KR20230012007A - Methods to improve the performance of downstream oil conversion - Google Patents

Abstract

The present technology provides a method for improving the performance of downstream oil conversion. Accordingly, the present technology provides methods for improving the yield of liquid hydrocarbons, inter alia, from thermal conversion processes. The method includes contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C to produce a mixture of sodium salt and converted feedstock. The hydrocarbon feedstock may comprise hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a residual microcarbon content of at least 5 wt %. The converted feedstock may include hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon content less than the residual microcarbon content in the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. there is. The method further comprises subjecting the converted feedstock to a thermal conversion process to produce a gaseous product, a purified product, and a residual product, wherein the ratio of refined product to residual product is the same for the hydrocarbon feedstock in the thermal conversion process. is greater than the ratio produced by applying

Description

Methods to improve the performance of downstream oil conversion

Cross reference to related applications

This application claims the priority of US Provisional Application No. 63/027052, filed on May 19, 2020, the contents of which are incorporated herein in their entirety.

technology field

The present technology relates to methods for improving the performance of downstream oil conversion processes by reducing sulfur and asphaltenes content as well as other impurities in hydrocarbon feedstocks. The performance of both catalytic conversion and thermal conversion can be improved.

Hydrocarbon oils, including many oil feedstocks, contain impurities that are usually difficult to remove, such as sulfur in the form of organosulfur compounds, as well as metals and other heteroatom-containing compounds that interfere with the use of hydrocarbons. Unwanted impurities present in hydrocarbon oils can concentrate in resins and asphaltenes found in vacuum resid distillation fractions, which are generally defined as boiling points above 510°C to 565°C (950°F to 1050°F). In addition, traditional refinery configurations concentrate unwanted impurities by separating high-value, low-boiling distillate fractions (gasoline, diesel, jet, and gas oil) from low-value, high-boiling bottom fractions (atmospheric and vacuum residue). The low boiling distillate fraction can be readily processed and converted to end products using established processes such as hydrotreating, alkylation, catalytic reforming, catalytic cracking, and the like. High-boiling resid streams cannot be easily processed because the excessively high metal content fouls the catalyst and the polyaromatic structure of asphaltenes prevents access to impurities.

Sulfur species present in hydrocarbons can be characterized as asphaltic sulfur (ie, sulfur-containing asphaltene species) and non-asphaltic sulfur (ie, sulfur-containing non-asphaltenic species). Non-asphaltic sulfur typically includes thiols, sulphides, benzothiophene and dibenzothiophene (DBT) derivatives, among others, and is located primarily in the vacuum residue fraction, but also saturates, aromatics and distillates located in any distillation fraction. It may also be present in the resin component. These sulfur species, especially those located in gasoline, naphtha, kerosene, diesel and gas oil fractions, can generally be removed using conventional catalytic treatment or conversion processes such as hydrotreating, hydrodesulfurization or hydrocracking. Asphaltic sulfur located in the asphaltenes in the heavy resid distillation fraction is characterized by a layer of condensed sulfur-containing polynuclear aromatic compounds bound primarily by saturated species and sulfur. DBT and DBT derivatives and sulfur bridges can account for a significant portion of asphaltic sulfur species. In addition, metals including nickel, vanadium and iron are usually concentrated in porphyrinic metal complexes located in the asphaltene fraction. Sulfur cannot be easily removed from asphaltenes without subjecting the asphaltic sulfur to harsh operating conditions.

Residue thermal or catalytic conversion units operate under harsh operating conditions, typically high temperature (>350°C/662°F), high hydrogen partial pressure (500-3000 psig), using special catalysts deactivated by metal and coke deposition. . Even after subjecting the resid stream to the most severe operating conditions, fractions of sulfur and metals are not removed and remain in the oil. As a result, the low value resid bottoms stream is either 1) converted to asphalt, 2) processed in a thermal conversion unit (such as a coker) to extract as many high value intermediates as possible, or 3) into a high sulfur bunker fuel. mixed

Surprisingly, methods have been discovered for preferentially removing sulfur and metals from sulfur-containing asphaltenes and/or converting a portion of the asphaltene fraction in a hydrocarbon feedstock to a non-asphaltenic liquid product. The process provides a converted feedstock with reduced sulfur (and other heteroatom) content and reduced metal content, particularly within the asphaltene fraction. Using this technology, impurities concentrated in the asphaltene fraction of hydrocarbon feedstocks can best be removed by contacting these feeds with sodium metal, while impurities concentrated elsewhere are best removed by conventional refining processes. can Additionally, the operation of downstream process units can be optimized by reducing the high concentration of impurities in the asphaltene fraction, improving refinery operability and profitability.

Accordingly, in a first aspect, the present technology is a method for improving the yield of liquid hydrocarbons from a thermal conversion process, comprising contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C. to produce a mixture of sodium salt and converted feedstock - the hydrocarbon feedstock having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a residual microcarbon content of at least 5 wt %. includes; The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon content less than the residual microcarbon content in the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. Ham ; and subjecting the converted feedstock to a thermal conversion process to produce a gaseous product, a purified product, and a residual product, wherein the ratio of refined product to residual product is the ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process. Greater than - provides a method, including A lower sulfur content translates into less H ₂ S to be handled by, for example, a Claus plant, lower loads on gas oil hydroprocessing and sweeter coke. Additionally, the amount of sodium metal used in the process can be varied to optimize downstream yield and economy.

In a second aspect, the present technology provides a method for producing anode grade coke from more contaminated feed than previously possible. The process comprises: contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, wherein the hydrocarbon feedstock has a sulfur content. at least 0.5 wt %, an asphaltene content of at least 1 wt %, a vanadium content of at least 15 ppm, and a residual microcarbon content of at least 5 wt %; The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content in the hydrocarbon feedstock— ; and subjecting the converted feedstock to a thermal conversion process to produce a premium anode grade coke product having less than 0.5 wt % sulfur and less than 150 ppm vanadium.

In a third aspect, the present technology provides a method for producing needle grade coke from more contaminated feed than previously possible. The method comprises: contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250° C.-500° C. to produce a mixture of sodium salt and converted feedstock, wherein the hydrocarbon feedstock has a sulfur content at least 0.5 wt %, an asphaltene content of at least 1 wt %, a nickel content of at least 10 ppm, and a residual microcarbon content of at least 5 wt %; The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content in the hydrocarbon feedstock— ; and subjecting the converted feedstock to a thermal conversion process to obtain less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10 ppm nickel, a thermal expansion coefficient greater than 2.5x10 ⁷ /°C, and 320 x 10 ⁶ Ohm- and producing a high purity needle coke product having an electrical resistivity of In.

In a fourth aspect, the technology provides a method for improving the conversion of a hydrocarbon feedstock in catalytic conversion processes. The method comprises: combining a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250° C.-500° C. to produce a mixture of sodium salt and converted feedstock, wherein the hydrocarbon feedstock has a sulfur content at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a total metal content of at least 100 ppm; The converted feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, an asphaltene concentration lower than the asphaltene concentration in the hydrocarbon feedstock, and/or a lower boiling point higher than that of the hydrocarbon feedstock. including hydrocarbons having a hydrocarbon (<538°C) to residual hydrocarbons (>538°C) ratio; optionally subjecting the converted feedstock to a thermal conversion process to provide a double converted product; and subjecting the converted feedstock or double converted feedstock to a catalytic conversion process (eg, catalytic hydroprocessing) to produce a fuel grade product without mixing or additional conversion processes. The process a) improves catalyst life, b) provides higher gasoline yields, and c) improves conversion and performance of hydrocarbon feeds, including resid streams, in downstream catalyst processing by allowing coker to be completely bypassed. do.

In a fifth aspect, the present technology provides a method for producing a low sulfur fuel grade product from an off-spec hydrocarbon feedstock with little or no blending. The method comprises: combining a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250° C.-500° C. to produce a mixture of sodium salt and converted feedstock, wherein the hydrocarbon feedstock has a sulfur content contains hydrocarbons with an asphaltene content of at least 0.5 wt% and an asphaltene content of at least 1 wt%, and does not meet one or more fuel grade specifications selected from the group consisting of viscosity, density, residual microcarbon, metal content, and cleanliness/compatibility; The converted product comprises hydrocarbons having a sulfur content of less than 0.5 wt % and meets one or more fuel grade specifications selected from the group consisting of viscosity, density, residual microcarbon, metal content and cleanliness/compatibility; The fuel grade specification is a viscosity of less than 380 cSt (@ 50C), a density of less than 991 kg/m ³ , a residual microcarbon content of less than 18 wt%, a vanadium content of less than 350 mg/kg, and a value of 1 or less as measured by ASTM D4740. It is the result of the cleanliness spot test of 2 - includes. For example, low sulfur bunker fuel may be produced through the disclosed method. In some embodiments, the product is a near fuel grade product that can be brought to specification by mixing a nominal amount of the blend stock, for example by mixing 0.5 wt%-10 wt%.

The foregoing is a summary of the disclosure and includes simplifications, generalizations, and omissions of detail where necessary. Consequently, those skilled in the art will understand that the summary is illustrative only and is not intended to be limiting in any way. As defined by the claims, other aspects, features and advantages of the devices and/or processes described herein will become apparent from the detailed description described herein and taken in conjunction with the accompanying drawings.

