CN115803416A - Process for improving performance of downstream oil conversion - Google Patents

Abstract

The present technology provides a process for improving the performance of downstream oil conversion. Thus, the present technology provides, among other things, processes for improving the yield of liquid hydrocarbons from thermal conversion processes. 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 ℃ to produce a mixture of sodium salts and converted feedstock. The hydrocarbon feedstock may include hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, and a trace carbon residue content of at least 5 wt%. The converted feedstock may include hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace carbon residue content of the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content of the hydrocarbon feedstock. The process further includes 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 purified product to residual product is greater than the ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process.

Description

Process for improving performance of downstream oil conversion

Cross Reference to Related Applications

This application claims priority to U.S. provisional application serial No. 63/027052, filed on 19/5/2020, which is hereby incorporated herein in its entirety

Technical Field

The present technology relates to processes for reducing sulfur and asphaltene content and other impurities in hydrocarbon feedstocks to improve the performance of downstream oil conversion processes. Both catalytic performance and thermal conversion performance can be improved.

Background

Hydrocarbon oils (which comprise many oil feedstocks) often contain impurities that are difficult to remove, such as sulfur in the form of organic sulfur compounds, as well as metals and other heteroatom-containing compounds, which hinder the use of the hydrocarbons. Undesirable impurities present in hydrocarbon oils may be concentrated in resins and asphaltenes found in vacuum residue distillation fractions, which are typically defined by boiling points of 510 ℃ to 565 ℃ (950 ° f to 1050 ° f) or higher. Conventional refining configurations further concentrate the undesirable impurities by separating high value, low boiling distillation fractions (gasoline, diesel, jet fuel and gas oil) from low value, high boiling bottoms (atmospheric and vacuum residuum). The low boiling distillation fraction can be readily processed and converted to the final product using established processes such as hydrotreating, alkylation, catalytic reforming, catalytic cracking, and the like. High boiling residuum streams are not easily handled because disproportionately high metal content contaminates the catalyst and the asphaltene polycyclic aromatic hydrocarbon structure hinders the entry of impurities.

The sulfur species present in hydrocarbons can be characterized as asphaltene sulfur (i.e., sulfur-containing asphaltene species) and non-asphaltene sulfur (i.e., sulfur-containing non-asphaltene species). Non-asphaltenic sulfur typically comprises mercaptans, sulfides, benzothiophenes, and Dibenzothiophene (DBT) derivatives, among others, primarily in the vacuum resid fraction, but may also be present in saturates, aromatics, and resin components located in any distillation fraction. These sulfur species, particularly 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. The asphaltene sulfur in the asphaltenes located in the heaviest resid distillate fraction is characterized primarily by multi-layer condensed sulfur-containing polynuclear aromatics connected by saturated species and sulfur. DBT and DBT derivatives and sulfur bridges may constitute a large proportion of the asphaltene sulfur species. In addition, metals including nickel, vanadium and iron are typically concentrated in porphyrin metal complexes located in the asphaltene fraction. Sulfur cannot be easily removed from asphaltenes without subjecting the asphaltene sulfur to harsh operating conditions.

Resid thermal or catalytic conversion units operate under severe operating conditions, typically high temperatures (> 350 ℃/662 ° f), high hydrogen partial pressures (500-3000 psig), and use specialized catalysts that deactivate due to metal and coke deposition. Even after subjecting the resid stream to the most severe operating conditions, a portion of the sulfur and metals are not removed and remain in the oil. Thus, the low value resid bottoms stream is 1) converted to bitumen, 2) processed in a thermal conversion unit (such as a coker) to extract as much of the high value intermediates as possible, or 3) mixed into a high sulfur marine fuel.

