Patent Description:
Light olefins (C<NUM> to C<NUM> olefins) 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.

Conventionally, light olefins and BTX is produced by steam cracking naphtha. However, naphtha is merely one of many fractions from crude oil. As the demand for light olefins and BTX have been consistently increasing, more feedstocks are needed for producing these chemicals. Furthermore, steam cracking of naphtha generally has high operating costs. One of the reasons for the high operating costs include that heavy byproducts produced by steam cracking including C<NUM>+ hydrocarbons, carbon black oil, and cracked distillates are merely used as low-value fuel.

<CIT> relates to an integrated process and system for converting crude oil to petrochemicals and fuel products.

Overall, while methods of producing light olefins and BTX via hydrocarbon stream upgrading exist, the need for improvements in this field persists in light of at least the aforementioned drawbacks for the methods.

A solution to at least some of the above-mentioned problems associated with producing light olefins and BTX via steam cracking naphtha has been discovered. The solution resides in a method of producing light olefins that includes hydrocracking vacuum residue from crude oil distillation and pyrolysis oil from steam cracking hydrocarbons to produce naphtha, which is further steam cracked to produce light olefins. This can be beneficial for fully utilizing pyrolysis oil to produce high-value products including light olefins and BTX as pyrolysis oil is conventionally used as low-value fuel oil. Furthermore, the unconverted oil produced by hydrocracking vacuum residue and/or pyrolysis oil can be deasphalted to produce deasphalted oil and pitch product. The deasphalted oil can be further hydrocracked to produce naphtha, resulting in an improved conversion rate of heavy hydrocarbons. The pitch product can be gasified to produce synthesis gas, resulting in high utilization rate of low-value hydrocarbon stream. Therefore, the method of the present invention provides a technical solution over at least some of the problems associated with the currently available methods of upgrading heavy hydrocarbon streams for light olefin production mentioned above.

The invention relates to a method of producing olefins as defined in claim <NUM>.

The terms "wt. %" 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, <NUM> moles of component in <NUM> moles of the material is <NUM> mol. % of component.

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 "crude oil," as that term is used in the specification and/or claims, 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 "vacuum gas oil," as that term is used in the specification and/or claims, refers to hydrocarbons that having a boiling range of <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>.

The term "pyrolysis oil," and its abbreviated form "py-oil," as used in the specification and/or claims, refers to a heavy hydrocarbon fraction containing C<NUM>+ hydrocarbons derived from steam cracking hydrocarbons.

The term "pyrolysis gasoline,," and its abbreviated form "py-gas," as used in the specification and/or claims refer to a C<NUM> to C<NUM> hydrocarbon fraction derived from thermal cracking products including steam cracking of hydrocarbons.

The term "vacuum residue," as that term is used in the specification and/or claims, refers to the asphaltene-containing portion of unconverted oil from hydroprocessed vacuum residue after de-asphalting process.

The term "pitch," as that term is used in the specification and/or claims, refers to the asphaltene-containing portion of unconverted oil from hydroprocessed vacuum residue after the deasphalting process.

The term "primarily," as that term is used in the specification and/or claims, means greater than any of <NUM> wt. %, <NUM> mol. %, and <NUM> vol. For example, "primarily" may include <NUM> wt. % to <NUM> wt. % and all values and ranges there between, <NUM> mol. % to <NUM> mol. % and all values and ranges there between, or <NUM> vol. % to <NUM> 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 scope of the invention as defined in the claims 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.

Currently, light olefins can be produced by steam cracking naphtha obtained from distillation of crude oil. However, more feedstocks for producing light olefins are needed as the demand for light olefins has been consistently increasing. Furthermore, steam cracking naphtha generally has a high operating cost partially because byproducts from steam cracking naphtha, including pyrolysis oil, is conventionally used as low-value fuel oil. The present invention provides a solution to at least some of these problems. The solution is premised on a method that comprises hydrocracking both vacuum residue from crude oil distillation and deasphalted pyrolysis oil from steam cracking naphtha to produce at least some additional naphtha, which can be used as additional feedstock for steam cracking. Furthermore, unconverted oil produced in the hydrocracking process can be further deasphalted to produce deasphalted oil, which can be recycled to the hydrocracking process. The pitch produced during the deasphalting process can be used to produce synthesis gas, which can be further converted to methanol. The methanol production process can be further integrated with an MTBE production unit, which uses isobutylene produced from steam cracking naphtha and the methanol to produce MTBE. Overall, this method is capable of improving the utilization rate of heavy hydrocarbon streams including vacuum residue and/or pyrolysis oil by integrating multiple refinery/petrochemical processes, thereby reducing production costs for olefins and other petrochemicals. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