To illustrate how the above-cited and other advantages and features of the present disclosure may be obtained, a more detailed description of the principles outlined above is given with reference to specific embodiments illustrated in the accompanying drawings. It will be. Understanding that these drawings illustrate only illustrative embodiments of the disclosure, and thus should not be considered limiting of its scope, the principles herein are described in additional detail and detail using the accompanying drawings, and explained
1 is a flow diagram of an exemplary embodiment of a first, second, or third aspect of a method of the present technology including optional separation and electrolysis steps.
2 is a flow diagram of an exemplary embodiment of a fourth aspect of a method of the present technology including optional separation and electrolysis steps.
3 is a flow diagram of another exemplary embodiment of a fourth aspect of the method of the present technology including optional separation and electrolysis steps.
4 is a flow diagram of an exemplary embodiment of a process of the present technology including optional pretreatment steps, and optional separation and electrolysis steps, and a refinery process step.

The following terms are used throughout as defined below.

As used herein, the terms “a,” and “the” and use of similar referents in the context of describing elements (particularly in the context of the following claims) are used unless otherwise indicated in this application or clearly contradicted by the context. should be considered to cover both the singular and the plural. Recitation of ranges of values herein is merely such that each separate value is incorporated into the specification as if it were individually recited herein, and unless otherwise indicated herein, each separate value falling within the range is referred to individually. It is intended to serve as a shorthand method. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any and all examples or use of exemplary language (eg, “such as”) provided herein is merely to better illustrate the embodiments and is not intended to limit the scope of the claims unless otherwise stated. . No language in this specification should be construed as indicating that any non-claimed element is required.

As used herein, “about” will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. Where there is a use of a term that is not apparent to one skilled in the art, "about" shall mean ±10% of the specified term, given the context in which the term is used.

As used herein, “asphaltenes” refers to constituents of oil that are insoluble in any C _3-8 alkanes. Asphaltenes include polyaromatic molecules containing at least one heteroatom selected from S, N, and O. Sulfur species found in asphaltenes are collectively referred to herein as "asphaltic sulfur". All other sulfur species found in non-asphaltic fractions of hydrocarbon oils and fractions thereof are collectively referred to herein as "non-sulfuric sulfur". The latter may include, for example, thiols, sulfates, thiophenes, including benzothiophenes and dibenzothiophenes, hydrogen sulfide and other sulfides.

As used herein, "hydrocarbon feedstock" refers to any material that may be an input for a refining, conversion or other industrial process in which hydrocarbons are major constituents. Hydrocarbon feedstocks can be solid or liquid at room temperature and can include non-hydrocarbon components such as heteroatom-containing (eg, S, N, O, P, metals) organic and inorganic materials. Crude oil, refinery streams, chemical plant streams (eg steam cracked tar) and recycling plant streams (eg lubricating oil and pyrolysis oil from tires or municipal solid waste) are non-limiting examples of hydrocarbon feedstocks.

The present technology provides methods for improving the yield of downstream oil conversion processes. Accordingly, in a first aspect of the method, a method for improving the yield of liquid hydrocarbons from a thermal conversion process, comprising contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C. make it A method comprising generating a mixture of converted feedstocks is provided. The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a residual microcarbon content of at least 5 wt %. The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon content less than the residual microcarbon content in the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. do. Residual microcarbon (MCR), measured according to ASTM D4530, indicates the propensity of hydrocarbons to form carbonaceous deposits after exposure to high temperatures. MCR is numerically equivalent to, and can be used interchangeably with, Conradson carbon residue (CCR) measured according to ASTM D189. In certain embodiments, the converted feedstock has a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon content less than the residual microcarbon content in the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. Includes hydrocarbons with The converted feedstock is subjected to a thermal conversion process (eg coking or visbreaking process) to produce gaseous products (eg steam, H ₂ S, C ₁ -C ₄ saturated gas, C ₂ -C ₄ olefins). and isobutane), refined products (e.g., naphtha, diesel, gas oil, and light and heavy cycle oil) and residual products (e.g., coke or non-breaker tar), wherein refined products for residual products The ratio of is greater than the ratio of refined product to residual product produced by subjecting the hydrocarbon feedstock to the same thermal conversion process.

In a second aspect, a method for producing premium anode grade coke or needle coke is provided. The method includes contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C to produce a mixture of sodium salt and converted feedstock. The hydrocarbon feedstock includes hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, a vanadium content of at least 15 ppm, and a residual microcarbon content of at least 5 wt%. The converted feedstock includes hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. In certain embodiments, the converted feedstock has a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. contains hydrocarbons. The converted feedstock is subjected to a thermal conversion process to produce a premium anode grade coke product with less than 0.5 wt % sulfur and less than 150 ppm vanadium.

In a third aspect, a method for producing acicular coke by contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250°C-500°C. A method comprising generating a mixture of converted feedstocks is provided. the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, a nickel content of at least 10 ppm, and a residual microcarbon content of at least 5 wt%; The converted feedstock comprises hydrocarbons having a sulfur content of less than 0.5 wt%, residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, an asphaltene content of less than 0.25 wt%, and/or an ash content of <0.1 wt%. . In certain embodiments, the converted feedstock has a sulfur content of less than 0.5 wt%, a residual microcarbon less than that of the hydrocarbon feedstock, an asphaltene content of less than 0.25 wt%, and an ash content of <0.1 wt%. contains hydrocarbons with The converted feedstock is subjected to a thermal conversion process to contain less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10 ppm nickel, a thermal expansion coefficient greater than 2.5x10 ⁷ /°C, and 320 x 10 ⁶ Ohm- Produces a high purity needle coke product with an electrical resistivity of In.

In a fourth aspect, the technology provides methods for improving the conversion of a feedstock in a catalytic conversion or treatment process. The method comprises combining a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of a mixture of: a sodium salt and a converted feedstock at a temperature of 250°C-500°C; optionally further subjecting the converted feedstock to a thermal conversion process to provide a double converted product; and subjecting the converted feedstock or double converted feedstock to a catalytic conversion process (eg, catalytic hydroprocessing, fluid catalytic cracking, etc.) to produce a fuel grade product without mixing or additional conversion processes. In the process, the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a total metal content of at least 100 ppm. The converted feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, an asphaltene concentration lower than the asphaltene concentration in the hydrocarbon feedstock, and/or a lower boiling point higher than that of the hydrocarbon feedstock. Includes hydrocarbons having a hydrocarbon (<528°C) to residual hydrocarbons (>538°C) ratio. In certain embodiments, the converted feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, an asphaltene concentration lower than the asphaltene concentration in the hydrocarbon feedstock, and/or a hydrocarbon Contains hydrocarbons with a higher ratio of low boiling hydrocarbons (<538°C) to residual hydrocarbons (>538°C) than in the feedstock.

In a fourth aspect, when the converted feedstock has a residual microcarbon content of at least 5 wt%, the method subject the converted feedstock to a thermal conversion process (e.g., in a coker) to produce a double converted feedstock and providing a solid coke product. In these embodiments, the double converted product has an impurity concentration lower than the impurity concentration in the hydrocarbon feedstock, and a higher ratio of low boiling hydrocarbons (<538 °C) to high boiling residual hydrocarbons (>538 °C) in the converted feedstock. Contains liquid hydrocarbons. In certain embodiments of the fourth aspect, the fuel grade product may be gasoline, diesel, kerosene, jet fuel, petroleum naphtha, or LPG.

In a fifth aspect, the present technology provides methods for producing a low sulfur fuel grade product. The method includes combining a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of a mixture of sodium salt and converted feedstock at a temperature of 250°C-500°C. The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt % and an asphaltene content of at least 1 wt %, and at least one fuel grade selected from the group consisting of viscosity, density, residual microcarbon, metal content and cleanliness/compatibility. does not meet specifications The converted product comprises hydrocarbons having a sulfur content of less than 0.5 wt % and meets one or more fuel grade specifications selected from the group consisting of viscosity, density, residual microcarbon, metal content and cleanliness/compatibility, and Silver viscosity less than 380 cSt (@ 50C), density less than 991 kg/m ³ , residual microcarbon content less than 18 wt %, vanadium content less than 350 mg/kg and purity of 1 or 2 as measured by ASTM D4740 It is also a spot test result. In some embodiments, the converted product meets at least 2, at least 3, at least 4 or all 5 fuel grade specifications. In some embodiments, the product is obtained by mixing a nominal amount of the blendstock, for example, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt% wt%, 8 wt%, 9 wt%, or 10 wt%, or a range between and including any two of the foregoing values, such as 0.5-10 wt%, 1-10 wt% or 2- It is an almost fuel grade product that can be brought to specification by mixing 7 wt%.

In any of the embodiments of the methods described herein, the methods may further include pretreating the hydrocarbon feedstock prior to the contacting step to provide a purified feedstock and a pretreated hydrocarbon feedstock. The purified feedstock contains a lower concentration of impurities than the hydrocarbon feedstock prior to pretreatment, the pretreated hydrocarbon feedstock contains a higher concentration of impurities than the refined feedstock, and the pretreated hydrocarbon feedstock produces a converted feedstock. It is a feedstock that is applied to the contacting step to In any of the embodiments of the present methods that include a pretreatment step, the pretreatment step includes phase separation by externally applied field, separation by addition of heat, hydrogen conversion, thermal conversion, catalytic conversion or treatment, solvent extraction, solvent desorption. It may include asphalt or any two or more of these. In certain embodiments, the pretreatment step may include contacting the hydrocarbon feedstock with extrinsic hydrogen and/or a catalyst to remove one or more of sulfur, nitrogen, oxygen, metals, and asphaltenes. Examples of pretreatment steps to produce refined feedstock and pretreated hydrocarbon feedstock include atmospheric distillation, vacuum distillation, steam cracking, catalytic cracking, thermal cracking, fluid catalytic cracking (FCC), solvent deasphalting, hydrogenation desulfurization, visbreaking, pyrolysis, catalytic reforming, alkylation, and combinations of any two or more of the foregoing. It will be appreciated that certain of the foregoing methods, such as atmospheric distillation and vacuum distillation, directly yield purified feedstock and pretreated hydrocarbon feedstock, while other methods require subsequent separation steps. For example, steam cracking, catalytic cracking, thermal cracking, FCC, and pyrolysis yield a mixture of products that can be subsequently separated by distillation or other separation processes into a purified feedstock and a pretreated hydrocarbon feedstock.

