MX2011002971A

MX2011002971A - Systems and methods for producing a crude product.

Info

Publication number: MX2011002971A
Application number: MX2011002971A
Authority: MX
Inventors: Shuwu Yang; Darush Farshid; Bruce Reynolds; Alexander E Kuperman; Kaidong Chen; Rahul S Bhaduri; Julie Chabot; Bo Kou; Vivion Andrew Brennan; Erin Maris; Goutam Biswas; Joseph N Nguyen; Axel Brait
Original assignee: Chevron Usa Inc
Priority date: 2008-09-18
Filing date: 2009-09-15
Publication date: 2011-04-11
Also published as: JP5764063B2; KR101592856B1; WO2010033487A2; EP2328995A2; CN102197115B; BRPI0918083A2; KR20110076940A; CA2737386A1; EA201170464A1; EP2328995A4; JP2012503072A; WO2010033487A3; CA2737386C; WO2010033487A9; WO2010033487A8; CN102197115A

Abstract

A flexible once-through process for hydroprocessing heavy oil feedstock is disclosed. The process employs a plurality of contacting zones and at least a separation zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons, forming upgraded products. The contacting zones operate under hydrocracking conditions, employing a slurry catalyst which comprises an active metal catalyst having an average particle size of at least 1 micron in a hydrocarbon oil diluent, at a concentration of greater than 500 wppm of active metal catalyst to heavy oil feedstock. The plurality of contacting zones and separation zones are configured in a permutable fashion allowing the once-through process to be flexible operating in various modes: a sequential mode; a parallel mode; a combination of parallel and sequential mode; all online; some online and some on stand-by; some online and some off-line; a parallel mode with the effluent stream from the contacting zone being sent to at least a separation zone in series with the contacting zone; a parallel mode with the effluent stream from the contacting zone being combined with an effluent stream from at least another contacting zone and sent to the separation zone; and combinations thereof. In one embodiment, the effluent from a contacting zone is sent to the next contacting zone in series for further upgrade, with the next contacting zone having a pressure drop of at most 100 psi, with the pressure drop is not due to a pressure reducing device as in the prior art. In one embodiment, at least an additive material selected from inhibitor additives, anti-foam agents, stabilizers, metal scavengers, metal contaminant removers, metal passivators, and sacrificial materials, in an amount of less than 1 wt. % of the heavy oil feedstock, is added to at least one of the contacting zones.

Description

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

Background of the Invention The oil industry is increasingly shifting to sources of heavy oils such as heavy crudes, waste, coal, tar sands, etc., as sources of raw materials. These raw materials are characterized by high concentrations of residues rich in asphaltenes, and low API gravities, with some being as low as 0o API.

The Patents of E. U. A. Nos. 7390398, 7431822, 7431823 and 7431831 describe processes, systems and catalysts for processing heavy oil sources. In various prior art embodiments, the spent slurry catalyst and unconverted oil sources are recycled back to the process and combined with fresh heavy oil sources, thereby maximizing heavy oil conversion.

There is still a need for improved systems and methods to enrich / treat the processes of heavy oil sources, particularly improved systems for better utilization of the Ref.218811 raw material with less use of catalysts.

Brief Description of the Invention In one embodiment, the invention relates to a process for hydroprocessing a heavy oil raw material, the process uses a plurality of contact zones and at least one separation zone, the process comprising: providing a gas source containing hydrogen; providing a slurry catalyst comprising an active catalyst in a hydrocarbon oil diluent; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material and at least a portion of the slurry catalyst in a first contact zone under hydrocracking conditions at a temperature sufficient and at a pressure sufficient to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons, forming enriched products; sending a first effluent stream from the first contact zone comprising a mixture of enriched products, slurry catalyst, the gas containing the hydrogen, and the heavy oil raw material converted as a feed to a first separation zone, wherein the volatile enriched products are removed with the hydrogen-containing gas as a first high current, and the slurry catalyst, the heavier hydrocracked liquid products and the un-converted heavy oil raw material are removed with a first non-volatile stream; wherein the plurality in contact zones and the separation zones are configured in an interchangeable manner so that the plurality of contact zones and separation zones operate therein in: a sequential mode; a parallel mode, a combination of parallel and sequential mode; all online; some online and some waiting; some online and some offline; a parallel mode with the effluent stream from the contact zone that is sent to at least one separation zone in series with the contact zone; a parallel mode with the effluent stream from the contact zone being combined with an effluent stream from at least one other contact zone and sending it to the separation zone; and combinations of these. In another aspect, the invention relates to a process for hydroprocessing a heavy oil raw material, the process uses a plurality of contact zones and at least one separation zone, which includes a first contact zone and a contact zone different from the first contact zone, the process comprises: providing a gas source containing hydrogen, providing heavy oil raw material; provide a source of slurry catalyst comprising an active metal catalyst having an average particle size of at least 1 mire in a hydrocarbon oil diluent, at a concentration of more than 500 wppm of an active metal catalyst for the raw material of heavy oil; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material, and at least a portion of the source of the slurry catalyst in a first contact zone under conditions of hydrocracking to convert at least a portion of the first raw material of heavy oil into lower boiling hydrocarbons, form enriched products; sending a first effluent stream from the first contact zone comprising the enriched products, the slurry catalyst, the hydrogen-containing gas, and the heavy oil raw material without converting to a first separation zone, where the enriched products The volatile materials are removed with the gas containing the hydrogen with a first high current, and the slurry catalyst, the heavier hydrocracked liquid products and the un-converted heavy oil raw material are separated and removed as a first non-volatile stream, in where the first non-volatile stream contains less than 30% solids; collect the first high current to further process it in a product purification unit; and collecting the first non-volatile streams to further process them including the separation and recovery of the slurry catalyst, where the slurry catalyst is separated from the raw material of un-converted heavy oil and the heavier hydrocracked liquid products are recovered.

In a third embodiment, the invention relates to a process for hydroprocessing a heavy oil raw material, the process uses a plurality of contact zones and at least one separation zone, which includes a first contact zone and a zone of contact. contact different from the first contact zone, the process comprises: providing a gas source containing hydrogen; provide a heavy oil raw material; providing at least one additive material selected from the inhibitory additives, anti-foaming agents, stabilizers, metal scavengers, metal contaminants removers, metal passivators, and sacrificial materials, in an amount of less than 1% by weight of the material heavy oil premium; providing a source of slurry catalyst comprising an active metal catalyst having an average particle size of at least 1 mire in a hydrocarbon oil diluent; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material, at least a portion of the additive material, and at least a portion of the source of the slurry catalyst in a first contact zone under hydrocracking conditions to convert at least a portion of the first heavy oil raw material to lower boiling hydrocarbons, forming enriched products; sending a first effluent stream from the first contact zone to a first separation zone, where the volatile enriched products are removed with the gas containing the hydrogen with a first high current, and the slurry catalyst, the hydrocracked liquid products more heavy and the unconverted heavy oil raw material is separated and removed as a first non-volatile stream, wherein the first non-volatile stream contains less than 30% solids; collect the first high current to further process it in a product purification unit; and collecting the first non-volatile stream to further process it in a catalyst recovery unit.

In yet another aspect, the invention relates to a process for a process for hydroprocessing a heavy oil raw material, the process uses a plurality of contact zones and at least one separation zone, the process comprises: providing a source of gas containing hydrogen, provide a heavy oil raw material; providing a source of slurry catalyst comprising an active metal catalyst having an average particle size of at least 1 mire in a hydrocarbon oil diluent; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material and at least a portion of the source of the slurry catalyst in a first contact zone under hydrocracking conditions , operating at a first pressure, to convert at least a portion of the first raw material of heavy oil to lower boiling hydrocarbons, forming enriched products; sending a first effluent stream from the first contact zone a first separation zone having an inlet pressure of at most 7.03 kg / cm2 (100 psi) lower than the first pressure, where the volatile enriched products are removed with the gas containing hydrogen as a first high current, and the slurry catalyst, the heavier hydrocracked liquid products, and the raw material of unconverted heavy oil are removed as a first non-volatile stream, wherein the first non-volatile stream contains less than 30% solids; collect the first high current to further process it in a product purification unit; and collecting the first non-volatile stream to further process it in a catalyst recovery unit.

Brief Description of the Figures Figure 1 is a flow chart schematically illustrating one embodiment of a one-pass enrichment system with two contact zones running in sequential (serial) mode.

Figure 2 is a flow chart of a second embodiment of an enrichment process with three contact zones running in sequential mode, each of the contact zones having a separation zone in series with an optional derivation.

Figure 3 is a flowchart of another embodiment of a one-pass enrichment process with three contact zones running in tandem (parallel), with each of the contact zones having a separation zone in series with a bypass optional.

Figure 4 is a flow diagram of one embodiment of a flexible pass-through enrichment process with a plurality of contact zones and separation zones and with some of the contact zones running in sequential mode, with the third reactor on hold , or tandem current with separate supply currents.

Figure 5 is a flowchart of another mode of the one-pass flexible enrichment process with units running in tandem (parallel) with steam injection, VGO and additive sources for some of the contact zones.

Figure 6 is a flow diagram of another embodiment of the flexible pass-through enrichment process with three contact zones running in tandem (parallel) and sharing a separation zone.

Figure 7 is a flowchart of another embodiment of a one-pass enrichment process with two contact zones running in sequential mode, whose sequential operation is in tandem with a single contact in an enrichment operation with its own source. heavy oil, optional VGO source and catalyst source.

Detailed description of the invention The present invention relates to an improved system for treating or enriching heavy oil sources, particularly heavy oil raw material having high levels of heavy metals.

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

As used herein, "heavy oil" source or raw materials refers to heavy and ultra-heavy crudes including, but not limited to, waste, coal, tar, shale oil, tar sands, etc. The heavy oil raw materials can be liquid, semi-solid and / or solid. Examples of heavy oil feedstock that could be enriched as described herein include, but are not limited to, Canada Tar Sand, Brazil's Santos Vacuum Waste and the Campo Basins, the Gulf of Suez in Egypt , Chad, Sulia Venezolana, Malaysia and Sumatra Indonesia. Other examples of heavy oil raw material include the bottom of the barrel and the residues that remain after the refinery processes, which include "the bottom of the barrel" and "residue" (or "residue"), the bottom of the atmospheric tower , which has a boiling point of at least 343 ° C (650 ° F), or the bottom of the vacuum tower, which has a boiling point of at least 524 ° C (975 ° F), or residue "and" vacuum residue ", which have a boiling point of 524 ° C (975 ° F) or higher.

The properties of the heavy oil raw material may include, but are not limited to: TAN of at least 0.1 m to at least 0.3, or at least 1; viscosity of at least 10 cSt; API gravity at most 15 in one modality, and at most 10 in another modality. One gram of heavy oil raw material typically contains at least 0.0001 grams of Ni / V / Fe; at least 0.005 grams of heteroatoms; at least 0.01 grams of residue; at least 0.04 grams of C5 asphaltenes; at least 0.02 grams of MCR; per gram of crude; at least 0.00001 grams of alkali metal salts of one or more organic acids; and at least 0.005 grams of sulfur. In one embodiment, the heavy oil raw material has a sulfur content of at least 5% by weight and an API gravity of -5 to +5.

In one embodiment, the heavy oil raw material comprises pitch Athabasea (Canada) having at least 50 volume% vacuum residues. In another modality, the raw material is a Boscan source (Venezuela) with at least 64% by volume of vacuum residue. In one embodiment, the heavy oil raw material contains at least 100 ppm V (per gram of heavy oil raw material). In another embodiment, the level of V is in the range of between 500 and 1000 ppm. In a third mode, at least 2000 ppm.

