US20230416620A1

US20230416620A1 - Integrated hydrocracking process to produce light olefins, aromatics, and lubricating base oils from crude oil

Info

Publication number: US20230416620A1
Application number: US17/768,738
Authority: US
Inventors: Nicolas Goyheneix; Mohammed AL DOSSARY
Original assignee: SABIC Global Technologies BV; Saudi Arabian Oil Co
Current assignee: SABIC Global Technologies BV; Aramco Overseas Co BV; Saudi Arabian Oil Co
Priority date: 2019-10-22
Filing date: 2020-10-20
Publication date: 2023-12-28
Also published as: KR20220159944A; JP2022553063A; WO2021079272A1; CN114729281A; EP4048763A1

Abstract

A method of producing one or more olefins and one or more lubricating base oils is disclosed. The method includes hydrocracking hydrocarbons of a hydrocarbon feed stream that include vacuum gasoil to produce a stream that includes hydrocracked hydrocarbons. The method further includes fractionating the stream that includes hydrocracked hydrocarbons to form intermediate streams. The method further includes steam cracking one or more of the intermediate streams to produce at least one olefin and processing one or more of the intermediate streams to produce at least one lubricating base oil.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 62/924,409, filed Oct. 22, 2019, the entire contents of which are hereby incorporated by reference in their entirety.

FIELD OF INVENTION

The present invention generally relates to systems and methods for producing high-value chemicals from hydrocarbon streams. More specifically, the present invention relates to integrated hydrocracking processes for producing chemicals from hydrocarbon streams including crude oil.

BACKGROUND OF THE INVENTION

Light olefins (C₂to C₄olefins) are building blocks for many chemical processes. Light olefins are used to produce polyethylene, polypropylene, ethylene oxide, ethylene chloride, propylene oxide, and acrylic acid, which, in turn, are used in a wide variety of industries such as the plastic processing, construction, textile, and automotive industries. BTX (benzene, toluene, and xylene) are a group aromatics that are used in many different areas of the chemical industry, especially the plastic and polymer sectors. For instance, benzene is a precursor for producing polystyrene, phenolic resins, polycarbonate, and nylon. Toluene is used for producing polyurethane and as a gasoline component. Xylene is feedstock for producing polyester fibers and phthalic anhydride. Lube base oils are a group of oils that are used to manufacture products including lubricating greases, motor oil and metal processing fluids.
Conventionally, light olefins and BTX are produced from light distillates, obtained from crude oil. Lube base oils, on the other hand, is produced from specific heavier fractions of crude oil. More particularly, conventional methods of lube base oil production are generally integrated with fuel production processes, in which straight run vacuum gasoils and/or vacuum gasoils produced by hydrocracking vacuum residue are hydrocracked to produce unconverted oil as feed for lube oil production. However, currently, the production of light olefins and BTX and the production of lube base oils are separated from each other, resulting in limited overall production efficiency from crude oil and limited control of the product ratio of light olefins and BTX to lube base oils. Furthermore, as the hydrocracking units for processing vacuum oils are designed for high production of transportation fuels and are operated with high severity, the resulting unconverted oil often contains too much aromatics to be used for lubricating base oil production and has to be used as low-value fuel oil.
Overall, while methods of producing lube base oils, light olefins, and BTX exist, the need for improvements in this field persists in light of at least the aforementioned drawbacks for the methods.