Disclosure of Invention

Surprisingly, processes have been found to preferentially remove sulfur and metals from sulfur-containing asphaltenes and/or to convert a portion of the asphaltene fraction in a hydrocarbon feedstock to a non-asphaltene liquid product. These processes provide a converted feedstock having a reduced sulfur (and other heteroatoms) content and a reduced metal content, particularly in the asphaltene fraction. Using the present techniques, impurities concentrated in the asphaltene fraction of a hydrocarbon feedstock can be optimally removed by contacting such feed with sodium metal, while impurities concentrated elsewhere can be optimally removed by conventional refining processes. In addition, the operation of downstream process units can be optimized by reducing high concentrations of impurities in the asphaltene fraction, resulting in improved operability and profitability of the refinery.

Accordingly, in a first aspect, the present technology provides a process for improving the yield of liquid hydrocarbons from a thermal conversion process, the 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 ℃ to produce a mixture of sodium salts and a converted feedstock, wherein 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 trace carbon residue content of at least 5 wt%; the converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace carbon residue content of the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content of the hydrocarbon feedstock; 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 purified product to residual product is greater than the ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process. In embodiments where the thermal conversion process is, for example, a coking process, the present process provides improved yields of vacuum gas oil, reduced coke loss and reduced sulfur content of all subsequent streams. The lower sulphur content is converted into less H to be treated by, for example, a Claus plant (Claus plant) ₂ S, lower gas oil hydrotreating load and sweeter coke. In addition, the amount of sodium metal used in the process can be varied to optimize downstream yields and economics.

In a second aspect, the present technology provides a process for making anode grade coke from a dirtier feed than previously possible. The process comprises the following steps: 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 to 500 ℃ to produce a mixture of sodium salts and a converted feedstock, wherein 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 15ppm, and a trace carbon residue content of at least 5 wt%; the converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, trace carbon residues less than the trace carbon residues of the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content of the hydrocarbon feedstock; and subjecting the converted feedstock to a thermal conversion process to produce a quality anode grade coke product having less than 0.5 wt% sulfur and less than 150ppm vanadium.

In a third aspect, the present technology provides a process for making needle grade coke from a dirtier feed than previously possible. The process comprises the following steps: 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 ℃ to 500 ℃ to produce a mixture of sodium salts and a converted feedstock, wherein 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 10ppm, and a trace carbon residue content of at least 5 wt%; the converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace carbon residue content of the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content of the hydrocarbon feedstock; and subjecting the converted feedstock to a thermal conversion process to produce a high purity needle coke product having less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10ppm nickel, greater than 2.5x10 ⁷ Coefficient of thermal expansion of 320x10 and/or/° C ⁶ Resistivity of Ohm-In.

In a fourth aspect, the present technology provides a process for improving the conversion of a hydrocarbon feedstock in a catalytic conversion process. The process comprises the following steps: 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 ℃ to 500 ℃ to produce a mixture of sodium salts and a converted feedstock, wherein 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 comprises hydrocarbons having a sulfur content of less than 0.5 wt%, a vanadium content of less than 50ppm, a nickel content of less than 50ppm, an asphaltene concentration lower than the hydrocarbon feedstock, and/or a ratio of low boiling hydrocarbons (< 538 ℃) to residual hydrocarbons (> 538 ℃) higher than the ratio in the hydrocarbon feedstock; optionally subjecting the converted feedstock to a thermal conversion process to provide a product of dual conversion; and subjecting the converted feedstock or dual converted feedstock to a catalytic conversion process (e.g., catalytic hydrotreating) to produce a fuel grade product without blending or additional conversion treatment. The process improves the conversion and performance of hydrocarbon feeds (including raffinate streams) in downstream catalytic processing by a) improving catalyst life, b) providing higher gasoline yields, and c) allowing for the complete bypass of coker units.