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

The enrichment or treatment of heavy oil sources is generally referred to herein as "hydroprocessing". Hydroprocessing means any process that is carried out in the presence of hydrogen, including, but not limited to, hydroconversion, hydrocracking, hydrogenation, hydrotreating, hydrodesulfurization, hydrodesitrogenization, hydrodemetalization, hydrodearomatization, hydroisomerization, hydrodescentration, and hydrocracking including selective hydrocracking . Hydroprocessing products can show improved viscosities, viscosity indexes, saturated contents, low temperature properties, volatilities and depolarization, etc.

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

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

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

VGO or vacuum gas oil, refers to hydrocarbons with a boiling range distribution between 343 ° C (650 ° F) and 538 ° C (1000 ° F) at 0.101 MPa. "wppm" means parts by weight per million.

As used herein, the term "catalyst precursor" refers to a compound that contains one or more catalytically active metals, of which a catalyst compound is optionally formed. It should be noted that a catalyst precursor can be catalytically active as a hydroprocessing catalyst. As used herein, "catalyst precursor" can be referred to herein as "catalyst" when used in the context of a catalyst source.

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

As used herein, the term "slurry catalyst" (or sometimes referred to as "slurry" or "dispersed catalyst") refers to a liquid medium, for example, oil, water or mixture thereof, wherein the catalyst and / or the catalyst precursor particles (aggregates, particles or crystallites) are dispersed therein. The term "slurry catalyst" refers to a fresh catalyst, or a catalyst that has been used in the enrichment of heavy oil and with decreased activity.

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

As used herein, the "catalyst source" includes any catalyst suitable for enriching supplies of heavy oil sources, for example, one or more bulk catalysts and / or one or more catalysts in a support. In one embodiment, the catalyst source is in the form of a slurry catalyst.

As used herein, the term "Volume catalyst" can be used interchangeably with "catalyst without support", which means that the catalyst composition is not of the conventional catalyst from which, for example, it has been preformed, the support of the molded catalyst which is then loaded with metals through impregnation or deposition catalyst. In one embodiment, the volume catalyst is formed through precipitation. In another embodiment, the volume catalyst has a binder incorporated in the catalyst composition. In yet another embodiment, the volume catalyst is formed of metal compounds and without any binder. In a fourth embodiment, the volume catalyst is a dispersion type catalyst for use as catalyst particles dispersed in a liquid mixture (for example hydrocarbon oil). In one embodiment, the catalyst comprises one or more commercially known catalysts, for example, MIcrocat ™ from ExxonMovil Corp.

As used herein, the term "contact zone" refers to equipment in which heavy oil sources are treated or enriched through contact with a source of slurry catalyst in the presence of hydrogen. In a contact zone, at least one property of the crude source can be changed or enriched. The contact zone can be a reactor, a portion of a reactor, multiple portions of a reactor or combinations thereof. The term "contact zone" can be used interchangeably with "reaction zone".

In one embodiment, the enrichment process comprises a plurality of reactors, used as contact zones, with reactors that are the same or different in configuration. Examples of reactors that may be used herein include stacked bed reactors, fixed bed reactors, recycle / expansion bed reactors, continuous stirred tank reactors, fluidized bed reactors, spray reactors, liquid / liquid contacts, grout reactors, liquid recirculation reactors and their combinations. In one embodiment, the reactor is an upflow reactor. In another embodiment, a downflow reactor.

In one embodiment, the contact zone refers to at least one slurry bed hydrocracking reactor in series with at least one fixed bed hydrotreating reactor. In another embodiment, at least one of the contact zones further comprises a hydrotreater in line, capable of removing about 70% of the sulfur, about 90% nitrogen, and about 90% of the heteroatoms in the crude product that it is being processed As used herein, the term "separation zone" refers to equipment in which the source of heavy oil enriched from the contact zone is either directly fed into the, or is subjected to one or more intermediate processes and then fed directly into the separation zone, for example, a high-pressure high-temperature emission drum or an emission separator, where gases and volatile liquids are separated of the non-volatile fraction. In one embodiment, the stream of the non-volatile fraction comprises a source of heavy crude oil, a small amount of heavier hydrocracked liquid products (synthetic or less volatile / non-volatile enriched products), the slurry catalyst and any insufflated solid ( asphaltenes, coke, etc.). In one embodiment, the separation zone provides a pressure drop from one contact zone to the next in the series. The pressure drop is induced by the separation zone that allows gas and volatile liquids to separate from the non-volatile fraction.

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

In one embodiment, the enrichment system comprises a single reactor followed by a separator. In another embodiment, the system comprises at least two reactors upstream in series with at least one spacer, with at least one spacer being positioned just after the last reactor in the series. In yet another embodiment, a plurality of series reactors operate as a single train. In a fourth embodiment, a parallel train with a plurality of reactors. In a fifth embodiment, a plurality of reactors configured in combination of parallel and series operations. There are other modalities in which the enrichment system is configured for flexible operation, going from one operational mode to another, for example, running in parallel (in tandem) to running in series (sequential) with different combinations of reactors / emission separators.

In one embodiment, the enrichment system may comprise a combination of reactors and separators in series with multi-stage separator reactors, with a solvent asphalt eliminating unit (SDA) that is placed as an interstage treatment system between any of the the reactors in series, or before the first reactor in the series.

The enrichment system is characterized as a one-pass mode, which differs from the prior art enrichment system in that the slurry catalyst and heavy oil raw material flow through the contact zone (s) once, instead of being recycled or recirculated around the system as in the prior art. In the one-pass enrichment system, virtually no unconverted material and the slurry catalyst mixture is recycled back to the first (or previous) contact zone or reactor in the series. The non-volatile materials of the last separation zone in the enrichment system comprise unconverted materials, heavier hydrocracked liquid products (less volatile synthetic products / enriched products), the slurry catalyst, small amounts of coke, asphaltenes, etc., in one mode it is sent off-site for further processing / regeneration of the catalyst or to an oil removal unit to separate the spent catalyst from the hydrocarbons, and subsequently to the metal recovery unit to recover the precious metals from the catalyst consumed The oil removal unit and / or the metal recovery unit may be in the same location as the one-pass enrichment system, or they may be in different locations in the one-step enrichment system, for example, the removal The oil is handled through a different part in a different location or country, and / or metal recovery is done off-site through a contact in a different location or country.

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

In one embodiment, the process temperature in the contact zone is in the range of about 400 ° C (752 ° F) to about 600 ° C (1112 ° F), less than 500 ° C (932 ° F) in another modality, and more than 425 ° C (797 ° F) in another modality. In one embodiment, the system operates with a temperature difference between the input and output of a contact zone in the range of minus 15 to 10 ° C (5 to 50 ° F).

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

The process pressure in the contact zones is in the range of about 10 MPa (1,450 psi) to about 25 MPa (3,625 psi), in one embodiment, from about 15 MPa (2,175 psi) to about 20 MPa (2,900 psi) in a second mode, less than 22 MPa (3,190 psi) in a third mode, and more than 14 MPa (2,030 psi) in a fourth mode.

The one-pass enrichment system is characterized by a much higher degree of performance when compared to a prior art enrichment system (with the recycling of unconverted heavy oil sources). The liquid hourly space velocity (LHSV) of the heavy oil source in each of the contact zones is generally in the range of 0.075 h "1 to about 2 h" 1 in one embodiment; from about 0.1 h "1 to about 1.5 h" 1 in a second mode, from about 0.15 h "1 to about 1.75 h" 1 in a third mode, from about 0.2 h "1 to about 1 h" 1 in a fourth mode , and from approximately 0.2 h "1 to approximately 0.5 h" 1 in a fifth modality. In one modality, the LHSV is at least 0.1 h "1. In another modality, the LHSV is at least 0.3 h" 1.

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

Minimization of the Pressure Drop: In the prior art, it is described that with a pressure drop in a heavy oil enrichment system, that is, a pressure drop over the entrance of the separation zone of up to 70.3 kg / cm2 (1000 psi) and preferably in the range of 21.9 to 49.21 kg / cm2 (300 to 700 psi), the lighter boiling materials can more easily be separated / removed from the enrichment system through the separation zone. A higher pressure drop can be induced with the introduction of pressure reducing devices. However, an enrichment system with a higher pressure drop is found to be operationally unstable particularly with a frequent shut-off due to the deposit in the equipment and / or common valve operating problems that include failure to open the set pressure due to the obturation of the entrance or exit of valve, corrosion or erosion of the valves.

In one embodiment, the one-pass enrichment system is configured for optimal operation, for example, efficiency with much less downtime due to the sealing of the equipment compared to the prior art with less than a 7.03 kg pressure drop. / cm2 (100 psi). The optimum efficiency is obtained in a mode with a minimum pressure drop in the system, where the pressure of the separation zone remains within ± 0. 703 to ± 70.03 kg / cm2 (± 10 to ± 100 psi) from the preceding contact zone in one mode, within +1.406 a 5. 272 kg / cm2 (+ 20 to + 75 psi) in a second mode, and , within + 3.515 to + 7.03 kg / cnr (± 50 to ± 100 psi) in a third mode. As used herein, the pressure drop refers to the difference between the outlet pressure of the preceding contact zone X and the inlet pressure of the separation Y, with (XY) being less than 7.03 kg / cm ( 100 psi).

Optimal efficiency can also be obtained with a minimum pressure from one contact zone to the next contact zone for a system operating sequentially, with the pressure drop being maintained as 7.04 kg / cm2 (100 psi) or less in one mode, and 5.27 kg / cm (75 psi) or less in a second mode, and less than 3.515 kg / cm2 (50 psi) in a third mode. The pressure drop in the present refers to the difference between the outlet pressure of a contact zone and the inlet pressure of the next contact.

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

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

In one embodiment, the minimum pressure drop is induced through friction loss, wall drag, volume increase and changes in height as the effluent flows from the contact zone to the next equipment in the series. If the valves are used in a single-pass system, the valves are selected / configured in such a way that the pressure drop of one device, for example, the contact area, to the next part of the equipment is maintained as being of 7.03 kg / cm2 (100 psi) or less.

Source of Hydrogen: In one embodiment, a source of hydrogen is provided to the process. Hydrogen can also be added to the heavy oil source before entering the pre-heater or after the pre-heater. In one embodiment, the hydrogen source enters the contact zone concurrently with the source of heavy oil in the same conduit. In another embodiment, the source of hydrogen can be added to the contact zone in a direction that is against the flow of the source. In a third embodiment, the hydrogen enters the contact zone through the gas conduit separated from the combined heavy oil and the stream from the source of the slurry catalyst. In a fourth embodiment, the source of hydrogen is introduced directly to the combined catalyst and the raw material of the heavy oil that is being introduced into the contact zone. In yet another mode, the hydrogen gas and. The combined heavy oil and catalyst source are introduced into the lower part of the reactor as a separate stream. In yet another embodiment, the hydrogen gas can be fed in several sections / places in the contact zone.

