactor, distributor, and internal thermocouple socket were visually inspected. All three elements showed a significant accumulation of deposits, while approximately 28.5% of the volume of the front (1st) reactor was lost due to the formation of heavy metal deposits. Analysis of the used suspended catalyst in the bleed stream after a 50-day period showed an increasing lack of vanadium, suggesting that the accumulation of deposits inside the front reactor not only occurred, but was actually exacerbated during the run. Due to the loss of volume for the reaction, the operational characteristics of the method were also affected.

Example 2. Example 1 was repeated except that the temperature of the 1st reactor was reduced by 20 ° P (11.1 ° C) (from about 825 ° P (440.6 ° C) to about 805 ° P (429.4 ° C) ), increasing the proportion of the catalyst sent for recycling from 30 wt.% (in example 1) to approximately 40 wt.% of the flow rate when feeding a feed stream based on heavy oil and adding water to the front reactor at a fraction equivalent to 5 wt.% of the flow rate when applying a feed stream based on heavy oil. Before shutting down, the system functioned for 54 days.

Water was injected as a result of adding water to the fresh catalyst, after which the water-catalyst mixture was added to the autoclave together with the feed stream based on heavy oil and hydrogen, while the mixture was pre-heated to a temperature of approximately 350 ° P (177 ° C).

Analysis of the used suspended catalyst in the etched stream after a 54-day period showed a fairly close correspondence between the amount of vanadium expected at the process outlet and the amount of vanadium in the catalyst in the etched stream, suggesting a significant reduction in vanadium capture and thus the formation of heavy metal deposits in equipment.

The analysis results were additionally confirmed by visual inspection of the internal equipment of the reactor, the distributor and the internal socket for the thermocouple. The equipment was significantly cleaner in Example 2, with only 6.6% of the front reactor volume lost due to the formation of heavy metal deposits.

Comparative example 3. Experiments on the refinement of heavy oil was carried out in a semi-industrial system, including three gas-liquid reactors with a suspension phase, connected in series with two hot separators. Hot separators were connected in series with the 1st and 3rd reactors, respectively, in the absence of a hot separator after the 2nd reactor. Gas-liquid reactors with a suspension phase were continuous reactors with mechanical stirring. The upgrading system has been continuously operating for approximately 70

- 23,023,427 days.

Used fresh suspended catalyst was obtained in accordance with the provisions of US patent No. 2006/0058174, i.e. Mo compound was first mixed with aqueous ammonia to obtain an aqueous mixture of Mo compound, sulfidated with hydrogen / sulfur compound, promoted with compound Νί, then transferred to hydrocarbon oil (different from the heavy oil feedstock) at a temperature of at least 350 ° P (177 ° C) and a pressure of at least 200 lb / ⁱⁿ² (g.) (1380 kPa (g.)), to obtain active catalyst suspended.

In comparative example 3, the entire suspension of fresh catalyst was sent to the first reactor in the system to obtain a concentration of freshly suspended catalyst in heavy oil in the range from 2000 to 5000 ppm when expressed as the mass of metal (molybdenum) based on the weight of the feed stream based on heavy oil. The hydroprocessing conditions were as follows: reactor temperature in the range of 815-825 ° P (435.0-440.6 ° C); the total pressure in the range from 2400 to 2600 lb / ⁱⁿ² (g.) (from 16500 to 17900 kPa (g).); the ratio of the quantities of fresh Mo / fresh feed stream based on heavy oil (wt.%) 0.20-0.40; the ratio of the amounts of fresh catalyst based on Mo / total catalyst based on Mo 0.1; the LHSV value for the total feed stream in the range from 0.10 to 0.15; and gaseous H ₂ flow rate (st. cubic foot / b.) in the range of 10,000 to 15,000 ((nm ³ / m ³ ) in the range of 1775 to 2660).

Waste products taken from the 1st and 3rd reactors were introduced into hot separators connected in series with the reactors and separated into a hot vapor stream and a non-volatile product stream. Vapor flows were removed from the top of the high pressure separators and collected for subsequent analysis (HPW or upper high pressure flows). A non-volatile product stream containing a suspended catalyst and unreacted heavy oil-based feed was removed from the bottom of the 1st separator and sent to the 2nd reactor in series. The waste products from the 2nd reactor were sent directly to the 3rd reactor as a feedstock.

Part of the flow of non-volatile products from the last separator in the amount of 5-15 wt.% Of the heavy oil-based feedstock was removed as a bypass stream with the total degree of conversion to distillate products in the range from 98 to 98.5% of the heavy oil-based feed stream . The remainder of the non-volatile product stream — the product of the stripping residue in the stripper or OROK — containing the bulk of the catalyst (in the range of 80 to 95% of the total suspended catalyst entering the system) was recycled to the first reactor to maintain the flow of the catalyst through gentrification system. The OROC stream contains from about 7 to 20 wt.% Suspended catalyst. The OROCs were also analyzed to evaluate the overall system performance.