In embodiments of the invention, the system for producing light olefins includes an integrated system for distilling crude oil, hydrocracking vacuum residue and pyrolysis oil, steam cracking naphtha, and producing MTBE using isobutylene from the steam cracking. With reference to <FIG>, a schematic diagram is shown of system <NUM> that is capable of producing light olefins using feedstocks produced by upgrading heavy hydrocarbons streams from refinery/petrochemical processes. According to embodiments of the diagram of <FIG>, system <NUM> may include distillation unit <NUM> configured to separate hydrocarbon feed stream <NUM> including crude oil into a plurality of streams. In embodiments of the diagram of <FIG>, the plurality of streams may include naphtha stream <NUM> and vacuum residue stream <NUM>. The plurality of streams may further include gasoline stream <NUM> and diesel stream <NUM>. In embodiments of the diagram of <FIG>, distillation unit <NUM> may comprise an atmospheric distillation column, a vacuum distillation, or combinations thereof.

In embodiments of the diagram of <FIG>, a first outlet of distillation unit <NUM> may be in fluid communication with steam cracking unit <NUM> such that naphtha stream <NUM> flows from distillation unit <NUM> to steam cracking unit <NUM>. According to embodiments of the diagram of <FIG>, steam cracking unit <NUM> may be adapted to crack naphtha under reaction conditions sufficient to produce at least some light olefins (e.g., ethylene and propylene). In embodiments of the diagram of <FIG>, effluent from steam cracking unit <NUM> may be separated into light olefins stream <NUM>, C<NUM> hydrocarbon stream <NUM>, pyrolysis gasoline stream <NUM>, pyrolysis oil stream <NUM>, or combinations thereof.

In embodiments of the diagram of <FIG>, a second outlet of distillation unit <NUM> may be in fluid communication with an inlet of hydrocracking unit <NUM> such that vacuum residue stream <NUM> flows from distillation unit <NUM> to hydrocracking unit <NUM>. In embodiments of the diagram of <FIG>, hydrocracking unit <NUM> may be adapted to hydrocrack vacuum residue of vacuum residue stream <NUM> in the presence of a catalyst under reaction conditions sufficient to produce at least some light distillate. In embodiments of the diagram of <FIG>, the light distillate may comprise at least some naphtha. According to embodiments of the diagram of <FIG>, effluent from hydrocracking unit <NUM> may further include vacuum gas oil, liquefied petroleum gas, middle distillate (including hydrocarbons in the boiling range of gasoil), unconverted oil, or combinations thereof. In embodiments of the diagram of <FIG>, the catalyst of hydrocracking unit <NUM> may include various transition metals, or metal sulfides with a solid support comprising alumina, silica, alumina-silica, magnesia and zeolites, or combinations thereof.

According to embodiments of the diagram of <FIG>, hydrocracking unit <NUM> may include a (i) hydrocracking reaction section comprising one or more hydrocrackers and (ii) a hydrocracking separation section adapted to separate effluent from hydrocracking reaction section into distillate stream <NUM> and heavy unconverted oil stream <NUM>. In embodiments of the diagram of <FIG>, a first outlet of hydrocracking separation section may be in fluid communication with an inlet of a separation unit that is adapted to further separate distillate stream <NUM> such that distillate stream <NUM> flows from hydrocracking separation section to the separation unit. In embodiments of the diagram of <FIG>, the separation unit may be distillation unit <NUM>. Distillate stream <NUM> may include light distillate, middle distillate, vacuum gasoil, or combinations thereof. In embodiments of the diagram of <FIG>, a second outlet of hydrocracking separation section may be in fluid communication with deasphalting unit <NUM> such that heavy-unconverted oil stream <NUM> flows from hydrocracking separation section to deasphalting unit <NUM>. In embodiments of the diagram of <FIG>, heavy unconverted oil stream <NUM> comprises unconverted oil from hydrocracking unit <NUM>.

