EA038171B1 - Integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals - Google Patents

Abstract

Integrated hydrotreating and steam pyrolysis processes for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals.

Description

This application claims priority to European Patent Application No. 17154394.5, filed February 2017, European Patent Application No. 17154395.2, filed February 2, 2017, European Patent Application No. 17154391.1, filed February 2, 2017, and European Patent Application No. 17154396.0, filed February 2, 2017, the entire contents of which in their entirety are incorporated by reference into this document.

The technical field to which the invention relates

The present invention relates to an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products.

State of the art

Refiners face the challenges of oil getting heavier and worse. The components that cause the greatest difficulties in the processing of heavy oils are asphaltenes, which are a complex macromolecule that contains a significant proportion of impurities such as S, N, Ni and V. The composition, structure and concentration of asphaltenes largely determine the quality and effect of processing of heavy oil. Hydroprocessing is one of the most efficient technologies for heavy oil refining. However, during hydroprocessing, carbon deposits and pore plugging on the surface of catalysts readily occur due to the congregation and coking of asphaltene constituents, which can greatly shorten the working life of the catalyst and the uptime of the production facility. These high molecular weight large multi-ring aromatic hydrocarbon molecules or associated heteroatom-containing (eg, S, N, O) multi-ring hydrocarbon molecules in heavy oils are called asphaltenes. The structure of these asphaltenes contains a significant proportion of sulfur. Due to the large aromatic structures of asphaltenes, sulfur can be difficult to thermally process in nature and can be difficult to remove.

Thus, asphaltenes are present in crude oil along with other components that help keep them dissolved. During the distillation of crude oil, most of these other components, which are in lower boiling ranges than asphaltenes, are removed from the crude oil. This concentrates the asphaltenes in the residue. Depending on the solubility of the asphaltenes in the crude oil residue, they can come out of the dissolved state in one gulp due to aggregation and precipitation as a solid. Precipitated asphaltenes in downstream hydroprocessing units cause fouling of the hydroprocessing reactors with catalyst and a shorter cycle time.

US Publication No. 2007295640 relates to a composition comprising an asphaltene solvent and a viscosity-lowering additive, wherein the asphaltene solvent and viscosity-lowering additive are present at a ratio such as to substantially reduce the viscosity of the asphaltene-containing material while negating the precipitation of asphaltenes either in the formation or in production string, or at both of these locations when mixing or otherwise.

Publication WO 2013033293 relates to a process for the production of a hydrotreated product, comprising: exposing a combined feed containing a heavy oil feed stream and solvent, a hydrotreating catalyst to produce a hydrotreated effluent stream, separating the hydrotreated effluent stream to produce at least a liquid effluent stream and fractionating the first portion of the liquid effluent stream to obtain at least a distillate product, wherein the solvent constitutes at least a portion of the distillate product, wherein at least 90 wt% of said at least a portion of the distillate product has a boiling point of boiling range from 149 to 399 ° C.

Publication WO 2013112967 relates to an integrated solvent deasphalting, hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce petrochemical products such as olefins and aromatics.

Publications US 2013220884 and US 2013197284 relate to an integrated hydrotreating, solvent deasphalting and steam pyrolysis process for the direct processing of crude oil to produce petrochemicals such as olefins and aromatics.

US Publication No. 2013197283 relates to an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce petrochemicals such as olefins and aromatics.

The cracked distillate is a by-product from the thermal cracking of a feed for a cracking unit, the by-product comprising a hydrocarbon mixture having a boiling point in the range of 80 to 260 ° C, at least 35 wt% which are composed of unsaturated hydrocarbons. The term "cracked distillate is also understood to mean the fraction of unsaturated compounds that can be polymerized to form a tar and which is obtained by distilling coal tar. The liquid product from the cracking process is known as carbon black oil. Oil for the production of carbon black is highly aromatic and constitutes a valuable feedstock for the production of carbon black and for the manufacture of electrodes.

In a situation where the commercial demand for both cracked distillate and oil for the production of carbon black is decreasing, new industrial markets and end-use options are required for these products.

Not only carbon deposition and clogging of pores on the surface of the catalysts are undesirable phenomena, but also the presence of large amounts of sulfur in the feed. These sulfur-containing and / or nitrogen-containing organic compounds can compete for active sites of the catalyst in the reaction zone in hydroprocessing units, thereby adversely affecting the progress of the hydrocracking reaction.

Objectives of the invention

One object of the present invention is to provide a method for producing a feed for a hydroprocessing unit, in which feed the aggregation of asphaltenes in the crude oil is minimized, i. E. so as to keep the asphaltenes dissolved.

Another object of the present invention is to provide a feed for a hydroprocessing unit, which results in a long catalyst life and a long facility life.

Another object of the present invention is to provide a valuable use case for a cracked distillate from a steam cracker (CD) and an oil for the production of carbon black from a steam cracker (SVO).

Yet another object of the present invention is to provide an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products, where crude oil fractions that do not benefit greatly from their solvent deasphalting are not exposed to such a solvent process. deasphalting, namely naphtha, kerosene and diesel fractions.

Another object of the present invention is to provide an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products, where the crude oil fractions are not subjected to such a hydrotreating process.

Disclosure of invention

Thus, the present invention relates to an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products, the process comprising the steps of: (a) separating the crude oil into light components containing naphtha, kerosene and diesel fractions. fractions and heavy components containing heavier hydrocarbon fractions containing asphaltenes; (b) loading heavy components into the solvent deasphalting zone together with an effective amount of solvent in order to obtain a stream of deasphalted and demetallized oil and the lower phase of asphalt, the solvent containing a pure liquid hydrocarbon selected from propane, butanes and pentanes, as well as mixtures thereof, while deasphalting is carried out at a temperature equal to or less than the critical temperature of the solvent, the ratio between solvent and oil in the range from 2: 1 to 50: 1, and a pressure in the range effective to maintain the mixture of solvent and feed stream in a liquid state; (c) loading said light components, a deasphalted and demetallized oil and hydrogen stream into a hydroprocessing zone operating under conditions effective to produce a hydroprocessing effluent stream characterized by reduced pollutant levels, increased wax content, reduced Geological Bureau of Mineralogy correction factor, and increased density degrees in the American petroleum Institute, the hydrotreating zone is operated at a temperature ranging from 300 to 450 ° C, a pressure ranging from 30 to 180 bar and LHSV of from 0.1 to 10 hours'^1; (d) thermally cracking the hydrotreated effluent stream in the presence of steam to produce a mixed product stream; (e) separating the mixed thermal cracking product stream to produce hydrogen, olefins and aromatics, and pyrolysis fuel oil; (f) purifying the hydrogen separated in step (e) and recycling it to step (c); (g) recovering olefins and aromatics from the split thermal cracked mixed product stream from step (e); and (h) recovering the pyrolysis fuel oil stream from the split thermal cracked mixed product stream from step (e), combining it with the asphalt bottom phase from step (b), and recovering the resulting combined stream as a fuel oil mixture; wherein step (d) of thermal cracking includes heating the hydro-processed 2,038,171st outlet stream in the convection section of the steam pyrolysis zone, separating the heated hydro-processed outlet stream into a vapor fraction and a liquid fraction using a vapor-liquid separation device based on physical and mechanical separation, passing the vapor fraction into a pyrolysis section of a steam pyrolysis zone and discharge of a liquid fraction, the discharged liquid fraction being mixed with the pyrolysis fuel oil recovered in step (h); moreover, the outlet streams of the reactor of the hydroprocessing zone are separated in a high-pressure separator to extract the gas part, which is purified and recirculated to the hydroprocessing zone as an additional source of hydrogen, and the liquid part, and said liquid part is separated from the high-pressure separator in the low-pressure separator into the gas part and a liquid portion, wherein the liquid portion from the low pressure separator is said hydroprocessing thermally cracked effluent stream, and the gas portion from the low pressure separator is combined with said mixed product stream after the steam pyrolysis zone and prior to separation in step (e); wherein said vapor-liquid separation device includes an element for pre-swirling the flow having an inlet section and a transition section, wherein the inlet section has an inlet for receiving the flowing fluid mixture and a curved circuit, a controlled cyclone section including an inlet adjacent to the element for pre-swirling the flow due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid collector / sump section through which the liquid passes; the method comprising the steps of compressing the mixed thermal cracked product stream obtained in step (d) using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to a caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and recovering olefins and aromatics in step (g) and pyrolysis fuel oils in step (h) from the residual stream of the dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; wherein step (f) includes purifying recovered hydrogen from the dehydrated compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide for recycling to the hydroprocessing zone; wherein the recovery of hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content also includes a separate methane recovery step for use as fuel for burners and / or heaters in the thermal cracking step.

The following includes definitions of various terms and phrases that may be used throughout this specification.

The terms "approximately" or "approximately" are defined as the closeness to the recited value in accordance with the understanding of specialists in the relevant field of technology. In one non-limiting embodiment, these terms are defined as being within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

The terms% (wt.),% (Vol.) Or% (mol.) Refer to the level of mass, volume or molar content of a component, respectively, calculated on the total mass, cumulative volume or cumulative number of moles of the substance that includes this component. In one non-limiting example, 10 moles of the component per 100 moles of the substance corresponds to 10% (moles) of the component.

The term essentially and its variations are defined as including ranges within 10%, within 5%, within 1%, or within 0.5%.

The terms inhibition or reduction or prevention or avoidance or any variation of these terms when used in the claims and / or in the description of the invention include any measurable reduction or complete inhibition to achieve the desired result.

The term effective in accordance with the use of this term in the description of the invention and / or in the claims denotes sufficiency to achieve the desired, expected or intended result.

The use of the singular in combination with the term containing, including, containing or having in the claims or in the description of the invention may correspond to the meaning of one, but it can also correspond to the meaning of one or more, at least one and one or more than one.

- 3 038171

Words containing (and any form of the word containing, such as contain and contain), having (and any form of the word having, such as have and has), including (and any form of the word including, such as include and include), or containing (and any forms of the word inclusive, such as accommodate and contain) are encompassing or non-limiting and do not exclude additional, unmentioned elements or process steps.

The method of the present invention may include the following, essentially consist of or consist of it: specific ingredients, components, compositions, and the like, as disclosed throughout the course of the description of the invention.

In the context of the present invention, four embodiments are now described.

Embodiment 1 is an integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products. The method includes the stages at which: (a) separating the crude oil into light components containing fractions of naphtha, kerosene and diesel fractions, and heavy components containing heavier hydrocarbon fractions containing asphaltenes; (b) charging heavy components into the solvent deasphalting zone together with an effective amount of solvent in order to obtain a stream of deasphalted and demetallized oil and the lower phase of asphalt, the solvent containing a pure liquid hydrocarbon selected from propane, butanes and pentanes, as well as mixtures thereof, at this deasphalting is carried out at a temperature equal to or less than the critical temperature of the solvent, the ratio between solvent and oil in the range from 2: 1 to 50: 1 and a pressure in the range effective to maintain the mixture of solvent and feed stream in a liquid state; (c) loading said light components, a deasphalted and demetallized oil stream and hydrogen into a hydroprocessing zone operating under conditions effective to produce a hydroprocessing effluent stream characterized by a reduced level of pollutants, increased wax content, a reduced correction factor of the U.S. Bureau of Geology and Mineralogy, and an increased density in degrees American petroleum Institute, the hydrotreating zone is operated at a temperature ranging from 300 to 450 ° C, a pressure ranging from 30 to 180 bar and LHSV of from 0.1 to 10 hours'^1; (d) thermally cracking the hydrotreated effluent stream in the presence of steam to produce a mixed product stream; (e) separating the mixed thermal cracking product stream to produce hydrogen, olefins and aromatics, and pyrolysis fuel oil; (f) purifying the hydrogen separated in step (e) and recycling it to step (c); (g) recovering olefins and aromatics from the split thermal cracked mixed product stream from step (e); and (h) recovering a pyrolysis fuel oil stream from the split thermal cracked mixed product stream from step (e), combining it with the asphalt bottom phase from step (b), and recovering the resulting combined stream as a fuel oil mixture; wherein step (d) of thermal cracking includes heating the hydroprocessing outlet stream in the convection section of the steam pyrolysis zone, separating the heated hydroprocessed outlet stream into a vapor fraction and a liquid fraction using a vapor-liquid separation device based on physical and mechanical separation, passing the vapor fraction into the pyrolysis section of the steam zone pyrolysis and tapping a liquid fraction, the tapped liquid fraction being mixed with the pyrolysis fuel oil recovered in step (h); moreover, the outlet streams of the reactor of the hydroprocessing zone are separated in a high-pressure separator to extract the gas part, which is purified and recirculated to the hydroprocessing zone as an additional source of hydrogen, and the liquid part, and the said liquid part is separated from the high-pressure separator in the low-pressure separator into the gas part and a liquid portion, wherein the liquid portion from the low pressure separator is said hydroprocessing thermally cracked effluent stream, and the gas portion from the low pressure separator is combined with said mixed product stream after the steam pyrolysis zone and prior to separation in step (e); wherein said vapor-liquid separation device includes an element for preliminary swirling of the flow, having an inlet section and a transition section, wherein the inlet section has an inlet for receiving a flowing fluid mixture and a curved circuit, a controlled cyclone section including an inlet adjacent to the element for preliminary swirling of the flow due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid collector / sump section through which the liquid passes; the method comprising the steps of compressing the mixed thermal cracked product stream obtained in step (d) using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to a caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration

- 4,038171 streams of compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and recovering olefins and aromatics in step (g) and pyrolysis fuel oils in step (h) from the residual stream of the dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; wherein step (f) includes purifying recovered hydrogen from the dehydrated compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide for recycling to the hydroprocessing zone; wherein the recovery of hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content also includes a separate methane recovery step for use as fuel for burners and / or heaters in the thermal cracking step.

Embodiment 2 is the integrated method of Embodiment 1, wherein the hydroprocessing zone comprises one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking.