In a fifth aspect, the present technology provides a process for producing low sulfur fuel grade products from off-spec hydrocarbon feedstocks with little or no mixing. The process comprises the following steps: 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 ℃ to 500 ℃ to produce a mixture of sodium salts and a converted feedstock, wherein 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 fails to meet one or more fuel grade specifications selected from the group consisting of viscosity, density, trace carbon residue, 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, trace carbon residue, metal content, and compatibility; and the fuel grade specifications are: a viscosity at 50 ℃ of less than 380cSt, less than 991kg/m ³ A trace carbon residue content of less than 18 wt%, a vanadium content of less than 350mg/kg, and a cleanliness field test result of 1 or 2 as measured by ASTM D4740. For example, low sulfur marine fuels can be prepared via the disclosed methods. In some embodiments, the product is a near fuel grade product that can be brought to specification by mixing a nominal amount of the mixed feedstock, for example, 0.5 wt% to 10 wt%.

The foregoing is a summary of the disclosure and thus contains, by necessity, simplifications, generalizations, and omissions of detail. Consequently, those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. Other aspects, features, and advantages of the processes described herein will become apparent from the detailed description set forth herein and in conjunction with the drawings, as defined solely by the claims.

Drawings

In order that the manner in which the above-recited and other features and advantages of the present technology are obtained will be readily understood, a more particular description of the present technology briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the technology and are not therefore to be considered to be limiting of its scope, the technology will be described and explained with additional specificity and detail through the use of the accompanying drawings.

Fig. 1 is a flow diagram of an illustrative embodiment of the first, second, or third aspect of the process of the present technology, including optional separation and electrolysis steps.

Fig. 2 is a flow diagram of an illustrative embodiment of a fourth aspect of the process of the present technology, including optional separation and electrolysis steps.

FIG. 3 is a flow diagram of another illustrative embodiment of the fourth aspect of the process of the present technology, including optional separation and electrolysis steps.

FIG. 4 is a flow diagram of an illustrative embodiment of a process of the present technology, including an optional pretreatment step, and optional separation and electrolysis steps, as well as a refining process step.

Detailed Description

As defined below, the following terms are used throughout.

As used herein, singular articles such as "a" and "an" and "the" and similar references in the context of describing elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate embodiments and does not pose a limitation on the scope of the claims unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential.

As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there is a use of a term that is not clear to one of ordinary skill in the art, then "about" will mean up to plus or minus 10% of the particular term, given the context in which the term is used.

As used herein, "asphaltene" means insoluble in any C _3-8 Oil composition of alkanes. Asphaltenes may comprise polyaromatic molecules including one or more heteroatoms selected from S, N and O. The sulfur species found in asphaltenes are collectively referred to herein as "asphaltene sulfur". All other sulfur species found in non-asphaltene fractions of hydrocarbon oils and fractions thereof are collectively referred to herein as "non-asphaltene sulfur". The latter include, for example, mercaptans, sulfates, thiophenes (including benzothiophenes and dibenzothiophenes), hydrogen sulfide, and other sulfides.

As used herein, "hydrocarbon feedstock" refers to any material that can be an input to a refinery, conversion, or other industrial process, where hydrocarbons are the major constituent. The hydrocarbon feedstock can be solid or liquid at room temperature and can contain non-hydrocarbon components such as organic and inorganic materials containing heteroatoms (e.g., S, N, O, P, metals). Crude oil, refinery streams, chemical plant streams (e.g., steam cracked tar), and recycle plant streams (e.g., lubricating oil and pyrolysis oil from tires or municipal solid waste) are non-limiting examples of hydrocarbon feedstocks.

The present technology provides processes for improving the yield of downstream oil conversion processes. Thus, in a first aspect, there is provided a process for improving liquid hydrocarbons from a thermal conversion processThe process for producing a yield of (a), the process comprising: contacting the hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250 to 500 ℃ to produce a mixture of sodium salts 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 trace carbon residue content of at least 5 wt%. The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace residue content of the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content of the hydrocarbon feedstock. Trace carbon residue (MCR) measured according to ASTM D4530 indicates the tendency of hydrocarbons to form carbonaceous deposits upon exposure to elevated temperatures. MCR is numerically equivalent to Conradson Carbon Residue (CCR) measured according to ASTM D189 and may be used interchangeably. In any embodiment, the converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace carbon residue content of the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content of the hydrocarbon feedstock. Subjecting the converted feedstock to a thermal conversion process (e.g., coking or visbreaking process) to produce gaseous products (e.g., steam, H) ₂ S、C ₁ -C ₄ Saturated gas, C ₂ -C ₄ Olefins and isobutane), purified products (e.g., naphtha, diesel, gas oil, and light and heavy cycle oils), and residual products (e.g., coke or visbroken tar), wherein the ratio of purified products to residual products is greater than the ratio produced by subjecting a hydrocarbon feedstock to the same thermal conversion process.