In one embodiment, the source of hydrogen is supplied to the process at a rate (based on the ratio of the source of hydrogen gas to the source of heavy oil) from 0.1 Nra3 / m3 to approximately 100, 000 Nm3 / m3 (0.563 to 563.380 SCF / bbl), from approximately 0.5 Nm3 / m3 to approximately 10,000 Nm3 / m3 (2.82 to 56,338 SCF / bbl), from approximately 1 Nm3 / m3 to approximately 8,000 Nm3 / m3 (5.63 a 45,070 SCF / bbl), from approximately 2 Nm3 / m3 to approximately 5,000 Nm3 / m3 (11.27 to 28.169 SCF / bbl), from approximately 5 Nm3 / m3 to approximately 3,000 Nm3 / m3 (28.2 to 16,901 SCF / bbl), or from approximately 10 Nm3 / m3 to approximately 800 Nm3 / m3 (56.3 to 4,507 SCF / bbl).

In one embodiment, some of the hydrogen (25-75%) is supplied to the first contact zone, and the remainder is added as complementary hydrogen to other contact zones in the system.

The source of hydrogen, in some embodiments, is combined with a carrier gas (s) and recirculated through the contact zone. The carrier gas can be, for example, nitrogen, helium and / or argon. The carrier gas can facilitate the flow of the heavy oil source and / or the flow of the hydrogen source in the contact zone (s). The carrier gas can also improve the mixing in the contact area (s). In some embodiments, the gas source (eg, hydrogen, methane or ethane) can be used as a carrier gas and recirculated through the contact zone.

Catalyst Source: In one embodiment of an enrichment system running in a sequential mode, the entire source of the slurry catalyst is provided in the first contact zone. In other embodiments of the sequential mode, at least a portion of the catalyst source is "divided" or diverted to at least other contact zones in the system (different from the first contact zone). In another embodiment with the contact zones running in tandem (parallel) all the contact zones in operation receive a source of slurry catalyst (together with a source of heavy oil).

In one embodiment, "at least one portion" means at least 10% of the catalyst source. In another modality, at least 20%. In a third modality, at least 40%. In a fourth embodiment, at least 50% of the catalyst source is diverted to at least one other contact zone different from the first.

In one embodiment of a sequential operation, less than 60% of the catalyst source is fed to the first contact zone in the system, with 40% or more of the fresh catalyst being diverted to another contact zone (s) in the system. In another embodiment, the catalyst source is equally divided between the contact zones in the system. In one embodiment, at least one source portion of the fresh catalyst is sent to at least one of the intermediate contact zones and / or the last contact zone in the system.

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

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

In one embodiment, the delivery of different catalysts to the front end and the rear end of the contact zones can be useful in mitigating the vanadium entrapment aspect and sustain the overall enrichment operation. In one embodiment, a Ni-only or Ni-rich NiMo slurry catalyst is sent to the front end reactor to help reduce the entrapment of vanadium in the system, with a different catalyst, for example, Mo sulfur or a Mo-rich NiMo sulfide catalyst, can be injected into the rear end reactor (s) to maintain a high degree of overall conversion, improve product quality and possibly reduce gas performance in one mode. As used herein, a Ni-rich slurry catalyst means that the Ni / Mo ratio is greater than 0.15 (in% by weight). Conversely, a Mo-rich slurry catalyst means that the Ni / Mo ratio is less than 0.5 (in% by weight).

In one embodiment, the grout catalyst source is first preconditioned before entering one of the contact zones, or before contacting the source of heavy oil before entering the contact zones. In one example, the catalyst enters a pre-conditioning unit together with hydrogen at a rate of 500 to 7500 SCF / BBL (BBL herein refers to the total volume of heavy oil source to the system). It is believed that instead of contacting the cold catalyst with a source of heavy oil, the pre-conditioning step assists with the absorption of hydrogen at the sites of the active catalyst, and finally the degree of conversion. In one embodiment of the pre-conditioning unit, the slurry catalyst / hydrogen mixture is heated to a temperature between 149 to 538 ° C (300 ° C to 1000 ° F). In another embodiment the catalyst is pre-conditioned in hydrogen at a temperature of 260 ° C to 385 ° C (500 to 725 ° F). In yet another embodiment, the mixture is heated under a pressure of 21.09 to 224.96 kg / cm2 (300 to 3200 psi) in one embodiment; from 35.15-210.9 kg / cm2 (500-3000 psi) in a second embodiment; and 42.18-75.75 kg / cm2 (600 - 2500 psi) in a third mode.

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

In one embodiment, the catalyst is a multi-metal bulk catalyst comprising at least one non-noble metal of Group VIII and at least two metals of group VIB, and wherein the ratio of at least two metals of Group VIB the non-noble metal of Group VIII is from about 10: 1 to about 1:10. In another embodiment, the catalyst is of the formula (Mt) a (Xu) b (Sv) d (Cw) e (Hx) f (Oy) g (Nz) h, wherein M represents at least one metal of the group VIB, such as o, W, etc., or a combination of these, - and X functions as a promoter metal, which represents at least one of: a non-noble Group VIII metal such as Ni, Co; a Group VIII metal such as Fe; a metal of Group VIB such as Cr; a Group IVB metal such as Ti; a metal of Group IIB such as Zn, and combinations thereof (X hereinafter referred to as "Metal Promoter"). Also in the equation t, u, v, w, x, y, z represent the total charge for each of the components (M, X, S, C, H, O and 'N, respectively); ta + ub + vd + we + xf + yg + zh = 0. The ratio of the subscripts from b to a has a value from 0 to 5 (0 <= b / oc < = 5). S represents sulfur with the value of subscript b on the scale from (a + 0.5b) to (5a + 2b). C represents carbon with a subscript e having a value from 0 to 11 (a + b). H is hydrogen with the value of f on the scale from 0 to 1 (a + b). 0 represents oxygen with the value of g on the scale from 0 to 5 (a + b); and N represents nitrogen with h having a value from 0 to 0.5 (a + b). In one embodiment, the subscript b has a value of 0 for a single metal component catalyst, for example, Mo as the sole catalyst (without promoter).

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

In one embodiment, the slurry catalyst has an average particle size of at least 1 miera. In another embodiment, the slurry catalyst has an average particle size in the range of 1-20 microns. In a third embodiment, the slurry catalyst has an average particle size in the range of 2-10 microns. In a particular embodiment, the slurry catalyst comprises aggregates of catalyst molecules and / or extremely small particles that are colloidal in size (eg less than 100 nm, less than about 10 nm, less than about 5 nm, and less than about 1 nm). In yet another embodiment, the catalyst particles comprise aggregates of MoS2 groups in a single layer of nanometer sizes, eg, 5-10 nm at the edge. In operations, the aggregate of the colloidal size / nanometer particles in a hydrocarbon diluent forms a slurry catalyst with an average particle size in the range of 1-20 microns.

In one embodiment, a sufficient amount of slurry catalyst is fed to the contact zone (s) so that each contact zone has a slurry catalyst (solid) concentration of at least 500 wppm to 3% by weight (ratio from catalyst metal to heavy oil).

In an embodiment for a conversion of at least 75% of the heavy oil raw material to materials with a boiling point of less than 538 ° C (1000 ° F) at a high yield of at least 0.15 LHSV, the amount of catalyst fed in the zone (s) is in the range of 500 to 7500 wppm of the catalyst metal in the source of heavy oil. In a second embodiment, the concentration of the fresh catalyst source is in the range of 750 to 5000 wppm of catalyst metal. In a third mode, from 1000 to 3000 wppm. In a fourth embodiment, the concentration is less than 3000 wppm. In a fifth embodiment, the concentration is at least 1200 ppm. "Metal catalyst" refers to an active metal in the catalyst, for example, a NiMo sulphide slurry catalyst wherein Ni is used as a promoter, the catalyst metal herein refers to the concentration of Mo.

It is conceivable to use less catalyst for the enrichment system, for example, media of 500 ppm or even less than 200 ppm or 100 ppm. However, this will result in a very poor / undesirable conversion degree of less than 50% in one embodiment, and even less than 10% in the second embodiment. The low catalyst level also results in unstable operations, eg, loosening, carbonization, or curing, etc., with heavy oils not converted into the equipment, particularly in the reactors.

Optional Treatment System-SDA: In one embodiment, a solvent asphalt removal unit is used before the first contact zone to pre-treat the heavy oil raw material. In yet another mode, the SDA is used as an intermediate unit located after one of the intermediate separation zones. SDA units are typically used in refineries to extract lighter hydrocarbons in increments of a heavy hydrocarbon stream, while the extracted oil is typically called asphalt-free oil (DAO), while leaving a residual stream behind that is more concentrated in heavy molecules and heteroatoms, typically known as SDA tar, SDA waste, etc. The SDA can be a separate unit with an integrated unit in the enrichment system.

Several solvents can be used in the SDA, in the range of propanes to hexanes, depending on the desired level of asphalt removal before feeding the contact zone. In one embodiment, the SDA is configured to produce an oil without asphalt (DAO) to bleed with the catalyst source or direct feed into the contact zones instead of, or in addition to the heavy oil source. That is, the type of solvent and the operating conditions can be optimized in such a way that a high volume and an acceptable DAO quality is produced and fed to the contact zone. In this modality, a suitable solvent to be used includes, but is not limited to hexane or a similar C6 + solvent for a low volume of SDA tar and a high DAO volume. This scheme could allow the vast majority of the source of heavy oil to be enriched in the subsequent contact zone, while the very heavy bottom of the barrel does not produce favorable incremental economic conversions due to the massive requirement of hydrogen addition, to be used. in some other way. In one embodiment, all sources of heavy oil are pre-treated in the SDA and the DAO product is fed into the first contact zone, or is fed according to a split feed scheme with at least one serving portion in contact with the different zone of the first in the series. In another embodiment, some of the source of heavy oil (depending on the source) is first pre-treated in the SDA and some of the raw material is fed directly into the untreated contact zone (s). In yet another embodiment, the DAO is combined with the untreated heavy oil raw material with a feed stream to the contact zone (s). In another embodiment, DAO and the untreated heavy oil raw material are fed into the system as in separate feed lines, with DAO going to one or more of the contact zones and the source of untreated heavy oil going to one or more of the same or different contact areas.

In an embodiment wherein the SDA is used as an intermediate unit, the non-volatile fraction comprising the slurry catalyst and optionally minimum amounts of coke / asphaltenes, etc., from at least one of the separation zones is sent to the SDA for treatment. From the SDA unit, the DAO is sent to at least one of the contact zones as a feed stream by itself, in combination with a heavy oil raw material as a source, or in combination with the bottom stream from one of the separation zones as a feed. DAO residues comprising asphaltenes are sent away from metal recovery in any transfer slurry catalyst, or for applications that require asphaltenes, for example, mixed with fuel oil, used in asphalt, or used in some other applications.

In one embodiment, the quality of the DAO and the DAO residues vary by adjusting the solvent used and the desired recovery of DAO relative to the source of heavy oil. In an optional pre-treatment unit such as the SDA, the more DAO oil is recovered, the poorer the overall quality of the DAO, and the poorer the overall quality of the DAO waste. With respect to the selection of the solvent, typically, as a lighter solvent is used for SDA, less DAO will reproduce, but the quality will be better, while if a heavier solvent is used, more DAO will be produced, but the quality will be lower. . This is due, among other factors, to the solubility of asphaltenes and other heavy molecules in the solvent.

Heavy Oil Source: The heavy oil source herein may comprise one or more different sources of heavy oil from different sources as a single feed stream, or as separate heavy oil feed streams. In one embodiment, a single pipe of the heavy oil conduit is brought into contact with the contact zones. In another embodiment, multiple heavy oil conduits are used to supply the source of heavy oil to different contact zones, with some heavy oil source stream (s) going to one or more of the contact zones and another stream ( s) of the heavy oil source that goes to one or more of the different contact zones.