Embodiment 3 is the integrated method of Embodiment 1 in which the hydroprocessing zone contains more than two catalyst beds.

Embodiment 4 is the integrated method of Embodiment 1 in which the hydroprocessing zone contains a plurality of reaction vessels, each containing one or more catalyst beds having a different function.

Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description of the invention, and examples. However, as is to be understood, the figures, detailed description of the invention, and examples, while giving indications of specific embodiments of the invention, are presented by way of illustration only and are not intended to be limiting. In addition, changes and modifications within the scope and spirit of the invention will become apparent to those skilled in the art, as contemplated by this detailed description of the invention. In additional embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment can be combined with features from any other embodiments. In additional embodiments, additional features may be added to the specific embodiments described herein.

Brief Description of Drawings

FIG. 1 is a schematic flow diagram of an embodiment of an integrated method according to the invention;

fig. 2 is a flow diagram including an integrated method and system for solvent deasphalting, hydroprocessing and steam pyrolysis, including bypass bypass for the residue;

fig. 3 is a schematic flow diagram of an embodiment of an integrated method according to the invention;

fig. 4 is a schematic flow diagram of an embodiment of an integrated method according to the invention.

Implementation of the invention

It is found by the present inventors in accordance with the present process that it is advantageous to use solvent deasphalting only for that portion of the crude oil that benefits from it. This means that the naphtha, kerosene and diesel cuts will be sent directly to a hydro-refining or steam cracker.

The present integrated method of Embodiment 1 described above preferably further comprises the step of separating the reactor effluent streams of the hydroprocessing zone in a high pressure separator to recover the gas portion that is purified and recycled to the hydroprocessing zone as an additional source of hydrogen and the liquid portion, and separating the liquid portion from a high pressure separator in a low pressure separator into a gas part and a liquid part, wherein the liquid part from the low pressure separator is a hydroprocessing effluent stream subjected to thermal cracking, and the gas part from the low pressure separator is combined with a mixed product stream after the steam pyrolysis zone and before separation at stage (d1). In accordance with one preferred embodiment of the present method, the thermal cracking step includes heating the hydrotreated effluent stream in a convection section of the steam pyrolysis zone, separating the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction, passing the vapor fraction into pi

- 5 038171 roller section of the steam pyrolysis zone and discharge of the liquid fraction. It is preferred that the discharged liquid fraction is mixed with the pyrolysis fuel oil recovered in step (g1). The separation of the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction is preferably carried out using a vapor-liquid separation device based on physical and mechanical separation. Such a vapor-liquid separation device preferably includes a pre-swirling element having an inlet portion and a transition portion, the inlet portion having an inlet for receiving the flowing fluid mixture and a curved circuit, a controllable cyclone section including an inlet adjacent to the pre-swirling element due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid header / sump section through which the liquid passes. Step (d1) of the integrated process according to the present invention preferably comprises compressing the mixed thermal cracked product stream using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and obtaining olefins and aromatics, as in step (e1), and pyrolysis fuel oils, as in step (f1), from the remainder of the stream of the dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; and step (e1) preferably comprises purifying recovered hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content for recycling to the hydroprocessing zone. One preferred embodiment of this integrated process further comprises the step of recovering hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content, which further includes separate recovery of methane for use as fuel for burners and / or heaters in the thermal step. cracking.

The invention will be described in more detail below and with reference to FIGS. 1, which is a schematic flow diagram of one embodiment of the present integrated process described herein and includes an integrated solvent deasphalting, hydroprocessing and steam pyrolysis process and system including a residue. The integrated system generally includes a feed stream separation zone, a solvent deasphalting zone, a selective catalytic hydroprocessing zone, a steam pyrolysis zone, and a product separation zone. The feed dividing zone 80 includes an inlet for receiving feed stream 1, an outlet for unloading a reject portion 83, and an outlet for unloading one or more remaining hydrocarbon portions 81, 82. The hydrocarbon portion 81 is sent to a solvent deasphalting zone. The hydrocarbon portion 82 is sent to a selective hydroprocessing zone. The cut-off boundary in the separation zone 80 can be set to be compatible with the residue oil mixture, for example at about 540 ° C. The separation zone 80 may be a one-stage separation device such as a flash separator. The cut-off boundary in the separation zone 80 can be set such that only separation into the reject portion 83 and the remaining hydrocarbon portion 81 takes place, i. E. with no remaining hydrocarbon portion 82.

Hydrocarbon fraction 82 can be mixed with an effective amount of hydrogen 2 and 15 (and a make-up hydrogen source as needed) and a DA / DMO oil stream 26 to form a combined stream 3, and mixture 3 is fed to the inlet of selective hydrotreating reaction zone 4 at temperatures ranging from 300 to 450 ° C.

In additional embodiments, the separation zone 80 can include or essentially consist of the following (i.e., when operating in the absence of a flash zone): a cyclonic phase separation device or other separation device based on physical or mechanical separation of vapors and liquids. In embodiments in which the separation zone comprises or essentially consists of the following: separation device based on physical or mechanical separation of vapors and liquids, the fraction separation boundary may be adjusted based on the vaporization temperature and fluid velocity for the material entering the device.

The solvent deasphalting zone includes a primary settling tank 19, a secondary settling tank 22, a zone 25 for the separation of deasphalted / demetallized oil (DA / DMO) and a zone 27 for separato

- 6 038171 ra. The primary settler 19 includes an inlet for receiving a combined stream 18 comprising feed stream 1 and a solvent which may be fresh solvent 16, recycle solvent 17, recycle solvent 28, or a combination of these solvent sources. The primary settler 19 also includes an outlet for the discharge of the primary phase 20 of DA / DMO oil and several pipe outlets for the discharge of the primary phase 21 of asphalt. The secondary sump 22 includes two T-distributors located at both ends for receiving the primary phase 20 of DSA / DMO oil, an outlet for discharging the secondary phase 24 of DA / DMO oil, and an outlet for discharging the secondary phase 23 of asphalt. The DA / DMO oil separation zone 25 includes an inlet for receiving a secondary phase 24 of DA / DMO oil, an outlet for discharging a solvent stream 26, and an outlet for discharging a stream 26 of solvent-free DA / DMO oil, which is used as feed stream for the selective hydroprocessing zone. The separator vessel 27 includes an inlet for receiving a primary asphalt phase 21, an outlet for discharging a solvent stream 28, and an outlet for discharging a lower asphalt phase 29 that can be mixed with pyrolysis fuel oil 71 from the product separation zone 70.

The rejected portion 83 from the feed stream separation zone and the optionally unvaporated heavy liquid fraction 38 from the vapor-liquid separation section 36 are combined with pyrolysis fuel oil 71 (for example, substances boiling at a temperature higher than the boiling point of the lowest boiling C10 compound known as stream C10 + ) from the separation zone 70, and this is taken as a mixture 72 of pyrolysis fuel oil, for example, for further processing at a third-party refinery (not shown).

The selective hydroprocessing zone includes a reactor zone 4 that includes an inlet for receiving a mixture from stream 26 of solvent-free DA / DMO oil and hydrogen 2 recirculated from the steam pyrolysis product stream and make-up hydrogen as needed (not shown). The zone 4 of the reactor also includes an outlet for discharging the hydrotreated effluent stream 5.

The reactor effluents 5 from the hydroprocessing reactor (s) are cooled in a heat exchanger (not shown) and sent to a high pressure separator 6. The separator overhead 7 is purified in an amine refinery 12 and the resulting hydrogen-rich gas stream 13 is passed to a recycle compressor 14 to be used as recycle gas 15 in the hydroprocessing reactor. The underflow stream 8 from the high pressure separator 6, which is essentially a liquid phase, is cooled and introduced into the cold low pressure separator 9, in which it is separated into a gas stream and a liquid stream 10. Gases from the cold low pressure separator include hydrogen , H ₂ S, NH ₃ and any light hydrocarbons such as C1-C4 hydrocarbons. Typically, these gases are sent for further processing such as flare gas processing or fuel gas processing. In accordance with certain embodiments herein, hydrogen is recovered by combining gas stream 11, which includes hydrogen, H ₂ , NH _3, and any light hydrocarbons such as C1-C4 hydrocarbons, with steam cracker products 44. Liquid stream 10 is used as feed stream for steam pyrolysis zone 30.

The steam pyrolysis zone 30 generally includes a convection section 32 and a pyrolysis section 34 which can operate based on the operations of a steam pyrolysis unit known in the art, i. E. loading the thermal cracking feed stream into the convection section in the presence of steam. In addition, in certain optional embodiments, as described herein (as indicated by dashed lines in FIG. 1), a vapor-liquid separation section 36 is included between sections 32 and 34. The vapor-liquid separation section 36, through which the heated steam cracking feed stream from the convection section 32 is passed, may be a separation device based on physical or mechanical separation of vapors and liquids.

The quenching zone 40 includes an inlet in fluid communication with the outlet of the steam pyrolysis zone 30, an inlet for supplying a quenching solution 42, an outlet for discharging a quenched mixed product stream 44, and an outlet for discharging a quenching solution 46.

In general, the intermediate quenched blended product stream 44 is separated in a compression and fractionation section. Such a compression and fractionation section is well known in the art.

In one embodiment, mixed product stream 44 is converted to intermediate product stream 65 and hydrogen 62, which is purified in the present process and used as recycle hydrogen stream 2 in hydroprocessing reaction zone 4. The intermediate product stream 65, which may further contain hydrogen, is generally fractionated into end products and residue in a separation zone 70, which may include, for example, one or more separation units as is known to those skilled in the art.

In general, product separation zone 70 includes an inlet in fluid communication with product stream 65 and a plurality of product outlets 73-78, including a methane discharge outlet 78, which may optionally be combined with stream 63, outlet 77 for unloading

- 7 038171 ethylene, outlet 76 for propylene offloading, outlet 75 for unloading butadiene, outlet 74 for unloading mixed butylenes and outlet 73 for unloading pyrolysis gasoline. In addition, a pyrolysis fuel oil 71 discharge is provided. Optionally, one or both of the lower asphalt phase 29 from the separator vessel 27 and the rejected portion 38 from the vapor-liquid separation section 36 are combined with the pyrolysis fuel oil 71, and the mixed stream may be selected as a mixture of 72 pyrolysis fuel oil, for example a mixture of low-sulfur fuel oil for further processing at a third-party refinery. As noted, although six product outlets have been demonstrated, fewer or more may be provided depending on, for example, the layout of the separation plants used and the outlet and distribution requirements.

In one preferred embodiment of the method using the arrangement shown in FIG. 1, a solvent from one or more sources 16, 17 and 28 is mixed with the crude oil of the feedstock 1. After that, the resulting mixture 18 is transferred to the primary settler 19. As a result of mixing and settling in the primary settler 19, two phases are formed: the primary phase 20 DA / DMA oils and asphalt primary phase 21. The temperature of the primary settler 19 is low enough to recover all DA / DMO oil from the feed. For example, for a system using n-butane, a suitable temperature range is about 60 to 150 ° C, and a suitable pressure range is such that the pressure is greater than the vapor pressure of n-butane at operating temperature, for example from about 15 to 25 bar, to keep the solvent in the liquid phase. In a system using n-pentane, a suitable temperature range is from about 60 ° C to about 180 ° C, and again a suitable pressure range is such that the pressure is greater than the vapor pressure of n-pentane at operating temperature , for example from about 10 to 25 bar, to keep the solvent in the liquid phase. The temperature in the second clarifier is usually higher than the temperature in the first clarifier.

The primary phase 20 of DA / DMO oil, containing a significant proportion of solvent and DA / DMO oil together with a minor amount of asphalt, is discharged through an outlet located at the top of the primary settler 19 and header pipes (not shown). The primary asphalt phase 21, which contains 40-50% (v / v) solvent, is discharged through several pipe outlets located at the bottom of the primary clarifier 19. The primary phase 20 of DA / DMO oil enters two T-distributors at both ends of the secondary clarifier. 22, which serves as the final extraction stage. A secondary asphalt phase 23 containing a small amount of solvent and DA / DMO oil is discharged from the secondary clarifier 22 and recycled back to the primary clarifier 19 to recover the DA / DMO oil. A secondary DA / DMO oil phase 24 is obtained and passed to a DA / DMO oil separation zone 25 to provide a solvent stream 17 and a solvent free DA / DMO oil stream 26. More than 90 wt% of the solvent charged to the settling tanks enters the DA / DMO oil separation zone 25, which is sized to quickly and efficiently separate the solvent and DA / DMO oil by flash. The primary asphalt phase 21 is transported to a separator vessel 27 to separate the solvent stream 28 and the lower asphalt phase 29 by flashing. Solvent streams 17 and 28 can be used as solvent for the primary settler 19, thus minimizing the need for fresh solvent 16.

Solvents used in the solvent deasphalting zone include pure liquid hydrocarbons such as propane, butanes, and pentanes, and mixtures thereof. The choice of solvents depends on the deasphalted oil (DAO) requirements and the quality and quantity of the end products. Operating conditions for the solvent deasphalting zone include a temperature equal to or less than the critical temperature of the solvent; the ratio between solvent and oil in the range from 2: 1 to 50: 1; and a pressure in a range effective to maintain the solvent / feed mixture in the settling tanks in a liquid state.

Stream 26 of the substantially solvent free DA / DMO oil is optionally steam stripped (not shown) to remove any remaining solvent and mixed with an effective amount of hydrogen and stream 15 (and make-up hydrogen source as needed) to form a combined stream. 3. The mixture 3 is charged to the reaction zone 4 of the hydroprocessing at a temperature in the range from 300 to 450 ° C. In certain embodiments, the hydroprocessing reaction zone 4 includes one or more installation steps as described in United States Patent Publication No. 2011/0083996 and in PCT Patent Application Publications No. WO 2010/009077, WO 2010/009082, WO 2010/009089 and WO 2009/073436. For example, a hydroprocessing zone may include one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking functions. In additional embodiments, the hydroprocessing reaction zone 4 includes more than two catalyst beds. V

8,038,171 additional embodiments, the hydroprocessing reaction zone 4 includes a plurality of reaction vessels, each comprising one or more catalyst beds, for example having a different function.