In a second aspect, a process for producing a quality anode grade coke or needle coke is provided. 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 ℃ to produce a mixture of sodium salts 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 15ppm, and a trace carbon residue content of at least 5 wt%. The converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, trace carbon residues less than the trace carbon residues of the hydrocarbon feedstock, and/or an asphaltene content less than the asphaltene content of the hydrocarbon feedstock. In any embodiment, the converted feedstock includes hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, trace amounts of carbon residues less than the carbon residues of the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content of the hydrocarbon feedstock. The converted feedstock is subjected to a thermal conversion process to produce a quality anode grade coke product having a sulfur content of less than 0.5 wt% and a vanadium content of less than 150 ppm.

In a third aspect, a process for producing needle coke is provided, the 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 ℃ to 500 ℃ to produce a mixture of sodium salts 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 10ppm, and a trace carbon residue content of at least 5 wt%; the converted feedstock comprises less than 0.5 wt% sulfur, less trace carbon residues than the carbon residues in the hydrocarbon feedstock, less than 0.25 wt% asphaltenes, and/or ash<0.1 wt% hydrocarbons. In any embodiment, the converted feedstock includes less than 0.5 wt% sulfur, less trace carbon residues than trace carbon residues in the hydrocarbon feedstock, less than 0.25 wt% asphaltene content, and an ash content<0.1 wt.% hydrocarbons. Treating the converted feedstock in a thermal conversion process to produce a high purity needle coke product having less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10ppm nickel, greater than 2.5x10 ⁷ Coefficient of thermal expansion of 320x10 and/or/° C ⁶ Resistivity of Ohm-In.

In a fourth aspect, the present technology provides a process for improving the conversion of a feedstock during catalytic conversion or treatment. The process may comprise: 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 ℃ to 500 ℃ to produce a mixture of sodium salts and a converted feedstock; optionally, further subjecting the converted feedstock to a thermal conversion process to provide a product of the dual conversion; and subjecting the converted feedstock or dual converted feedstock to a catalytic conversion process (e.g., catalytic hydrotreating, fluid catalytic cracking, etc.) to produce fuel grade products without mixing or further conversion processing. 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 comprises hydrocarbons having a sulfur content of less than 0.5 wt%, a vanadium content of less than 50ppm, a nickel content of less than 50ppm, a concentration of asphaltenes lower than that in the hydrocarbon feedstock and/or a ratio of lower boiling hydrocarbons (< 538 ℃) to residual hydrocarbons (> 538 ℃) higher than that in the hydrocarbon feedstock. In any embodiment, the converted feedstock comprises hydrocarbons having a sulfur content of less than 0.5 wt%, a vanadium content of less than 50ppm, a nickel content of less than 50ppm, a concentration of asphaltenes that is less than that in the hydrocarbon feedstock, and a ratio of lower boiling hydrocarbons (< 538 ℃) to residual hydrocarbons (> 538 ℃) that is greater than that in the hydrocarbon feedstock.

In a fourth aspect, when the converted feedstock has a trace carbon residue content of at least 5 wt%, the process can further comprise subjecting the converted feedstock to a thermal conversion process (e.g., in a coking unit) to provide a doubly converted feedstock and a solid coke product. In such embodiments, the product of the dual conversion comprises liquid hydrocarbons having a concentration of impurities lower than the concentration of impurities in the hydrocarbon feedstock, and the ratio of lower boiling hydrocarbons (< 538 ℃) to higher boiling residuum hydrocarbons (> 538 ℃) is greater than the ratio of the converted feedstock. In any embodiment of the fourth aspect, the fuel grade product can be gasoline, diesel, kerosene, jet fuel, petroleum naphtha, or LPG.