In any aspects or embodiments of the present methods described herein that include a thermal conversion process, the thermal conversion process is visbreaking, retarded coking, fluid coking, Flexicoking™, pyrolysis, a variation thereof, or any two or more of these. It may be or include a combination. In certain embodiments, the thermal conversion process may be operated at a temperature of about 400 °C to about 570 °C. In certain embodiments, the thermal conversion process may be operated at a pressure of about 10 to about 200 psig. In certain embodiments, the thermal conversion process may be operated at about 450° C. to about 500° C. and about 20-100 psig, such as in a coker.

In any aspects or embodiments of the present methods described herein that include a thermal conversion process, the catalytic conversion process is fluid catalytic cracking (FCC), resid FCC, hydroprocessing, resid hydroprocessing, hydrocracking, catalyst reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, or resid upgrading/hydroconversion (e.g., ARDS®, LC-Fining®, H-Oil®), variations thereof, or combinations of any two or more thereof. can include The catalyst may include cobalt, molybdenum, nickel, tungsten, platinum, palladium, alumina, silica, zeolites, isomers thereof, oxides, sulfides, or combinations of any two or more thereof. In certain embodiments, the catalytic conversion process may be operated at a temperature of about 250°C to about 575°C. In certain embodiments, the catalytic conversion process may operate at a pressure of about 10 to about 3000 psig. In certain embodiments, the catalytic conversion process may be operated at about 400°C to about 575°C and about 1000 to about 3000 psig. In certain embodiments, the catalytic conversion process may be operated at about 450°C to about 575°C and about 15 to about 100 psig.

It will be appreciated that in any aspects or embodiments of the methods described herein, other oil refining processes such as distillation (both atmospheric or vacuum distillation) may be employed as part of the method. Alternatively, in certain aspects or embodiments, other oil refining processes may be used in place of thermal or catalytic conversion processes (eg, see FIG. 4 ).

The hydrocarbon feedstock for the present methods may be or be derived from pure crude oil (eg, petroleum, heavy oil, bitumen, shale oil, and oil shale). The hydrocarbon feedstock may also be a residual feedstock, eg, a product of a thermal cracking process. Residual feedstock may be produced by the various pretreatment processes of the art and will be referred to as "pretreated hydrocarbon feedstock", which may also be contacted with sodium metal and extrinsic capping agents. Accordingly, the pretreated feedstock may include distillation products of hydrocarbon feedstocks (atmospheric or vacuum residue, gasoline, diesel, kerosene, and gasoil), and refinery intermediate streams. In certain embodiments, the pretreated hydrocarbon feedstock is a hydrotreated product, hydrocracked resid, hydroconversion resid (e.g., LC- ^Finer® Global Lummus resid, or H- ^Oil® resid). , FCC slurry, residual FCC slurry, atmospheric or vacuum residual oil, solvent deasphalted tar, deasphalted oil, steam cracked tar, visbreaker tar, high sulfur fuel oil, low sulfur fuel oil, asphaltenes, including asphalt and coke can do. The aforementioned hydrocarbon feedstocks (including pretreated hydrocarbon feedstocks) may be derived from any geologic formation (similar, conventional or dense reservoirs, shale oil, oil shale) or geographic location (North America, South America, Middle East, etc.). In certain aspects and embodiments of the methods, particularly the second and third aspects, the hydrocarbon feedstock is present in a significant amount, e.g., at least 10 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt % of aromatic compounds.

In the methods of the present technology, the hydrocarbon feedstock includes hydrocarbons (eg, hydrocarbon oils) and impurities. Similarly, the residual feedstock also contains hydrocarbons and impurities. In some embodiments, the residual feedstock has a higher concentration of impurities than the hydrocarbon feedstock. As used herein, “impurity” refers to heteroatoms (ie, atoms other than carbon and hydrogen), such as sulfur, oxygen, nitrogen, phosphorus, and metals. Impurities may be found in or include substances such as naphthenic acid, water, ammonia, hydrogen sulfide, thiols, thiophenes, benzothiophenes, porphyrins, Fe, V, Ni, and the like. In certain embodiments of the methods, the residual feedstock includes hydrocarbons having a sulfur content of at least 0.5 wt % and an asphaltene content of at least 1 wt %. Sulfur content includes asphaltic sulfur and non-asphaltic sulfur, but is measured as wt% of sulfur atoms in the feedstock. In certain embodiments, the sulfur content can range from 0.5 wt% to 15 wt%, for example 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt % or any two of the foregoing values and ranges therebetween. Accordingly, the sulfur content is, in certain embodiments, between 1 wt% and 15 wt%, between 0.5 wt% and 8 wt%, or between 1.5 wt% and 10 wt%. range can be

In the methods of the present art, asphaltene content refers to the total amount of asphaltenes in a feedstock measured as the n-pentane insoluble fraction of the feedstock. However, in some aspects or embodiments of the methods, the asphaltene content may be measured as an insoluble fraction precipitated or otherwise separated from the feedstock after it has been mixed with a sufficient amount of one or more C _3-8 alkanes. The C _3-8 alkane can be propane, butane, pentane, hexane, heptane, octane, isomers thereof, or mixtures of any two or more thereof. In certain embodiments, the asphaltene content of the feed may be defined as a component that is insoluble in heptane. A detailed discussion of the physical properties and structure of asphaltenes, and the process conditions (temperature, pressure, solvent/oil ratio) required to produce specific asphaltenes, can be found in JG Speight, "Petroleum Asphaltenes Part 1: Asphaltenes, Resins and the Structure of Petroleum”, Oil & Gas Science and Technology - Rev IFP, Vol 59 (2004) pp. 467-477, the entire disclosure of which is incorporated herein for all purposes. C7) The standard test method for determining insoluble asphaltene content is described in ASTM Standard D6560-17 and may be extended to any alkane, including pentane.

In certain embodiments of the present methods, the asphaltenes content of the hydrocarbon feedstock or residual feedstock may be at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt% or at least 5 wt%. For example, the asphaltene content can range from 1 wt% to 100 wt%, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35 , 40, 45, 50, 55, 60, 70, 80, 90, 95 or 100 wt %, or any two of the foregoing values, and between Accordingly, in certain embodiments, the asphaltene content is between 2 wt % and 100 wt %, 1 wt % and 30 wt %, 2 wt % and 30 wt %, 5 wt % and 100 wt %, 10 wt % and 10 wt %. 100 wt%, or in the range of 20 wt% to 100 wt%.

In certain embodiments of the method, it may be necessary to dilute the hydrocarbon feedstock with a diluent if the elevated asphaltene content in the hydrocarbon feedstock results in a viscosity that is too high for the sodium treatment process. Because of the aromatic nature of asphaltenes, diluents will typically include an aromatic (i.e., a compound having an aromatic ring). The diluent may be a single compound (e.g., benzene, toluene, xylene, ethylbenzene, cumene, naphthalene, 1-methylnaphthalene), a mixture of any two or more of these, or an essential oil intermediate that is aromatic (e.g., light cycle oil, reformate oil). The amount of diluent required will depend on the asphaltene content of the feedstock and the viscosity required for processing. A higher asphaltene content in the feedstock may require more diluent than a feedstock with a lower asphaltene content. It is within the skill of the art to select an appropriate amount of diluent to enable processing of the asphaltenes in the present methods.

The methods may also reduce/eliminate the naphthenic acid content and/or metal content in the converted feedstock relative to the hydrocarbon and pretreated hydrocarbon feedstock. In certain embodiments, the hydrocarbon feedstock or pretreated hydrocarbon feedstock includes (combinedly or individually) from about 1 to about 10,000 ppm metal. The metals can be native metals bound to hydrocarbon structures or residual metal fragments (eg, corrosion products or catalyst fragments) incorporated into pretreated hydrocarbon feedstocks during upstream processing. In certain embodiments, the metal is selected from the group consisting of alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids having an atomic weight of 82 or less. In certain embodiments, the metal is vanadium, nickel, iron, arsenic, lead, cadmium, copper, zinc, chromium, molybdenum, silicon, calcium, potassium, aluminum, magnesium, manganese, titanium, mercury, and any two of these. It is selected from the group of combinations of species or more. In certain embodiments, the metal is selected from the group consisting of vanadium, nickel, iron, and combinations of any two or more thereof. In certain embodiments, the metal concentration of the hydrocarbon feedstock or pretreated hydrocarbon feedstock is (combined or individually) 2 to about 10,000 ppm, about 10 to about 10,000 ppm, about 100 to about 10,000 ppm, about 100 to about 100 ppm. 5,000 ppm, about 10 to about 1,000 ppm, about 100 to about 1,000 ppm, and the like.