In some embodiments, at least a portion of the heavy oil source (to be enriched) is "divided" or diverted to at least one other contact zone (other than the first contact zone), or to an SDA unit before to be fed in the contact area. In one embodiment of a sequential operation, less than 90% of the source of un-converted heavy oil is fed to the first rector of the system, with 10% or more of the source of heavy oil converted without being diverted to the other zone (s) of contact in the system. In another embodiment of a tandem operation, the heavy oil source is equally divided between the contact zones in the system. In another embodiment, less than 80% of the crude oil source not converted is fed to the first contact zone in the system, and the remaining heavy oil source is diverted to the last contact zone of the system. In a fourth embodiment, less than 60% of the heavy oil source is fed into the first contact zone in the system, and the remainder of the source of the unconverted oil is equally divided between the other contact zones in the system.

In one embodiment, the heavy oil raw material is preheated before being mixed with the slurry catalyst source stream (s). In another embodiment, the mixture of heavy oil raw material and the source of slurry catalyst are preheated to create a raw material having sufficiently low viscosity to allow good mixing of the catalyst in the raw material. In one embodiment, the pre-heating is conducted at a temperature that is at least about 100 ° C (212 ° F) lower than the hydrocracking temperature within the contact zone. In another embodiment, preheating is a temperature that is approximately 50 ° C lower than the hydrocracking temperature within the contact zone. In a third embodiment, the preheating of the raw material in heavy oil and / or a mixture of heavy oil raw material and slurry catalyst is at a temperature of 260-371 ° C (500-700 ° F).

Optional Additive-Anti-foaming Injection: As used herein, the front end contact zone (or the first contact zone) means the first reactor in a sequential operation with a plurality of contact zones. In one embodiment of a system with at least three contact zones, the first contact area of the front end may include both the first and the second reactor. In one embodiment, at least one anti-foaming agent is injected into at least one contact zone in the system to minimize the amount of foam and allow full utilization of the reaction zone. As used herein, the term "anti-foaming" includes both anti-foaming and defoaming materials, to prevent the foam from appearing and / or reducing. Additionally some anti-foaming material can have both functions, for example reducing / mitigating foaming under certain conditions, and preventing foam from appearing under other operating conditions.

The anti-foaming agents can be selected from a wide range of commercially available products such as silicones, for example, polydimethyl siloxane (PDMS), polydiphenyl siloxane, fluorinated siloxane, etc., in an amount of 1 to 500 ppm of the raw material of heavy oil. In one embodiment, high molecular PDMS is used, for example, with a viscosity above 60,000 cSt in one embodiment, over 100,000 cSt in another embodiment, and over 600,000 cSt in a third embodiment. It is believed that an anti-foaming agent with a higher viscosity (higher molecular weight) decomposes more slowly and is less prone to poison the catalyst due to Si contamination.

In one embodiment, the anti-foaming agent is added to the hydrocarbon solvent such as kerosene, which reduces the viscosity of the anti-foam and makes it pumpable. In one embodiment, the ratio of anti-foam to solvent is in the range of 1: 1 to 1: 1000. In another modality, from 1: 2 to 1: 100. In a third mode, from 1: 3 to 1:50. In one embodiment, the anti-foaming agent is diluted in a sufficient amount of hydrocarbon solvent to have a viscosity of less than 1000 cSt, such that it can be handled using the standard type.

In one embodiment, the anti-foam is added directly onto the heavy oil raw material. In another embodiment, the mixture is injected at multiple points along an upflow reactor. In another embodiment, the anti-foaming solvent mixture is injected into the upper part of the upstream flow reactor. In a fourth embodiment, the injection is in a region within the upper 30% of the reactor height. Injecting the anti-foaming agent into the upper part of the reactor in one embodiment increases a liquid back into the mixture in the reactor.

Additives-Inhibitors / Stabilizers / Materials Sacrifice Optional: In one embodiment, in addition to, or in place of anti-foaming agents, at least one additive selected from inhibitors, stabilizers, metal scrubbers and metal contaminants removers, metal passivators and sacrificial materials is added to the contact zone in an amount in the range of 1 to 20,000 ppm of the heavy oil source (collectively, "additive material"). In a second embodiment, the additive material is added in an amount of not less than 10,000 ppm. In a third embodiment, the additive material is in the range of 50 to 1000 ppm.

It should be noted that some additives can have multiple functions. In one embodiment, some metal scrubbers can also function as metal contaminants and / or metal passivators under appropriate conditions. In another embodiment, the sacrificial material used can function as a metal scrubber to absorb heavy metals in the heavy oil source. Some other sacrificial materials, apart from functioning as metal scavengers for absorbent metals, also absorb or trap other materials that include deposited coke.

In one embodiment, the additive material is added directly onto the heavy oil raw material. In another embodiment, the additive material is added to the source of the slurry catalyst. In a third embodiment, the additive material is added to the contact zone as a separate feed stream.

In one embodiment, the additive material can be added as such, or a suitable carrier solvent or solvent. Exemplary carrier solvents include, but are not limited to, aromatic hydrocarbon solvents such as toluene, xylene, and aromatic distillates derived from crude oil. Illustrative diluents include vacuum gas oil, diesel, decanted oil, cycle oil, and / or light gas oil. In some embodiments, the additive material may be dispersed in a small portion of the heavy oil raw material.

In one embodiment, the additive material is injected into the upper section of the reactor. In another embodiment, the additive material is injected into a plurality of feed ports along the upstream flow direction.

In one embodiment, the additive material is selected to effect a good emulsion or dispersion of the asphaltenes in the heavy oil. In still mode, the additive is selected to increase storage stability and / or improve the pumpability of the heavy oil raw material. In yet another embodiment, the additive is a stabilizing compound containing polar bonds such as acetone, diethyl ketone, and nitrobenzene, added in an amount between 0.001 to 0.01% by weight of the heavy oil source.

In one embodiment, the additive material is an inhibitory additive, selected from the group of polynuclear or oil-soluble aromatic compounds, agents that decrease the elastic modulus, for example, organic and inorganic acids and bases and metalloporphyrins. In another embodiment, the additive is a selected alkoxylated fatty amine or fatty amine derivative and a special metal salt compound, for example, metallic soap.

In one embodiment, the additive material is a "sacrificial material" (or "entrapment material") that functions to trap, or to deposit, and / or immobilize deposited coke and / or metals (Ni, V, Fe , Na) in the source of heavy oil, mitigating the harmful effects of these materials on the catalyst and / or in equipment. In another embodiment, the additive material functions to immobilize / absorb the asphaltenes in the heavy oil raw material, thereby mitigating deactivation of the catalyst. In one embodiment, the sacrificial material has large pores, for example it has a BET surface area of at least 1 m2 / g in one embodiment, of at least 10 m2 / g in a second embodiment, and of at least 25 m2 / g in another modality. In yet another embodiment, the additive material is a sacrificial material having a pore volume of at least 0.005 cm 3 / g. In a second embodiment, a pore volume of at least 0.05 cm3 / g. In a third embodiment, a total pore volume of at least 0.1 cm3 / g. In a fourth embodiment, a pore volume of at least 0.1 cm3 / g. In one embodiment, the slaughter material has a pore volume of at least 0.5 cm3 / g. In another embodiment, of at least 1 cm3 / g.

In one embodiment, the sacrificial material comprises an inert material of large pores such as calcined kaolin clay microspheres. In another embodiment, the sacrificial material is characterized by having at least 20% of its pore volume constituted by pores of at least 100 Angstroms; and 150-600 Angstrom in a second mode.

Examples of additive materials for use in metal trapping / purification tanks include but are not limited to silicate compounds such as Mg2Si04 and Fe2Si04; inorganic oxides such as iron oxide compounds, for example, FeO, Fe203, FeO, Fe304, Fe203, etc. Other examples of additive materials include silicate compounds such as fuming silica, A1203, MgO, MgAl204, zeolites, calcined kaolin clay microspheres, titanium, activated carbon, carbon black and combinations thereof. Examples of metal passivators include but are not limited to alkaline earth metal, antimony and bismuth compounds.

In one embodiment, the additive material is a metal scrubber commercially available from sources such as Degussa, Albermale, Phosphonics, and Polysciences. In one embodiment, the metal scrubber is a macroporous, organo-functional polysiloxane from Degussa under the trade name DELOXA E ™.

In one embodiment, the purifying / trapping / purifying material originates from a slurry catalyst, specifically, a slurry catalyst consumed in a dry powder form. In one embodiment, the spent slurry catalyst is from a heavy oil enrichment system having at least 75% heavy oil removed using means known in the art, e.g., removing oil through a membrane filtration, solvent extraction and similar. The grout catalyst consumed to be used as a sacrificial material in one embodiment has a BET surface area of at least 1 m2 / g to trap the coke and / or metals that can instead be deposited along the internal parts. of the reactor. In a second embodiment, the spent grout catalyst has a BET surface area of at least 10 m2 / g. In a third embodiment, the BET surface area is greater than 100 m2 / g.

In one embodiment, the additive is a purifying / entrapment / purifying material originated from a grout catalyst without oil consumed, where some or most of the metals have been removed. In one embodiment, the additive is in the form of drying-consumed slurry catalyst having at least some or most of the metals such as nickel, molybdenum, cobalt, etc., removed from the spent catalyst. In one embodiment, the sacrificial material is in the form of a solid waste comprising coke and some metal complex of the VB group, such as ammonium metavanadate, the residue of which is obtained after most of the metals such as molybdenum and nickel have been eliminated in a pressure pre-casting process. In yet another embodiment, the sacrificial material is in the form of a solid waste comprising mainly coke with very little residual vanadium (in the form of ammonium metavanadate).

In another embodiment, the sacrificial material is carbon black which is selected due to its high surface area, various pore size structures, and easy recovery / separation of heavy metals through combustion. In addition, the carbon material is relatively smooth, thus minimizing damage to loosening valves and other plant materials. In one embodiment, the carbon material may be any generally known and commercially available common material. Examples include but are not limited to porous particulate carbon solid characterized by a size distribution in the range of 1 to 100 microns and a BET surface area in the range of 10 to over 2,000 m2 / g. In one embodiment, the carbon material has an average particle size in the range of 1 to 50 microns and a BET surface area of about 90 to about 1,500 m2 / g. In another embodiment, the carbon material has an average particle size in the range of 30 microns. Optionally, the catalyst material can be pre-treated through one or more techniques generally known in the art such as calcination and / or impregnation first with the slurry catalyst before feeding into the enrichment system and / or mixing with the raw material of heavy oil.

In one embodiment, the additive material comprises activated carbon having a large surface area, for example, a pore area of at least 100 m2 / g, and a pore diameter in the range of 100 to 400 Angstrom. In one embodiment, the additive material is a powdered activated carbon commercially available from Norit as DARCO KB-G ™ with D-90 of 40 microns. In another embodiment, the commercially available carbon material is DARCO INSUL ™ with a D-90 of 23 microns. In yet another embodiment, the additive material comprises carbon black obtained through the calcination of the slurry catalyst consumed in heavy residual oil from a metal recovery process to recover / remove metals from a spent slurry catalyst. In one embodiment, the additive material serves a plurality of functions, for example, deposit by metal trapping / debugging and anti-foaming, entrapment by metal deposition / debugging and suppression of mesophases, etc., with the use of a surface treated with the sacrificial material. In one embodiment, the sacrificial material is a treated (or coated) surface with at least one additive material such as an inhibitor and / or an anti-foaming agent.