In a fifth aspect, the present technology provides a process for producing a low sulfur fuel grade product. The process 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 ℃ to 500 ℃ to produce a mixture of sodium salts 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 does not meet one or more fuel grade specifications selected from the group consisting of viscosity, density, trace carbon residue, 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, trace carbon residue, metal content, and compatibility,wherein the fuel grade specification is a viscosity of less than 380cSt at 50 ℃, less than 991kg/m ³ A trace carbon residue content of less than 18 wt%, a vanadium content of less than 350mg/kg and a cleanliness field test result of 1 or 2 as measured by ASTM D4740. In some embodiments, the converted products meet two or more, three or more, four or more, or all five fuel grade specifications. In some embodiments, the product is a near fuel grade product that can be brought to specification by mixing a nominal amount of the mixed feedstock, for example, 0.5, 1, 2, 3, 4, 5,6, 7, 8, 9, or 10 weight percent, or within a range between and including any two of the foregoing values, such as 0.5-10, 1-10, or 2-7 weight percent.

In any embodiment of the processes described herein, the process can further comprise pretreating the hydrocarbon feedstock prior to the contacting step to provide a purified feedstock and a pretreated hydrocarbon feedstock. The purified feedstock comprises a lower concentration of impurities than the pre-treated hydrocarbon feedstock, the pre-treated hydrocarbon feedstock comprising a higher concentration of impurities than the purified feedstock; and the pretreated hydrocarbon feedstock is a feedstock that is subjected to a contacting step to produce a converted feedstock. In any embodiment of the present process comprising a pretreatment step, the pretreatment step can comprise phase separation by an externally applied field, separation by addition of heat, hydroconversion, thermal conversion, catalytic conversion or treatment, solvent extraction, solvent deasphalting, or a combination of any two or more thereof. In any embodiment, the pretreating step can comprise contacting the hydrocarbon feedstock with exogenous hydrogen and/or a catalyst to remove one or more of sulfur, nitrogen, oxygen, metals, and asphaltenes. Examples of pretreatment steps that produce a purified feedstock and a pretreated hydrocarbon feedstock include atmospheric distillation, vacuum distillation, steam cracking, catalytic cracking, thermal cracking, fluid Catalytic Cracking (FCC), solvent deasphalting, hydrodesulfurization, visbreaking, pyrolysis, catalytic reforming, alkylation, and combinations of any two or more of the foregoing. It will be appreciated that some of the foregoing processes, such as atmospheric distillation and vacuum distillation, directly produce purified feedstocks and pretreated hydrocarbon feedstocks, while others require subsequent separation steps. For example, steam cracking, catalytic cracking, thermal cracking, FCC, and pyrolysis produce a mixture of products that can subsequently be separated into a purified feedstock and a pretreated hydrocarbon feedstock by distillation or other separation processes.

In any aspect or embodiment of the process described herein comprising a thermal conversion process, the thermal conversion process can be or can comprise visbreaking, delayed coking, fluid coking, flexicoking (TM), pyrolysis, variants thereof, or combinations of any two or more thereof. In any embodiment, the thermal conversion process may be operated at a temperature of about 400 ℃ to about 570 ℃. In any embodiment, the thermal conversion process may be operated at a pressure of about 10 to about 200 psig. In any embodiment, the thermal conversion process can be operated at about 450 ℃ to about 500 ℃ and at about 20 to 100psig, for example in a coker.