BRIEF SUMMARY OF THE INVENTION

A solution to at least some of the above-mentioned problems associated with the production process for light olefins and BTX, and/or lube base oils from crude oil has been discovered. The solution resides in a method of producing olefins and/or aromatics and lubricating base oils in an integrated production system. Notably, the products including naphtha and/or LPG produced from hydrocracking vacuum oils are further used to produce light olefins and/or BTX, increasing the overall production efficiency from crude oil. Additionally, this method uses both a partial conversion hydrocracker with a limited hydrocracking severity and a maximum conversion cracker with a high hydrocracking severity. Thus, the composition of unconverted oil produced via hydrocracking as feedstock of lube base oils can be optimized, resulting in high lube oil production and minimized production of low value fuel oil. Therefore, the method of the present invention provides a technical solution to at least some of the problems associated with the currently available methods for producing lubricating base oils and/or light olefins and BTX mentioned above.
Embodiments of the invention include a method of producing olefins and/or aromatics and lubricating base oils. The method comprises hydrocracking a vacuum residue stream to produce a first stream comprising gasoil and a second stream comprising heavy unconverted oil. The method comprises de-asphalting the second stream to produce a third stream comprising de-asphalted oil. The method comprises processing a first portion of the third stream to produce one or more lubricating base oils. The processing of the first portion of the third stream comprises subjecting the first portion of the third stream to partial conversion hydrocracking conditions. The method comprises processing at least a portion of the first stream to produce one or more olefins and/or one or more aromatics. The processing of the at least a portion of the first stream comprises subjecting the at least a portion of the first stream to maximum conversion hydrocracking conditions.
Embodiments of the invention include a method of producing olefins and/or aromatics and lubricating base oils. The method comprises hydrocracking a vacuum residue stream to produce a first stream comprising gasoil and a second stream comprising heavy unconverted oil. The method comprises de-asphalting, in a de-asphalting unit, the second stream to produce a third stream comprising de-asphalted oil. The method comprises processing a first portion of the third stream to produce one or more lubricating base oils. The processing of the first portion of the third stream comprises subjecting the first portion of the third stream, in a first hydrocracker, to partial conversion hydrocracking conditions. The method comprises processing a second portion of the third stream to produce one or more olefins and/or one or more aromatics. The processing of the second portion of the third stream comprises subjecting the second portion of the third stream, in a second hydrocracker, to maximum conversion hydrocracking conditions. The method comprises flowing a fourth stream comprising a heavy fraction from the second hydrocracker to the de-asphalting unit.
Embodiments of the invention include a method of producing olefins and/or aromatics and lubricating base oils. The method comprises hydrocracking a vacuum residue stream to produce a first stream comprising gasoil and a second stream comprising heavy unconverted oil. The method comprises de-asphalting, in a de-asphalting unit, the second stream to produce a third stream comprising de-asphalted oil. The de-asphalting comprises contacting the second stream with one or more of: propane, butane, and pentane. The method comprises processing, in a first hydrocracker, a first portion of the third stream to produce one or more lubricating base oils. The processing of the first portion of the third stream comprises subjecting the first portion of the third stream to partial conversion hydrocracking conditions. The method comprises processing at least a portion of the first stream to produce one or more olefins and/or one or more aromatics. The processing of the at least a portion of the first stream comprises subjecting the at least a portion of the first stream to maximum conversion hydrocracking conditions. The method comprises processing a second portion of the third stream to produce one or more olefins and/or one or more aromatics. The processing of the second portion of the third stream comprises subjecting the second portion of the third stream to maximum conversion hydrocracking conditions. The method comprises flowing a fourth stream comprising a heavy fraction from the second hydrocracker to the de-asphalting unit.
The following includes definitions of various terms and phrases used throughout this specification.
The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.
The terms “wt. %”, “vol. %” or “mol. %” refer to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol. % of component.
The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification, include any measurable decrease or complete inhibition to achieve a desired result.
The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
The use of the words “a” or “an” when used in conjunction with the term “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The process of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc., disclosed throughout the specification.
The phrase “middle distillate” refers to any of kerosene, jet fuel, and diesel. Kerosene is a hydrocarbon liquid having a boiling range of 180 to 260° C. Jet fuel is a hydrocarbon liquid having a boiling range of 180 to 260° C. Jet fuel is the name of the final product using the kerosene cut. Diesel is a hydrocarbon liquid having a boiling range of 260 to 340° C. Light gasoil is a hydrocarbon liquid having a boiling range of 260 to 340° C. Heavy gasoil is a hydrocarbon liquid having a boiling range of 340 to 365° C.
The phrase “crude oil” refers to an unrefined petroleum product having naturally occurring hydrocarbons and other organic materials. An “unrefined petroleum product,” in this context, means a petroleum product that has not been subjected to a distillation process to produce products such as gasoline, naphtha, kerosene, gasoil, and residue. Refining in this context does not include pre-treatment of crude oil that does not make such products. Thus, crude oil, as used herein, includes petroleum products that have been subjected to a selection from water-oil separation, gas-oil separation, desalting, stabilization, and combinations thereof.
The term “primarily,” as that term is used in the specification and/or claims, means greater than any of 50 wt. %, 50 mol. %, and 50 vol. %. For example, “primarily” may include 50.1 wt. % to 100 wt. % and all values and ranges there between, 50.1 mol. % to 100 mol. % and all values and ranges there between, or 50.1 vol. % to 100 vol. % and all values and ranges there between.
Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

FIG. 1A shows a schematic diagram of a system for producing lubricating base oils, light olefins and BTX from vacuum gasoils and vacuum residue, according to embodiments of the invention;

FIG. 1B shows a schematic diagram of a system for producing lubricating base oils and light olefins, and BTX from vacuum gasoils and vacuum residue, where the vacuum gasoil and vacuum residue are produced from a crude oil distillation unit; and