Hydroprocessing zone 4 operates at parameters effective for hydrodemetallization, hydrodearomatization, hydrodenitrogenation, hydrodesulfurization and / or hydrocracking of the crude oil of the feedstock. In certain embodiments, the hydroprocessing is carried out using the following conditions: operating temperature ranging from 300 to 450 ° C; operating pressure in the range from 30 to 180 bar and hourly space velocity of the liquid in the range from 0.1 to 10 h- ¹ . As it should be noted, the use of crude oil as feedstock in the hydroprocessing zone demonstrates advantages, for example, in comparison with the operation of the same hydroprocessing unit used for the atmospheric residue. For example, with a start-up or operating temperature of the plant in the range of 370 to 375 ° C, the deactivation rate is approximately 1 ° C / month. In contrast, if it was necessary to process the residue, the decontamination rate would be close to a value in the range of about 3 to 4 ° C / month. When treating the atmospheric residue, a pressure of about 200 bar is generally used, while the present process, in which crude oil is treated, can be operated at a pressure of as little as 100 bar. In addition, in order to achieve the high level of saturation required to increase the hydrogen level in the feed stream, the process can operate at high throughput compared to that of the atmospheric residue. The LHSV can be as much as 0.5, while the atmospheric residue is typically 0.25. An unexpected discovery is that in the processing of crude oil, the rate of decontamination moves in the opposite direction compared to what is usually observed. Decontamination at low productivity (0.25 h ^-1 ) is 4.2 ° C / month, and decontamination at higher productivity (0.5 h ^-1 ) is 2.0 ° C / month. The opposite is true for every feed stream considered in the industry. This can be attributed to the catalyst washout effect.

The reactor effluents 5 from the hydroprocessing zone 4 are cooled in a heat exchanger (not shown) and sent to separators, which may include a cold or hot high pressure separator 6. The separator overhead 7 is purified in an amine refinery 12 and the resulting hydrogen-rich gas stream 13 is passed to a recycle compressor 14 to be used as a recycle gas 15 in the hydroprocessing reaction zone 4. The separator bottom 8 from the high pressure separator 6, which is substantially in the liquid phase, is cooled and then introduced into the cold low pressure separator 9. The remaining gases in stream 11, including hydrogen, H ₂ S, NH _3, and any light hydrocarbons that may include C1-C4 hydrocarbons, can typically be purged from a cold low pressure separator and sent for further processing such as flare gas processing or fuel gas processing. In certain embodiments of the present process, hydrogen is recovered by combining stream 11 (as indicated by dashed lines) with the cracked gas stream 44 from the steam cracker product. The bottom product 10 from the low pressure separator 9 is optionally sent to a steam pyrolysis zone 30.

Hydrotreated effluent stream 10 is characterized by reduced levels of contaminants (ie, metals, sulfur and nitrogen), increased paraffin content, reduced PCGB, and increased API gravity.

The hydrotreated effluent stream 10 is passed to a convection section 32 and an effective amount of steam is introduced, for example through a steam inlet (not shown). In the convection section 32, the mixture is heated to a predetermined temperature, for example using one or more waste heat streams or other suitable heating arrangement. The heated mixture from the pyrolysis feed and steam is passed to the pyrolysis section 34 to obtain a mixed product stream 39. In certain embodiments, the heated mixture from section 32 is passed through a vapor-liquid separation section 36 in which portion 38 is discarded as a low-sulfur fuel oil component suitable for use when mixed with pyrolysis fuel oil 71.

The steam pyrolysis zone 30 operates at parameters effective to crack the hydrotreated effluent stream 10 into desired products including ethylene, propylene, butadiene, mixed butenes, and pyrolysis gasoline. In certain embodiments, steam cracking is carried out using the following conditions: a temperature in the range of 400 to 900 ° C in the convection section and in the pyrolysis section; the ratio between water vapor and hydrocarbon in the convection section is in the range from 0.3: 1 to 2: 1; and the residence time in the pyrolysis section is in the range from 0.05 to 2 s.

A mixed product stream 39 is passed to an inlet of a quench zone 40 using a quench solution 42 (e.g., water and / or pyrolysis fuel oil) introduced through a separate inlet to provide a quenched mixed product stream 44 having a reduced

- 9 038171 a temperature of, for example, about 300 ° C, and the spent quench solution 46 is sent for recirculation and / or blown out.

The cracking unit gas mixture effluent stream 39 is typically a mixture of hydrogen, methane, hydrocarbons, carbon dioxide and hydrogen sulfide. After cooling with water and / or quenching in oil, the mixture 44 is subjected to compression and separation. In one non-limiting example, stream 44 is compressed in a multistage compressor, which typically includes 4-6 stages, wherein said multistage compressor may include a compressor zone 51 to produce a compressed gas mixture 52. The compressed gas mixture 52 may be treated in a caustic treatment unit 53 to obtaining a gas mixture 54, depleted in hydrogen sulfide and carbon dioxide. The gas mixture 54 can be further compressed in the zone 55 of the compressor. The resulting cracked gas 56 can be cryogenically treated in dehydration unit 57 and can be further dried using molecular sieves.

The cold cracked gas stream 58 from unit 57 may be passed to a methane stripper 59 from which an overhead stream 60 containing hydrogen and methane is obtained from the cracked gas stream. Thereafter, the underflow stream 65 from the desoldering column 59 is sent for further processing in the product separation zone 70, which includes fractionation columns, including an ethanolic, desiccant, and butane-stripper. Process configurations may also be used including a different sequence of a desoldering column, an ethanizing column, a desoldering column, and a butane desoldering column.

In accordance with the methods described herein with reference to FIG. 1, after separation from methane in a desoldering column 59 and hydrogen recovery in unit 61, hydrogen 62 is obtained having a purity typically in the range of 80-95% (v / v). Recovery processes in unit 61 include cryogenic recovery (eg, at a temperature of approximately -157 ° C). Thereafter, hydrogen stream 62 is passed to a hydrogen purification unit 64, such as a pressure swing adsorption (PSA) unit to produce a 99.9% + purity hydrogen stream 2, or a membrane separation unit to produce a hydrogen stream 2 of 99.9% + purity. , amounting to approximately 95%. Thereafter, purified hydrogen stream 2 is recycled back to serve as the major portion of the required hydrogen for the hydroprocessing zone. In addition, the minority can be used for hydrogenation reactions of acetylene, methylacetylene and propadienes (not shown). In addition, in accordance with the methods herein, the methane stream 63 may optionally be recycled to a steam cracker for use as a fuel for burners and / or heaters.

The underflow stream 65 from de-methanizer 59 is transported to the inlet of product separation zone 70 for separation into methane, ethylene, propylene, butadiene, mixed butylenes and pyrolysis gasoline, respectively, via outlets 78, 77, 76, 75, 74, and 73. Pyrolysis gasoline generally comprises C5-C9 hydrocarbons, and benzene, toluene and xylenes can be separated from this cut. Optionally, one or both of the lower asphalt phase 29 and the non-vaporized heavy liquid fraction 38 from the vapor-liquid separation section 36 are combined with the pyrolysis fuel oil 71 (e.g., substances boiling at a temperature greater than the boiling point of the lowest boiling C10 compound known under the designation stream C10 +) from the separation zone 70 and the mixed stream is taken as a mixture 72 of pyrolysis fuel oil, for example, for further processing at a third-party refinery (not shown). In certain embodiments, the bottom asphalt phase 29 may be sent to an asphalt stripper (not shown) where any remaining solvent is stripped, for example by steam.

Another embodiment of the invention is shown with reference to Embodiment 9 described above and with reference to FIG. 2. In the process of the present invention, the first solvent deasphalting zone makes it possible to remove certain asphaltenes, metals and carbonaceous residues from heavy components while obtaining a relatively high yield of the first deasphalted and demetallized oil, but at the expense of a certain level of contamination. The subsequently produced hydrotreated effluent is then processed in a second solvent deasphalting zone to remove remaining asphaltenes, metals and carbonaceous residues so that they are not thermally cracked. In one embodiment, the solvent used in the first solvent deasphalting zone is different from the solvent used in the second solvent deasphalting zone. Preferably, the solvent used in the first solvent deasphalting zone is pentane and the solvent used in the second solvent deasphalting zone is propane or butane. In accordance with this preferred embodiment, the integrated method further comprises the steps of separating the stream of the second deasphalted and demetallized oil in a separation zone to recover a vapor portion that is sent to the steam pyrolysis zone and a liquid portion, the liquid portion being discharged and mixed with the pyrolysis fuel oil from the product separation zone in accordance with the representation in step (f1). The thermal cracking step in accordance with the foregoing discussion of the invention preferably includes heating the hydrotreated effluent in the convection section of the steam pyrolysis zone, separating the heated hydrotreated effluent into a vapor fraction and a liquid fraction, passing the vapor fraction to the pyrolysis section of the steam pyrolysis zone, and discharging the liquid fraction. It is preferred that the discharged liquid fraction is mixed with the pyrolysis fuel oil recovered in step (g1). In addition, it is also preferred that the separation of the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction be carried out using a vapor-liquid separation apparatus based on physical and mechanical separation. In addition, it is also preferred that the first solvent deasphalting zone and the second solvent deasphalting zone are combined in one single solvent deasphalting unit. The vapor-liquid separation device preferably includes an element for pre-swirling the flow, having an inlet section and a transition section, wherein the inlet section has an inlet for receiving a flowing fluid mixture and a curved circuit, a controllable cyclone section including an inlet adjacent to the element for preliminary swirling of the flow due to convergence a curved contour and a cyclone section, a riser section at the upper end of the cyclone element through which the vapors pass; and a liquid header / sump section through which the liquid passes. Step (d1) in the integrated process preferably comprises compressing the mixed thermal cracked product stream using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and obtaining olefins and aromatics, as in step (e), and pyrolysis fuel oil, as in step (f), from the remainder of the stream of dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; and step (e) includes purifying recovered hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content for recycling to the hydroprocessing zone.

This integrated process is preferably carried out when the recovery of hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content further comprises separate recovery of methane for use as fuel for burners and / or heaters in the thermal cracking step. FIG. 2 shows a flow diagram of one embodiment of the invention including an integrated solvent deasphalting, hydrotreating and steam pyrolysis process and system including bypass for the residue. The integrated system generally includes a feed stream separation zone, a solvent deasphalting zone, a selective catalytic hydroprocessing zone, a steam pyrolysis zone, and a product separation zone. The feed split zone 180 includes an inlet for receiving feed stream 101, an outlet for discharging a reject portion 183, and an outlet for unloading one or more remaining hydrocarbon portions 181, 182. The hydrocarbon portion 181 is sent to a solvent deasphalting zone. The hydrocarbon portion 182 is sent to a selective hydroprocessing zone. The cut-off in separation zone 180 180 can be set to be compatible with the residue fuel oil mixture, for example, at about 540 ° C. The separation zone 180 may be a one-stage separation device such as a flash separator. The cut-off boundary in the separation zone 180 may be set such that only separation into the reject portion 183 and the remaining hydrocarbon portion 81 takes place, i. E. in the absence of a remaining hydrocarbon portion 182.

Hydrocarbon cut 182 can be mixed with effective amounts of hydrogen 102 and 115 (and make-up hydrogen source as needed) and solvent-free DA / DMO oil stream 126 to form combined stream 103, and mixture 103 is fed to the inlet of selective hydroprocessing reaction zone 104. at temperatures ranging from 300 to 450 ° C.

In additional embodiments, the separation zone 180 may include or essentially consist of the following (i.e., when operating in the absence of a flash zone): a cyclonic phase separation device or other separation device based on physical or mechanical separation of vapors and liquids. In embodiments in which the zone

- 11 038171 separation includes the following or essentially consists of it: separation device based on physical or mechanical separation of vapors and liquids, the separation boundary of the fraction can be corrected based on the evaporation temperature and fluid velocity for the substance entering the device.

The rejected portion 183 from the feed separation zone and optionally unvaporized heavy liquid fraction 138 from the vapor-liquid separation section 136 are combined with pyrolysis fuel oil 171 (e.g., substances boiling above the boiling point of the lowest boiling C10 compound known as C10 + stream) from the separation zone 170 and this is taken as a pyrolysis fuel oil mixture 172, for example, for further processing at a third party refinery (not shown).

The selective hydroprocessing zone includes a reactor zone 104 including an inlet for receiving a combined stream 103 comprising feed stream 182 and stream 126 and hydrogen 102 recirculated from the steam pyrolysis product stream and make-up hydrogen as needed (not shown). The reactor zone 104 also includes an outlet for discharging the hydrotreated effluent stream 105.

Reactor effluents 105 from the hydroprocessing reactor (s) are cooled in a heat exchanger (not shown) and sent to a high pressure separator 106. The separator overhead 107 is purified in an amine refinery 112 and the resulting hydrogen-rich gas stream 113 is passed to a recycle compressor 114 to be used as recycle gas 115 in the hydroprocessing reactor. The underflow stream 108 from the high pressure separator 106, which is essentially a liquid phase, is cooled and introduced into the cold low pressure separator 109, in which it is separated into a gas stream 111 and a liquid stream 110. Gases from the cold low pressure separator include hydrogen, H ₂ S, NH ₃ and any light hydrocarbons such as C1-C4 hydrocarbons. Typically, these gases are sent for further processing such as flare gas processing or fuel gas processing. In accordance with certain embodiments herein, hydrogen is recovered by combining gas stream 111, which includes hydrogen, H ₂ S, NH _3, and any light hydrocarbons such as C1-C4 hydrocarbons, with steam cracker products 144. All or part of the liquid stream 110 is used as the feed stream for the solvent deasphalting zone.