The mixture of the feed stream into the system was a feed stream based on heavy oil, having the properties shown in table. 2.

table 2

AFP properties Density in degrees ANI at 60/60 % b Relative density 1,04 Sulfur (% (mass.)) 1.48 Nitrogen (ppm) 11069 Nickel (ppm) 118.8 Vanadium (ppm) 108.7 Carbon (ΐ (mass.)) 83.57 Hydrogen (% (mass.)) 10.04 Microcarbon residue (% (mass.)) 20.7 Viscosity at 100 ° C (cSt) 20796 Asphaltenes recovered in pentane (% (mass)) 13.9 The fraction boiling above 1000 ° G (538 ° C), (% (mass.)) one hundred%

- 24,023,427

Example 4. After 70 days, when all fresh catalyst was fed into the 1st reactor (in comparative example 3), the fresh catalyst supply position was shifted from 1- to 3rd reactor, while for the first 28 days the first two reactors relied solely on the feed stream of catalyst sent for recycling. All other technological conditions remained the same. VPVD and OROK products were collected, analyzed and compared with the results of comparative example 3. There was no significant change in the quality of the VPVD product. Regarding the OROC product, the results were as follows:

Table 3

OROC product properties Comparative example 3 Example 4 % (mass.) ORP (temperature boiling 1000 ° G (538 ° C)) 15, 9 15.3 % (mass.) TVGO [temperature boiling 800 ° G (427 ° C)) 49, 8 48.6 % (mass.) VGO (temperature boiling point 650 ° P (343 ° C)) 79.8 80.0 Density in degrees ANI 2.7 4,5 Sulfur (% (mass.)) 0.12 0.16 Nitrogen (ppm) 12711 12335 Microcarbon residue (% (mass.}) 14.7 12,4 Quantity ratio hydrogen / carbon 0,098 0, 102 Νί (ppm) 10, 8 7.9 Asphaltenes recovered in hot heptane, ppm 174255 119713 Viscosity at 70 ° С, cSt 68,4 47.3

As the results demonstrate, the removal of fresh catalyst to the last contacting zone in the system did not cause changes in the levels of nitrogen in the product. However, there was a change in the sulfur level, which could be due to an unexpectedly low level of sulfur in the feed stream based on the heavy oil in the system and a high level of sulfur in the VGO oil used in the feed stream of the suspended catalyst. Therefore, it is possible that the injection of fresh catalyst into the last reactor had a negative effect on the level of sulfur in the product due to the provision of less time for the reaction of the VGO oil carrier (in the suspended catalyst), which resulted in a higher level of sulfur content in the product. In addition, it should be noted that as a result of the removal of fresh catalyst into the last reactor, the OROK product was obtained, which has improved properties, including density in degrees ANI, viscosity, level of micro carbon residue, AHG value, level of nickel content, and N / C ratio. The improvement in the density of the OROK product in degrees ANI did not correlate with the improvement in the distillation of the OROK product. In other words, the density of the OROK product in degrees ANI did not improve due to additional cracking during distillation of lighter products, but due to improved catalytic activity, which resulted in an increased ratio of the amounts of H / C.

Regarding the functioning of the system in a 28-day run, there were no signs of an increase in pressure drop or clogging in the area of the front reactors, suggesting any coking or accumulation of solid matter. There was no measurable negative effect on the total degree of conversion. As the results suggest, the catalyst used retained sufficient activity during hydrogenation to reduce coking even in the presence of fresh / untreated heavy oil-based feedstocks, suggesting that coking was still adequately suppressed by the fresh catalyst division scheme.

Example 5. Repeat comparative example 3 with the exception of the removal of 20% of the feedstock based on heavy oil from the 1st reactor to the 3rd reactor, while other technological conditions remain identical.

As you can imagine, based on a comparison of the stability of the method, the operating characteristics of the reactor and the conditions in the reactor between the examples, in comparative example 3, the third reactor is characterized by a reduced liquid throughput (in the absence of a feed stream based on heavy oil) and an increased catalyst concentration, which is special

- 25,023,427 profitable for conversion purposes. However, these conditions also tend to bring the last reactor into a state of greater susceptibility to abnormal conditions during operation, leading to insufficient fluid throughput and, consequently, increased accumulation of solid matter, violation of thermometry and a reduction in the duration of continuous operation in the method.