FIG. 2 shows a schematic flowchart of a method of producing lubricating base oils, light olefins and BTX, according to embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Currently, light olefins, BTX, and lube base oils can be produced from fractions of crude oil. However, the production processes for light olefins, BTX and lube base oils are not efficiently integrated, resulting in limited overall production efficiency from crude oil and limited control of the product ratio of light olefins and BTX to lube base oils. Moreover, the conventional hydrocracking units are designed for high production of transportation fuels and are operated with high severity. Therefore, the unconverted oil produced from these conventional hydrocracking units often has high aromatics content, which prevents it from being used for lube oil production. The present invention provides a solution to these problems. The solution is premised on a method of producing light olefins, BTX, and lubricating base oils in an integrated system for processing crude oil fractions. This can be beneficial for improving overall production efficiency for lubricating base oils, light olefins, and BTX from crude oil. Furthermore, this method uses a partial conversion hydrocracking unit for processing vacuum gasoil and/or de-asphalted oil, thus preventing the production of unconverted oil that has high aromatic content and so it is unusable for producing lubricating base oils. Moreover, in the discovered method, the amount of the produced de-asphalted oil feeding into the partial conversion hydrocracking unit and/or a maximum conversion hydrocracking unit can be varied to adjust the product ratio of lubricating base oils to light olefins and BTX, thereby increasing product flexibility. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.
A. System for Producing Lubricating Base Oils, Light Olefins and/or BTX
In embodiments of the invention, the system for producing lubricating base oils, light olefins, and/or BTX can include a residue hydrocracking unit, a de-asphalting unit, a partial conversion hydrocracking unit, a maximum conversion hydrocracking unit, a lube base oil processing unit, and a steam cracking unit. With reference to FIG. 1A, a schematic diagram is shown for system 100, which is capable of producing lubricating base oils, light olefins, and BTX with improved production efficiency and adjustable product ratio of lubricating base oils to light olefins and BTX, compared to conventional methods.
According to embodiments of the invention, system 100 comprises residue hydrocracking unit 101 configured to hydrocrack hydrocarbons of vacuum residue stream 10 to produce first stream 11 comprising gasoil and second stream 12 comprising heavy unconverted oil. In embodiments of the invention, residue hydrocracking unit 101 comprises a fixed bed reactor, a ebullated bed reactor, a slurry reactor, or combinations thereof. Residue hydrocracking unit 101 may include a catalyst comprising one or more of various transition metals, or metal sulfides with the solid support including alumina, silica, alumina-silica, magnesia, zeolites, or combinations thereof. In embodiments of the invention, the gasoil of first stream 11 has a boiling range of 240 to 550° C. The heavy unconverted oil may have a boiling range of 550 to 800° C.
According to embodiments of the invention, an outlet of residue hydrocracking unit 101 is in fluid communication with an inlet of de-asphalting unit 102 such that second stream 12 comprising heavy unconverted oil flows from residue hydrocracking unit 101 to de-asphalting unit 102. De-asphalting unit 102 may be configured to separate unconverted oil of second stream 12 to produce third stream 13 comprising de-asphalted oil and tenth stream 20 comprising pitch. In embodiments of the invention, de-asphalting unit 102 includes a solvent de-asphalting unit. Exemplary solvents used in the solvent de-asphalting unit may include propane, butane, pentane, and combinations thereof. De-asphalted oil of third stream 13 may comprise primarily hydrocarbons with boiling points above 400° C.
According to embodiments of the invention, a second outlet of residue hydrocracking unit 101 is in fluid communication with an inlet of maximum conversion hydrocracking unit 103 such that gasoil of first stream 11 flows from residue hydrocracking unit 101 to maximum conversion hydrocracking unit 103. An outlet of de-asphalting unit 102 may be in fluid communication with maximum conversion hydrocracking unit 103 such that at least a portion of third stream 13 flows from de-asphalting unit 102 to maximum conversion hydrocracking unit 103. In embodiments of the invention, maximum conversion hydrocracking unit 103 is configured to hydrocrack gasoil of first stream 11 and/or a portion of the unconverted oil of third stream 13 in the presence of hydrogen and a second catalyst to produce fifth stream 15 comprising naphtha and sixth stream 16 comprising diesel. The second catalyst may include one or more of various transition metals, or metal sulfides with a solid support including