The methods of the present technology can upgrade employed hydrocarbons and pretreated hydrocarbon feedstocks by removal/reduction of impurities, as well as improve physical properties such as viscosity and density. The hydrocarbon feedstock or pretreated hydrocarbon feedstock may have a viscosity of 1 to 10,000,000 cSt at 50°C. For example, the viscosity is 1, 10, 25, 50, 100, 200, 300, 400, 500, 1,000, 2,000, 5,000, 10,000, 25,000, 50,000, 100,000, 500,000, 1,000,000, 2,000,000, 3,000,000, 4,000,000, 5,000,000, 6,000,000, 7,000,000, 8,000,000, or 9,000,000 cSt or inclusive and between any two of the foregoing values. Accordingly, in certain embodiments, the viscosity of the hydrocarbon feedstock or pretreated hydrocarbon feedstock may be between 100 and 10,000,000 cSt, 380 and 9,000,000 cSt, 500 and 9,000,000 cSt, or 500 and 5,000,000 cSt, among others, for example. there is.

The hydrocarbon feedstock or pretreated hydrocarbon feedstock may have a density of 800 to 800 to 1200 kg/m ³ at 15.6° C. or 60° F. For example, the density is 800, 825, 850, 875, 900, 925, 975, 1000, 1050, 1100, 1150, or 1200 kg/m ³ or any two of the foregoing values, and any two values therebetween. can Accordingly, in certain embodiments, the density can be, for example, 850 to 1200 kg/m ³ , 900 to 1200 kg/m ³ , 950 to 1200 kg/m ³ , or 925 to 1100 kg/m ³ . there is.

In the methods of the present technology, a hydrocarbon feedstock or pretreated hydrocarbon feedstock is contacted with an effective amount of sodium metal and an effective amount of an exogenous capping agent. Any suitable source of sodium metal may be used including, but not limited to, electrochemically produced sodium metal as described, for example, in US 8,088,270, incorporated herein in its entirety. "Effective amount" means the amount of a substance or agent that produces a desired result. For example, an effective amount of sodium metal in the present methods may include a stoichiometric, greater than or less than stoichiometric amount of sodium metal sufficient to reduce the amount of asphaltenes and/or sulfur in the hydrocarbon feedstock. .

Extrinsic capping agents used in the present methods are typically used to cap radicals formed when sulfur and other heteroatoms are extracted by sodium metal during the contacting step. Some feedstocks may contain inherently small amounts of natural capping agents ("endogenous capping agents"), but such amounts are insufficient to cap substantially all of the free radicals generated by the present methods. An effective amount of an exogenous (ie, added) capping agent is used in the methods, such as 1-1.5 moles of capping agent (eg, hydrogen) per mole of sulfur, nitrogen, or oxygen present may be used. Based on the disclosure herein, it is within the skill of the art to determine the effective amount of exogenous capping agent required to perform the present methods for a particular hydrocarbon feedstock or pretreated hydrocarbon feedstock used. The extrinsic capping agent may include hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethene, propene, butene, pentene, dienes, isomers thereof, or mixtures of any two or more thereof. _In certain embodiments, the extrinsic capping agent can be hydrogen and/or C _1-6 acyclic alkane and/or C _2-6 acyclic alkene or a mixture of any _two or more thereof.

The effective amount of sodium in the metallic phase used in the contacting step will depend on the hydrocarbon and the level of heteroatom, metal and asphaltene impurities in the hydrocarbon and pretreated hydrocarbon feedstock, the degree of conversion or removal desired of the impurities, the temperature used and other conditions. . In certain embodiments, more than a stoichiometric amount of sodium metal may be used to remove all or nearly all of the sulfur content, for example, 1-3 molar equivalents of sodium metal to sulfur content. In certain embodiments, the hydrocarbon feedstock or pretreated hydrocarbon feedstock contains greater than 1 molar equivalent of sodium metal relative to sulfur content therein, eg, 1.1, 1.15, 1.2, 1.25, 1.3, 1.4, 1.5, 2 , with 2.5 or 3 molar equivalents of sodium metal.

Surprisingly, it is possible to preferentially lower the amount of asphaltic sulfur over non-sulfuric sulfur using a sub-stoichiometric ratio of metallic sodium to sulfur content (in the hydrocarbon/pretreated hydrocarbon feedstock). Accordingly, in certain embodiments, the pretreated hydrocarbon feedstock (or alternatively the hydrocarbon feedstock) may be contacted with less than a stoichiometric amount of sodium metal relative to the sulfur content therein. In the present art, it will be appreciated that the stoichiometric amount of sodium metal to sulfur content is the theoretical amount of sodium metal required to convert all of the sulfur content in the pretreated hydrocarbon (or hydrocarbon) feedstock to sodium sulfide. For example, one skilled in the art will understand that the stoichiometric amount of sodium metal required to convert all the sulfur to sodium sulfide in a feedstock containing about 1 mole of sulfur atoms is 2 moles of sodium metal. The less than stoichiometric amount of sodium metal for sulfur content in this example would be less than 2 moles, such as 1.6 moles, or 0.8 mole equivalents of sodium metal. In certain embodiments, the stoichiometric amount of sodium metal relative to sulfur content may be from 0.1 equivalent to less than 1 equivalent. Examples of such substoichiometric amounts are less than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or less than 1 equivalent of sodium metal or any two of the foregoing values and between includes Accordingly, in certain embodiments, the substoichiometric amount may range from 0.1 to 0.9 equivalents, 0.2 to 0.8 equivalents, 0.4 to 0.8 equivalents, and the like.

When the contacting step occurs at a temperature of about 250° C. to about 500° C., the sodium metal will be in a molten (ie, liquid) state. For example, the contacting step may be performed at about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, about 375°C, about 400°C, about 425°C, about 450°C, about 500°C or any of the foregoing. ranges inclusive of and between any two of the values. Accordingly, in certain embodiments, contacting may occur between about 275°C and about 425°C, or between about 300°C and about 400°C (eg, about 350°C).

In certain embodiments, the contacting step is about 400 to about 3000 psi, for example at about 400 psi, about 500 psi, about 600 psi, about 750 psi, about 1000 psi, about 1250 psi, about 1500 psi, ranges between and including about 2000 psi, about 2500 psi, about 3000 psi or any two of the foregoing values.

The reaction of sodium metal with heteroatomic contaminants in hydrocarbons/pretreated hydrocarbon feedstocks is relatively fast, complete in minutes if not seconds. Mixing a combination of metallic sodium and the feedstock results in a faster reaction rate and is common for this reaction on an industrial scale. However, certain embodiments may require extended residence times to improve the degree of conversion or to adjust operating conditions to target removal of specific heteroatom impurities. Accordingly, in certain embodiments, the contacting step is between about 1 minute and 120 minutes, such as about 1, about 5, about 7, about 9, about 10, about 15 minutes, about 30, about 45, about 60 , about 75, about 90, about 105, or about 120 minutes, or a range of time between and including any two of the foregoing values. Accordingly, in certain embodiments, the time may range from about 1 to about 60 minutes, from about 5 minutes to about 60 minutes, from about 1 to about 15 minutes, from about 60 minutes to 120 minutes, and the like.

The methods produce a converted feedstock comprising a hydrocarbon oil having a sulfur content less than that in the hydrocarbon feedstock (or pretreated hydrocarbon feedstock). In certain embodiments, the sulfur content of the converted feedstock is less than 0.5 wt%, such as about 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, 0.1 wt% or less, and 0.05 wt% or less. , or a range between and including any two of the foregoing values. The removal efficiency (conversion efficiency) of the sulfur content from the hydrocarbon or pretreated hydrocarbon feedstock is at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% compared to the converted feedstock. , at least 90 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt% or at least 100 wt%, or including any two of the above values and may range in between. When the effective amount of sodium metal is greater than the stoichiometric amount, the sulfur content conversion efficiency can be very high, for example 90% or more.

When a substoichiometric amount of sodium metal is used in the present methods (including but not limited to those of the first, second, third and fourth aspects), lower conversion efficiencies are observed, but asphaltic sulfur The sulfur content from is preferentially reduced compared to that from non-asphaltic sulfur. For example, the (total) sulfur content conversion efficiency can range from about 10% to about 80%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, or any two of the foregoing values and in between. At the same time, the corresponding sulfur content conversion efficiency of asphaltic sulfur is higher than the total sulfur conversion efficiency at each point. For example, the sulfur content conversion efficiency of asphaltic sulfur for any given feed ranges from 1% to 40% or more (e.g., 1%, 2%, 3%, 4 %, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, greater than or equal to 22%, 24%, 25%, 27%, 30%, 32%, 35%, 37%, or 40% or a range between and including any two of the foregoing values). .

The converted feedstock of the present technology has a reduced concentration of metals compared to the hydrocarbon or pretreated hydrocarbon feedstock. The metal content of the converted feedstock may be reduced by at least 20%, for example 20% to 100%, relative to the hydrocarbon feedstock or pretreated hydrocarbon feedstock. Examples of reduction of metals in the converted feedstock (either collectively or individually) compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock are 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 97%, 98%, 99%, 100%, or any two of the foregoing values and inclusive ranges therebetween. Accordingly, in certain embodiments the percent reduction may be 20% to 99%, 20% to 95%, 70% to 99% or 100%. The metal may be any of the metals disclosed herein. In some embodiments, the metal is selected from iron, vanadium, nickel or a combination of any two or more thereof. For example, the iron and vanadium content of the converted feedstock is reduced by at least 20% compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock. Similarly, in certain embodiments of the present methods, the nickel content of the converted feedstock is reduced by at least 20% relative to the hydrocarbon feedstock or pretreated hydrocarbon feedstock.