In one embodiment, the additive material is carbon black modified on the surface. In one embodiment, the surface treated carbon black contains reactive functional groups on the surface that provide the anti-foaming properties, and with requisite surface area and pore size structure to trap and / or immobilize the deposited coke and / or the metals (Ni, V, Fe, Na) in the source of heavy oil. In one embodiment, the additive is a carbon black treated at the surface, with the carbon having been contacted with a heavy oil additive, for example, a silicone compound such as alkyl siloxane polymers, polydimethyl siloxane, polydiphenyl siloxane. , polydiphenyl dimethyl siloxane, fluorinated siloxanes and their mixtures.

In another embodiment, the multi-functional additive is a surface-treated sacrificial material with oil-soluble metal compounds such as carboxylic acids and salts of carboxylic acids, oil-soluble polynuclear aromatics, agents that decrease the elastic modulus, and other additive materials known in the art.

In yet another embodiment, anti-foaming agents, for example, silicone compounds, hydrocarbon-based anti-foaming agents, are sprayed onto a carrier such as carbon black, titanium, etc., one after the other to generate a additive treated on the multifunctional surface for use in the enrichment system.

Optional Water Injection-Heavy Metal Tank Control: As used herein, the front end contact zone (or the first contact zone), means the first reactor in the system with a plurality of contact zones that they operate in a sequential mode (series). In one embodiment of a system with at least three contact zones, the first contact area of the front end can include both the first and second reactors. In another embodiment, the first contact zone means the first reactor only.

As used herein, the term "water" is used to indicate either water and / or steam.

In one embodiment for controlling the heavy metal deposit, the water is optionally injected in a one-pass enrichment system at a rate of about 1 to 25% by weight (relative to the heavy oil raw material). In one embodiment, a sufficient amount of water is injected for a concentration of water in the system in the range of 2 to 15% by weight. In one embodiment, a sufficient amount is injected for a water concentration in the range of 4 to 10% by weight.

The water can be added (injected) continuously or intermittently as necessary to control the deposit of heavy metals and / or improve the activity of the catalyst. Water can be added to the heavy oil raw material before or after preheating. In one embodiment, a substantial amount of water is added to the mixture of the heavy oil raw material to be preheated, and a substantial amount of water is added directly to the contact area (s) of the front end. In another embodiment, the water is added to the contact area (s) of the front end through the heavy oil raw material only. In yet another mode, at least 50% in the water is added to the heavy oil raw material mixture that is going to be heated, and the rest of the water is added directly to the contact area (s) of the front end.

In one embodiment, water is introduced to the system as part of the source of slurry catalyst. In one embodiment, the water is added to the source of the slurry catalyst and pre-conditioned together with the slurry and hydrogen catalyst, before being fed into the system together with the heavy oil source, or as a separate feed stream.

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

In one embodiment, water is added directly to the contact zone at multiple points along the contact zone, at a ratio of 1 to 25% by weight of the heavy oil raw material. In yet another mode, water is added directly in the first few contact zones in the process that are more prone to heavy metal deposits.

In one embodiment, some of the water is added to the process in the process in the form of vapor in dilution. In one embodiment, at least 30% of the added water is in the vapor form. In the modalities where the water is added as steam in dilution, the steam can be added at any point in the process. For example, it can be added to the heavy oil raw material before or after preheating, to the catalyst / heavy oil mixture stream, and / or directly in the vapor phase of the contact zones, or to multiple points as required. length of the first contact zone. The dilution vapor stream may comprise process steam or clean steam. Steam can be heated or superheated in an oven before feeding in the enrichment process. It is believed that the presence of water in the process favorably alters the molecular balance of the sulfur of the metal compound, thereby reducing the deposit of heavy metals. The water / steam in the first contact zone is expected to remove the heavy metal deposits in the equipment. In one embodiment, the addition of water is also believed to help control / maintain a desired temperature profile in the contact zones. In yet another embodiment, it is believed that the addition of water in the contact area (s) of the front end decreases the temperature of the reactor (s). The temperature of the first contact zone can be maintained at least 15-3.9 ° C (5-25 ° F) less than the temperature of the next contact zone in the series.

When the reactor temperature is lowered, it is believed that the degree of reaction of the more reactive vanadium species is decreased, allowing the deposition of the vanadium on the slurry catalyst to advance in a more controlled manner and for the catalyst to carry the deposits of vanadium out of the reactor in this way limiting the deposit of solids in the reactor equipment.

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

Additional Optional Hydrocarbon Feeding: In one embodiment, the source of additional hydrocarbon oil, for example, VGO (vacuum gas oil), naphtha, MCO (medium cycle oil), light cycle oil (LCO), oil Heavy cycle (HCO), solvent donor or other aromatic solvents, etc., in an amount in the range10 from 2 to 40% by weight of the heavy oil source, can optionally be added as part of the heavy oil feed stream to any of the contact zones in the system. In one embodiment, the additional hydrocarbon source functions as a diluent for 15 decrease the viscosity of the heavy oil source.

Control of Heavy Metal Tanks with Reactor Temperature: In one mode, instead of and / or in addition to the addition of water to the contact area (s) of the front end in a sequential operation, the temperature 20 of the contact area (s) of the front end most prone to heavy metal deposits is decreased.

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

System Performance: In one embodiment of the one-pass enrichment system and a catalyst concentration substantially less than that of the prior art process with a recycle stream, for example, at a concentration of less than 5000 wppm of the catalyst metal, at least 75% by weight of the heavy oil source is converted into lighter products in a one-pass performance process (only one reactor is used or used in multiple reactors running in tandem / parallel). In another embodiment, a degree of conversion of at least 80% is obtained with a slurry catalyst concentration in the range of a catalyst metal of 750-4,000 wppm in a process with two reactors running in a sequential mode. In a third embodiment, a conversion degree of at least 80% with a catalyst concentration in the range of 750-2,500 wppm and a high heavy oil yield of 0.15 LHSV. In a fourth embodiment, a concentration in the range of 1000-1500 wppm of catalyst metal. In one embodiment, with all three reactors in series, it was surprisingly found that the degree of conversion was equal to or better than the one-pass enrichment system with a substantially lower catalyst concentration (eg, 2500 ppm) of a prior art with recycling and a higher catalyst concentration (eg, 4200 ppm). As used herein, the degree of conversion refers to the conversion of heavy oil raw materials to materials with a boiling point of less than 538 ° C (1000 ° F).

In one embodiment, at least 98% of the heavy oil source is converted into lighter products with less than 5000 wppm of catalyst metal in a process with three reactors in series and without recycling. In another embodiment, the degree of conversion is at least 98% with less than 2500 wppm of catalyst metal. In another embodiment, the degree of conversion is at least 80% with a slurry catalyst having a concentration of 1500-5000 wppm of catalyst metal. In a fourth embodiment, the degree of conversion is at least 95% with a slurry catalyst having a concentration of 1500-5000 wppm of catalyst metal.

In one embodiment, the one-pass enrichment system provides a sulfur conversion ratio of at least 60%, a nitrogen conversion of at least 20%, and an MCR conversion of at least 50% for a catalyst concentration of slurry in the range of 750 - 5000 wppm of catalyst metal.

In one embodiment, the one-pass enrichment system produces a volume yield of over 100% (compared to heavy oil input) in enriched products when hydrogen is added which expands the total volume of the heavy oil. The enriched products, for example, lower boiling hydrocarbons, in one mode include liquefied petroleum gas (LPG), gasoline, diesel, vacuum gas oil (VGO), and jet oil and fuel. In a second embodiment, the enrichment system provides a volume yield of at least 110% in the form of LPG, naphtha, jet oils and fuels and VGO. In a third embodiment, a volume yield is at least 115%.

Depending on the conditions of the location of the separation zone, in one embodiment, the amount of heavier hydrocracked products in the nonvolatile fraction stream is less than 50% by weight (of the total weight of the non-volatile stream). In a second embodiment, the amount of heavier hydrocracked products in the non-volatile stream of the separation zone is less than 25% by weight. In a third embodiment, the amount of heavier hydrocracked products in the non-volatile stream of the separation zone is less than 15% by weight.

The amount of solids in the waste stream varies depending on the level of conversion as well as the optional additive materials used, if any, for example, slaughter materials. In one embodiment, the level of solids in the waste stream is in the range of 1 to 10% solids in one embodiment, 2-5% solids in another embodiment, less than 30% solids in a third embodiment , and less than 40% by weight of solids in a fourth mode.

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

Figure 1 is a block diagram schematically illustrating an enrichment system 110 for enriching heavy oil raw material using a slurry catalyst in a one-pass mode. First, a heavy oil raw material 104 is introduced into the first contact zone 120 in the system together with a source of slurry catalyst 110. In the figure, the heavy oil raw material 104 can be reheated in a heater ( not shown) before feeding in the contact area. The hydrogen 121 may be introduced together with the heavy oil source / slurry catalyst in the same conduit 122 as shown, or optionally, with a separate feed stream. As shown, water and / or steam can be introduced together with the feed and the slurry catalyst into the same conduit or into a separate feed stream. Additionally, the water mixture, the heavy oil source, and the slurry catalyst can be preheated in a heater prior to feeding in the contact zone. The additional hydrocarbon oil source 105, for example, VGO, naphtha, in an amount in the range of 2 to 30% by weight of the heavy oil source can optionally be added as part of the feed stream to any of the zones of contact in the system. In one embodiment, more than half of the source of heavy oil becomes the first contact zone and at least 25% of the hydrogen source is consumed in the first contact zone.

The effluent stream 123 comprising the enriched material, the spent slurry catalyst and the source of unconverted heavy oil, hydrogen etc., is withdrawn from the first contact zone 120 and sent to the separation zone 130, for example, a heat separator.

The separation zone 130 causes or allows separation of the gas and volatile liquids from the non-volatile fractions. In one embodiment, gaseous and volatile liquid fractions 131 are extracted from the upper part of the separation zone and are taken for further processing in an inclined contact or downstream process 160. The bottom stream 133 comprises the slurry catalyst and insufflated solids, coke, un-converted heavy oil raw material, hydrocarbons newly generated in the heat separator, etc., which are extracted and fed into the next contact zone 140 in the series, resulting in an additional reaction for more material enriched. In another embodiment (not shown) the effluent stream 123 deviates from the separation zone 130 and is sent directly to the next contact zone 140 in the series.

In one embodiment, the additional portions of the fresh catalyst source 110 and the heavy oil raw material 104 are fed directly into the contact zone 146 in series as separate streams or as a combined feed stream. In yet another modality, the optional hydrocarbon oil raw material 105 such as VGO (empty gas oil) is also fed into the next contact zone 140. In one embodiment (not shown), water and / or steam are also provided in the contact zone 140 as a separate feed stream, or are introduced together with the feed and slurry catalyst in the same conduit. Hydrogen 141 can be introduced together with the feed into the same conduit, or optionally, with a separate feed stream. In yet another embodiment (not shown) at least a portion or all of the source of hydrogen is mixed with the liquid stream 133 of the separation zone and fed into the reactor 140. Hydrogen extinct in one mode supplies the reaction hydrogen as most of the hydrogen in the first contact zone 120 remaining with the vapor stream 131. The effluent stream 142 comprising enriched materials together with the slurry catalyst, hydrogen gas, coke, crude oil without converting, etc. , flows to the next separation zone 150 in the series for the separation of the gas and the volatile liquids 151 from the volatile fractions 152. The volatile gas and liquid fractions are extracted from the upper part of the separation zone and combined with the gaseous and volatile liquid fractions of a preceding separation zone such as stream 161 for further processing in a hydrotreating system 60 or a system ema of downstream product purification. The non-volatile (or less volatile) fraction stream is withdrawn and sent away as a waste stream 152 to remove the oil and / or recover the metal. In yet another embodiment, (not shown), stream 161 is extinguished as a stream of hydrocarbons such as LGO in an inclined oil contact.