alumina, silica, alumina-silica, magnesia, zeolites, or combinations thereof. In embodiments of the invention, maximum conversion hydrocracking unit 103 is configured to hydrocrack hydrocarbons such that remaining heavy hydrocarbons exiting maximum conversion hydrocracking unit 103 comprise less than 10 wt. % heavy hydrocarbons that have a boiling range of greater than 400° C. Maximum conversion hydrocracking unit 103 may include more than one reaction stages so as to maximize the conversion rate of heavy hydrocarbons with a boiling range of greater than 550° C. into lighter hydrocarbons. In embodiments of the invention, an outlet of maximum conversion hydrocracking unit 103 may be in fluid communication with de-asphalting unit 102 such that fourth stream 14 comprising heavy hydrocracker bleed flows from maximum conversion hydrocracking unit 103 to de-asphalting unit 102. Heavy hydrocracker bleed of fourth stream 14 may comprise primarily polyaromatic hydrocarbons and other hydrocarbons with a boiling range of above 350° C., collectively.
According to embodiments of the invention, an outlet of de-asphalting unit 102 may be in fluid communication with an inlet of partial conversion hydrocracking unit 104 such that de-asphalted oil of a first portion of third stream 13 flows from de-asphalting unit 102 to partial conversion hydrocracking unit 104. In embodiments of the invention, vacuum gasoil feed stream 22 comprising light and heavy vacuum gasoils is fed into partial conversion hydrocracking unit 104. Partial conversion hydrocracking unit 104 may be configured to process hydrocarbons of third stream 13 and/or vacuum gasoil feed stream 22 in the presence of hydrogen and a third catalyst to produce seventh stream 17 comprising naphtha, eight stream 18 comprising diesel, and ninth stream 19 comprising white unconverted oil. Exemplary third catalyst may include one or more of various transition metals, or metal sulfides with a solid support including alumina, silica, alumina-silica, magnesia, and zeolites, and combinations thereof. In embodiments of the invention, partial conversion hydrocracking unit 104 is adapted to process heavy hydrocarbons such that hydrocarbons exiting partial conversion hydrocracking unit 104 contain 10 to 40 wt. % heavy hydrocarbons having a boiling range of greater than 400° C. In embodiments of the invention, partial conversion hydrocracking unit 104 comprises a single reaction stage followed by a separation unit. In embodiments of the invention, at least a portion of vacuum gasoil feed stream 22 can be fed into maximum conversion hydrocracking unit 103 for producing naphtha and diesel.
According to embodiments of the invention, an outlet of partial conversion hydrocracking unit 104 is in fluid communication with an inlet of lube processing unit 105 such that white unconverted oil of ninth stream 19 flows from partial conversion hydrocracking unit 104 to lube processing unit 105. In embodiments of the invention, lube processing unit 105 is configured to process white unconverted oil of ninth stream 19 under hydroprocessing conditions sufficient to produce the lubricating base oils. Lube processing unit 105 may include a hydrotreater or hydrofinisher. According to embodiments of the invention, system 100 comprises steam cracking complex 106 configured to steam-crack naphtha of seventh stream 17 and/or fifth stream 15 to produce light olefins, BTX, C₄hydrocarbons, and/or pyrolysis gasoline. In embodiments of the invention, system 100 is configured to control a ratio of lubricating base oil to light olefins and BTX. In embodiments of the invention, lubricating base oil comprises some paraffinic hydrocarbons. Production of heavy lubricating base oil can be increased by increasing the amount of de-asphalted oil of third stream 13 flowed into partial conversion hydrocracking unit 104. Production of light olefins and BTX can be increased by increasing the amount of de-asphalted oil of third stream 13 flowed into maximum conversion hydrocracking unit 103.
As shown in FIG. 1B, system 100′ may include all the units and streams of system 100. System 100′ may further include distillation unit 107 configured to process crude oil to produce vacuum gasoil feed stream 22, and vacuum residue stream 10, and straight-run naphtha stream 24. In embodiments of the invention, distillation unit 107 includes an atmospheric distillation column and/or a vacuum distillation column. An outlet of distillation unit 107 may be in fluid communication with steam cracking unit 106 such that straight-run naphtha stream 24 flows from distillation unit 107 to steam cracking unit 106. According to embodiments of the invention, residue hydrocracking unit 103 of system 100′ is further configured to produce naphtha. Steam cracking unit 106 of system 100′ may be configured to further produce pyrolysis oil stream 23 comprising pyrolysis oil. In embodiments of the invention, an outlet of steam cracking unit 106 is in fluid communication with an inlet of residue hydrocracking unit 101 such that pyrolysis oil stream 23 flows from steam cracking unit 106 to residue hydrocracking unit 101.