The solvent deasphalting zone includes a primary clarifier 119, a secondary clarifier 122, a deasphalted / demetallized oil (DA / DMO) separation zone 125, and a separator zone 127. The primary settler 119 includes an inlet for receiving a hydrotreated effluent stream 110 and a solvent, which may be fresh solvent 116, recycle solvent 117, recycle solvent 128, or a combination of these solvent sources. The primary settler 119 also includes an outlet for the primary phase discharge 120 of DA / DMO oil and several pipe outlets for the primary phase discharge 121 of asphalt. The secondary sump 122 includes two T-distributors located at both ends for receiving primary phase 120 of DSA / DMO oil, an outlet for discharging secondary phase 124 of DA / DMO oil, and an outlet for discharging secondary phase 123 of asphalt. The DA / DMO oil separation zone 125 includes an inlet for receiving secondary phase 24 of DA / DMO oil, an outlet for discharging solvent stream 117, and an outlet for discharging stream 126 of solvent-free DA / DMO oil used as feed stream for steam pyrolysis zone 130 ... The separator vessel 127 includes an inlet for receiving primary asphalt phase 121, an outlet for discharging a solvent stream 28, and an outlet for discharging a lower asphalt phase 129 that may be mixed with pyrolysis fuel oil 171 from product separation zone 170.

The steam pyrolysis zone 130 generally includes a convection section 132 and a pyrolysis section 134, which may operate based on the operations of a steam pyrolysis unit known in the art, i. E. loading the thermal cracking feed stream into the convection section in the presence of steam. In addition, in certain embodiments, in accordance with the description of the invention herein (as indicated by dashed lines in the single figure), a vapor-liquid separation section 136 is included between sections 132 and 134. The vapor-liquid separation section 136, through which the heated steam cracking feed stream from the convection section 132 is passed and fractionated, may be a flash separation device, a separation device based on physical or mechanical separation of vapors and liquids, or a combination of at least one from these device types. In additional optional embodiments, a vapor-liquid separation zone 147 is included upstream of section 132, either in combination with a vapor-liquid separation zone 136, or in the absence of a vapor-liquid separation zone 136. Stream 126 is fractionated in separation zone 147, which may be a flash separation device, separation device

- 12 038171 based on physical or mechanical separation of vapors and liquids, or a combination including at least one of these types of devices.

In additional optional embodiments, stream 126 is recycled back to the inlet of the hydroprocessing zone 104.

The quenching zone 140 includes an inlet in fluid communication with the outlet of the steam pyrolysis zone 130 for receiving a mixed product stream 139, an inlet for supplying a quenching solution 142, an outlet for discharging an intermediate quenched mixed product stream 144, and an outlet for discharging a quenching solution 146.

In general, the intermediate hardened blended product stream 144 is subjected to separation in a compression and fractionation section. Such a compression and fractionation section is well known in the art.

In one preferred embodiment, mixed product stream 144 is converted to intermediate product stream 165 and hydrogen 162, which is purified in the present process and used as hydrogen recycle stream 102 in hydrotreating reaction zone 104. The intermediate product stream 165, which may further contain hydrogen, is generally fractionated into end products and residue in a separation zone 170, which may be, for example, one or more separation units, such as a plurality of fractionation columns including a de-ethanizer, a desoldering and butaning columns, as is known to those skilled in the art.

In general, product separation zone 170 includes an inlet in fluid communication with product stream 165 and a plurality of product outlets 173-178, including a methane discharge outlet 178, which may optionally be combined with stream 163, outlet 177 for ethylene unloading, outlet 176 for unloading propylene, outlet 175 for unloading butadiene, outlet 174 for unloading mixed butylenes, and outlet 173 for unloading pyrolysis gasoline. In addition, a pyrolysis fuel oil 171. Optionally, one or both of the lower asphalt phase 129 from the solvent deasphalting zone separator tank 127 and the fuel oil portion 138 from the vapor-liquid separation section 136 are optionally combined with the pyrolysis fuel oil 171. and the blended stream may be sampled as a pyrolysis fuel oil mixture 172, such as a low-sulfur fuel oil mixture, for further processing at a third-party refinery. As it should be noted, despite the demonstration of six releases, fewer or more of them may be provided for products depending, for example, on the layout of the separation plants used and the requirements for output and distribution.

In one embodiment of the process using the arrangement shown in the single figure, DA / DMO solvent free oil stream 126 and optionally stream 182 are mixed with effective amounts of hydrogen 2 and 15 (and make-up hydrogen source as needed) to produce a combined stream 103. The mixture 103 is charged to the reaction zone 104 of the hydroprocessing at a temperature in the range from 300 to 450 ° C. In certain embodiments, the hydroprocessing reaction zone 104 includes one or more installation steps as described in United States Patent Publication No. 2011/0083996 and in PCT Patent Application Publications No. WO 2010/009077, WO 2010/009082, WO 2010/009089 and WO 2009/073436. For example, a hydroprocessing zone may include one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking functions. In additional embodiments, the hydroprocessing zone 104 includes more than two catalyst beds. In additional embodiments, the hydroprocessing reaction zone 104 includes a plurality of reaction vessels, each including one or more catalyst beds, for example, having a different function.

The hydroprocessing zone 104 operates at parameters effective for hydrodemetallization, hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking of the crude oil of the feedstock. In certain embodiments, the hydroprocessing is carried out using the following conditions: operating temperature ranging from 300 to 450 ° C; operating pressure in the range from 30 to 180 bar and hourly space velocity of the liquid in the range from 0.1 to 10 h ^-1 . As it should be noted, the use of crude oil as feedstock in the hydroprocessing zone 104 demonstrates advantages, for example, in comparison with the operation of the same hydroprocessing unit used for the atmospheric residue. For example, with a start-up or operating temperature between 370 and 375 ° C, the deactivation rate is approximately 1 ° C / month. In contrast, if it was necessary to process the residue, the decontamination rate would be close to a value in the range of about 3 to 4 ° C / month. When treating the atmospheric residue, a pressure of about 200 bar is usually used, while the present method, which treats crude oil, can

- 13 038171 operate at a pressure of only 100 bar. In addition, in order to achieve the high level of saturation required to increase the hydrogen level in the feed stream, the process can operate at high throughput compared to that of the atmospheric residue. The LHSV can be ^{as much as 0.5 h -1} , while the atmospheric residue typically has a value of 0.25 h ^-1 . An unexpected discovery is that in the processing of crude oil, the rate of decontamination moves in the opposite direction compared to what is usually observed. Decontamination at low capacity (0.25 h ^-1 ) is 4.2 ° C / month and decontamination at higher capacity (0.5 h ^-1 ) is 2.0 ° C / month. The opposite is true for every feed stream considered in the industry. This can be attributed to the catalyst washout effect.

Reactor effluents 105 from hydroprocessing zone 104 are cooled in a heat exchanger (not shown) and sent to separators, which may include a cold or hot high pressure separator 106. The separator overhead 107 is purified in an amine refinery 112 and the resulting hydrogen-rich gas stream 113 is passed to a recycle compressor 114 to be used as recycle gas 115 in the hydroprocessing reaction zone 104. The separator bottom 108 from the high pressure separator 106, which is substantially in the liquid phase, is cooled and then introduced into the cold low pressure separator 109. The remaining gases in stream 111, including hydrogen, H ₂ S, NH _3, and any light hydrocarbons that may include C1-C4 hydrocarbons, can typically be purged from a cold low pressure separator and sent for further processing such as flare gas processing or fuel gas processing. In certain embodiments of the process, hydrogen and optionally also C1-C4 compounds are recovered by combining stream 111 (as indicated by dashed lines) with the cracking gas stream 144 from the steam cracker product.

Hydrotreated effluent stream 110 has reduced levels of contaminants (ie, metals, sulfur, and nitrogen), increased paraffin content, reduced PCGB, and increased API gravity.

Solvent from one or more sources 116, 117 and 128 is admixed to the hydrotreated effluent stream 110. The resulting mixture 118 is then transferred to a primary settler 119. Mixing and settling in the primary settler 119 results in two phases: primary phase 120 of DA oil / DMA and primary phase 121 asphalt. The temperature of the primary settler 119 is low enough to recover all DA / DMO oil from the feed. For example, for a system using n-butane, a suitable temperature range is about 60 to 150 ° C, and a suitable pressure range is such that the pressure is greater than the vapor pressure of n-butane at operating temperature, for example from about 15 to 25 bar, to keep the solvent in the liquid phase. In a system using n-pentane, a suitable temperature range is from about 60 ° C to about 180 ° C, and again a suitable pressure range is such that the pressure is greater than the vapor pressure of n-pentane at operating temperature , for example from about 10 to 25 bar, to keep the solvent in the liquid phase. The temperature in the second clarifier is usually higher than the temperature in the first clarifier.

The primary phase 120 of DA / DMO oil, containing a significant proportion of solvent and DA / DMO oil together with a minor amount of asphalt, is discharged through an outlet located at the top of the primary settler 119 and header pipes (not shown). The primary asphalt phase 121, which contains 20-50% (v / v) solvent, is discharged through several pipe outlets located at the bottom of the primary settler 119.

The primary phase 120 of DA / DMO oil enters two T-shaped distributors at both ends of the secondary settler 122, which serves as the final extraction stage. A secondary asphalt phase 123 containing a small amount of solvent and DA / DMO oil is discharged from the secondary clarifier 122 and recycled back to the primary clarifier 119 to recover the DA / DMO oil. A secondary DA / DMO oil phase 124 is obtained and passed to a DA / DMO oil separation zone 125 to produce a solvent stream 117 and a solvent free DA / DMO oil stream 126. More than 90 wt% of the solvent charged to the settling tanks enters the DA / DMO oil separation zone 125, which is sized to quickly and efficiently separate the solvent and DA / DMO oil by flashing. The primary asphalt phase 121 is transported to a separator vessel 127 to separate the solvent stream 128 and the bottom asphalt phase 129 by flashing. Solvent streams 117 and 128 can be used as solvent for the primary settler 119, thereby minimizing the need for fresh solvent 116.

Solvents used in the solvent deasphalting zone include pure liquid hydrocarbons such as propane, butanes, and pentanes, and mixtures thereof. The choice of solvents depends on the requirements for the DAO oil and the quality and quantity of the end products. Working conditions for the zone

- 14,038171 solvent deasphalting include a temperature equal to or less than the critical temperature of the solvent; the ratio between solvent and oil in the range from 2: 1 to 50: 1 (v: v); and a pressure in a range effective to maintain the solvent / feed mixture in the settling tanks in a liquid state.

The substantially solvent free DA / DMO oil stream 126 is optionally steam stripped (not shown) to remove the solvent. In certain embodiments, deasphalted and demetallized oil stream 126 is feed stream 148 for steam pyrolysis zone 130. In additional embodiments, deasphalted and demetallized oil stream 126 is sent to separation zone 147, where the vapor discharged portion is feed stream 148 to steam pyrolysis zone 130. The vapor portion may have, for example, an initial boiling point corresponding to that of deasphalted and demetallized oil stream 126 and a final boiling point in the range of about 370 ° C to about 600 ° C. Separation zone 147 may include the operation of a suitable vapor-liquid separation unit such as a flash tank, a physical or mechanical vapor-liquid separation device, or a combination of at least one of these types of devices.

The feed stream 148 is transported to the convection section 132 in the presence of a predetermined amount of water vapor, which, for example, is introduced through a water vapor inlet (not shown). In the convection section 132, the mixture is heated to a predetermined temperature, for example using one or more waste heat streams or other suitable heating arrangement. The heated mixture from the pyrolysis feed and additional steam is passed to the pyrolysis section 134 to produce a mixed product stream 139. In certain embodiments, the heated mixture from section 132 is passed through a vapor-liquid separation section 136 in which portion 138 is discarded as a low sulfur fuel oil component suitable for use when mixed with pyrolysis fuel oil 171.

The steam pyrolysis zone 130 operates at parameters effective to crack the DA / DMO oil stream to produce the desired products including ethylene, propylene, butadiene, blended butenes and pyrolysis gasoline. In certain embodiments, steam cracking is carried out using the following conditions: a temperature in the range of 400 to 900 ° C in the convection section and in the pyrolysis section; the ratio between water vapor and hydrocarbon in the convection section is in the range from 0.3: 1 to 2: 1 (wt.: wt.) and the residence time in the pyrolysis section is in the range from 0.05 to 2 s.

Mixed product stream 139 is passed to an inlet of a quench zone 140 using a quench solution 142 (e.g., water and / or pyrolysis fuel oil) introduced through a separate inlet to provide a quenched mixed product stream 144 having a reduced temperature of, for example, approximately 300 ° C, and the spent quenching solution 146 is sent for recirculation and / or blown out.

The cracker gas mixture effluent 139 is typically a mixture of hydrogen, methane, hydrocarbons, carbon dioxide and hydrogen sulfide. After cooling with water and / or quenching in oil, the mixture 144 is subjected to compression and separation. In one non-limiting example, stream 144 is compressed in a multistage compressor, which typically includes 4-6 stages, wherein said multistage compressor may include a compressor zone 151 to produce a compressed gas mixture 152. The compressed gas mixture 152 may be treated in a caustic treatment unit 153 to obtaining a gas mixture 154, depleted in hydrogen sulfide and carbon dioxide. The gas mixture 154 can be further compressed in the zone 155 of the compressor. The resulting cracked gas 156 can be cryogenically treated in dehydration unit 157 and can be further dried using molecular sieves.

Cold cracked gas stream 158 from unit 157 may be passed to a desoldering column 159 from which an overhead stream 160 containing hydrogen and methane is obtained from the cracked gas stream. Thereafter, the underflow stream 165 from the desoldering column 159 is sent for further processing in the product separation zone 170, which includes fractionation columns, including an ethanolic, desiccant, and butane-stripper. Process configurations may also be used including a different sequence of a desoldering column, an ethanizing column, a desoldering column, and a butane desoldering column.