Hydrotreater 160 in one embodiment utilizes conventional hydrotreating catalysts, operates similarly to a high pressure (within 0.7030 kg / cm2 (10 psig) as the rest of the enrichment system, and is capable of removing sulfur, nitrogen and other impurities of the enriched products with an HDN conversion level of 99.99%, decreasing the sulfur level in the fraction to a boiling point above 21.11 ° C (70 ° F) in stream 62 to less than 20 ppm in a mode, and less than 10 ppm in a second mode In another embodiment, the in-line hydrotreater operates at a temperature within minus -12.22 ° C (10 ° F) of the contact zone temperature.

Figure 2 is a flowchart of another embodiment of a one-pass enrichment process with three contact zones running in sequential mode, for example reactors 120-135 and 140, with each of the contact zones having one zone of separation in series with an optional derivation. As shown, the effluent stream 126 comprising the enriched material, the spent slurry catalyst and the source of unconverted heavy oil, hydrogen, etc., extracted from the first contact zone 120 is sent to the separation zone 130, or directly to the second contact zone 135 in series for additional enrichment. Alternatively (shown as dotted line) the effluent stream 123 may deviate from the separation zone 130 and go directly to the next contact zone 135 in series. The source of the additional catalyst, the heavy oil feedstock and other hydrocarbon feedstock such as PGO can also be fed to the second contact zone together with an additional hydrogen source 137. The effluent stream 136 leaves the contact zone 135 and flows to the separation zone 145, where the gases (including hydrogen) and the products enriched in the form of volatile liquids are separated from the non-volatile liquid fraction 147 and are removed in a high form as the stream 146. The stream is not volatile 147 is sent to the next contact zone 140 in series for further enrichment.

The non-volatile stream 147 contains the slurry catalyst in combination with unconverted oils, heavier hydrocracked liquid products, optional sacrificial material and small amounts of coke and asphaltenes in some embodiments continues to the next reactor 140 as shown. The additional feed stream (s) comprising hydrogen, comprises gas, optionally VGO source, optionally heavy (additional) oil source, and optionally catalyst source that can be combined with the non-volatile stream 147 for an additional enrichment reaction in the next reactor 140. The effluent stream 142 of the reactor comprising enriched heavy oil feedstock flows to the separation zone 150, where the enriched products combine with hydrogen and are removed as the high stream 151. The bottom stream that comprises non-volatile fractions, eg catalyst slurry, coke containing unconverted oil, and asphaltenes, heavier hydrocracked liquid products, optional sacrificial material, etc., are removed as residue 152 for catalyst recovery / downstream regeneration.

Figure 3 is a flowchart of another embodiment of a one-pass enrichment process as a parallel train with contact fractions, for example, reactors 120, 135, and 140, and with an optional deviation such that a separation zone can be used for all three reactors. In one embodiment, the system is operated at a high performance grade with the three reactors operating in parallel with each reactor having its own source of heavy oil, catalyst source, optional VGO source etc., with the effluent going to the same separator 150 or individually to separate reactors, and the non-volatile fractions of the separators are collected for further processing as residue 152. In one embodiment (not shown, or indicated by dotted lines), the system operates at a slower speed with at least two of the reactors operating. in series, with the non-volatile fraction of the separator being sent to the next reactor in series. In one embodiment, the effluent stream withdrawn from the reactor can be sent to the separator located in series after each reactor, for example, streams 126 flowing to separator 130, stream 136 to separator 145, and stream 142 to separator 150, and the non-volatile streams from any of the separation zones can be removed (sent out of the waste tank 152 for catalyst recovery / downstream regeneration.

In one embodiment (as shown by dotted lines), with all reactors sharing a separator, all effluent streams are sent to separator 150, where the high current is drawn as current 151 and sent to an inclined contact or a downstream process 160. Flexible Operation: A single pass enrichment process is illustrated in Figure 3 with a plurality of contact zones and separation zones constructed in an interchangeable manner to provide flexible operation, accommodating different modes of operation. Although not shown in Figure 3, the appropriate valves can be installed in the process pipes to open / close accordingly, allowing the one-pass process system to change from one mode of operation to another.

The different modes include but are not limited to the following and their combinations: a) an operation with a reactor for two, or three (or more) reactors; b) an operation with a low degree of performance but a high degree of conversion with the plurality of reactors operating in a sequential manner, that is, operating in series, with the effluent of a reactor or the liquid stream from the bottom of a separator which is sent to the next reactor in series for additional conversion; c) a high performance operation with at least some of the reactors running in tandem (parallel) and heavy oil raw material for each of the reactors, and some of the reactors being in the idle or off mode of line; d) a mixed mode of operation with a reactor running in tandem (parallel) with another plurality of reactors running in series; e) an operation with the reactors running in tandem (parallel) with the effluent stream of each reactor being sent to a separator in series with the reactor (s); and f) an operation with reactors running in tandem (parallel), and the operation with the effluent stream (s) of the reactors being combined and sent to one or two separators for the separation and recovery of the enriched products.

Although not described herein, there may be other permutations of the above operating modes, such as a combined mode wherein the effluent from a reactor or the liquid stream from the bottom of a separator is divided into multiple feed streams for two or more reactors in series. Additionally, since the system is established as a flexible operation, any of the reactors can be operated as a primary reactor or only a first reactor (a second reactor, a third reactor, etc.) in a process that runs in a sequential manner (or a mixed / tandem sequential model), and any of the separation zones can be operated as a primary or single separator, a first separation zone (second or third, etc.) or the only continuous separation zone.

In one embodiment, the process allows flexible operation with different types of heavy oil sources, catalyst types, etc., with the reactors running in parallel with their own power systems. The flexibility of running in parallel or in series also allows a reactor to shut down to clean itself, remove deposits, etc., while the rest of the system remains operational. This means that the efficiency of the overall operating process is increased with minimum rest time of the global system.

In one mode, the process allows flexible conversion from one operational mode to another, without the need to shut down or restart the unit. In a mode where only one of the contact zones is kept in operation such as a single reactor operates, the other reactor (s) is maintained in a warm standby mode, ie at a pressure and elevated temperatures such as the reactor (s) in operation. In one embodiment, pressure and temperature are maintained in standby equipment with hot hydrogen circulating through the reactor or reactors not in operation and kept on hold.

In one embodiment, a sufficient quantity of heated hydrogen-containing gas is supplied to each of the standby reactors for the reactors to be at approximately the same temperature and pressure as the reactors in operation. As used herein, approximately the same (or similar to) temperature means that the standby reactor temperature is within 10 ° C (50 ° F) of the temperature of the reactors that are in operation, and the pressure of the standby reactor is within 7.03 kg / cm2 (100 psi) of the pressure of the reactors in operation.

In one embodiment, the sufficient amount of hydrogen is in the range of 10 to 100% of the hydrogen supplied to the reactor (s) in operation. In another embodiment, this sufficient amount of hydrogen is in the range of 10 to 30%. In a fourth embodiment, the sufficient amount of hydrogen is in the range of 15 to 25% of the total amount of hydrogen supplied in the reactors still in operation. The hot hydrogen stream leaves the waiting reactor or reactors and enters the separation zones, where it is then combined with the high current and sent to an inclined contact to a downstream process for the purification of the product.

Figure 4 illustrates one embodiment of a flexible pass enrichment process (a variation of Figure 3), wherein only two of the reactors 120 and 135 in the system are connected for enrichment of the heavy oil, and the third system reactor 140 is placed on standby or in the backup mode with an H2 source only, or it can be used for the enrichment of the heavy oil as shown (using a catalyst and / or different heavy oil raw material). The third reactor system 140 can also be turned off for maintenance while the other two remain in line.

As shown, the reactors 120 and 135 run in series, with the liquid stream from the bottom 133 of the high temperature and high pressure separator (HPHT) 130 which it sends to the reactor 135 for further enrichment. The volatile product streams of the high HPHT separators are combined with hot hydrogen 151 of the standby unit (or high stream with enriched products if the reactor 140 is in operation) and are sent to an inclined contact or to a downstream purification process. . The bottom stream comprising unconverted heavy oil, spent catalyst slurry, asphaltenes, etc., from the separator, for example, 147 are collected as residue 152 and sent to a downstream process to remove the oil and / or recover the metal in a metal recovery unit.

Figure 5 illustrates another embodiment of the flexible pass enrichment system (variation of Figure 3), where all units are connected for heavy oil enrichment to maximize performance, running in parallel with the heavy oil source 104 , the source of the grout catalyst 110, the optional steam injection to some of the reactors, optional additive materials such as anti-foam, injection and / or slaughter materials to some of the reactors and optional VGO source for some of the reactors that run in tandem. Although not shown, it is noted that the effluents from any or all of the reactors can be directed to a single HPHT separator instead of running through a separator connected in series to the reactor, for example, effluent streams 123 and 136 of the reactors 120. 140 respectively that can be combined with the effluent stream 142 of the last reactor in the train, the reactor 140, as the HPHT 150 separator feed. If the reactors run with separate units with their own respective HPHT separators, the bottom currents comprising oil heavy without converting, the catalyst consumed, for example 133, 147 may be collected in a waste stream 152 and sent to a downstream process to remove the oil and / or recover the metal in a unit for metal recovery.

Residual stream 152 contains small amounts of coke and asphaltenes, optional sacrificial material if any exists and the slurry catalyst consumed in an amount of 5 to 30% by weight in unconverted oils. The volatile product streams of the high HPHT separators are combined and sent to the sloped contact to a downstream product purification process.

Figure 6 is a flow chart of another embodiment of a one-pass enrichment process with three contact zones running in tandem (parallel) and sharing a separation zone. As shown, each reactor 120, 135 and 140 run in tandem with its own separate heavy oil, catalyst, optional VGO, optional steam injection (not shown) and optional additive sources (not shown), effluent streams 123, 136 and 142 of the reactors are combined and sent to a single separation zone 150 so that the enriched products are separated from the waste stream comprising the spent slurry catalyst, the heavier hydrocarbons and the source of heavy crude oil. As the reactors operate in tandem as separate enriched reactions, the heavy oil feedstock as well as the catalyst source may be the same or different through the reactors.

Figure 7 is another permutation of the flexible enrichment system, wherein the first two reactors 120 and 135 occur in sequential mode. Although not shown, the additional heavy oil source as well as the catalyst, the optional additives, the VGO source, etc., can be added to the second reactor 135 together with the effluent stream 123 of the first reactor. The last reactor can be kept in the standby mode with hot H2 flowing through the reactor, or it can also be used to enrich the heavy oil as shown, with the last reactor 140 running in tandem with the sequential operation (reactors 120 and 135) . The heavy oil raw material, the catalyst source and the VGO source for the last reactor 140 may be the same or different from the sources of the sequential operation. As shown, the effluent streams 136 and 142 of both operations are combined and sent to the separation zone 150.

Although not shown in all figures, the one-pass enrichment system may comprise recirculating / recycling channels and pumps (not shown) to promote the dispersion of reactants, catalyst and heavy oil feedstock in the contact zones, particularly with a high degree of recirculation flow to the first contact zone to induce turbulent mixing in the reactor, thereby reducing heavy metal deposits. In one embodiment, a recirculation pump circulates through the cycle reactor, thereby maintaining the temperature difference between the feed point of the reactor to the outlet point in the range of less than -17.22 to -10 ° C (1 at 50 ° F) or between -16.67 to -3.9 ° C (2-25 ° F). In another embodiment, the recirculation is to limit the temperature difference between the contact zone (s) due to the exothermic reactions and to ensure a good counting of the hydrogen and the reactants.