According to embodiments of the diagram of <FIG>, an outlet of steam cracking unit <NUM> may be in fluid communication with deasphalting unit <NUM> such that at least a portion of pyrolysis oil stream <NUM> flows from steam cracking unit <NUM> to deasphalting unit <NUM>. Alternatively or additionally, the outlet of steam cracking unit <NUM> may be in fluid communication with an inlet of hydrocracking separation section such that at least a portion of pyrolysis oil stream <NUM> flows from steam cracking unit <NUM> to hydrocracking separation section. In embodiments of the diagram of <FIG>, deasphalting unit <NUM> may be adapted to separate asphalt from unconverted oil and/or pyrolysis oil to form streams including pitch product stream <NUM>, and/or deasphalted oil stream <NUM>. In embodiments of the diagram of <FIG>, deasphalting unit <NUM> may comprise a solvent deasphalting unit.

In embodiments of the diagram of <FIG>, a first outlet of deasphalting unit <NUM> may be in fluid communication with hydrocracking unit <NUM> such that deasphalted oil stream <NUM> flows from deasphalting unit <NUM> to hydrocracking unit <NUM>. Hydrocracking unit <NUM> may be further adapted to hydrocrack deasphalted oil stream <NUM> to produce additional light distillate, middle distillate, vacuum gasoil, unconverted oil, or combinations thereof. In the invention, as shown <FIG>, a second outlet of deasphalting unit <NUM> is in fluid communication with gasification unit <NUM> such that pitch product stream <NUM> flows from deasphalting unit <NUM> to gasification unit <NUM>. According to the invention, gasification unit <NUM> is adapted to react pitch product under reaction conditions sufficient to gasify pitch product and produce at least some synthesis gas. In the invention, an outlet of gasification unit <NUM> is in fluid communication with methanol plant <NUM> such that synthesis gas stream <NUM> flows from gasification unit <NUM> to methanol plant <NUM>.

According to the invention, methanol plant <NUM> is adapted to react carbon monoxide and hydrogen of synthesis gas stream <NUM> in the presence of a catalyst under reaction conditions sufficient to produce at least some methanol. In embodiments of the invention, methanol plant <NUM> may be further adapted to purify synthesis gas stream <NUM> and adjust the ratio between carbon monoxide and hydrogen of synthesis gas stream <NUM> for methanol production before the reaction of carbon monoxide and hydrogen. In the invention, the catalyst for catalyzing the production of methanol from synthesis gas may include metal or metal oxides including copper, zinc, other transition metals, or oxides thereof supported on a solid support including alumina, silicates, or combinations thereof.

In embodiments of the invention, an outlet of methanol plant <NUM> may be in fluid communication with MTBE unit <NUM> such that methanol stream <NUM> flows from methanol plant <NUM> to MTBE unit <NUM>. According to embodiments of the invention, an outlet of steam cracking unit <NUM> may be in fluid communication with butadiene unit <NUM> such that C<NUM> hydrocarbon stream <NUM> flows from steam cracking unit <NUM> to butadiene unit <NUM>. In embodiments of the invention, butadiene unit <NUM> may be adapted to separate butadiene from C<NUM> hydrocarbon stream <NUM> to form butadiene stream <NUM> comprising primarily butadiene, and C<NUM> raffinate stream <NUM> comprising n-butane, isobutane, <NUM>-butene, <NUM>-butene, isobutylene, or combinations thereof. In embodiments of the invention, butadiene unit <NUM> may include one or more extraction units.

In embodiments of the invention, an outlet of butadiene unit <NUM> may be in fluid communication with MTBE unit <NUM> such that C<NUM> raffinate stream <NUM> flows from butadiene unit <NUM> to MTBE unit <NUM>. According to embodiments of the invention, MTBE unit <NUM> may be adapted to react isobutylene of C<NUM> raffinate stream <NUM> with methanol of methanol stream <NUM> in the presence of a catalyst under reaction conditions to produce MTBE stream <NUM> and unreacted C<NUM> stream <NUM>. In embodiments of the invention, the catalyst adapted to catalyze production of MTBE from isobutylene and methanol may include weakly or strongly acidic ion exchange resins incorporated with acid groups comprising one or more sulfonic groups and/or one or more carboxylic groups.