B. Method of Producing Lubricating Oil, Light Olefins, and BTX

Methods for producing lubricating base oils, light olefins, and BTX from crude oil fractions have been discovered. The methods may include processing vacuum residue and vacuum gasoil in an integrated system comprising a residue hydrocracking unit, a partial conversion hydrocracking unit, and a maximum hydrocracking unit to maximize the production efficiency of lubricating base oil, light olefins, and BTX from vacuum residue and vacuum gasoil. As shown in FIG. 2 , embodiments of the invention include method 200 for producing lubricating base oils, light olefins, and BTX. Method 200 may be implemented by system 100, as shown in FIG. 1A and/or system 100′ as shown in FIG. 1B and described above.
According to embodiments of the invention, as shown in block 201, method 200 comprises hydrocracking, in residue hydrocracking unit 101, vacuum residue stream 10 to produce first stream 11 comprising gasoil and second stream 12 comprising heavy unconverted oil. The hydrocracking in residue hydrocracking unit 101 at block 201 may further produce naphtha. In embodiments of the invention, vacuum residue stream 10 is obtained by vacuum distilling an atmospheric residue fraction of crude oil. The atmospheric residue may have a boiling range of 350 to 800° C. The hydrocracking at block 201 may be conducted under first hydrocracking conditions including a hydrocracking temperature of 200 to 450° C. and a hydrocracking pressure of 20 to 220 bar. The first hydrocracking conditions at block 201 may further include a weight hourly space velocity of 0.1 to 20 hr⁻¹and all ranges and values there between including ranges of 0.1 to 0.2 hr⁻¹, 0.2 to 0.4 hr⁻¹, 0.4 to 0.6 hr⁻¹, 0.6 to 0.8 hr⁻¹, 0.8 to 1.0 hr⁻¹, 1.0 to 2.0 hr⁻¹, 2.0 to 4.0 hr⁻¹, 4.0 to 6.0 hr⁻¹, 6.0 to 8.0 hr⁻¹8.0 to 10.0 hr⁻¹, 10.0 to 12.0 hr⁻¹, 12.0 to 14.0 hr⁻¹, 14.0 to 16.0 hr⁻¹, 16.0 to 18.0 hr⁻¹, and 18.0 to 20.0 hr⁻¹. The first hydrocracking conditions at block 201 may further still include a hydrogen to feed mass ratio of 0.1% to 15% and all ranges and values there between including ranges of 0.1 to 0.2%, 0.2 to 0.4%, 0.4 to 0.6%, 0.6 to 0.8%, 0.8 to 1.0%, 1.0 to 3.0%, 3.0 to 6.0%, 6.0 to 9.0%, 9.0 to 12.0%, and 12.0 to 15.0%.
According to embodiments of the invention, as shown in block 202, method 200 comprises de-asphalting, in de-asphalting unit 102, second stream 12 to produce third stream 13 comprising de-asphalted oil. In embodiments of the invention, the de-asphalting at block 202 includes, in de-asphalting unit 102, contacting second stream 12 with a solvent. Exemplary solvents may include propane, butane, pentane, and combinations thereof. In embodiments of the invention, de-asphalting at block 202 may be conducted at a hydrocarbon (second stream 12) to solvent ratio in a range of 0.5 to 20 and all ranges and values there between including ranges of 0.5 to 1.0, 1.0 to 2.0, 2.0 to 4.0, 4.0 to 6.0, 6.0 to 8.0, 8.0 to 10, to 12, 12 to 14, 14 to 16, 16 to 18, and 18 to 20. The de-asphalting, at block 202 may further produce tenth stream 20 comprising pitch.
According to embodiments of the invention, as shown in block 203, method 200 comprises processing, in partial conversion hydrocracking unit 104, at least a first portion of third stream 13 to produce ninth stream 19 comprising white unconverted oil. Processing at block 203 may further produce eight stream 18 comprising diesel and seventh stream 17 comprising primarily naphtha. Processing at block 203 may further still produce liquefied petroleum gas (LPG), naphtha, or combinations thereof. In embodiments of the invention, the processing at block 203 comprises subjecting the first portion of third stream 13 to partial conversion hydrocracking conditions. The partial conversion hydrocracking conditions at block 203 may include a hydrocracking temperature of 300 to 450° C. and all ranges and values there between including ranges of 300 to 310° C., 310 to 320° C., 320 to 330° C., 330 to 340° C., 340 to 350° C., 350 to 360° C., 360 to 370° C., 370 to 380° C., 380 to 390° C., 390 to 400° C., 400 to 410° C., 410 to 420° C., 420 to 430° C., 430 to 440° C., and 440 to 450° C. The partial conversion hydrocracking conditions at block 203 may include a hydrocracking pressure of 80 to 200 bar and all ranges and values there between including ranges of 80 to 100 bar, 100 to 120 bar, 120 to 140 bar, 140 to 160 bar, 160 to 180 bar, and 180 to 200 bar. The partial conversion hydrocracking conditions at block 203 may further include a weight hourly space velocity of 0.05 to 10 hr⁻¹and all ranges and values there between including ranges of 0.05 to 0.06 hr⁻¹, 0.06 to 0.07 hr⁻¹, 0.07 to 0.08 hr⁻¹, 0.08 to 0.09 hr⁻¹, 0.09 to 0.10 hr⁻¹, 0.10 to 0.20 hr⁻¹, 0.20 to 0.30 hr⁻¹, 0.30 to 0.40 hr⁻¹, 0.40 to 0.50 hr⁻¹, 0.50 to 0.60 hr⁻¹, 0.60 to 0.70 hr⁻¹, 0.70 to 0.80 hr⁻¹, 0.80 to 0.90 hr⁻¹, 0.90 to 1.0 hr⁻¹, 1.0 to 2.0 hr⁻¹, 2.0 to 3.0 hr⁻¹, 3.0 to 4.0 hr⁻¹, 4.0 to 5.0 hr⁻¹, 5.0 to 6.0 hr⁻¹, 6.0 to 7.0 hr⁻¹, 7.0 to 8.0 hr⁻¹, 8.0 to 9.0 hr⁻¹, and 9.0 to 10.0 hr⁻¹. The partial conversion hydrocracking conditions at block 203 may further still include a hydrogen to hydrogen mass ratio in a range of 0.1% to 15% and all ranges of values there between including ranges of 0.1 to 0.2%, 0.2 to 0.4%, 0.4 to 0.6%, 0.6 to 0.8%, 0.8 to 1.0%, 1.0 to 3.0%, 3.0 to 6.0%, 6.0 to 9.0%, 9.0 to 12.0%, and 12.0 to 15.0%. In embodiments of the invention, at least a portion of vacuum gasoil feed stream 22 may be fed to partial conversion hydrocracker 104 for producing additional naphtha, diesel, white unconverted oil, or combinations thereof.