In the contact zones under the hydrocracked conditions, at least a portion of the raw material in heavy oil (hydrocarbons a higher boiling point) is converted to hydrocarbons with a lower boiling point, forming an enriched product. It should be noted that at least a portion of the slurry catalyst remains with the raw material without enrichment as the slurry catalyst consumed, how the enriched materials are removed from the contact zone and fed into the separation zone; and the spent slurry catalyst continues to be available in the separation zone and leaves the separation zone with the non-volatile liquid fraction.

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

Examples: The heavy oil enrichment experiments were carried out in a system that has three gas-liquid slurry phase reactors connected in series with two heat separators, each being connected in series with the 2nd and 3rd reactors respectively.

For all the examples, a fresh slurry catalyst was prepared in accordance with the teachings of the U.S. Patent. No. 2006/0058174, for example, a Mo compound was first mixed with aqueous ammonia to form a mixture of the aqueous Mo compound, sulfurized with a sulfur-containing compound, promoted with a Ni compound, then transformed into a hydrocarbon oil, for example, VGO, at a temperature of at least 176.66 ° C (350 ° F) and a pressure of at least 14.06 kg / cm2 (200 psig), forming an active slurry catalyst to be sent to the first reactor. The concentration of Mo in VGO is 5% and the Ni / Mo ratio is 10% by weight.

The heavy oil raw material in the examples has properties as indicated in Table 1.

Description of the source VR-1 VR-H VR-2 Source API 2.5 1.35 2.70 Specific Gravity of the 1.06 1.07 1.06 source Viscosity (100C), cst 14548 - - Viscosity (130C), cst 1547 51847 8710 Viscosity (150C), cst NA 5647 2102 Sulfur Feeding,% in 5.53 4.3675 5.12 weight Nitrogen feed, ppm 5688 9907 7900 Feed MCR,% by weight 25.4 27.09 29.9 Vanadium feed, ppm 517.7 759.8 671.6 Nickel feed, ppm 102.2 174.3 141.9 Hot Heptane asphaltenes, 16.3 19.2 25.7% in weight Feed VR content 86.4 95.5 95.7 (1000F +),% by weight HVGO content of 97.8 98.9 100 feed (800F +),% by weight VGO content of 99.6 100 100 feed (650F +),% by weight C of feed,% by weight 83.71 84.30 83.24 H of feed,% by weight 9.88 9.75 9.53 Proportion of H / C 0.118 0.116 0.114 The enrichment system was operated in two modes: recycled and in one pass. In the recycling mode as in the prior art, a portion of the non-volatile stream (STB product or "scrubber bottoms") of the last reactor was recycled back to the first reactor and a portion was removed as a bleed stream. The STB current represents approximately 30% of the heavy oil raw material of the system. The bleed stream represents approximately 15% by weight of the heavy oil raw material for the system. The STB stream contains approximately 10 to 15% by weight of slurry catalyst.

In all runs, effluent taken from the first reactor was sent to the second reactor to continue the enrichment reaction. The effluent streams of the second and third reactors were sent to the separators connected in series to the second and third reactors respectively, and were separated into hot steam stream and non-volatile stream. The vapor currents ("HPO" or high high pressure currents) were removed from the top of the high pressure separators and collected for further analysis. The non-volatile stream comprising the unbleached heavy oil slurry catalyst and raw material from the first separator was sent to the third reactor. The non-volatile stream comprising the slurry catalyst and heavy oil raw material without converting from the second separated (last) is the STB stream, which was either recycled to the first reactor (for "recycling" experiments) or sent away as a residual current (for "one-pass" experiments).

The hydroprocessing conditions were as follows: reactor temperature (in three reactors) in the range of 426.67 - 437.78 ° C (805 - 820 ° F), with the average reactor temperature as indicated in the Tables; a total pressure in the range of 168.72 - 182.78 kg / cm2 (2400 to 2600) psig; LHSV is as indicated in the table, in the range of 0.1 to 0.30h ~ 1; and H2 gas velocity (SCF / bbl) from 7500 to 20,000. For some of the runs, some of the reactors were taken offline to increase overall feeding performance (as indicated in the Tables with the number of reactors in operation) As shown in Table 3 and a comparable LHSV, Example 8 in one-pass mode and low catalyst concentration (2500 ppm or / VR) gives a degree of conversion that is comparable to the degree of conversion obtained in Example Comparative 3, for an enrichment process that operates in a recycling mode and at a much higher concentration of the catalyst (4200 ppm). HVGO and VGO conversions were 93% and 78% respectively, along with high HDS, HDN, HD MCR and HDM conversions. The API gravity of the complete product gained about 31 degrees, similar to the recycling operation. The experiments indicated that the recycle stream could be eliminated without affecting the overall performance, and decreasing by increasing the catalyst niel (2500? 4200 ppm) does not significantly change the performance.

Attempts to run the enrichment system in a comparable (low) recycling mode and concentration of 2500 ppm Mo / VR were not successful in Comparative Example 4, since the system was never stabilized and equipment problem due to the low degree of conversion in the recycling mode (formation of coke and deposition of solids in the reactor).

The results of Example 1, Comparative Example 1 and Comparative Example 2 were evaluated to compare the degree of conversion to different performance grades and a high degree of catalyst (2.1% Mo). The degree of conversion of the residue to vacuum (VR) decreased as expected at higher degrees of yield, but was still at a degree of conversion of > 70% (71.74%). Additionally, more than 95% of the V and Ni in the feed were removed from the products and the API gravity of the complete product gained approximately 17 degrees compared to the VR feed.

Examples 2-7 were to evaluate the one-step enrichment system at various performance grades and low catalyst concentration (1500-2500 ppm). As shown in Example 2, > 75% conversion VR at 0.3 VR LHSV and 4200 ppm Mo. The conversion rates of HVGO and VGO were 62% and 50% respectively, which indicates that most of the VR had been converted to hydrocarbons / light oils. When the oil level was reduced to 2500 ppm (Example 3) or 1500 ppm (Example 4), the VR conversion was slightly increased due to the slight decrease in the overall LHSV. When the reactor temperature was increased from 436.67-437.22 ° C (818-819 ° F) to 440.55 ° C (825 ° F), the degree of conversion increased to 79% with a low catalyst level of 2500 ppm Mo, which is a 40% reduction in the use of the catalyst compared to the use in the recycling mode (Comparative Example 3). As shown in Examples 6-7, a conversion of 92-94% VR to 2500 ppm Mo was obtained with an API gain of complete product of more than 26 degrees.

As noted, at a low catalyst to oil ratio (1500-4200 ppm) in one-pass mode, at least 75% VR conversion is obtained (537.78 ° C (1000 ° F)) (75-79%) ) at a high VR yield (0.3 LHSV) and at a high reactor temperature of 436.67-440.55 ° C (818-825 ° F). The degree of conversion VR was increased to 92-94% at 0.15 LHSV and at an almost complete degree of conversion of > 98% at 0.1 LHSV and a high reactor temperature of 436.67-440.55 ° C (818-825 ° F). Also as noted, the catalyst concentration in the reactors increased from one reactor to the next (in series), without the enrichment system operating in either the recycle mode or the one-pass mode.

Comparative Example 10. It is expected that running the enrichment system in one pass mode with a very low catalyst concentration (250 ppm Mo / VR) would have been unsuccessful, since the system would not stabilize with plugging problems , presumably with a low degree of conversion due to a low concentration of the catalyst.

Example 13. In this example, a sacrificial material was used to test the absorbency of asphaltenes and other deposits in the enrichment system. A material with a high capacity was used to selectively adsorb problematic asphaltenes. The material adsorbed in this way prevents the asphaltenes from deactivating the catalyst, allowing the system to run with less catalyst while still maintaining a high conversion.

In Example 13 (see table 4), two different sacrificial adsorbent materials were evaluated. C-2 is a commercial carbon black material from STREM Chemicals that has an average size of 2-12 microns. Cl is a carbon black obtained by the carbonization of the spent slurry catalyst in residual heavy oil obtained from a previous enrichment run, having a D-90 of 10 microns (with a particle size in the range of 2 to 12 microns ), and BET surface area of 400 m2 / g. The carbon material was charged to 3000 ppm Coal / VR w / w in a batch reaction experiment with 112.5 g of a heavy oil mixture VR-1 / cycle oil (ratio 3: 2), and a catalyst level from 1.25% Mo to heavy oil feed VR-1. The reaction was carried out at a pressure of 112.48 kg / cm2 (1600 psig) of hydrogen and with 2 to 5 hours of impregnation at 440.55 ° C (825 ° F). The runs with the carbon material were compared with the batch reaction experiments without the sacrificial adsorbent. Table 4 summarizes the performance of the catalyst.

Table 4 HDN means hydronitrogenation; HDS means hydrodesulfurization; HDMCR means hydro-hydrocarbon residue; VR means vacuum residue; at H / C means ratio of atomic hydrogen to carbon; and the dry solids values were measured according to the methods known in the art. HDN is a common measure for the hydrogenation activity of a catalyst. As shown, the runs using carbon-sacrificial material showed a consistent increase in HDN activity at both impregnation times of 2 and 5 hours compared to the control without the carbon.

For the purpose of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are understood as being modified in all instances by the term "approximately". Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired properties sought to be obtained and / or the accuracy of an instrument for measuring the value, in this way including the deviation of standard error for the device or method that is being used to determine the value. The use of the term "or" in the claims is used to mean "and / or" unless it is explicitly stated that it refers to alternatives only or the alternative is mutually exclusive, although the description supports a definition that refers only to alternatives e "and / or": The use of the word "a," or "an, a" when used in conjunction with the term "comprising" in the claims and / or specification may mean "one", but also it is consistent with the meaning of "one or more", "at least one", and "one or more than one". In addition, all the ranges described herein are inclusive of the endpoints and independently combinable. In general, unless otherwise indicated, the singular elements may be plural and vice versa if the loss of generality. As used herein, the term "includes" and its grammatical variants are intended to be non-limiting, such that the recitation of items in a list is not the exclusion of other similar articles that may be substituted or added to the items listed.

It is contemplated that any embodiment of the invention explained in the context of one embodiment of the invention may be implemented or applied with respect to any other embodiment of the invention. Likewise, any composition of the invention may be the result or may be used in any method or method of the invention. This written description uses examples to describe the invention, including the best mode, and also allows the person skilled in the art to make and use the invention. The patentable scope is defined by the claims, and may include other examples that occur to the person skilled in the art. Such other examples are intended to be within the scope of the claims if they have the structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with non-substantial differences of the literal languages of the claims. All citations referred to herein are hereby expressly incorporated by reference.

OR LO H Table 3 Com .