As can be assumed, in Example 5, when a portion of the heavy oil-based feedstock was fed directly to the last reactor, the previous reactors (1st and 2nd), characterized by a decrease in liquid throughput (as part of the heavy oil-based feedstock are diverted) and corresponding an increase in catalyst concentration will function more efficiently and with a greater degree of conversion. In addition to this, with greater dilution with liquid in the 3rd reactor, a more uniform catalyst concentration profile is observed across all three reactors.

In addition, as can be assumed, since the last reactor in the sequence receives a portion of the heavy oil-based feed stream, dry conditions associated with insufficient fluid flow are prevented. Since the latter reactor is protected from the occurrence of excessive conversion events or dry conditions, less accumulation of solids or coke deposits occur. It is also expected that the latter reactor is less prone to abnormal conditions during operation, for example, the appearance of large amplitudes of changes in temperature, pressure, flow, etc.

For the purposes of this description of the invention and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or fractions, and other numerical values used in the description of the invention and the claims should be construed as in all cases modified by the term about. Accordingly, unless otherwise indicated, all numerical parameters presented in the following description of the invention and the attached claims will be approximations, which may vary depending on the desired properties required to obtain, and / or the accuracy of the device to measure a quantity, thus including the standard deviation in the form of the error of the device or method used to determine the quantity. The use of the term or in the claims is intended to mean and / or, unless the alternatives are explicitly referred to, or the alternatives are not mutually exclusive, although the description of the invention substantiates a definition that relates to single alternatives and and / or. The use of the word one or some, if used in connection with the term, may include one in the claims and / or description of the invention, but it also agrees with the meaning of one and several, at least one and one or more than one. In addition, all ranges described herein are inclusive of boundary points and independently combinable. In the general case, unless otherwise indicated, elements in the singular can be in the plural and, conversely, without loss of generality. In accordance with the use in this document, the term include and its grammatical variants assume the absence of restriction, so that listing items in the list does not imply the exclusion of other similar items that can be substituted or added to the listed items.

As expected, any aspect of the invention discussed in the context of one embodiment of the invention can be implemented or applied to any other embodiment of the invention. Similarly, any composition of the invention can be a result or can be used in any method or method of the invention. In this text of the description of the invention, examples are used to describe the invention, including the best option, as well as to provide any specialist in the relevant field of technology with the opportunity to make and use the invention. The patented volume is defined by the claims and may include other examples that exist for specialists in the relevant field of technology. Such other examples suggest that they fall within the scope of the claims if they have structural elements that do not differ from the literal formulation of the claims, or if equivalent structural elements are included in them with insignificant differences from the literal formulations of the claims. All citations listed herein by reference are incorporated herein.

Claims (19)