In accordance with the methods herein, after separation from methane in a desoldering column 159 and hydrogen recovery in a unit 161, hydrogen 162 is produced having a purity typically in the range of 80-95% (v / v). Recovery processes in unit 161 include cryogenic recovery (eg, at a temperature of approximately -157 ° C).

- 15 038171

The hydrogen stream 162 is then passed to a hydrogen purification unit 164, such as a pressure swing adsorption (PSA) unit to produce a 99.9% + purity hydrogen stream 102, or a membrane separation unit to produce a hydrogen stream 102 at a purity , amounting to approximately 95%. Thereafter, the purified hydrogen stream 102 is recycled back to serve as the major portion of the required hydrogen for the hydroprocessing zone. In addition, a minority fraction can be used for hydrogenation reactions of acetylene, methylacetylene and propadienes (not shown). In addition, in accordance with the methods herein, the methane stream 163 may optionally be recycled to a steam cracker for use as a fuel for burners and / or heaters.

A bottoms stream 165 from de-methanizer 159 is conveyed to an inlet for product separation zone 170 for separation into methane, ethylene, propylene, butadiene, mixed butylenes and pyrolysis gasoline, respectively, via outlets 178, 177, 176, 175, 174 and 173. Pyrolysis gasoline generally includes C5-C9 hydrocarbons, and benzene, toluene and xylenes can be separated from this cut. Optionally, one or both of the lower asphalt phase 129 and non-vaporized heavy liquid fraction 138 from vapor-liquid separation section 136 are combined with pyrolysis fuel oil 171 (e.g., substances boiling at a temperature higher than the boiling point of the lowest boiling C10 compound known as the name of the stream C10 +) from the separation zone 170 and the mixed stream is taken as a mixture 172 of pyrolysis fuel oil, for example, for further processing at a third-party refinery (not shown). In certain embodiments, the bottom asphalt phase 129 may be sent to an asphalt stripper (not shown) where any remaining solvent is stripped, for example by steam.

In the method of the present invention as described in Embodiment 17 and shown in FIG. 3, the first solvent deasphalting zone makes it possible to remove certain asphaltenes, metals and carbonaceous residues from heavy components while obtaining a relatively high yield of the first deasphalted and demetallized oil, but at the expense of a certain level of contamination. The subsequently produced hydrotreated effluent is then processed in a second solvent deasphalting zone to remove remaining asphaltenes, metals and carbonaceous residues so that they are not thermally cracked. In one embodiment, the solvent used in the first solvent deasphalting zone is different from the solvent used in the second solvent deasphalting zone. Preferably, the solvent used in the first solvent deasphalting zone is pentane and the solvent used in the second solvent deasphalting zone is propane or butane. This integrated method further includes separating the stream of the second deasphalted and demetallized oil in a separation zone to recover a vapor portion that is sent to a steam pyrolysis zone and a liquid portion, wherein the liquid portion is discharged and mixed with pyrolysis fuel oil from the product separation zone in accordance with the representation on stage (e3). In accordance with one preferred embodiment of this method, the thermal cracking step includes heating the hydrotreated effluent stream in a convection section of the steam pyrolysis zone, separating the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction, passing the vapor fraction into the pyrolysis section of the steam pyrolysis zone, and discharging the liquid fraction. In addition, it is also preferred that the first solvent deasphalting zone and the second solvent deasphalting zone are combined in one single solvent deasphalting unit. It is preferred that the discharged liquid fraction is mixed with the pyrolysis fuel oil recovered in step (g3). The separation of the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction is preferably carried out using a vapor-liquid separation device based on physical and mechanical separation. Such a vapor-liquid separation device preferably includes a pre-swirling element having an inlet portion and a transition portion, the inlet portion having an inlet for receiving the flowing fluid mixture and a curved circuit, a controllable cyclone section including an inlet adjacent to the pre-swirling element due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid header / sump section through which the liquid passes. Step (d3) of the integrated process according to the process preferably further comprises compressing the mixed thermal cracked product stream using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; Compression of a mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide

- 16 038171 yes; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and obtaining olefins and aromatics, as in step (e3), and pyrolysis fuel oils, as in step (B), from the residual stream of the dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; and step (e3) preferably comprises purifying recovered hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content for recycling to the hydroprocessing zone. One preferred embodiment of this integrated process includes the step of recovering hydrogen from the dehydrated compressed blended thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content, further comprising separately recovering methane for use as fuel for burners and / or heaters in the thermal cracking step.

The invention will be described in more detail below and with reference to FIGS. 3. In FIG. 3 shows a process flow diagram including an integrated solvent deasphalting, hydroprocessing and steam pyrolysis process and system, including a bypass for the residue. The integrated system generally includes a solvent deasphalting zone, a selective catalytic hydroprocessing zone, a steam pyrolysis zone, and a product separation zone. The solvent deasphalting zone includes a primary clarifier 219, a secondary clarifier 222, a deasphalted / demetallized oil (DA / DMO) separation zone 225, and a separator zone 227. The primary settler 219 includes an inlet for receiving a combined stream 218 comprising feed 201 and solvent, which may be fresh solvent 216, recycle solvent 217, recycle solvent 228, or a combination of these solvent sources. The primary settler 219 also includes a primary phase discharge outlet 220 for DA / DMO oil and several pipe outlets for primary phase discharge 221 of asphalt. The secondary sump 222 includes two T-distributors located at both ends for receiving the primary phase 220 of DSA / DMO oil, an outlet for discharging the secondary phase 224 of DA / DMO oil, and an outlet for discharging secondary phase 223 of asphalt. The DA / DMO oil separation zone 225 includes an inlet for receiving secondary phase 224 of DA / DMO oil, an outlet for discharging a solvent stream 217, and an outlet for discharging a stream 226 of a solvent-free DA / DMO oil that is used as feed stream for the selective hydroprocessing zone. Stream 226 can be further separated in separator 288 into stream 286 and stream 287, stream 287 being used as feed stream for the selective hydroprocessing zone. Stream 286 may be further separated in separator 280 into stream 282 and stream 281, stream 282 being used as feed stream for steam pyrolysis zone 230, in particular convection section 232. In one preferred alternative, stream 226 is separated in separator 288 into stream 281 and stream 286, said stream 286 being used as feed to separator 280 to separate into stream 282 and stream 287, said stream 282 being used as feed to steam pyrolysis zone 230, in particular convection section 232, and stream 287 being used as a feed stream for the selective hydroprocessing zone. Separator vessel 227 includes an inlet for receiving primary asphalt phase 221, an outlet for discharging a solvent stream 228, and an outlet for discharging a lower asphalt phase 229 that may be mixed with pyrolysis fuel oil 271 from product separation zone 270 and with stream 281 from separator 280.

The selective hydroprocessing zone includes a reactor zone 204 that includes an inlet for receiving a mixture of a solvent-free DA / DMO oil stream 226 and hydrogen 202 recirculated from the steam pyrolysis product stream and make-up hydrogen as needed (not shown). The reactor zone 204 further includes an outlet for discharging the hydrotreated effluent stream 205.

Reactor effluents 5 from the hydroprocessing reactor (s) are cooled in a heat exchanger (not shown) and sent to a high pressure separator 206. The separator overhead 207 is purified in an amine refinery 212 and the resulting hydrogen-rich gas stream 213 is passed to a recycle compressor 214 for use as a recycle gas 215 in the hydroprocessing reactor. The underflow stream 208 from the high pressure separator 206, which is essentially a liquid phase, is cooled and introduced into the cold low pressure separator 209 where it is separated into a gas stream and a liquid stream 210. Gases from the cold low pressure separator include hydrogen , H ₂ S, NH ₃ and any light hydrocarbons such as C1-C4 hydrocarbons. Typically, these gases are sent for further processing such as flare gas processing or fuel gas processing. In accordance with certain embodiments herein, hydrogen is recovered by combining gas stream 211, which includes hydrogen, H ₂ S, NH _3, and any light hydrocarbons such as C1-C4 hydrocarbons, with steam cracker products 244. Liquid flow 210 can

- 17 038171 used directly as feed stream for steam pyrolysis zone 230 230.

In one preferred embodiment, liquid stream 210 is separated in splitter 283 into stream 285 and stream 284, stream 285 being sent to steam pyrolysis zone 230 and stream 284 used as an additional feed stream to inlet to the solvent deasphalting zone in accordance with the above discussion of the invention. This means re-treatment in the solvent deasphalting zone of the liquid stream 210, and this stream 210 has already been processed in the solvent deasphalting zone and in the selective hydroprocessing zone. In the flow diagram corresponding to FIG. 3, only one solvent deasphalting zone is demonstrated, but in practice, two different solvent deasphalting zones can also function.

The steam pyrolysis zone 230 generally includes a convection section 232 and a pyrolysis section 234 which may operate based on the operations of a steam pyrolysis unit known in the art, i. E. loading the thermal cracking feed stream into the convection section in the presence of steam. In addition, in certain optional embodiments, as described herein (as indicated by dashed lines in FIG. 3), a vapor-liquid separation section 236 is included between sections 232 and 234. The vapor-liquid separation section 236, through which the heated steam cracking feed stream from the convection section 232 is passed, may be a separation device based on physical or mechanical separation of vapors and liquids.

The quenching zone 240 includes an inlet in fluid communication with the outlet of the steam pyrolysis zone 230, an inlet for supplying a quench solution 242, an outlet for discharging a quenched mixed product stream 244, and an outlet for discharging a quench solution 246.

In general, the intermediate quenched blended product stream 244 is separated in a compression and fractionation section. Such a compression and fractionation section is well known in the art.

In one embodiment, mixed product stream 244 is converted to intermediate product stream 265 and hydrogen 262, which is purified in the present process and used as hydrogen recycle stream 202 in hydroprocessing reaction zone 224. Intermediate stream 265, which may further contain hydrogen, is generally fractionated into end products and residue in a separation zone 270, which may include, for example, one or more separation units as is known to those skilled in the art.

In general, product separation zone 270 includes an inlet in fluid communication with product stream 265 and a plurality of product outlets 273-278, including a methane discharge outlet 278, which may optionally be combined with stream 263, an outlet 277 for ethylene unloading, outlet 276 for propylene unloading, outlet 275 for unloading butadiene, outlet 274 for unloading mixed butylenes and outlet 273 for unloading pyrolysis gasoline. In addition, a pyrolysis fuel oil outlet 271 is provided for discharge to discharge the pyrolysis fuel oil 271. Optionally, one or both of the lower asphalt phase 229 from the separator vessel 227 and the reject portion 238 from the vapor-liquid separation section 236 is combined with the pyrolysis fuel oil 271, and the mixed stream may be selected as a pyrolysis fuel oil mixture 272, for example, a low-sulfur fuel oil mixture for further processing at a third-party refinery. As noted, although six product outlets have been demonstrated, fewer or more may be provided depending on, for example, the layout of the separation plants used and the outlets and distribution requirements.

In one preferred embodiment of the method using the arrangement shown in FIG. 3, a solvent from one or more sources 216, 217, 284 and 228 is admixed to the crude oil of the feedstock 201. The resulting mixture 218 is then transferred to the primary settler 219. As a result of mixing and settling in the primary settler 219, two phases are formed: primary phase 220 of DA / DMA oil and primary phase 221 of asphalt. The temperature of the primary settler 219 is low enough to recover all DA / DMO oil from the feed. For example, for a system using n-butane, a suitable temperature range is about 60 to 150 ° C, and a suitable pressure range is such that the pressure is greater than the vapor pressure of n-butane at operating temperature, for example from about 15 to 25 bar, to keep the solvent in the liquid phase. In one system using n-pentane, a suitable temperature range is from about 60 to about 180 ° C, and again a suitable pressure range is such that the pressure is greater than the vapor pressure of n-pentane at operating temperature. for example about 10 to 25 bar to keep the solvent in the liquid phase. The temperature in the second clarifier is usually higher than the temperature in the first clarifier.

- 18 038171

Primary phase 220 of DA / DMO oil containing a significant proportion of solvent and oil

DA / DMO, together with a minor amount of asphalt, is discharged through an outlet located at the top of the primary clarifier 219 and header pipes (not shown). The primary asphalt phase 221, which contains 40-50% (v / v) solvent, is discharged through several pipe outlets located at the bottom of the primary settler 219.

The primary phase 220 of the DA / DMO oil enters two T-shaped distributors at both ends of the secondary clarifier 222, which serves as the final extraction stage. A secondary asphalt phase 223 containing a small amount of solvent and DA / DMO oil is discharged from the secondary clarifier 222 and recycled back to the primary clarifier 219 to recover the DA / DMO oil. A secondary DA / DMO oil phase 224 is prepared and passed to a DA / DMO oil separation zone 225 to produce a solvent stream 217 and a solvent free DA / DMO oil stream 226. More than 90 wt% of the solvent charged to the settling tanks enters the DA / DMO oil separation zone 225, which is sized to rapidly and efficiently separate the solvent and DA / DMO oil by flashing. The primary asphalt phase 221 is transported to a separator vessel 227 to separate the solvent stream 228 and the bottom asphalt phase 229 by flashing. Solvent streams 217 and 228 can be used as solvent for primary settler 219, thereby minimizing the need for fresh solvent 216. Solvents used in the solvent deasphalting zone include neat liquid hydrocarbons such as propane, butanes, and pentanes, and their mixtures. The choice of solvents depends on the requirements for the DAO oil and the quality and quantity of the end products. Operating conditions for the solvent deasphalting zone include a temperature equal to or less than the critical temperature of the solvent; a solvent to oil ratio in the range of 2: 1 to 50: 1; and a pressure in a range effective to maintain the solvent / feed mixture in the settling tanks in a liquid state.