According to embodiments of the invention, as shown in block 204, method 200 includes processing ninth stream 19 under hydroprocessing conditions sufficient to produce one or more lubricating base oils. The one or more lubricating oils may include paraffinic hydrocarbons. In embodiments of the invention, hydroprocessing conditions include a hydroprocessing temperature of 200 to 450° C., a hydroprocessing pressure of 20 to 220 bar, a weight hourly space velocity of 0.1 to 20 hr⁻¹, and a mass ratio of hydrogen to hydrocarbon in a range of 0.1% to 15%. The processing at block 204 may further produce LPG, naphtha, or combinations thereof.
According to embodiments of the invention, as shown in block 205, method 200 includes processing, in maximum conversion hydrocracking unit 103, at least a portion of first stream 11 to produce fifth stream 15 comprising primarily naphtha and sixth stream 16 comprising diesel. In embodiments of the invention, at least a second portion of third stream 13 is processed in maximum conversion hydrocracking unit 103 for producing additional naphtha in fifth stream 15 and additional diesel in sixth stream 16. The processing of the at least a portion of first stream 11 at block 205 may comprise subjecting the second portion of third stream 13 to maximum conversion hydrocracking conditions. The maximum conversion hydrocracking conditions of maximum conversion hydrocracking unit 103 at block 205 may include a hydrocracking temperature of 300 to 450° C. and all ranges and values there between including ranges of 300 to 310° C., 310 to 320° C., 320 to 330° C., 330 to 340° C., 340 to 350° C., 350 to 360° C., 360 to 370° C., 370 to 380° C., 380 to 390° C., 390 to 400° C., 400 to 410° C., 410 to 420° C., 420 to 430° C., 430 to 440° C., and 440 to 450° C. The maximum conversion hydrocracking conditions at block 205 may include a hydrocracking pressure of 80 to 200 bar and all ranges and values there between including ranges of 80 to 100 bar, 100 to 120 bar, 120 to 140 bar, 140 to 160 bar, 160 to 180 bar, and 180 to 200 bar. The maximum conversion hydrocracking conditions at block 205 may further include a weight hourly space velocity of 0.05 to 10 hr⁻¹and all ranges and values there between including ranges of 0.05 to 0.06 hr⁻¹, 0.06 to 0.07 hr⁻¹, 0.07 to 0.08 hr⁻¹, 0.08 to 0.09 hr⁻¹, 0.09 to 0.10 hr⁻¹, 0.10 to 0.20 hr⁻¹, 0.20 to 0.30 hr⁻¹, 0.30 to 0.40 hr⁻¹, 0.40 to 0.50 hr⁻¹, 0.50 to 0.60 hr⁻¹, 0.60 to 0.70 hr⁻¹, 0.70 to 0.80 hr⁻¹, 0.80 to 0.90 hr⁻¹, 0.90 to 1.0 hr⁻¹, 1.0 to 2.0 hr⁻¹, 2.0 to 3.0 hr⁻¹, 3.0 to 4.0 hr⁻¹, 4.0 to 5.0 hr⁻¹, 5.0 to 6.0 hr⁻¹, 6.0 to 7.0 hr⁻¹, 7.0 to 8.0 hr⁻¹, 8.0 to 9.0 hr⁻¹, 9.0 to 10.0 hr⁻¹. The maximum conversion hydrocracking conditions at block 205 may further still include a hydrogen to hydrocarbon mass ratio in a range of 0.1% to 15% and all ranges of values there between including ranges of 0.1 to 0.2%, 0.2 to 0.4%, 0.4 to 0.6%, 0.6 to 0.8%, 0.8 to 1.0%, 1.0 to 3.0%, 3.0 to 6.0%, 6.0 to 9.0%, 9.0 to 12.0%, and 12.0 to 15.0% . . . According to embodiments of the invention, as shown in block 206, method 200 includes flowing fourth stream 14 comprising heavy fraction (heavy hydrocracker bleed) from maximum conversion hydrocracking unit 103 to de-asphalting unit 102.
According to embodiments of the invention, as shown in block 207, method 200 may further include steam-cracking naphtha in steam cracking unit 106 to produce light olefins and/or BTX. In embodiments of the invention, the naphtha at block 207 may include naphtha from seventh stream 17, naphtha from fifth stream 15, naphtha from residue hydrocracking unit 101. The naphtha processed at block 207 may further include straight run naphtha produced from distilling crude oil by distillation unit 107, as shown in FIG. 1B. The distilling of crude oil may produce vacuum gasoil stream 22 and/or vacuum residue stream as shown in FIG. 1B.
In embodiments of the invention, steam cracking at block 207 is conducted at a temperature of 750 to 950° C. for a residence time of 50 to 1000 ms. In embodiments of the invention, steam cracking at block 207 is conducted at a steam to hydrocarbon ratio in a range of 0.1 to 1 and all ranges and values there between. In embodiments of the invention, steam cracking at block 207 further produces C₄hydrocarbons including n-butane, isobutane, isobutene, 1-butene, 2-butene, butadiene, or combinations thereof. Steam cracking at block 206 may further produce pyrolysis gasoline comprising BTX. In embodiments of the invention, as shown in FIG. 1B, steam cracking at block 207 may further produce pyrolysis oil stream 23 comprising primarily pyrolysis oil. Pyrolysis oil may comprise hydrocarbons having a boiling range of 200 to 700° C. In embodiments of the invention, pyrolysis oil stream 23 is fed to residue hydrocracking unit 101.