The methods also provide a converted feedstock with improved physical properties compared to hydrocarbon feedstock or pretreated hydrocarbon feedstock. However, it has been found that the physical properties of the converted feedstock of the present methods do not necessarily change proportionally with the sodium to sulfur ratio. For example, the extent of metal demetallization, particularly metals detrimental to catalyst life including iron, vanadium and nickel, will generally be greater than the extent of desulfurization for a given sodium to sulfur ratio. Example 6 demonstrates the insensitivity of sodium treatment to initial metal content, unlike catalytic conversion processes. Sodium demetalation at low sodium/total sulfur addition ratios could be highly desirable for pretreating hydrocarbon feeds with undesirably high metal content prior to catalyst conversion or treatment.

Additional physical properties that greatly reduce the value of the heavy residual feedstock are improved after treatment with sodium. Desulphurization of the asphaltene fraction occurs without hydrogen saturation observed in hydroconversion or carbon removal exhibited by thermal cracking processes. As a result, at least a portion of the asphaltene content is converted by the present methods into a converted liquid product that is soluble, stable, and desulfurized, yielding a higher value liquid product (e.g., hydrocarbon oil derived from asphaltenes). increases Accordingly, the converted feedstock produced by the present methods may have a lower asphaltene content than the hydrocarbon feedstock (or pretreated hydrocarbon feedstock). In certain embodiments, the methods convert at least some of the asphaltenes to hydrocarbon oils, such as paraffins. In certain embodiments, at least 5%, at least 10%, at least 15%, at least 20% of the asphaltenes content in the pretreated hydrocarbon feedstock is converted to liquid hydrocarbon oil in the converted feedstock. The conversion efficiency for the asphaltene content removed from the hydrocarbon or pretreated hydrocarbon feedstock depends on the amount of sodium used, but is, for example, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% %, at least 95%, up to 98%, up to 99% or even up to 99.9% or 100%, or a range between and including any two of the foregoing values (e.g., 70% to 100% , or 75% to 99.9%, etc.).

The conversion of asphaltenes to smaller lower molecular weight components with fewer attached functional groups typically reduces the viscosity by at least 40% by 5 orders of magnitude (10,000x) and from about 1 to about 1 for each wt% sulfur removed. Causes an increase in API Gravity by 3 units. In certain embodiments, the viscosity of the converted feedstock can be reduced by at least 50 cSt or more or by at least 40% at 50°C. In certain such embodiments, the viscosity is reduced by at least 100 cSt, at least 200 cSt, at least 300 cSt, or more at 50°C. For any of the hydrocarbon feedstocks or pretreated hydrocarbon feedstocks disclosed herein (reference) having a viscosity greater than 1,000 cSt, the reduction is particularly large, by at least 50%, at least 60%, at least 70%, at least 80%, a reduction in viscosity of at least 90%, at least 95%, at least 99%, or even 100% (eg, at least 40-99%). In certain embodiments, the density of the converted feedstock is reduced by about 5 to about 25 kg/m ³ per wt% reduction in sulfur content in the converted feedstock relative to the hydrocarbon feedstock or pretreated hydrocarbon feedstock. For example, the reduction in density may be about 5, about 10, about 15, about 20, about 25 kg/m ³ , or a range between and including any two of the foregoing values (eg, about 5 to about 5 kg/m 3 ). about 20 kg/m ³ or about 10 to about 25 kg/m ³ , etc.).

As noted above, in certain embodiments, the methods may include pre-treating a hydrocarbon feedstock containing an impurity prior to contacting with sodium metal. In some cases, the hydrocarbon feedstock may be pretreated to concentrate impurities in the pretreated hydrocarbon feedstock, thereby reducing the volume of the feedstock to be processed. For example, pure crude oil is one as refined feedstock and atmospheric residue (pretreated hydrocarbon feedstock) having higher sulfur content and higher asphaltene content than both of refined feedstock and pure crude oil (hydrocarbon feedstock). It can be distilled to produce more light-distillate cuts. Alternatively, the hydrocarbon feedstock can be pretreated to remove some of the undesirable impurities to provide a purified feedstock with lower concentrations of impurities and a pretreated hydrocarbon feedstock with impurities remaining after pretreatment. The pretreated hydrocarbon feedstock may contain impurities either because of the conversion level selected or because the pretreatment process is unable to remove the impurities. For example, vacuum resid may be treated in a hydroprocessing reactor (such as an LC-Fining® unit or H- ^Oil® unit) to remove sulfur and convert the resid fraction to higher value products. However, after hydroprocessing in the presence of a catalyst at operating conditions in excess of 350 C and 1500-3000 psig, recalcitrant sulfur and asphaltene fractions remain in the hydroprocessed bottoms stream. The pretreatment process may include a separation process, a thermal or catalytic conversion process or a treatment process, or a combination of any two or more of these.

In certain embodiments, the pretreatment process may include physical separation using energy (heat), phase addition (solvent or absorbent), pressure change, or application of an external field or gradient to concentrate impurities in the pretreated hydrocarbon feedstock. It may include a separation process comprising one or more. Separation processes may include gravity separation, flash evaporation, distillation, condensation, drying, liquid-liquid extraction, stripping, absorption, centrifugation, electrostatic separation, and variations thereof. The separation process includes a solvent deasphalting process, which may further include solvent deasphalting processes such as Residuum Oil Supercritical Extraction (ROSE ^® ). For example, a hydrocarbon feedstock can be desalted to remove salts and water, an API separator can be used to separate water and solids from oil, or a distillation column can be used to reduce high sulfur, high boiling point products in crude oil. Sulfur, low-boiling products can be separated. Separation processes such as adsorption, filtration, osmosis or variations thereof may also require solid formulations or barriers. Each of the disclosed separation processes produces a refined hydrocarbon feedstock having a lower concentration of impurities than the hydrocarbon feedstock and a pretreated hydrocarbon feedstock having a higher concentration of impurities than the refined feedstock. In certain embodiments, the pretreated hydrocarbon feedstock includes a higher concentration of impurities than the refined feedstock.

In certain embodiments, the pretreatment process may include thermal or catalytic processes that modify the molecular structure or exclude at least a portion of the carbon content of the hydrocarbon feedstock. Thermal conversion methods may include cokers, visbreakers or other processes that increase the yield of cracked distillate by excluding carbon as coke. Catalytic processes include fixed bed and fluidized bed processes such as but not limited to catalytic cracking (FCC or resid FCC), hydrocracking, resid hydrocracking and hydroconversion (e.g. LC Fining®, H-Oil®) can include The conversion process may be a hydroprocessing process requiring both hydrogen and a catalyst.

The pretreatment step of the methods may include a treatment process that results in hydrocarbon saturation or removal of certain impurities on a total feed basis. Accordingly, in certain embodiments, the pretreatment process is solvent deasphalting, hydrotreating, resid hydrotreating (RHT), hydrodesulfurization (RDS), hydrodesulfurization (HDM) or hydrodenitrification (HDN) or any of these. A combination of two or more may be included. Although the overall concentration of the impurity (or impurities) may be reduced, treatment processes generally include a refined feedstock having a lower concentration of impurities than the hydrocarbon feedstock and a pretreated hydrocarbon feed having a higher concentration of impurities than the refined feedstock. create raw materials Nonetheless, the concentration of impurities in the pretreated hydrocarbon feedstock may be lower than in the hydrocarbon feedstock. In addition, catalyst treatment processes are typically unable to process feedstocks with high concentrations of impurities in asphaltenes due to accelerated catalyst deactivation from metals and micro-carbon residue.

The methods of the present technology produce a mixture comprising the converted feedstock and sodium salt. The methods may further include isolating the sodium salt from the converted feedstock. Sodium salts can be very fine (eg < 10 μm) and consist of particles that cannot be completely removed by standard separation techniques (eg filtration or centrifugation). In certain embodiments, the separation comprises heating elemental sulfur and a mixture of sodium salt and converted feedstock to a temperature of about 150° C. to 500° C. to provide a sulfur treated mixture comprising an agglomerated sodium salt; and separating the agglomerated sodium salt from the sulfur treated mixture to provide a desulfurized liquid hydrocarbon and a separated sodium salt. This separation can be performed as described in US Pat. No. 10,435,631, the entire contents of which are incorporated herein for all purposes.

The methods may further include recovering metallic sodium from the separated sodium salt. In certain embodiments, the methods may further include electrolyzing the separated sodium salt to provide sodium metal. The isolated sodium salt may include one or more of sodium sulfide, sodium hydrosulfide, or sodium polysulfide. Electrolysis can be performed in an electrochemical cell according to, for example, US Patent No. 8,088,270, or US Provisional Application Serial No. 62/985,287, the entire contents of each of which are incorporated herein for all purposes. The electrochemical cell can include an anolyte compartment, a catholyte compartment, and a NaSICON membrane separating the anolyte compartment from the catholyte compartment. A cathode comprising sodium metal is disposed in the catholyte in the catholyte compartment. An anode comprising a sodium salt is placed in the anolyte in the anolyte compartment. A power source is electrically connected to the anode and cathode. In certain embodiments, the isolated sodium salt is dissolved in an organic solvent prior to electrolysis of the salt to provide sodium metal.