The substantially solvent free DA / DMO oil stream 226 is optionally steam stripped (not shown) to remove any remaining solvent and is mixed with an effective amount of hydrogen and stream 215 (and make-up hydrogen source as needed) to produce combined stream 203. Mixture 203 is charged to hydroprocessing reaction zone 204 at temperatures ranging from 300 to 450 ° C. In certain embodiments, the hydroprocessing reaction zone 204 includes one or more plant operations as described in United States Patent Publication No. 2011/0083996 and in PCT Patent Application Publications No. WO 2010/009077, WO 2010/009082, WO 2010/009089 and WO 2009/073436. For example, a hydroprocessing zone may include one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking functions. In additional embodiments, the hydroprocessing reaction zone 204 includes more than two catalyst beds. In additional embodiments, the hydroprocessing reaction zone 204 includes a plurality of reaction vessels, each including one or more catalyst beds, for example, having a different function.

In yet another embodiment, stream 226 is further separated into stream 286 and stream 287, stream 287 being mixed with an effective amount of hydrogen and 215 (and a make-up hydrogen source as needed) to provide a combined stream 203.

Stream 286 may be further split in unit 280 into stream 281 and stream 282, stream 282 being sent to steam pyrolysis zone 230. Thus, the feed stream to the steam pyrolysis zone 230 may be a combination of stream 285 and stream 282.

Zone 204 hydroprocessing operates at parameters effective for hydrodemetallization, hydrodearomatization, hydrodenitrogenation, hydrodesulfurization and / or hydrocracking of the crude oil of the feedstock. In certain embodiments, the hydroprocessing is carried out using the following conditions: operating temperature ranging from 300 to 450 ° C; operating pressure in the range from 30 to 180 bar and hourly space velocity of the liquid in the range from 0.1 to 10 h ^-1 . As it should be noted, the use of crude oil as feedstock in the hydroprocessing zone 204 demonstrates advantages, for example, in comparison with the operation of the same hydroprocessing unit used for the atmospheric residue. For example, with a start-up or operating temperature between 370 and 375 ° C, the deactivation rate is approximately 1 ° C / month. In contrast, if it was necessary to process the residue, the decontamination rate would be close to a value in the range of about 3 to 4 ° C / month. When treating the atmospheric residue, a pressure of about 200 bar is generally used, while the present process, in which crude oil is treated, can be operated at a pressure of as little as 100 bar. In addition, in order to achieve the high level of saturation required to increase the hydrogen level in the feed stream, the process can operate at a high throughput compared to that of the atmospheric residue. The LHSV can be as much as 0.5, while the atmospheric residue is typically 0.25. An unexpected discovery is that in the processing of crude oil, the rate of decontamination moves in the opposite direction compared to what is usually observed. Decontamination at low capacity (0.25 h ^-1 ) is 4.2 ° C / month and decontamination at higher capacity (0.5 h ^-1 ) is 2.0 ° C / month. The opposite is true for every feed stream considered in the industry. This can be attributed to the catalyst washout effect.

Reactor effluents 205 from hydroprocessing zone 204 are cooled in a heat exchanger (not shown) and sent to a cold or hot high pressure separator 206. The separator overhead 207 is purified in an amine refinery 212 and the resulting hydrogen-rich gas stream 213 is passed to a recycle compressor 214 for use as a recycle gas 215 in the hydroprocessing reaction zone 204. The separator bottom 208 from the high pressure separator 206, which is substantially in the liquid phase, is cooled and then introduced into the cold low pressure separator 209. Residual gases in stream 211, including hydrogen, H ₂ S, NH _3, and any light hydrocarbons that may include C1-C4 hydrocarbons, can typically be purged from a cold low pressure separator and sent for further processing such as flare gas processing or fuel gas processing. In certain embodiments of the present process, hydrogen is recovered by combining stream 211 (as indicated by dashed lines) with cracked gas stream 244 from the steam cracker product. Bottom product 210 from low pressure separator 209 is optionally sent to separation zone 220 or directly passed to steam pyrolysis zone 230.

Hydrotreated effluent stream 210 has reduced levels of contaminants (ie, metals, sulfur, and nitrogen), increased wax content, reduced PCGB, and increased API gravity.

The hydrotreated effluent stream 210 can be passed directly to the convection section 232 where an effective amount of steam is introduced, for example through a steam inlet (not shown). In yet another embodiment, hydrotreated effluent stream 210 is separated in separator 283 into stream 285 and stream 284, stream 285 being passed to convection section 232 in the presence of an effective amount of steam, such as from a steam inlet (not shown). In addition, the feed stream for convection section 232 may also include stream 282 from separator 280.

As shown in FIG. 3, stream 282 is also used as the feed stream for convection section 232.

In the convection section 232, the mixture is heated to a predetermined temperature, for example using one or more waste heat streams or other suitable heating arrangement. The heated mixture from the pyrolysis feed and additional steam is passed to the pyrolysis section 234 to produce a mixed product stream 239. In certain embodiments, the heated mixture from section 232 is passed through a vapor-liquid separation section 236 in which portion 238 is discarded as a low sulfur fuel oil component suitable for use when mixed with pyrolysis fuel oil 271.

Steam pyrolysis zone 230 operates at parameters effective to crack hydroprocessing effluent 210 to produce desired products including ethylene, propylene, butadiene, blended butenes, and pyrolysis gasoline. In certain embodiments, steam cracking is carried out using the following conditions: a temperature in the range of 400 to 900 ° C in the convection section and in the pyrolysis section; the ratio between water vapor and hydrocarbon in the convection section in the range from 0.3: 1 to 2: 1; and the residence time in the pyrolysis section in the range of 0.05 to 2 seconds.

A mixed product stream 239 is passed to an inlet for a quench zone 240 using a quench solution 242 (e.g., water and / or pyrolysis fuel oil) introduced through a separate inlet to provide a quenched mixed product stream 244 having a reduced temperature of, for example, about 300 ° C, and the spent quench solution 246 is recycled and / or blown out.

The cracker gas mixture effluent stream 239 is typically a mixture of hydrogen, methane, hydrocarbons, carbon dioxide and hydrogen sulfide. After cooling with water and / or quenching in oil, the mixture 244 is subjected to compression and separation. In one non-limiting example, stream 244 is compressed in multistage compressor zone 251 to produce compressed gas mixture 252. Compressed gas mixture 252 may be treated in caustic treatment unit 253 to produce hydrogen sulfide and carbon dioxide depleted gas mixture 254. The gas mixture 254 can be further compressed in the zone 255 of the compressor. The resulting cracked gas 256 can be subjected to

- 20 038171 cryogenic treatment in unit 257 for dehydration and can be further dried using molecular sieves.

Cold cracked gas stream 258 from unit 257 may be passed to desoldering column 259 from which an overhead stream 260 containing hydrogen and methane is obtained from the cracked gas stream. Thereafter, the bottom stream 265 from the desoldering column 259 is sent for further processing in the product separation zone 270, which includes fractionation columns, including an ethanolic, propane-stripper, and butane-stripper. Process configurations may also be used including a different sequence of a desoldering column, an ethanizing column, a desoldering column, and a butane desoldering column.

In accordance with the methods herein, after separation from methane in desoldering column 259 and hydrogen recovery in unit 261, hydrogen 262 is produced, typically in a purity range of 80-95% (v / v). Recovery processes in unit 261 include cryogenic recovery (eg, at a temperature of approximately -157 ° C). The hydrogen stream 262 is then passed to a hydrogen purification unit 264, such as a pressure swing adsorption (PSA) unit to produce a 99.9% + purity hydrogen stream 202, or a membrane separation unit to produce a hydrogen stream 202 at a purity level , amounting to approximately 95%. Thereafter, purified hydrogen stream 202 is recycled back to serve as the major portion of the required hydrogen for the hydroprocessing zone. In addition, a minority fraction can be used for hydrogenation reactions of acetylene, methylacetylene and propadienes (not shown). In addition, in accordance with the methods herein, the methane stream 263 may optionally be recycled to a steam cracker for use as a fuel for burners and / or heaters.

The underflow stream 265 from desoldering column 259 is conveyed to the inlet of product separation zone 270 for separation into methane, ethylene, propylene, butadiene, mixed butylenes and pyrolysis gasoline, respectively, via outlets 278, 277, 276, 275, 274, and 273. Pyrolysis gasoline generally comprises C5-C9 hydrocarbons, and benzene, toluene and xylenes can be separated from this cut. Optionally, one or both of the lower asphalt phase 229 and the non-vaporized heavy liquid fraction 238 from the vapor-liquid separation section 236 are combined with the pyrolysis fuel oil 271 (e.g., substances boiling at a temperature greater than the boiling point of the lowest boiling C10 compound known as the name of the stream C10 +) from the separation zone 270 and the mixed stream is taken as a mixture 272 of pyrolysis fuel oil, for example, for further processing at a third-party refinery (not shown). In certain embodiments, the bottom phase 229 of the asphalt can be sent to an asphalt stripper (not shown) where any remaining solvent is stripped, for example by steam.

The inventors have found that it is beneficial to use hydrotreating and solvent deasphalting only for that portion of the crude oil that benefits from it. This means that unrefined crude oil fractions will be discharged. The integrated method of embodiment 25 in accordance with the above description of the invention preferably comprises separating a stream of deasphalted and demetallized oil in a separation zone to recover a vapor portion that is sent to a steam pyrolysis zone and a liquid portion, the liquid portion being discharged and mixed with the pyrolysis fuel oil. from the product separation zone in accordance with the presentation of the invention in step (e4) of embodiment 25 in accordance with the above description of the invention. Thus, in accordance with one preferred embodiment of the invention, corresponding to embodiment 25, the thermal cracking step comprises heating the hydrotreated effluent in the convection section of the steam pyrolysis zone, separating the heated hydrotreated effluent into a vapor fraction and a liquid fraction, passing the vapor fraction into the pyrolysis section steam pyrolysis zones and discharge of liquid fraction. It is preferred that the discharged liquid fraction is mixed with the pyrolysis fuel oil recovered in step (g4). The separation of the heated hydrotreated effluent stream into a vapor fraction and a liquid fraction is preferably carried out using a vapor-liquid separation device based on physical and mechanical separation. Such a vapor-liquid separation device preferably includes a pre-swirling element having an inlet portion and a transition portion, the inlet portion having an inlet for receiving the flowing fluid mixture and a curved circuit, a controllable cyclone section including an inlet adjacent to the pre-swirling element due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid header / sump section through which the liquid passes. Step (d4) of the integrated process according to the present invention preferably comprises compressing the thermal cracked mixed product stream using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and producing olefins and aromatics as in step (e4) and pyrolysis fuel oils as in step (f4) from the residual hydrogen sulfide / carbon dioxide reduced dehydrated compressed thermal cracked mixed product stream. Step (e4) preferably includes purifying recovered hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content for recycling to the hydroprocessing zone. In accordance with one preferred embodiment, the present integrated method further comprises the step of recovering hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content, further comprising separately recovering methane for use as fuel for burners and / or heaters on thermal cracking stages. The invention will be described in more detail below and with reference to FIGS. 4, which is a process flow diagram of one embodiment of the invention including an integrated separation, hydrotreating, solvent deasphalting, and steam pyrolysis process and system.

This system includes an initial feed stream separation zone, a selective hydroprocessing zone, a solvent deasphalting zone, a steam pyrolysis zone and a product separation zone. The feed split zone 380 includes an inlet for receiving feed stream 301, an outlet for discharging reject portion 383, and an outlet for unloading one or more remaining hydrocarbon portions 382. Hydrocarbon portion 383 is mixed with one or more streams such as streams 329, 349, 338 and 371. Hydrocarbon portion 382 is sent to a selective hydroprocessing zone. The cutoff in separation zone 380 can be set to be compatible with the residue oil mixture, for example at about 540 ° C. The separation zone 380 may be a one-stage separation device such as a flash separator. The cut-off boundary in the separation zone 380 may be set such that only separation takes place in order to obtain the rejected portion 383 and the remaining hydrocarbon portion 382.

In additional embodiments, the separation zone 380 may include or essentially consist of the following (i.e., when operating in the absence of a flash zone): a cyclonic phase separation device or other separation device based on physical or mechanical separation of vapors and liquids. In embodiments in which the separation zone comprises or essentially consists of the following: separation device based on physical or mechanical separation of vapors and liquids, the fraction separation boundary may be adjusted based on the vaporization temperature and fluid velocity for the material entering the device.

The selective hydroprocessing zone includes a reactor zone 304 including an inlet for receiving a combined stream 303 including feed stream 382 originating from separator 380 and hydrogen 302 recycled from the steam pyrolysis product stream and make-up hydrogen as needed (not shown). The reactor zone 304 also includes an outlet for discharging the hydrotreated effluent stream 305.

Reactor effluents 305 from the hydroprocessing reactor (s) are cooled in a heat exchanger (not shown) and sent to a high pressure separator 306. The separator overhead 307 is purified in an amine refinery 312 and the resulting hydrogen-rich gas stream 313 is passed to a recycle compressor 314 to be used as recycle gas 315 in the hydroprocessing reactor. The underflow stream 308 from high pressure separator 306, which is essentially a liquid phase, is cooled and introduced into cold low pressure separator 309, where it is separated into gas stream 311 and liquid stream 310. Gases from cold low pressure separator include hydrogen, H ₂ S, NH ₃ and any light hydrocarbons such as C1-C4 hydrocarbons. Typically, these gases are sent for further processing such as flare gas processing or fuel gas processing. In accordance with certain embodiments herein, hydrogen is recovered by combining gas stream 311, which includes hydrogen, H ₂ S, NH _3, and any light hydrocarbons such as C1-C4 hydrocarbons, with steam cracker products 344. All or part of the liquid stream 310 is used as feed stream for the solvent deasphalting zone.

- 22 038171 tions.