Methods of producing light olefins have been discovered. The methods may include upgrading heavy hydrocarbons from refinery/petrochemical processes to provide additional feedstock for producing light olefins via steam cracking. Furthermore, the methods may integrate processes to fully utilize heavy hydrocarbons produced in various refinery/petrochemical units, resulting in reduced production cost for light olefins and/or other petrochemicals. As shown in <FIG>, embodiments outside of the invention include method <NUM> for producing light olefins. Method <NUM> may be implemented by system <NUM>, as shown in <FIG>. According to embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may comprise distilling, in distillation unit <NUM>, a feedstock comprising crude oil to produce a plurality of distilling product streams. In embodiments of the diagram of <FIG>, the distilling product streams may include naphtha stream <NUM> and vacuum residue stream <NUM>. In embodiments of the invention, the distilling product streams may further include gasoline stream <NUM> and/or diesel stream <NUM>. In embodiments of the diagram of <FIG>, the distilling at block <NUM> may be carried out at an overhead boiling range of <NUM> to <NUM> and a reboiler boiling range of <NUM> to <NUM>. The distilling at block <NUM> may be carried at a pressure of <NUM> to <NUM> bar and all ranges and values there between including <NUM> bar, <NUM> bar, <NUM> bar, <NUM> bar, <NUM> bar, <NUM> bar, <NUM> bar, and <NUM> bar.

According to embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further include steam cracking naphtha stream <NUM> in steam cracking unit <NUM> to produce a plurality of cracking product streams. In embodiments of the diagram of <FIG>, the cracking product streams may include light olefin stream <NUM>, C<NUM> hydrocarbon mixture stream <NUM>, pyrolysis oil stream <NUM>, or combinations thereof. In embodiments of the diagram of <FIG>, the cracking product streams may further include pyrolysis gasoline stream <NUM>. According to embodiments of the diagram of <FIG>, steam cracking at block <NUM> may be carried out at a temperature of <NUM> to <NUM> and all ranges and values there between including ranges of <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. The steam cracking at block <NUM> may be carried out with a steam to hydrocarbon weight ratio of <NUM> to <NUM> and all ranges and values there between including <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>. A residence time for steam cracking unit <NUM> at block <NUM> may be in a range of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. In embodiments of the diagram of <FIG>, light olefin stream <NUM> may include <NUM> to <NUM> wt. % ethylene and <NUM> to <NUM> wt. % propylene. C<NUM> hydrocarbon mixture stream <NUM> may include n-butane, isobutane, isobutylene, <NUM>-butene, <NUM>-butene, butadiene, or combinations thereof. Pyrolysis oil stream <NUM> may include benzene, toluene, xylenes, or combinations thereof.

According to embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further include hydrocracking vacuum residue stream <NUM> to produce distillate stream <NUM> having a boiling range less than vacuum residue stream and heavy unconverted oil stream <NUM> having a boiling range higher than vacuum residue stream <NUM>. In embodiments of the diagram of <FIG>, hydrocracking at block <NUM> may be carried out at a reaction temperature of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM> and <NUM> to <NUM>. A reaction pressure for hydrocracking at block <NUM> may be in a range of <NUM> to <NUM> bar and all ranges and values there between, including <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, and <NUM> to <NUM> bar. In embodiments of the diagram of <FIG>, hydrocracking at block <NUM> may be carried out at a hydrogen to hydrocarbon volumetric ratio of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. In embodiments of the diagram of <FIG>, distillate stream <NUM> may be separated in a separation unit to produce at least some naphtha, middle distillate, vacuum gas oil, or combinations thereof. In embodiments of the diagram of <FIG>, one or more of the naphtha, middle distillate, vacuum gas oil produced from separating distillate stream <NUM> may be cracked in steam cracking unit <NUM> to produce additional light olefins, additional mixed C<NUM> hydrocarbons, additional pyrolysis gasoline, additional pyrolysis oil, or combinations thereof.

According to embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further include deasphalting heavy unconverted oil stream <NUM> and/or at least a portion of pyrolysis oil stream <NUM> from steam cracking unit <NUM> in deasphalting unit <NUM> with a solvent to produce deasphalted oil stream <NUM> and pitch product stream <NUM>. In embodiments of the diagram of <FIG>, the solvent may include propane, pentane, butane, or combinations thereof. As an alternative to or in addition to flowing a portion of pyrolysis oil stream to deasphalting unit <NUM>, a portion of pyrolysis oil stream <NUM> may be flowed to the separation section of hydrocracking unit <NUM> to produce additional heavy unconverted oil and/or additional distillate stream <NUM>. The additional heavy unconverted oil may be further deasphalted in deasphalting unit <NUM>.