Current thermal and catalytic desulfurization processes produce a hydrogen sulphide by-product that must be treated in a sulfur recovery unit such as a Claus plant. Sulfur recovery units (SRUs) are very efficient, but emit sulfur emissions during operation; Accordingly, essential oil complexes are subject to strict sulfur emission limits regulated by local and national authorities. In many cases, essential oil complexes operate at or near their sulfur emission limits. Desulfurization with sodium produces an elemental sulfur product that can be stored as a solid or liquid and sold to the market. Each organically bound sulfur removed using sodium replaces an equivalent amount of sulfur as H ₂ S that has to be processed in the SRU. As a result, the refinery complex provides operational flexibility to reduce the throughput and operating costs of existing SRUs (and the resulting sulfur emissions) or to increase the plant's sulfur processing capacity by desulphurizing at least a portion of the hydrocarbon feedstock into sodium. get In certain embodiments, the methods include a sulfur recovery step employing a sulfur recovery unit (eg, Claus plant, SCOT unit, etc.). In any of these embodiments, the capacity of the sulfur recovery unit is increased proportionally to the sulfur recovered during sodium treatment of the hydrocarbon feedstock.

Exemplary embodiments of the methods of the present technology will now be described with reference to the flowcharts of FIGS. 1 to 4 . With respect to the purification and conversion system 10 of FIG. 1 , sulfur and asphaltene impurities as described herein (e.g., a sulfur content of at least 0.5 wt% (“wt%” herein refers to “weight percent”) ) and an asphaltene content of at least 1 wt. is charged (continuously or batchwise). The reaction can be carried out at elevated temperature and pressure as described herein—although higher asphaltene containing feeds may require longer times than described herein—and is typically complete within minutes to convert the sodium salt Provides a mixture 121 of the feedstock. The converted feedstock may include a hydrocarbon oil having a sulfur content less than the sulfur content in the hydrocarbon feedstock and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock as described herein. Additionally, the ratio of asphaltic to non-asphalt sulfur in the converted feedstock is lower than in the hydrocarbon feedstock. Optionally, mixture 121 is transported from reactor 120 to another vessel 130, where the sodium salts are agglomerated into particles large enough to be readily separated from the converted feedstock. Although any suitable method of aggregation may be used, agglomeration with elemental sulfur 107 at elevated temperatures as described herein may be used. Next, the resulting mixture 131 of the aggregated sodium salt, metal and converted feedstock is separated by any suitable process and device 140, such as by a centrifuge, to separate the metal 143 and the sodium salt ( The converted feedstock 141 without 145) can be provided. Optionally, as described herein, sodium salt 145 is electrolyzed in an electrolysis cell 150 having a sodium ion-selective ceramic membrane 152, such as a NaSiCON membrane, to form sodium metal 153 and elemental sulfur ( 157) can be provided. Sodium metal 153 and elemental sulfur 157 can be reused as 103 and 107, respectively, in the present method. Converted feedstock 141 is subjected to a thermal conversion process 160, such as a coking process, a visbreaking process, or other such processes as described herein to produce a purified product 161 (e.g., eg naphtha, diesel, gas oil and light and heavy cycle oil), gaseous products 163 (eg steam, H ₂ S, C ₁ -C ₄ saturated gases, C ₂ -C ₄ olefins and isobutane). , and a residual product 165 (eg, coke or vis breaker tar). The ratio of purified product (161) to residual product (165) is obtained by subjecting hydrocarbon feedstock (101) to the same thermal conversion process without first desulphurizing the feed with sodium as described herein. greater than the ratio.

In some embodiments of the present methods utilizing purification and conversion system 10 of FIG. 1 , hydrocarbon feedstock 101 has a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a vanadium content of at least 0.5 wt %. at least 15 ppm and containing hydrocarbons with a residual microcarbon content of at least 5 wt%. The converted feedstock 121/141 has a sulfur content less than the sulfur content in the hydrocarbon feedstock 101, a residual microcarbon less than the residual microcarbon in the feedstock 101, and an asphaltene content in the hydrocarbon feedstock 101. hydrocarbons that may contain lower asphaltene content. After subjecting the converted feedstock 141 to a suitable thermal conversion process, premium anode grade coke with less than 0.5 wt % sulfur and less than 150 ppm vanadium can be produced.

2 shows another method embodiment of the present technology using purification and conversion system 20 . The impure hydrocarbon feedstock 201 may include hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a total metal content of at least 100 ppm. This feedstock is charged into reactor 220 along with sodium metal 203 and extrinsic capping agent 205 similar to the process shown in FIG. 1 and described herein. The resulting mixture of sodium salt and converted feedstock 221 is processed as described herein to agglomerate 230 (with elemental sulfur 207) and obtain sodium salt 245 from converted feedstock 241. It can be separated (240). The converted feedstock 241 has a sulfur content of less than 0.5 wt %, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, an asphaltene concentration lower than the asphaltene concentration in the hydrocarbon feedstock, and/or a hydrocarbon feedstock ( 201) contains hydrocarbons with a higher ratio of low-boiling hydrocarbons (<538 °C) to residual hydrocarbons (>538 °C). Again, sodium salt 245 can be electrolyzed 250 to provide sodium metal 253 and elemental sulfur 257 as described herein. The converted feedstock 241 is then subjected to a catalytic conversion process (eg, hydrotreating 270 using hydrogen 265), or other such processes as described herein. Fuel grade product 272 is produced in this manner.

Alternatively, as shown in FIG. 3 , the same process embodiments may be performed using purification and conversion system 30 but employing an optional thermal conversion step 360 to produce a doubly converted product 361 , which can then be applied to a catalytic conversion process 370 using hydrogen to again produce a fuel grade product 372 . Similar to FIG. 2 , thermal conversion process 360 also produces gas product 363 and residual product 365 .

4 depicts another process embodiment of the present technology using a purification and conversion system 40, wherein an impure hydrocarbon feedstock 401 is pretreated 400 in a process/device to produce a residual feedstock 402 and purified feedstock 404. Any suitable pretreatment process that produces first residual feedstock 402 and first purified feedstock 404 can be used as described herein. Residual feedstock 402 may optionally be further pretreated 410 to provide a second residual feedstock 411 and purified feedstock 413 . Optionally, one or more impurities (eg, gaseous impurities, such as H ₂ S, NH ₃ , water, light hydrocarbons, etc.) are removed from a separate stream during the first and/or second (as shown) pretreatment step. It can be removed at (415). Next, the second residual feedstock 411 is treated with sodium metal 403 and extrinsic capping agent 405 in reactor 420 as described herein to form a mixture of sodium salt and converted feedstock 421 ) can be provided. Next, the sodium salt in mixture 421 can be flocculated 430 and separated 440 as described above to provide converted feedstock 441, metal 443, and sodium salt 445. . Sodium salt 445 is electrolyzed in an electrolysis cell 450 having a sodium ion-selective ceramic membrane 452 (eg, NaSiCON) as described herein to yield recovered sodium metal 453 and elemental sulfur. (457) can be provided. Converted feedstock 441 is subjected to any refinery process(s) 480 (eg, distillation, thermal conversion, catalytic conversion, etc.) to provide fuel grade products 482 and residual products 481. can do.

examples

Example 1 - Desulfurization of Hydrocarbon Feedstock with Sodium

Various hydrocarbon feedstocks were treated with sodium metal to demonstrate the broad applicability of sodium metal treatment to remove impurities and improve physical properties. Hydrocarbon feedstocks included virgin crude oil from different geographic locations and geological formations, and various converted and processed feedstocks located within typical refinery and upgrading facilities. 700 g of the hydrocarbon feedstock was treated with an appropriate mass of sodium in a 1.8 L Parr continuous stirred tank reactor using a batch or semi-batch system under the following conditions to obtain a mixture of converted hydrocarbon and sodium salt. Reaction conditions, feed and product attributes are shown in Table 1.

The results from Table 1 clearly indicate that the molten sodium metal effectively removes impurities and improves the physical properties of the converted feedstock, thereby improving the substitutability of the converted feedstock. The now converted feedstock is not sold as asphalt or high sulfur bunker fuel oil, but can be sold directly as a fuel grade product or converted to a higher value product at downstream refinery units.

Example 2 - Desulfurization of Hydrocarbon Feedstock with Sodium

In order to further demonstrate the wide applicability of sodium metal treatment to remove impurities and improve physical properties during continuous operation essentially, for example, supplying various hydrocarbons in a pilot plant using a continuous system as shown in FIG. 4 Raw and pretreated hydrocarbon feedstocks were treated with sodium metal. Hydrocarbons and pretreated hydrocarbon feedstocks included pure crudes, vacuum residues and partially converted feedstocks produced in typical refinery and upgrading facilities. Each feedstock was treated with the appropriate mass of sodium in a 12 L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbon and sodium salt. Hydrogen was the exogenous capping agent for all test campaigns. Reaction conditions, feed and product attributes are shown in Table 2.

Similar to Example 1, the results in Table 2 clearly indicate that molten sodium metal effectively removes impurities, improves the physical properties of the converted feedstock, and thus improves the substitutability of the converted feedstock. The now converted feedstock is not sold as asphalt or high sulfur bunker fuel oil, but can be sold directly as a fuel grade product or converted to a higher value product at downstream refinery units.

Example 3: asphaltenes Preferential removal of sulfur during fractionation

Mixed vacuum resid streams were treated with increasing molar equivalents of sodium in five separate experiments. 700 g of the vacuum residue was contacted with sodium at 350° C. and a hydrogen partial pressure of 750 psig. The main results are summarized in Table 3. The effect of sodium treatment on the preferential removal of sulfur from the asphaltene fraction is summarized as follows:

One. The fraction of total sulfur located in the asphaltenes decreased from 28.5% to 7.9% of the converted product at a sodium to sulfur ratio of 0.94.