The solvent deasphalting zone generally includes a primary settler 319, a secondary settler 322, a solvent deasphalted deasphalted / demetallized oil (DA / DMO) separation zone 325, and a separator zone 327. The primary settler 319 includes an inlet for receiving a hydrotreated effluent stream 310 and a solvent, which may be fresh solvent 316, recycle solvent 317, recycle solvent 328, or a combination of these solvent sources. The primary settler 319 also includes a primary discharge 320 of DA / DMO oil and several pipe outlets for discharging the primary phase 321 of asphalt. The secondary sump 322 includes two T-distributors located at both ends for receiving primary phase 320 of DSA / DMO oil, an outlet for discharging secondary phase 324 of DA / DMO oil, and an outlet for discharging secondary phase 323 of asphalt. The DA / DMO oil separation zone 325 includes an inlet for receiving secondary phase 324 of DA / DMO oil, an outlet for discharging a solvent stream 317, and an outlet for discharging a stream 326 of a solvent-free DA / DMO oil used as feed stream for a steam pyrolysis zone 330. ... The separator vessel 327 includes an inlet for receiving primary asphalt phase 321, an outlet for discharging a solvent stream 328, and an outlet for discharging a lower asphalt phase 329 that may be mixed with pyrolysis fuel oil 371 from product separation zone 370.

The steam pyrolysis zone 330 generally includes a convection section 332 and a pyrolysis section 334, which may operate based on the operations of a steam pyrolysis unit known in the art, i. E. loading the thermal cracking feed stream into the convection section in the presence of steam. In addition, in certain optional embodiments, as described herein (as indicated by dashed lines in FIG. 4), a vapor-liquid separation section 336 is included between sections 332 and 334. The vapor-liquid separation section 336, through which the heated steam cracking feed stream from the convection section 332 is passed and fractionated, may be a flash separation device, a separation device based on physical or mechanical separation of vapors and liquids, or a combination of at least one from these device types. In additional optional embodiments, a vapor-liquid separation zone 347 is included upstream of section 332, either in combination with a vapor-liquid separation zone 336, or in the absence of a vapor-liquid separation zone 336. Stream 326 is fractionated in separation zone 347, which may be a flash separation device, a separation device based on physical or mechanical separation of vapors and liquids, or a combination of at least one of these types of devices.

The quenching zone 340 includes an inlet in fluid communication with the outlet of the steam pyrolysis zone 330 for receiving a mixed product stream 339, an inlet for supplying a quenching solution 342, an outlet for discharging a stream 344 of an intermediate quenched mixed product, and an outlet for discharging a quenching solution 346 ...

In general, the intermediate quenched blended product stream 344 is separated in a compression and fractionation section. Such a compression and fractionation section is well known in the art.

In one embodiment, mixed product stream 344 is converted to intermediate product stream 365 and hydrogen 362, which is purified in the present process and used as hydrogen recycle stream 302 in hydroprocessing reaction zone 304. The intermediate product stream 365, which may further contain hydrogen, is generally fractionated into end products and residue in a separation zone 370, which may include, for example, one or more separation units such as a plurality of fractionation columns including an ethanolic, desiccant and a butane column as known to those skilled in the art.

In general, product separation zone 370 includes an inlet in fluid communication with product stream 365 and a plurality of product outlets 373-378, including a methane discharge outlet 378, which may optionally be combined with stream 363, outlet 377 for ethylene unloading, outlet 376 for unloading propylene, outlet 375 for unloading butadiene, outlet 374 for unloading mixed butylenes and outlet 373 for unloading pyrolysis gasoline. In addition, a pyrolysis fuel oil 371 discharge is provided for unloading. Optionally, one or both of the lower asphalt phase 329 from the solvent deasphalting zone separator tank 327 and the fuel oil portion 338 from the vapor-liquid separation section 336 are combined with the pyrolysis fuel oil 371, and the blended stream may be sampled as a pyrolysis fuel oil mixture 372, such as a low-sulfur fuel oil mixture, for further processing at a third-party refinery. As it should be noted, despite the demonstration of six editions for products, there may be fewer or more of them depending, for example, on the layout of the installations used.

- 23 038171 for separation and exit and distribution requirements.

In one embodiment of the method using the arrangement shown in FIG. 4, feedstock crude oil 301 is sent to separator 380 and separated into stream 382 and stream 383, with stream 382 being mixed with effective amounts of hydrogen 302 and 315 (and make-up hydrogen source as needed) to provide combined stream 303. Mix 303 is charged in the zone 304 of the reaction of hydroprocessing at a temperature in the range from 300 to 450 ° C. In certain embodiments, the hydroprocessing reaction zone 304 includes one or more installation steps as described in the Applicant's United States Patent Publication No. 2011/0083996 and in PCT Patent Application Publications No. WO 2010/009077, WO 2010 / 009082, WO 2010/009089 and WO 2009/073436, all of which are incorporated herein by reference in their entirety. For example, a hydroprocessing zone may include one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking functions. In additional embodiments, the hydroprocessing zone 304 includes more than two catalyst beds. In additional embodiments, the hydroprocessing zone 304 includes more than two catalyst beds. In additional embodiments, the hydroprocessing reaction zone 304 includes a plurality of reaction vessels, each including one or more catalyst beds, for example, having a different function.

The hydroprocessing zone 304 operates at parameters effective for hydrodemetallization, hydrodearomatization, hydrodenitrogenation, hydrodesulfurization, and / or hydrocracking of the feedstock crude oil. In certain embodiments, the hydroprocessing is carried out using the following conditions: operating temperature ranging from 300 to 450 ° C; working pressure in the range from 30 to 180 bar; and hourly space velocity of the liquid in the range from 0.1 to 10 h ^-1 . As should be noted, the use of crude oil as feedstock to hydroprocessing zone 304 304 demonstrates advantages, for example, over the operation of the same hydroprocessing unit used on the atmospheric residue. For example, with a start-up or operating temperature between 370 and 375 ° C, the deactivation rate is approximately 1 ° C / month. In contrast, if it was necessary to process the residue, the decontamination rate would be close to a value in the range of about 3 to 4 ° C / month. When treating the atmospheric residue, a pressure of about 200 bar is generally used, while the present process, in which crude oil is treated, can be operated at a pressure of as little as 100 bar. In addition, in order to achieve the high level of saturation required to increase the hydrogen level in the feed stream, the process can operate at high throughput compared to that of the atmospheric residue. The LHSV can be ^{as much as 0.5 h -1} , while the atmospheric residue typically has a value of 0.25 h ^-1 . An unexpected discovery is that in the processing of crude oil, the rate of decontamination moves in the opposite direction compared to what is usually observed. Decontamination at low capacity (0.25 h ^-1 ) is 4.2 ° C / month and decontamination at higher capacity (0.5 h ^-1 ) is 2.0 ° C / month. The opposite is true for every feed stream considered in the industry. This can be attributed to the catalyst washout effect.

Reactor effluents 305 from hydroprocessing zone 304 are cooled in a heat exchanger (not shown) and sent to separators, which may include a cold or hot high pressure separator 306. The separator overhead 307 is purified in an amine refinery 312 and the resulting hydrogen-rich gas stream 313 is passed to a recycle compressor 314 to be used as recycle gas 315 in the hydroprocessing reaction zone 304. The separator bottom 308 from the high pressure separator 306, which is substantially in the liquid phase, is cooled and then introduced into the cold low pressure separator 309. Residual gases in stream 311, including hydrogen, H ₂ S, NH _3, and any light hydrocarbons that may include C1-C4 hydrocarbons, can typically be purged from a cold low pressure separator and sent for further processing such as flare gas processing or fuel gas processing. In certain embodiments of the present process, hydrogen is recovered by combining stream 311 (as indicated by dashed lines) with the cracked gas as steam cracker product stream 344.

Hydrotreated effluent stream 310 has reduced levels of contaminants (ie, metals, sulfur, and nitrogen), increased paraffin content, reduced PCGB, and increased API gravity.

Solvent from one or more sources 316, 317, and 328 is admixed to hydrotreated effluent stream 310. The resulting mixture 318 is then transferred to primary settler 319. Mixing and settling in primary settler 319 results in two phases: primary phase 320 of DA oil / DMA and primary phase 321 asphalt. Primary temperature

- 24 038171 Sump 319 is low enough to recover all DA / DMO oil from the feed. For example, for a system using n-butane, a suitable temperature range is about 60 to 150 ° C, and a suitable pressure range is such that the pressure is greater than the vapor pressure of n-butane at operating temperature, for example from about 15 to 25 bar, to keep the solvent in the liquid phase. In one system using npentane, a suitable temperature range is from about 60 to about 180 ° C, and again a suitable pressure range is such that the pressure is greater than the vapor pressure of n-pentane at operating temperature, for example, about 10 to 25 bar, to keep the solvent in the liquid phase. The temperature in the second clarifier is usually higher than the temperature in the first clarifier.

The primary phase 320 of DA / DMO oil, containing a significant proportion of solvent and DA / DMO oil together with a minor amount of asphalt, is discharged through an outlet located at the top of the primary clarifier 319 and header pipes (not shown). The primary asphalt phase 321, which contains 20-50% (v / v) solvent, is discharged through several pipe outlets located at the bottom of the primary settler 319.

The primary phase 320 of DA / DMO oil enters two T-shaped distributors at both ends of the secondary clarifier 322, which serves as the final extraction stage. A secondary asphalt phase 323 containing a small amount of solvent and DA / DMO oil is discharged from the secondary clarifier 322 and recycled back to the primary clarifier 319 to recover the DA / DMO oil. A secondary phase 324 of DA / DMO oil is obtained and passed to a DA / DMO oil separation zone 325 to produce a solvent stream 317 and a solvent-free DA / DMO oil stream 326. More than 90 wt% of the solvent charged to the settling tanks enters the DA / DMO oil separation zone 325, which is sized to rapidly and efficiently separate the solvent and DA / DMO oil by flashing. The primary asphalt phase 321 is transported to a separator vessel 327 for flash separation of the solvent stream 328 and the bottom asphalt phase 329. Solvent streams 317 and 328 can be used as solvent for primary settler 319, thereby minimizing the need for fresh solvent 316.

Solvents used in the solvent deasphalting zone include pure liquid hydrocarbons such as propane, butanes, and pentanes, and mixtures thereof.

The choice of solvents depends on the requirements for the DAO oil and the quality and quantity of the end products. Operating conditions for the solvent deasphalting zone include a temperature equal to or less than the critical temperature of the solvent; a solvent to oil ratio in the range of 2: 1 to 50: 1 (v: v) and a pressure in the range effective to maintain the solvent / feed mixture in the settling tanks in a liquid state.

The substantially solvent free DA / DMO oil stream 326 is optionally steam stripped (not shown) to remove the solvent. In certain embodiments, deasphalted and demetallized oil stream 326 is feed stream 348 to steam pyrolysis zone 330. In additional embodiments, deasphalted and demetallized oil stream 326 is sent to separation zone 347, where the vapor discharged portion is feed stream 348 to steam pyrolysis zone 330. The vapor portion may have, for example, an initial boiling point corresponding to that of deasphalted and demetallized oil stream 326 and a final boiling point in the range of about 370 ° C to about 600 ° C. Separation zone 347 may include the operation of a suitable vapor-liquid separation unit such as a flash tank, a separation device based on physical or mechanical separation of vapors and liquids, or a combination of at least one of these types of devices.

Feed stream 348 is conveyed to convection section 332 and introduced, for example through a water vapor inlet (not shown), a predetermined amount of water vapor. In convection section 332, the mixture is heated to a predetermined temperature, for example using one or more waste heat streams or other suitable heating arrangement. The heated mixture from the pyrolysis feed and additional steam is passed to pyrolysis section 334 to produce a mixed product stream 339. In certain embodiments, the heated mixture from section 332 is passed through a vapor-liquid separation section 336 in which portion 338 is discarded as a low sulfur fuel oil component suitable for use when mixed with pyrolysis fuel oil 371.

The steam pyrolysis zone 330 operates at parameters effective to crack the DA / DMO oil stream to produce the desired products including ethylene, propylene, butadiene, blended butenes and pyrolysis gasoline. In certain embodiments, steam cracking is carried out using the following conditions: a temperature in the range of 400 to 900 ° C in the convection section and in the pyrolysis section; the ratio between water vapor and hydrocarbon in the convection zone in the range from 0.3: 1 to 2: 1 (wt.: wt.) and the residence time in the pyrolysis section in the range from 0.05 to 2 s.

Mixed product stream 339 is passed to an inlet for quench zone 340 using quench solution 342 (e.g., water and / or pyrolysis fuel oil) introduced through a separate inlet to provide a quenched mixed product stream 344 having a reduced temperature of, for example, about 300 ° C, and the spent quench solution 346 is recycled and / or blown out.

The cracker gas mixture effluent stream 339 is typically a mixture of hydrogen, methane, hydrocarbons, carbon dioxide and hydrogen sulfide. After cooling with water or quenching in oil, the mixture 344 is subjected to compression and separation. In one non-limiting example, stream 344 is compressed in a multistage compressor, which typically includes 4-6 stages, wherein said multistage compressor may include a compressor zone 351 to produce a compressed gas mixture 352. The compressed gas mixture 352 may be treated in a caustic treatment unit 353 to obtaining a gas mixture 354, depleted in hydrogen sulfide and carbon dioxide. The gas mixture 354 can be further compressed in the zone 355 of the compressor. The resulting cracked gas 356 can be cryogenically treated in dehydration unit 357 and can be further dried using molecular sieves.

Cold cracked gas stream 358 from unit 357 may be passed to desoldering column 359 from which an overhead stream 360 containing hydrogen and methane is obtained from the cracked gas stream. Thereafter, the underflow stream 365 from the desoldering column 359 is sent for further processing in the product separation zone 370, which includes fractionation columns, including the de-ethanizer, propane-stripper, and butane-stripper. Process configurations may also be used including a different sequence of a desoldering column, an ethanizing column, a desoldering column, and a butane desoldering column.