CLAIM 1. A method of hydrocracking a feedstock based on heavy oil using multiple contact zones and separation zones, the method comprising the steps of combining the feedstock based on heavy oil, a hydrogen-containing gas, a suspended catalyst and water in the first contacting zone under conditions of hydrocracking to convert at least a portion of the heavy oil-based feedstock to lower boiling hydrocarbons to obtain refined products, the amount of water being present from 1 to 25 wt.% of the total feedstock based on heavy oil; a mixture containing the refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feed is supplied to the first separation zone, whereby the refined products are removed together with the hydrogen-containing gas from the first separation zone as a first overhead stream, and the suspended catalyst heavier hydrocracked liquid products and unreacted heavy oil feeds are removed from the first zone tions as a first non-volatile stream of products; supplying a first flow of non-volatile products to the contacting zone, different from the first contacting zone, which is maintained under conditions of hydrocracking using an additional hydrogen-containing gas feed stream to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to obtain additional ennobled products; supplying a mixture containing additional refined products, a suspended catalyst, additional hydrogen-containing gas and unreacted heavy oil-based feed to a separation zone other than the first separation zone, whereby the refined products are removed together with the additional hydrogen-containing gas as an overhead stream, and the suspended catalyst and unreacted heavy oil feed are removed as a second non-volatile product stream in; and where the suspended catalyst supplied to the first contact zone contains at least a portion of the flow of non-volatile products from one of the separation zones as a catalyst stream sent for recycling, and where the catalyst stream sent for recycling is from 3 to 50% by weight of the feedstock per heavy oil base. 2. The method according to claim 1, where a sufficient amount of hydrogen-containing gas is supplied to obtain in the method a volumetric yield of more than 100% for refined products, including liquefied petroleum gas, gasoline, diesel fuel, vacuum gas oil, and jet and fuel oil. 3. The method according to claim 1, where the stream sent for recycling of the catalyst is at least 10 wt.% Of the total feedstock based on heavy oil. 4. The method according to claim 1, where at least part of the second stream of non-volatile products is recycled to at least one of the contacting zones in the form of a stream sent for recycling, and the remaining part of the second stream of non-volatile products is removed from the method in the form descent flow. 5. The method according to claim 4, where the stream sent for recycling is fed into the first contacting zone. 6. The method according to claim 4, where a sufficient amount of discharged stream is removed to obtain in the method a degree of conversion equal to at least 98%. 7. The method according to claim 1, where the contact zone is maintained under conditions of hydrocracking at a temperature in the range from 410 to 600 ° C and a pressure in the range from 10 to 25 MPa, and the first contact zone is operated at a temperature of at least 10 ° P (5.56 ° C) less than in the subsequent contact zone. 8. The method according to claim 7, where part of the suspended catalyst is intended to be fed into the contact introduction zone other than the first contact contact zone. 9. The method according to claim 1, further comprising the steps of supplying an input stream of freshly suspended catalyst, wherein at least a portion of the supplied stream of freshly suspended catalyst is intended to be supplied to a contacting zone different from the first contacting zone; supplying a suspended catalyst comprising the used suspended catalyst and optionally a portion of the fresh catalyst suspension feed stream; where at the stage at which the first flow of non-volatile products is fed into the contacting zone different from the first contacting zone, said other contacting zone is kept under hydrocracking conditions using an additional supplied stream of hydrogen-containing gas and at least part of the fresh suspended a catalyst for converting at least a portion of the unreacted heavy oil feedstock to lower boiling hydrocarbons to provide further refinement ennyh products. - 27 023427 10. The method according to claim 1, where at least a portion of the heavy oil-based feedstock is intended to be supplied to the contacting zone different from the first contacting zone. 11. The method according to claim 10, where at least 5% of the feedstock based on heavy oil is intended to be fed into the contacting zone different from the first contacting zone. 12. The method according to claim 1, where at least a portion of the water is added to the first contacting zone by injection of water vapor. 13. The method according to claim 1, where the first contacting zone has a pressure at the outlet X, the first separation zone has an inlet pressure Υ and between the pressure at the outlet X of the first contacting zone and the pressure at the inlet Υ of the first separation zone, the pressure drop падение is less than 100 lb / ⁱⁿ² (689 kPa). 14. The method according to claim 1, where the suspended catalyst is characterized by an average particle size in the range of 1-20 microns. 15. The method according to claim 1, where the suspended catalyst includes clusters of particles of colloidal size, size smaller than 100 nm, and where the clusters are characterized by an average particle size in the range of 1-20 μm. 16. The method according to claim 1, where in any of the zones of contact, add an additional feed stream of hydrocarbon oil, different from the feedstock based on heavy oil, in an amount of from 2 to 30% (vol.) From the feedstock based on heavy oil . 17. The method according to claim 1, further comprising sending for recycling to at least one of the contacting zones of at least a portion of the flow of non-volatile products. 18. A method of hydrocracking a feedstock based on heavy oil using many contact zones and separation zones, the method comprising the steps of combining the feedstock based on heavy oil, a hydrogen-containing gas and a suspended catalyst in the first contacting zone under conditions hydrocracking to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons to obtain refined products; a mixture of refined products, a suspended catalyst, a hydrogen-containing gas and unreacted heavy oil-based feed is fed into the separation zone, whereby the volatile refined products are removed together with the hydrogen-containing gas from the separation zone in the form of a first overflow, and the suspended catalyst, non-volatile refined products and unreacted heavy oil-based feeds are removed from the separation zone as a first stream n volatile products; supplying at least a portion of the first non-volatile product stream to a solvent deasphalting unit; two streams are obtained from the solvent deasphalting unit — a stream containing deasphalted oil and a stream containing asphaltenes and a suspended catalyst; the deasphalted oil is supplied to the contacting zone different from the first contacting zone, where this contacting zone is maintained under hydrocracking conditions using an additional feed stream of hydrogen-containing gas and an additional feed stream of suspended catalyst to convert at least a portion of the deasphalted oil to lower boiling hydrocarbons with additional enriched products; a mixture of additional refined products, a suspended catalyst, additional hydrogen-containing gas and unreacted deasphalted oil are fed into a second separation zone, where volatile additional refined products and additional hydrogen-containing gas are removed as a second overhead stream, and suspended catalyst, non-volatile additional refined products and deasphalted oil is removed as a second non-flow sneeze products; and recycled to at least one of the contacting zones of the stream sent for recycling and containing at least one representative of a) a portion of the stream containing asphaltenes and a suspended catalyst; B) parts of the first flow of non-volatile products; c) parts of a second stream of non-volatile products; and L) mixtures thereof. 19. The method according to p. 18, in which at least one part of the flow of non-volatile products is recycled to at least one of the contacting zones.