2. The ratio of asphaltic sulfur to non-asphaltic sulfur decreases as a function of increasing molar equivalents of sodium. A reduction in the ratio indicates that a greater proportion of sulfur is removed from asphalt sulfur than from non-asphaltic sulfur at all practical sodium to sulfur ratios - releasing hydroprocessing catalysts in downstream oil refining processes (e.g., the process shown in Figure 2). - Demonstrate significant results for

Example 4: Improvement of hydrocarbon conversion in a catalytic conversion process by sodium pretreatment

Refinery intermediate streams (i.e., pretreated hydrocarbon feedstocks) were treated with various molar equivalents of sodium to demonstrate how selection of molar equivalents of sodium can be used to improve the conversion of hydrocarbons in downstream catalytic conversion processes. 700 g of each essential oil intermediate was treated with sodium at 350°C and 750 psig or 400°C and 1500 psig partial pressure of hydrogen. The main results are summarized in Table 4.

Treatment of hydrocarbon feedstocks with substoichiometric molar equivalents of sodium improves FCC or Residuum Hydrotreater (RHT) feedstocks by preferentially removing catalyst-fouling impurities, i.e. asphaltic sulfur, metals and asphaltenes. It may be desirable to pre-treat. A larger proportion of sulfur was removed from the asphaltene fraction in all cases. Additionally, the fraction of metals removed exceeds the fraction of total sulfur removed, which is why the low sodium/sulfur addition ratio produces a partially converted product with low metal and asphaltic sulfur content for further processing in downstream refinery processes. indicates that it may be beneficial.

Example 5: Decompression residue On-from feedstock Specifications low sulfur fuel oil generation

To demonstrate the production of on-spec low sulfur condensed milk, vacuum resid feedstock was treated with sodium metal in a pilot plant, eg, using a continuous system as shown in FIG. 1 . The vacuum resid feedstock was treated with an appropriate mass of sodium in a 12 L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbon and sodium salt. Hydrogen was the exogenous capping agent for all test campaigns. Reaction conditions, feed and product attributes are shown in Table 5.

This example clearly demonstrates that an on-spec low sulfur fuel oil can be produced when a hydrocarbon feedstock is contacted with an effective amount of sodium and an effective amount of an exogenous capping agent.

Example 6: cocker supplies by pretreatment with sodium cocker Product yield and quality improvement

Four feedstocks from Table 1: Vacuum Resid, SDA Tar, Visbreaker Resid, and Hydrocracker Resid, to demonstrate the improvement in the yield and quality of the coker product when the coker feedstock is pretreated with sodium metal prior to thermal conversion. The reason was treated with sodium metal. 700 g of the hydrocarbon feedstock was treated with an appropriate mass of sodium in a 1.8 L Parr continuous stirred tank reactor using a batch or semi-batch system under the following conditions to obtain a mixture of converted hydrocarbon and sodium salt. Reaction conditions, feed and product attributes are shown in Table 1. Produced yield and quality of coker product are estimated using accepted industry correlations for both 'as-is' hydrocarbon feedstocks and converted feedstocks after sodium treatment (Gary, J.H., and Handwerk, G.E. 2001)."Petroleum Refining." Marcel Dekker, NewYork]). Coker products are summarized in Table 6.

The results from Table 6 show that, when compared to thermal conversion of the as-received feedstock, treating the feed with molten sodium metal prior to thermal conversion increased total liquid yield, decreased coke yield, and reduced the residual product yield. It is clearly shown to increase the proportion of refined product and reduce the sulfur content of all coker products.

In addition, the results demonstrate how treating the feedstock with molten sodium metal can relieve sulfur recovery processes (i.e., Claus or SCOT plants). In four examples, sulfur to gas processing (as H ₂ S) is reduced by over 90%. This process configuration is advantageous for increasing the sulfur handling capacity for the refinery without increasing sulfur emissions or exceeding limits.

Example 7: Advanced high purity by sodium pretreatment anode Production of coke or needle coke

The coke product quality for the same four feedstocks from Example 6, i.e., vacuum resid, SDA tar, visbreaker resid and hydrocracker resid, was measured for the 'as received' hydrocarbon feedstock and the converted feed after sodium treatment. Estimated using accepted industry correlations for both raw materials (Gary, J.H., and Handwerk, G.E. (2001). “Petroleum Refining.” Marcel Dekker, New York) and summarized in Table 7. None of the coke produced from the as-received feed meets the anode grade coke specifications, while all coke products produced from the converted feedstock approach or exceed the anode grade coke specifications. Vanadium specification can be achieved by slightly increasing the molar equivalent of sodium in the sodium contacting step.

Example 8: supplies Improving Distillation Properties of Petroleum Products by Pretreatment with Sodium

Distillation properties for hydrocarbon feedstock before and after treatment with sodium according to the procedure of Example 1 were compared. The results in Table 8 show improved attributes with reductions in the resid fraction of 1-10% and associated increases in higher value distillate and gas oil fractions of 0.5-3% and 0.5-8%, respectively. This improved product profile provides a higher value product from a given volume of feed, for example when distillation is performed after desulfurization with sodium.

Equivalents

Although specific examples have been illustrated and described, those skilled in the art, after reading the foregoing specification, will be able to make alterations, substitutions of equivalents and other types of alterations to the PDC or derivatives, prodrugs or pharmaceutical compositions thereof of the present technology set forth herein. You will be able to. Each aspect and embodiment described above also includes or can be included in such variations or aspects as disclosed in relation to any or all of the other aspects and embodiments.

The technology is also not to be limited in terms of the specific aspects described herein, which are intended as single examples of individual aspects of the technology. As will be apparent to those skilled in the art, many modifications and variations of the present technology may be made without departing from its spirit and scope. Functionally equivalent methods within the scope of the present technology will be apparent to those skilled in the art from the foregoing description in addition to the methods recited herein. Such modifications and variations are intended to fall within the scope of the appended claims. It should be understood that this technology is not limited to specific methods, reagents, compound compositions or biological systems, which can of course be varied. It is also to be understood that the terminology used herein is merely for describing specific embodiments and is not intended to limit the present invention. Accordingly, this specification is intended to be regarded as illustrative, and the breadth, scope and spirit of the present technology is indicated only by the appended claims, the definitions therein and the equivalents thereof.

The embodiments illustratively described herein may be suitably practiced without any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, the terms “comprising”, “comprising”, “including” and the like are to be read as inclusive and without limiting the invention. Additionally, the terms and expressions used herein are used only as terms of description and not of limitation of the present invention, and the use of such terms and expressions does not intend to exclude equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the scope of the claimed technology without Similarly, use of the terms "comprising", "including", "including" and the like should be understood as disclosing embodiments using the terms "consisting essentially of" and "consisting of". The phrase “consisting essentially of” is understood to include the specifically recited elements and additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not recited.

Further, when a feature or aspect of the present invention is described in terms of a Markush group, those skilled in the art will recognize that the present invention is also described in terms of any individual element or subgroup of elements of the Markush group. There will be. Each of the subgenus groups belonging to the narrower species and genus ranges also form part of this description. This includes genus descriptions of the subject matter with a proviso or negative limitation removing any subject matter from the genus, whether or not the restrained material is specifically recited herein.

As will be appreciated by those skilled in the art, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also include any and all possible subranges and combinations of subranges thereof. Any range recited is readily recognized as sufficiently descriptive that the same range can be divided into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each of the ranges discussed herein can be readily categorized as lower third, middle third, and upper third, etc. Also, as will be appreciated by those of ordinary skill in the art, all language such as "at most", "at least", "greater than", "less than", etc., includes the stated numbers and ranges that may subsequently be divided into subranges as discussed above. say Finally, as will be understood by those skilled in the art, ranges include each individual member.

All publications, patent applications, issued patents, and other documents (eg, journals, articles, and/or textbooks) mentioned in this specification indicate that each individual publication, patent application, issued patent, or other document is incorporated herein in its entirety. It is incorporated herein as if specifically and individually set forth. Definitions contained in documents, the entire content of which is incorporated herein, are excluded to the extent that they contradict the definitions herein.

Other embodiments are presented in the following claims, along with the full scope of equivalents given in the claims.