In accordance with the methods herein, after separation from methane in desoldering column 359 and hydrogen recovery in unit 361, hydrogen 362 is produced, typically in a purity range of 80-95% (v / v). Recovery processes in unit 361 include cryogenic recovery (eg, at a temperature of approximately -157 ° C). Thereafter, hydrogen stream 362 is passed to a hydrogen purification unit 364, such as a pressure swing adsorption (PSA) unit, to produce a 99.9% + purity hydrogen stream 302, or a membrane separation unit to produce a hydrogen stream 302 of 99.9% + purity. a purity of approximately 95%. Thereafter, purified hydrogen stream 302 is recycled back to serve as the major portion of the required hydrogen for the hydroprocessing zone. In addition, the minority can be used for hydrogenation reactions of acetylene, methylacetylene and propadienes (not shown). Additionally, in accordance with the methods herein, the methane stream 363 may optionally be recycled to a steam cracker for use as a fuel for burners and / or heaters.

The underflow stream 365 from demethanizer 359 is conveyed to the inlet of product separation zone 370 for separation into methane, ethylene, propylene, butadiene, mixed butylenes and pyrolysis gasoline, respectively, via outlets 378, 377, 376, 375, 374 and 373. Pyrolysis gasoline generally comprises C5-C9 hydrocarbons, and benzene, toluene and xylenes can be separated from this cut. Optionally, one or both of the lower asphalt phase 329 and the unvaporated heavy liquid fraction 338 from the vapor-liquid separation section 336 are combined with the pyrolysis fuel oil 371 (e.g., substances boiling at a temperature greater than the boiling point of the lowest boiling C10 compound known as the name of the stream C10 +) from the separation zone 370 and the mixed stream is taken as a mixture 372 of pyrolysis fuel oil, for example, for further processing at a third-party refinery (not shown). In certain embodiments, the bottom phase 329 of the asphalt can be sent to an asphalt stripper (not shown) where any remaining solvent is stripped, for example by steam.

Solvent deasphalting is a unique separation process in which the residue is separated by molecular weight (density) instead of boiling point separation as in a vacuum distillation process. Thus, the solvent deasphalting process allows the production of low contaminated deasphalted oil (DAO) enriched in paraffinic molecules, and therefore reduces the value of the PCGB relative to that of the original feedstock or hydro-processed feedstock.

Solvent deasphalting is typically carried out using paraffin streams having carbon atoms in the range of 3-7, in certain embodiments in the range of 4-5, and under conditions lower than the critical conditions for the solvent.

- 26 038171

The feed stream is mixed with a light paraffinic solvent having a carbon number in the range of 3-7, and the deasphalted oil is solubilized in the solvent. The mixed solution will precipitate insoluble pitch, which is separated from the DAO oil phase (solvent-DAO oil mixture) in the extractor.

Solvent deafaltization is carried out in the liquid phase and therefore the temperature and pressure are adjusted accordingly. In solvent deasphalting, there are two stages of phase separation. In the first stage of phase separation, a temperature is maintained lower than the temperature in the second stage to separate the main volume of asphaltenes. The temperature of the second stage is held to control the quality and quantity of deasphalted / demetallized oil (DA / DMO). Temperature has a large impact on the quality and quantity of DA / DMO oil. An increase in the extraction temperature will result in a lower deasphalted / demetallized oil yield, which means a lighter, lower viscosity DA / DMO oil and lower levels of metals, asphaltenes, sulfur and nitrogen. A decrease in temperature will have the opposite effect. In general, the yield of DA / DMO oil decreases when a higher quality oil is displayed as a result of an increase in temperature in the extraction system, and increases when a lower quality is demonstrated as a result of a decrease in the temperature of the extraction system.

One important process variable is the solvent composition. The dissolving power of the solvent increases with an increase in the critical temperature, generally in accordance with the sequence C3 <iso-C4 <n-C4 <iso-C5. Increasing the critical solvent temperature increases the DA / DMO oil yield. However, it should be noted that a solvent with a lower critical temperature exhibits lower selectivity, resulting in a lower quality DA / DMO oil.

The volumetric ratio between solvent and solvent deasphalting unit loading has an effect on selectivity and to a lesser extent on DA / DMO oil yield. Higher solvent to oil ratios result in higher DA / DMO oil quality for a fixed DA / DMO oil yield. A higher solvent to oil ratio is desirable due to better selectivity, but can result in increased operating costs, thereby often limiting the solvent to oil ratio to a narrow range. The composition of the solvent will also assist in establishing the desired ratios between solvent and oil. The required ratio between solvent and oil decreases as the critical temperature of the solvent increases. Therefore, the ratio between solvent and oil depends on the desired selectivity, operating cost and solvent composition.

In certain embodiments, selective hydroprocessing or hydrotreating methods can increase the paraffin content (or decrease the PVHB value) of the feedstock by saturation followed by mild hydrocracking of aromatics, especially polyaromatics. In the case of hydrotreating crude oil, contaminants such as metals, sulfur and nitrogen can be removed by passing the feed through a series of layered catalysts that perform the catalytic functions of demetallization, desulfurization and / or denitrogenation.

In one embodiment, the sequence of catalysts for performing hydrodemetallization (HDM) and hydrodesulfurization (HDS) is as follows.

a) Hydrodemetallization catalyst. The catalyst in the HDM section is generally based on a γ-alumina support having a specific surface area in the range of about 140-240 m ² / g. This catalyst is best described as having a very high pore volume, for example in excess of 1 cm ³ / g. The pore size itself usually corresponds predominantly to macroporosity. This is required to provide a high metal uptake capacity on the surface of the catalysts and optionally dopants. Typically, the active metals on the catalyst surface are nickel and molybdenum sulfides with a Ni / Ni + Mo ratio of <0.15. The concentration of nickel is lower on the HDM catalyst than on other catalysts because some nickel and vanadium are believed to precipitate from the feed itself during removal, acting as a catalyst. The dopant used may be one or more selected from phosphorus (United States Patent Publication No. US 2005/0211603), boron, silicon, and halogens. The catalyst can be in the form of alumina extrudates or alumina beads. In certain embodiments, alumina beads are used to facilitate unloading of the HDM catalyst beds in the reactor, as metal uptake at the top of the bed will range from 30% to 100%.

b) An intermediate catalyst can also be used to effect the transition between the HDM and HDS catalyst functions. It is characterized by intermediate levels of metal introduction and pore size distribution. The catalyst in the HDM / HDS reactor is

27 038171 essences an alumina support in the form of extrudates, optionally at least one Group VI catalytic metal (e.g. molybdenum and / or tungsten) and / or at least one Group VIII catalytic metal (e.g. nickel and / or cobalt). The catalyst also optionally contains at least one dopant selected from boron, phosphorus, halogens and silicon. Physical properties include a specific surface area in the range of about 140-200 m ² / g, a pore volume of at least 0.6 cm ³ / g, and pores that are mesoporous and range from 12 to 50 nm.

c) The catalyst in the HDS section may include suitable catalysts containing γ-alumina support materials having a typical specific surface area close to the upper end of the HDM catalyst range, for example in the range of about 180-240 m ² / g. This increased surface required for HDS catalyst resulting in obtaining relatively reduced volume since, for example, constituting less than 1 cm ³ / g. The catalyst contains at least one Group VI element such as molybdenum and at least one Group VIII element such as nickel. The catalyst also contains at least one dopant selected from boron, phosphorus, silicon and halogens. In certain embodiments, cobalt is used to obtain relatively increased levels of desulfurization. The metal addition levels for the active phase are increased because the required activity is increased so that the Ni / Ni + Mo molar ratio is in the range of 0.1 to 0.3 and the (Co + Ni) / Mo molar ratio is in the range of 0.25 to 0.85.

d) The final catalyst (which could optionally be replaced by a second and third catalyst) is designed to effect hydrogenation of the feedstock feed (instead of the primary function of hydrodesulfurization), for example as described in Appl. Catal. A General, 204 (2000) 251. The catalyst will also be promoted using Ni and the support will be wide pore γ-alumina. Physical properties include surface area close to the upper end of the HDM catalyst range, eg 180-240 m ² / g. This increased surface required for HDS catalyst resulting in obtaining relatively reduced volume since, for example, is less than 1 cm ³ / g.

The processes and systems herein provide improvements over prior art steam pyrolysis cracking processes: using crude oil as feedstock to produce petrochemicals such as olefins and aromatics; the hydrogen content of the feed to the steam pyrolysis zone is rich to obtain a high yield of olefins; coke precursors are largely removed from the original crude oil itself, allowing for reduced coke formation in the radiant coil; and additional impurities such as metal, sulfur and nitrogen compounds are also largely removed from the initial feed stream, thereby avoiding subsequent treatments of the end products.

In addition, hydrogen produced from the steam cracking zone is preferably recycled to the hydroprocessing zone in order to minimize the need for fresh hydrogen. In certain embodiments, the integrated systems described herein require the use of fresh hydrogen only to initiate operation. Once the reaction has reached equilibrium, the hydrogen purification system can provide sufficient high purity hydrogen to support the operation of the entire system.

Claims (4)

CLAIM 1. An integrated hydrotreating and steam pyrolysis process for the direct processing of crude oil to produce olefinic and aromatic petrochemical products, the process comprising the steps of (a) separating the crude oil into light components containing naphtha, kerosene and diesel fractions, and heavy components containing heavier hydrocarbon fractions containing asphaltenes; (b) charging heavy components into the solvent deasphalting zone together with an effective amount of solvent in order to obtain a stream of deasphalted and demetallized oil and the lower phase of asphalt, the solvent containing a pure liquid hydrocarbon selected from propane, butanes and pentanes, as well as mixtures thereof, at this deasphalting is carried out at a temperature equal to or less than the critical temperature of the solvent, the ratio between solvent and oil in the range from 2: 1 to 50: 1 and a pressure in the range effective to maintain the mixture of solvent and feed stream in a liquid state; (c) loading said light components, a deasphalted and demetallized oil stream and hydrogen into a hydroprocessing zone operating under conditions effective to produce a hydroprocessing effluent stream characterized by a reduced level of contaminants, increased wax content, reduced correction factor. - 28 038171 US Bureau of Geology and an increased gravity in degrees of the American Petroleum Institute, while the hydroprocessing zone operates at temperatures ranging from 300 to 450 ° C, pressures in the range from 30 to 180 bar and hourly space velocity of the liquid from 0, 1 to 10 h '¹; (d) thermally cracking the hydrotreated effluent stream in the presence of steam to produce a mixed product stream; (e) separating the mixed thermal cracking product stream to produce hydrogen, olefins and aromatics, and pyrolysis fuel oil; (f) purifying the hydrogen separated in step (e) and recycling it to step (c); (g) recovering olefins and aromatics from the split mixed thermal cracker stream from step (e) and (h) recovering a pyrolysis fuel oil stream from the split mixed thermal cracked product stream from step (e) and combining it with the bottom phase asphalt from step (b) and recover the resulting combined stream as a fuel oil mixture; wherein step (d) of thermal cracking includes heating the hydroprocessing outlet stream in the convection section of the steam pyrolysis zone, separating the heated hydroprocessed outlet stream into a vapor fraction and a liquid fraction using a vapor-liquid separation device based on physical and mechanical separation, passing the vapor fraction into the pyrolysis section of the steam zone pyrolysis and tapping a liquid fraction, the tapped liquid fraction being mixed with the pyrolysis fuel oil recovered in step (h); moreover, the outlet streams of the reactor of the hydroprocessing zone are separated in a high-pressure separator to extract the gas part, which is purified and recirculated to the hydroprocessing zone as an additional source of hydrogen, and the liquid part, and said liquid part is separated from the high-pressure separator in the low-pressure separator into the gas part and a liquid portion, wherein the liquid portion from the low pressure separator is said hydroprocessing thermally cracked effluent stream, and the gas portion from the low pressure separator is combined with said mixed product stream after the steam pyrolysis zone and prior to separation in step (e); wherein said vapor-liquid separation device includes an element for pre-swirling the flow having an inlet section and a transition section, wherein the inlet section has an inlet for receiving the flowing fluid mixture and a curved circuit, a controlled cyclone section including an inlet adjacent to the element for pre-swirling the flow due to the convergence of the curved contour and the cyclone section, the riser section at the upper end of the cyclone element through which the vapors pass; and a liquid collector / sump section through which the liquid passes; the method comprising the steps of compressing the mixed thermal cracked product stream obtained in step (d) using a plurality of compression stages; subjecting the compressed thermal cracked mixed product stream to a caustic treatment to obtain a thermal cracked mixed product stream with reduced levels of hydrogen sulfide and carbon dioxide; compressing the mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; dehydration of the compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide; recovering hydrogen from the stream of dehydrated compressed mixed thermal cracking product with reduced levels of hydrogen sulfide and carbon dioxide; and recovering olefins and aromatics in step (g) and pyrolysis fuel oils in step (h) from the residual stream of the dehydrated compressed mixed thermal cracked product with reduced levels of hydrogen sulfide and carbon dioxide; wherein step (f) includes purifying recovered hydrogen from the dehydrated compressed mixed thermal cracking product stream with reduced levels of hydrogen sulfide and carbon dioxide for recycling to the hydroprocessing zone; wherein the recovery of hydrogen from the dehydrated compressed mixed thermal cracker stream with reduced hydrogen sulfide and carbon dioxide content also includes a separate methane recovery step for use as fuel for burners and / or heaters in the thermal cracking step. 2. An integrated process according to claim 1, wherein the hydroprocessing zone comprises one or more beds containing an effective amount of a hydrodemetallization catalyst and one or more beds containing an effective amount of a hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization and / or hydrocracking functions. 3. The integrated process of claim 1, wherein the hydroprocessing zone comprises more than two catalyst beds. 4. The integrated method of claim 1, wherein the hydroprocessing zone comprises a plurality of reactions - 29 038171 onny tanks, each of which contains one or more catalyst beds with different functions.