Ex. 8 Ex. 9 Ex. 10 Com. 3 Comp. 4 10 Power supply type VR-H VR-H VR-H VR-H VR-H VR-H Mode of operation One One One One Recycling Recycling last last passed last Number of reactors 3 3 3 3 3 3 in service VR LHSV, h "1 0.10 0.10 0.10 0.10 0.10 0.10 LHSV Global (VR-VGO 0. 105 0.107 0.109 0.109 0.109 0.109 in catalyst), h "1 Unitary pressure, 2502 2505 2497 2497 2505 2505 psig Total H2 speed 13500 13500 13500 13500 13500 13500 - scf / bbl-VR Average temperature of the reactors at 818.7 818.7 819.3 819.3 819 819 service, F Proportion Mo / VR, ppm 2500 3000 4200 250 4200 2500 Power API 1. 35 1.35 1.35 1.35 1.35 1.35 VR STB API 0.8 2.3 3.3 - 3.9 - HPO API 36.2 36.3 36.1 '- 35.9 - Product API 32. 2 32.2 32.2 - 32.3 - complete Conversion of sulfur, 91. 71 91.12 92.83 - 92.81 -% Conversion of 55. 96 59.94 61.11 - 58.90 - nitrogen,% Com .

Ex. 8 Ex. 9 Ex. 10 Com. 3 Com. 4 10 MCR Conversion,% 94.18 94.47 94.77 - 94.36 - VR Conversion (1000 98. 34 98.37 98.37 - 98.18 - F +),% Conversion HVGO (800 92. 85 92.54 92.74 - 92.11 - F +),% VGO conversion (650 78. 28 78.07 78.15 - 77.61 - F +),% - HD-vanadium,% 99.79 99.83 99.86 - 99.83 - HD-nickel,% 97.54 97.55 97.66 - 97.88 - Molecular concentration 4050 na na - 16500 -in 1st. reactor, ppma Mo Concentration 11500 na na - 26600 - in 2nd. reactor, ppma Mo Concentration 51900 66900 93500 - 44500 -in 3rd. reactor, ppma Mo Concentration in product STB 17700 21700 30900 - 32500 - (OUT), ppm It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims

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

1. A process for hydroprocessing heavy oil raw material, which uses a plurality of contact zones and at least one separation zone, including a first contact zone and a contact zone different from the first contact zone, characterized in that it comprises: provide a gas source containing hydrogen; provide heavy oil raw material; providing a source of slurry catalyst comprising an active metal catalyst having an average particle size of at least 1 miera in a hydrocarbon oil diluent, at a concentration of more than 500 wppm of the active metal catalyst for the raw material of heavy oil; combining at least a portion of the source containing hydrogen, at least a portion of the heavy oil raw material, and at least a portion of the source of slurry catalyst in a first contact zone under hydrocracking conditions to convert at least a portion of the first source of heavy oil raw material in lower boiling hydrocarbons, forming enriched products; sending a first effluent stream of the first contact zone comprising the enriched products, the slurry catalyst, the hydrogen-containing gas, and the un-converted heavy oil raw material to a first separation zone, where the volatile enriched products they are removed with the hydrogen-containing gas as a first high current, and the slurry catalyst and the unconverted heavy oil raw material are removed from the first non-volatile stream, wherein the first non-volatile stream contains less than 30% solids; collect the first high current for additional processing; Y collect the first non-volatile stream for additional processing.

2. A process according to claim 1, characterized in that it also comprises: providing an additive material selected from the group consisting of inhibitory additives, anti-foaming agents, stabilizers, metal scavengers, metal contaminants removers, metal passivators, sacrificial materials, and mixtures thereof, in an amount of less than 1% by weight from the heavy oil raw material; and wherein, in the combination step, at least a portion of the additive material is combined with the gas source containing hydrogen, the heavy oil raw material, and the source of slurry catalyst in the first contact zone.

3. A process according to claim 1, characterized in that the plurality of contact zones and separation zones is configured in an interchangeable form so that the plurality of contact zones and separation zones operate in: a sequential mode; a parallel mode; a combination of parallel mode and sequential mode; all online; at least one online and at least one waiting; some online and some offline; a parallel mode with the effluent stream of the contact zone being sent to at least one separation zone in series with the contact zone; a parallel mode with the effluent stream of the contact zone combined with an effluent stream from a different contact zone and sent to the separation zone; and its combinations.

4. A process in accordance with the claim 1, characterized in that the first contact zone operates at a first pressure and has an outlet pressure of X, where the first separation zone has an inlet pressure of Y, and where there is a pressure drop Z between the pressure output X of the first contact zone and the inlet pressure Y of the first separation zone, and Z is less than 0.703 kg / cm2 (100 psi).

5. The process according to claim 4, characterized in that the pressure drop Z is less than 5.27 kg / cm2 (75 psi), and where the pressure drop Z is not due to a pressure reducing device.

6. The process according to claim 1, characterized in that the active metal catalyst has an average particle size in the range of 1 to 20 microns.

7. The process according to claim 1, characterized in that the slurry catalyst comprises groups of colloidal sized particles of less than 100 mm in size, and wherein the groups have an average particle size in the range of 1 to 20 microns.

8. The process according to claim 1, characterized in that it also comprises: adding an amount of water of up to 30% by weight of the first heavy oil raw material to the first contact zone.

9. The process according to claim 1, characterized in that it also comprises: adding a source of additional hydrocarbon oil different from the heavy oil raw material, in an amount on the scale of 2 to 30% by weight of the heavy oil raw material, to the first contact zone.

10. The process in accordance with the claim 1, characterized in that a sufficient amount of gas source containing hydrogen is provided to the processes to have a volume yield greater than 100% in enriched products comprising liquefied petroleum gas, gasoline, diesel, vacuum gas oil, and Jet and fuel oils.

11. The process according to claim 2, characterized in that the additive material is a sacrificial material for trapping metals in the raw material source of heavy oil and coke, having a BET surface area of at least 1 m2 / g and a volume of total pore of at least 0.005 cm3 / g.

12. The process in accordance with the claim 2, characterized in that the additive is a spent slurry catalyst.

13. The process according to claim 1, characterized in that at least one of the contact zones is maintained in a standby mode and the process further comprises: maintaining the contact zone in standby mode at a temperature and pressure similar to the temperature and pressure under hydrocracking conditions of the first contact zone; and wherein a sufficient amount of gas source containing hydrogen is provided to the contact zone in standby mode to maintain a temperature and pressure similar to that of the first contact zone.

14. The process in accordance with the claim 1, characterized in that the plurality of contact zones operate in a parallel mode, and the process further comprises: providing a second contact zone, also operated under hydrocracking conditions, at least a portion of the hydrogen-containing gas source, at least a portion of the heavy oil raw material, and at least a portion of the catalyst source of grout; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil feedstock, and at least a portion of the source of slurry catalyst in the second contact zone to convert at least a portion from the raw material of heavy oil to lower boiling hydrocarbons, forming additional enriched products; send the first effluent stream and a second effluent stream from the second contact zone comprising additional enriched products, the slurry catalyst, the hydrogen-containing gas, and the heavy oil raw material without converting to the first separation zone, where the first high current and the first nonvolatile current are removed for further processing; and wherein the source of heavy oil raw material is fed into the second contact zone.

15. The process in accordance with the claim 1, characterized in that the plurality of contact zones operates in sequential mode, and further comprises, before sending the first effluent stream to the first separation zone: sending the first effluent stream from the first contact zone to a second contact zone which is also maintained under hydrocracking conditions with gas source containing additional hydrogen to convert at least a portion of the heavy oil raw material without converting it into the effluent stream to lower boiling hydrocarbons, forming additional enriched products; Y collecting the enriched product mixture, the slurry catalyst, the hydrogen-containing gas, and the un-converted heavy oil raw material from the second contact zone as a feed in the first separation zone.

16. The process according to claim 1, characterized in that the plurality of contact zones operates in a parallel mode with at least two contact zones that are run in parallel, which further comprises: combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material, and at least a portion of the slurry catalyst in a second contact zone under hydrocracking conditions to convert at least one portion of the raw material from heavy oil to lower boiling hydrocarbons, forming additional enriched products, wherein the second contact zone runs parallel to the first contact zone; and sending the first effluent stream of the first contact zone and an effluent stream of the second contact zone comprising a mixture of additional enriched products, the slurry catalyst, the hydrogen-containing gas to the first separation zone.

17. The process according to claim 1, characterized in that the plurality of contact zones operates in a parallel mode with at least two contact zones that are run in parallel, which further comprises: providing a second slurry catalyst, wherein the slurry catalyst is different from the slurry catalyst provided for the first contact zone; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil raw material, and at least a portion of the second slurry catalyst in a second contact zone under hydrocracking conditions to convert at least a portion of the raw material from heavy oil to lower boiling hydrocarbons, forming additional enriched products, wherein the second contact zone runs parallel to the first contact zone; sending a second effluent stream from the second contact zone comprising a mixture of additional enriched products, the slurry catalyst, the hydrogen-containing gas, and un-converted heavy oil raw material as a feed for a second separation zone, in where the additional volatile enriched products are removed with the hydrogen-containing gas as a second high stream, and the grout catalyst and the un-converted heavy oil raw material are removed as a second non-volatile stream.

18. The process according to claim 1, characterized in that the plurality of contact zones operates in a parallel mode, and further comprises: providing a second contact zone, also operated under hydrocracking conditions, at least a portion of the hydrogen-containing gas source, at least a portion of the heavy oil raw material, and at least a portion of the catalyst source of grout; combining at least a portion of the gas source containing hydrogen, at least a portion of the heavy oil feedstock, and at least a portion of the source of slurry catalyst in the second contact zone to convert at least a portion from the raw material of heavy oil to lower boiling hydrocarbons, forming additional enriched products; sending the second effluent stream from the second contact zone comprising additional enriched products, the slurry catalyst, the hydrogen-containing gas, and the un-converted heavy oil raw material to the first separation zone, wherein the first high stream and the first nonvolatile current are removed for further processing; and optionally wherein the source of slurry catalyst for the second contact zone is a slurry catalyst different from the source of slurry catalyst for the first contact zone.

19. The process according to claims 14-18, characterized in that it also comprises: adding an amount of water of up to 30% by weight of the heavy oil raw material to at least one of the first contact zone and the second contact zone.

20. The process according to claims 14-18, characterized in that the source of the slurry catalyst for the first contact zone is a Ni slurry catalyst alone or a Ni-rich slurry catalyst, and the catalyst source for the second Contact zone is a Mo-only slurry catalyst or a Mo-rich slurry catalyst. SUMMARY OF THE INVENTION A flexible one-pass process for hydroprocessing heavy oil raw material is described. The process employs a plurality of contact zones and at least one separation zone to convert at least a portion of the heavy oil raw material into lower boiling hydrocarbons, forming enriched products. The contact zones operate under hydrocracking conditions, using a slurry catalyst comprising an active metal catalyst having an average particle size of at least 1 mire in a hydrocarbon oil diluent, at a concentration greater than 500 wppm of the catalyst of active metal for the heavy oil raw material. The plurality of contact zones and separation zones is configured in an interchangeable form that allows the process of a pass to be flexible operating in several modes: a sequential mode; a parallel mode; a combination of parallel and sequential mode; all online; some online and some waiting; some online and some offline; a parallel mode with the effluent stream of the contact zone being sent to at least one separation zone in series with the contact zone; a parallel mode with the effluent stream of the contact zone being combined with an effluent stream from the least other contact zone and sent to the separation zone; and its combinations. In one embodiment, the effluent from a contact zone is sent to the next serial contact zone for further enrichment, with the next contact zone having a pressure drop of at most 7.03 kg / cm2 (100 psi), the Pressure drop is not due to a pressure reducing device as in the prior art. In one embodiment, at least one additive material selected from inhibitory additives, anti-foaming agents, stabilizers, metal scavengers, metal contaminant scavengers, metal passivators, and sacrificial materials is added in an amount of less than 1% by weight of the heavy oil raw material, to at least one of the contact zones.