Claims (42)

A method for improving the yield of liquid hydrocarbons from a thermal conversion process, comprising:
contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C to produce a mixture of sodium salt and converted feedstock -
the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a residual microcarbon content of at least 5 wt %;
The converted feedstock is a hydrocarbon having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon content less than the residual microcarbon content in the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. including ―; and
subjecting the converted feedstock to a thermal conversion process to produce a gaseous product, a purified product and a residual product -
wherein the ratio of refined product to residual product is greater than a ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process. As a method,
contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250-500°C to produce a mixture of sodium salt and converted feedstock -
the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, a vanadium content of at least 15 ppm, and a residual microcarbon content of at least 5 wt%;
The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content in the hydrocarbon feedstock, a residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content in the hydrocarbon feedstock. Ham ; and
subjecting the converted feedstock to a thermal conversion process to produce a premium anode grade coke product having less than 0.5 wt % sulfur and less than 150 ppm vanadium. As a method,
contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250°C-500°C to produce a mixture of sodium salt and converted feedstock -
the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, a nickel content of at least 10 ppm, and a residual microcarbon content of at least 5 wt%;
The converted feedstock comprises hydrocarbons having a sulfur content of less than 0.5 wt%, residual microcarbon less than the residual microcarbon in the hydrocarbon feedstock, and an asphaltene content of less than 0.25 wt% and an ash content of <0.1 wt% -; and
The converted feedstock is subjected to a thermal conversion process to contain less than 0.5 wt % sulfur, less than 0.7 wt % nitrogen, less than 10 ppm nickel, a thermal expansion coefficient greater than 2.5×10 ⁷ /° C., and 320×10 ⁶ Ohm- producing a high purity needle coke product having an electrical resistivity of In. As a method,
contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250°C-500°C to produce a mixture of sodium salt and converted feedstock -
the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt %, an asphaltene content of at least 1 wt %, and a total metal content of at least 100 ppm;
The converted feedstock has a sulfur content of less than 0.5 wt %, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, an asphaltene concentration lower than the asphaltene concentration in the hydrocarbon feedstock, and a higher than that of the hydrocarbon feedstock. including hydrocarbons having a ratio of low boiling hydrocarbons (<538°C) to residual hydrocarbons (>538°C);
optionally further subjecting the converted feedstock to a thermal conversion process to provide a double converted product; and
subjecting the converted feedstock or double converted feedstock to a catalytic conversion process to produce a fuel grade product without mixing or additional conversion processes. As a method,
contacting a hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250°C-500°C to produce a mixture of sodium salt and converted feedstock -
The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt % and an asphaltene content of at least 1 wt %, and at least one fuel selected from the group consisting of viscosity, density, residual microcarbon, metal content and cleanliness/compatibility. not meeting class specifications;
the converted product comprises hydrocarbons having a sulfur content of less than 0.5 wt % and meets one or more fuel grade specifications selected from the group consisting of viscosity, density, residual microcarbon, metal content and cleanliness/compatibility;
The fuel grade specifications are a viscosity of less than 380 cSt (@ 50 C), a density of less than 991 kg/m ³ , a residual microcarbon content of less than 18 wt%, a vanadium content of less than 350 mg/kg, and a value of 1 as measured by ASTM D4740. or is the result of a cleanliness spot test of 2. According to claim 4,
subjecting the converted feedstock to a thermal conversion process to provide the double converted feedstock and solid coke product;
here
the converted feedstock has a residual microcarbon content of at least 5 wt %;
The double converted product is
an impurity concentration lower than the impurity concentration in the hydrocarbon feedstock, and
wherein the converted feedstock comprises hydrocarbons having a higher ratio of low-boiling hydrocarbons (<538° C.) to high-boiling residual hydrocarbons (>538° C.). 7. The step of any one of claims 1 to 6, wherein pre-treating the hydrocarbon feedstock prior to the contacting step to provide a purified feedstock and a pretreated hydrocarbon feedstock -
The purified feedstock contains impurities at a lower concentration than the hydrocarbon feedstock before pretreatment,
The pretreated hydrocarbon feedstock contains a higher concentration of impurities than the purified feedstock,
wherein the pretreated hydrocarbon feedstock is a feedstock subjected to the contacting step to produce the converted feedstock. 8. The method of claim 7, wherein the pretreatment step comprises phase separation by an externally applied field, separation by the addition of heat, hydrogenation conversion, thermal conversion, catalytic conversion, catalytic treatment, solvent extraction, solvent deasphalting, or any two of these. A method comprising a combination of the above. 9. The method of claim 7 or 8, wherein the pretreatment step further comprises contacting the hydrocarbon feedstock with exogenous hydrogen and/or a catalyst to remove one or more of sulfur, nitrogen, oxygen, metals, and asphaltenes. in, how. 10. The method of any one of claims 1-9, wherein the thermal conversion process comprises visbreaking, retarded coking, fluid coking, Flexicoking™, pyrolysis, variations thereof, or a combination of any two or more thereof. . 11. The method of claim 10, wherein the thermal conversion process is operated at a temperature of about 400 °C to about 570 °C. 12. The method of claim 10 or 11, wherein the thermal conversion process is operated at a pressure of about 10 to about 200 psig. 13. The method of any one of claims 1-12, wherein the thermal conversion process is operated at about 450°C to about 500°C and about 20-100 psig. The method of claim 4, wherein the catalytic conversion process is fluid catalytic cracking (FCC), resid FCC, hydrotreating, resid hydrotreating, hydrocracking, catalytic reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, or resid upgrading/hydrogenation conversion, a variant thereof, or a combination of any two or more thereof. 15. The method of claim 14, wherein the catalyst comprises cobalt, molybdenum, nickel, tungsten, platinum, palladium, alumina, silica, zeolites, isomers thereof, oxides, sulfides, or combinations of any two or more thereof. . 16. The method of claim 15, wherein the catalytic conversion process is operated at a temperature of about 250 °C to about 575 °C. 16. The method of claim 15, wherein the catalytic conversion process is operated at a pressure of about 10 to about 3000 psig. 18. The method of any one of claims 4 or 6-17, wherein the thermal conversion process is operated at about 400 °C to about 575 °C and about 1000 to 3000 psig. 18. The method of any one of claims 4 or 6-17, wherein the thermal conversion process is operated at about 450 °C to about 575 °C and about 15 to 100 psig. 20. The method of any one of claims 1 to 19, further comprising recovering hydrogen sulfide using a sulfur recovery unit in conjunction with the thermal conversion or the catalytic conversion step, wherein the sulfur recovery unit has a capacity to treat sodium The method, which is increased in proportion to the sulfur converted to the sodium salt during the process. 21. The process according to any one of claims 1 to 20, wherein the hydrocarbon feedstock is pure crude oil or a product of or derived from a thermal cracking process. 21. The method according to any one of claims 1 to 20, wherein the hydrocarbon feedstock is selected from the group consisting of petroleum, heavy oil, bitumen, shale oil, and oily shale. 23. The method according to any one of claims 1 to 22, wherein the sulfur content ranges from 0.5 wt% to 15 wt%. 24. The method according to any one of claims 1 to 23, wherein the asphaltene content ranges from 1 wt% to 100 wt%. 25. The method of claim 24, wherein the asphaltene content ranges from 2 wt% to 40 wt%. 26. The method of any one of claims 1 to 25, wherein the hydrocarbon feedstock is refined oil midstream, hydrocracked residue, hydroprocessed residue, FCC slurry, residual FCC slurry, atmospheric or vacuum residue, solvent deasphalted Tar, Deasphalted Oil, Visbreaker Tar, High Sulfur Fuel Oil, Low Sulfur Fuel Oil, Asphaltene, Asphalt, Steam Cracked Tar, LC-Fining® Residue Oil, or H-Oil® A method comprising at least one of the residue oils. 27. The method of any preceding claim, wherein the hydrocarbon feedstock has a viscosity of 1 to 10,000,000 cSt at 50°C and a density of 800 to 1200 kg/m ³ at 15.6°C. 28. The method of any one of claims 1 to 27, wherein the hydrocarbon feedstock has a viscosity of 400 to 9,000,000 cSt at 50 °C. 29. The method of any one of claims 1-28, wherein the hydrocarbon feedstock is a solid at room temperature. 30. The method of any one of claims 1-29, wherein the sulfur content comprises asphaltic sulfur and non-asphaltic sulfur, and the ratio of asphaltic sulfur to non-asphaltic sulfur in the converted feedstock is the hydrocarbon feedstock The lower-than-average method. 31. The method of any one of claims 1 to 30, wherein the viscosity of the converted feedstock is reduced by at least 50 cSt or 40% at 50 °C, and the density of the converted feedstock is at least as high as that of the hydrocarbon feedstock. and about 5 to about 25 kg/m ³ per wt% reduction in sulfur content of the converted feedstock. 32. The process of any preceding claim, wherein the iron and vanadium content of the converted feedstock is reduced by at least 40% relative to the hydrocarbon feedstock. 33. The process of any preceding claim, wherein the nickel content of the converted feedstock is reduced by at least 40% relative to the hydrocarbon feedstock. 34. The process of any preceding claim, wherein at least 40% of the asphaltenes content in the hydrocarbon feedstock is converted to liquid hydrocarbon oil in the converted feedstock. 35. The method of any one of claims 1-34, wherein the extrinsic capping agent is hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethene, propene, butene, pentene, diene, isomers thereof Or a mixture of any two or more of them, the method. 36. The method of any one of claims 1-35, wherein the hydrocarbon feedstock is combined with sodium metal at a pressure of about 400 psig to about 3000 psig. 37. The method of any one of claims 1 to 36, wherein the reaction of the hydrocarbon feedstock with sodium metal occurs for a time period of 1 minute to 120 minutes. 38. The method of any one of claims 1-37, further comprising isolating sodium salt from the converted feedstock. 39. The method of claim 38, wherein the separation
a. heating the mixture of the sodium salt and converted feedstock and elemental sulfur to a temperature of about 150° C. to 500° C. to provide a sulfur treated mixture comprising an agglomerated sodium salt; and
b. separating the agglomerated sodium salt from the sulfur treated mixture to provide a desulfurized liquid hydrocarbon and an isolated sodium salt. 40. The method of claim 39, further comprising electrolyzing the separated sodium salt to provide sodium metal and elemental sulfur. 41. The method of any one of claims 1 to 40, wherein the sodium salt comprises one or more of sodium sulfide, sodium hydrosulfide, or sodium polysulfide. 42. The method of claim 40 or 41, wherein the electrolysis is performed in an electrochemical cell comprising an anolyte compartment, a catholyte compartment and a NaSICON membrane separating the anolyte compartment from the catholyte compartment, and comprising sodium metal. wherein a cathode is disposed in the catholyte in the catholyte compartment, an anode comprising the sodium salt is disposed in the anolyte compartment, and a power source is electrically connected to the anode and cathode.

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