Although embodiments of the present invention have been described with reference to blocks of FIG. 2 , it should be appreciated that operation of the present invention is not limited to the particular blocks and/or the particular order of the blocks illustrated in FIG. 2 . Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of FIG. 2 .
The systems and processes described herein can also include various equipment that is not shown and is known to one of skill in the art of chemical processing. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, and the like may not be shown.
In the context of the present invention, at least the following 17 embodiments are described. Embodiment 1 is a method of producing olefins and/or aromatics and lubricating base oils. The method includes hydrocracking a vacuum residue stream to produce a first stream containing gasoil and a second stream containing heavy unconverted oil. The method further includes de-asphalting the second stream to produce a third stream containing de-asphalted oil. The method still further includes processing at least a first portion of the third stream to produce one or more lubricating base oils, wherein the processing of the first portion of the third stream includes subjecting, in a partial conversion hydrocracking unit, the first portion of the third stream to partial conversion hydrocracking conditions. The method also includes processing at least a portion of the first stream to produce one or more olefins and/or one or more aromatics, wherein the processing of the portion of the first stream includes subjecting, in a maximum conversion hydrocracking unit, the portion of the first stream to maximum conversion hydrocracking conditions. Embodiment 2 is the method of embodiment 1, further including flowing a fourth stream containing a heavy fraction from the maximum conversion hydrocracking unit to the de-asphalting unit. Embodiment 3 is the method of embodiment 2, wherein the heavy fraction of the fourth stream contains primarily polyaromatic hydrocarbons and other hydrocarbons with a boiling range of above 350° C., collectively. Embodiment 4 is the method of any of embodiments 1 to 3, wherein the de-asphalting includes contacting the second stream with one or more of propane, butane, and pentane. Embodiment 5 is the method of any of embodiments 1 to 4, wherein the de-asphalted oil contains primarily hydrocarbons with boiling points above 400° C. Embodiment 6 is the method of any of embodiments 1 to 5, wherein the partial conversion hydrocracking conditions include a reaction temperature of 300 to 450° C. and a reaction pressure of 80 to 200 bar. Embodiment 7 is the method of any of embodiments 1 to 6, wherein the partial conversion hydrocracking conditions include a weight hourly space velocity of 0.05 to 10 hr⁻¹. Embodiment 8 is the method of any of embodiments 1 to 7, wherein the maximum conversion hydrocracking conditions include a reaction temperature of 300 to 450° C. and a reaction pressure of 80 to 200 bar. Embodiment 9 is the method of any of embodiments 1 to 8, wherein the maximum conversion hydrocracking conditions include a weight hourly space velocity of 0.05 to 10 hr⁻¹. Embodiment 10 is the method of any of embodiments 1 to 9, wherein the subjecting of the first portion of the third stream to partial conversion hydrocracking conditions produces a seventh stream containing naphtha, an eighth stream containing diesel, and a ninth stream containing white unconverted oil. Embodiment 11 is the method of embodiment 10, wherein the processing of the first portion of the third stream further includes processing the ninth stream under hydroproces sing conditions sufficient to produce the one or more lubricating oils. Embodiment 12 is the method of embodiment 11, wherein the hydroprocessing conditions include a weight ratio of hydrogen to feed in a range of 0.1% to 15%. Embodiment 13 is the method of either of embodiments 11 or 12, wherein the hydroprocessing conditions include a hydroprocessing temperature of 200 to 450° C. and a hydroprocessing pressure of 20 to 200 bar. Embodiment 14 is the method of any of embodiments 1 to 13, wherein the step of subjecting the at least a portion of the first stream to maximum conversion hydrocracking conditions is adapted to produce a fifth stream containing naphtha and a sixth stream containing diesel. Embodiment 15 is the method of embodiment 14, further including subjecting, in a maximum conversion hydrocracking unit, a second portion of the third stream to the maximum conversion hydrocracking conditions to produce additional naphtha in the fifth stream and additional diesel in the sixth stream. Embodiment 16 is the method of embodiment 15, further including steam-cracking the naphtha of the fifth stream to produce the light olefins and/or BTX. Embodiment 17 is the method of any of embodiments 1 to 16, wherein the de-asphalting step further produces a tenth stream containing pitch.
Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A method of producing olefins and/or aromatics and lubricating base oils, the method comprising:

hydrocracking a vacuum residue stream to produce a first stream comprising gasoil and a second stream comprising heavy unconverted oil;

de-asphalting the second stream to produce a third stream comprising de-asphalted oil;

processing at least a first portion of the third stream to produce one or more lubricating base oils, wherein the processing of the first portion of the third stream comprises subjecting, in a partial conversion hydrocracking unit, the first portion of the third stream to partial conversion hydrocracking conditions; and

processing at least a portion of the first stream to produce one or more olefins and/or one or more aromatics, wherein the processing of the portion of the first stream comprises subjecting, in a maximum conversion hydrocracking unit, the portion of the first stream to maximum conversion hydrocracking conditions.

2. The method of claim 1, further comprising:

flowing a fourth stream comprising a heavy fraction from the maximum conversion hydrocracking unit to the de-asphalting unit.

3. The method of claim 2, wherein the heavy fraction of the fourth stream comprises primarily polyaromatic hydrocarbons and other hydrocarbons with a boiling range of above 350° C., collectively.

4. The method of claim 1, wherein the de-asphalting comprises contacting the second stream with one or more of propane, butane, and pentane.

5. The method of any of claims 1 to 2, wherein the de-asphalted oil comprises primarily hydrocarbons with boiling points above 400° C.

6. The method of claim 1, wherein the partial conversion hydrocracking conditions comprise a reaction temperature of 300 to 450° C. and a reaction pressure of 80 to 200 bar.

7. The method of claim 1, wherein the partial conversion hydrocracking conditions comprise a weight hourly space velocity of 0.05 to 10 hr⁻¹.

8. The method of claim 1, wherein the maximum conversion hydrocracking conditions comprise a reaction temperature of 300 to 450° C. and a reaction pressure of 80 to 200 bar.

9. The method of claim 1, wherein the maximum conversion hydrocracking conditions comprise a weight hourly space velocity of 0.05 to 10 hr⁻¹.

10. The method of claim 1, wherein the subjecting of the first portion of the third stream to partial conversion hydrocracking conditions produces a seventh stream comprising naphtha, an eighth stream comprising diesel, and a ninth stream comprising white unconverted oil.

11. The method of claim 10, wherein the processing of the first portion of the third stream further comprises:

processing the ninth stream under hydroprocessing conditions sufficient to produce the one or more lubricating oils.

12. The method of claim 11, wherein the hydroprocessing conditions include a weight ratio of hydrogen to feed in a range of 0.1% to 15%.

13. The method of claim 11, wherein the hydroprocessing conditions include a hydroprocessing temperature of 200 to 450° C. and a hydroprocessing pressure of 20 to 200 bar.

14. The method of claim 11, wherein the step of subjecting the at least a portion of the first stream to maximum conversion hydrocracking conditions is adapted to produce a fifth stream comprising naphtha and a sixth stream comprising diesel.

15. The method of claim 14, further comprising:

subjecting, in a maximum conversion hydrocracking unit, a second portion of the third stream to the maximum conversion hydrocracking conditions to produce additional naphtha in the fifth stream and additional diesel in the sixth stream.

16. The method of claim 15, further comprising steam-cracking the naphtha of the fifth stream to produce the light olefins and/or BTX.

17. The method of claim 1, wherein the de-asphalting step further produces a tenth stream comprising pitch.

18. The method of claim 3, wherein the de-asphalting step further produces a tenth stream comprising pitch.

19. The method of claim 4, wherein the de-asphalting step further produces a tenth stream comprising pitch.

20. The method of claim 5, wherein the de-asphalting step further produces a tenth stream comprising pitch.