According to embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further comprise gasifying pitch product stream <NUM> in gasification unit <NUM> to produce synthesis gas stream <NUM> comprising primarily carbon monoxide and hydrogen, collectively. In embodiments of the diagram of <FIG>, gasifying at block <NUM> may be carried out at a temperature of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. A reaction pressure of gasification at block <NUM> may be in a range of <NUM> to <NUM> bar and all ranges and values there between, including <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, and <NUM> to <NUM> bar. In embodiments of the diagram of <FIG>, gasifying at block <NUM> may be carried out at a weight-based oxygen-to-hydrocarbon ratio of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to.

In embodiments of the diagram of <FIG>, synthesis gas stream <NUM> may comprise <NUM> to <NUM> wt. % carbon monoxide and <NUM> to <NUM> wt. % hydrogen.

In embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further comprise reacting carbon monoxide and hydrogen of synthesis gas stream <NUM> in the presence of a catalyst under reaction conditions sufficient to produce methanol (methanol stream <NUM>). In embodiments of the diagram of <FIG>, synthesis gas stream <NUM> may be purified and the carbon monoxide-to-hydrogen molar ratio of synthesis gas stream <NUM> may be adjusted before reacting at block <NUM>. In embodiments of the diagram of <FIG>, the adjusted hydrogen-to-carbon monoxide molar ratio at block <NUM> may be in a range of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. According to embodiments of the diagram of <FIG>, the reaction conditions at block <NUM> may include a reaction temperature of <NUM> to <NUM> and all ranges and values there between, including <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM> to <NUM>. The reaction conditions at block <NUM> may further include a reaction pressure of <NUM> to <NUM> bar and all ranges and values there between, including <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, <NUM> to <NUM> bar, and <NUM> to <NUM> bar. The reaction conditions at block <NUM> may further include a weight hourly space velocity of <NUM> to <NUM> hr-<NUM> and all ranges and values there between, including <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, <NUM> to <NUM> hr-<NUM>, and <NUM> to <NUM> hr-<NUM>.

In embodiments of the diagram of <FIG>, as shown in block <NUM>, method <NUM> may further include removing butadiene from C<NUM> hydrocarbon mixture stream <NUM> in butadiene unit <NUM> to produce C<NUM> raffinate stream <NUM> comprising isobutylene. In embodiments of the diagram of <FIG>, C<NUM> raffinate stream <NUM> may comprise <NUM> to <NUM> wt. % isobutylene and all ranges and values there between, including <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, <NUM> to <NUM> wt. %, and <NUM> to <NUM> wt. In embodiments of the diagram of <FIG>, removing at block <NUM> may include solvent extraction, extractive distillation, or combinations thereof.

Claim 1:
A method of producing olefins, the method comprising:
distilling (<NUM>) a feedstock (<NUM>) comprising crude oil to produce a plurality of distilling product streams comprising a naphtha stream (<NUM>) and a vacuum residue Z stream (<NUM>);
steam cracking (<NUM>) the naphtha stream to produce a plurality of cracking product streams comprising a C<NUM> to C<NUM> olefins stream (<NUM>), a mixed C<NUM> hydrocarbon stream (<NUM>), and a pyrolysis oil stream (<NUM>);
hydrocracking (<NUM>) the vacuum residue stream to produce a distillate stream (<NUM>) having a boiling range less than the vacuum residue stream and a heavy unconverted oil stream (<NUM>) having a boiling range higher than the vacuum residue stream;
deasphalting (<NUM>) the heavy unconverted oil stream and the pyrolysis oil from steam-cracking with a solvent to produce a deasphalted oil stream (<NUM>) and a pitch stream (<NUM>);
hydrocracking the deasphalted oil to produce naphtha;
gasifying (<NUM>) the pitch stream to produce a synthesis gas stream (<NUM>);
reacting (<NUM>) carbon monoxide and hydrogen of the synthesis gas stream in the presence of a catalyst under reaction conditions sufficient to produce methanol (<NUM>);
wherein the catalyst comprises metals including copper, zinc, other transitions metals, and/or oxides thereof combined with solid support including alumina, silicates, or combinations thereof.