In any aspect or embodiment of the process described herein comprising a catalytic conversion process, the catalytic conversion process comprises Fluid Catalytic Cracking (FCC), residue FCC, hydrotreating, residue hydrotreating, hydrocracking, catalytic reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, or residue upgrading/hydroconversion (e.g., for example

/LC-

) A variant thereof, or a combination of any two or more thereof. The catalyst may comprise cobalt, molybdenum, nickel, tungsten, platinum, palladium, alumina, silica, zeolites, isomers thereof, oxides, sulfides, or combinations of any two or more thereof. In any embodiment, the catalytic conversion process may be operated at a temperature of about 250 ℃ to about 575 ℃. In any embodiment, the catalytic conversion process can be operated at a pressure of about 10 to about 3000 psig. In any embodiment, the catalytic conversion process may be at about 400 ℃ to about 575 ℃ and at about 1000 to about 300 ℃Operating at 0 psig. In any embodiment, the catalytic conversion process can be operated at about 450 ℃ to about 575 ℃ and at about 15 to about 100 psig.

In any aspect or embodiment of the methods described herein, it is understood that other refining processes, such as distillation (atmospheric or vacuum distillation), may be used as part of the process. Alternatively, in certain aspects or embodiments, other refining processes may be used in place of the thermal or catalytic conversion process (e.g., see fig. 4).

The hydrocarbon feedstock for the present process is or can be derived from a crude oil (e.g., petroleum, heavy oil, bitumen, shale oil, and oil shale). The hydrocarbon feedstock may also be a residual feedstock, such as a product of a thermal cracking process. The residual feedstock can be produced by various pretreatment processes of the present technology and will be referred to as "pretreated hydrocarbon feedstock," which can also be contacted with sodium metal and exogenous capping agents. Thus, the pretreated feedstock may comprise distillation products of hydrocarbon feedstocks, (atmospheric or vacuum residues, gasoline, diesel, kerosene and gas oils), as well as refinery intermediate streams. In any embodiment, the pretreated hydrocarbon feedstock can comprise hydroprocessed products, hydrocracker residue, hydroconversion residue (e.g., such as

(Chevron Global Lummus) residue or

(Axens) residue), FCC slurry, residual FCC slurry, atmospheric or vacuum residuum, solvent deasphalted tar, deasphalted oil, steam cracked tar, visbroken tar, high sulfur fuel oil, low sulfur fuel oil, asphaltenes, pitch, and coke. The aforementioned hydrocarbon feedstocks, including pretreated hydrocarbon feedstocks, may be from any geological formation (oil sands, conventional or tight reservoirs, shale oil, oil shale) or geographic location (north america, south america, middle east, etc.). In certain aspects and embodiments of the present process, particularly the second and third aspects, the hydrocarbon feedstock comprises a significant amount of aromatics, for example at least 10 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%,

in the process of the present technology, the hydrocarbon feedstock comprises hydrocarbons (e.g., hydrocarbon oils) and impurities. Similarly, the residual feedstock contains hydrocarbons and impurities. In some embodiments, the residual feedstock has a higher concentration of impurities than the hydrocarbon feedstock. As used herein, "impurities" refers to heteroatoms (i.e., atoms other than carbon and hydrogen), such as sulfur, oxygen, nitrogen, phosphorus, and metals. The impurities may be found in or comprise materials such as: naphthenic acid, water, ammonia, hydrogen sulfide, mercaptan, thiophene, benzothiophene, porphyrin, fe, V, ni, and the like. In any embodiment of the present process, the hydrocarbon feedstock or residual feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt% and an asphaltene content of at least 1 wt%. The sulfur content includes both asphaltene and non-asphaltene sulfur, but is measured as the weight percent of sulfur atoms in the feed. In any embodiment, the sulfur content can be in a range of from 0.5 wt.% to 15 wt.%, including, 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 a range between and including any two of the foregoing values. Thus, in any embodiment, the sulfur content may range from 1 wt% to 15 wt%, from 0.5 wt% to 8 wt%, or from 1.5 wt% to 10 wt%.

In the process of the present technology, asphaltene content refers to the total amount of asphaltenes in the feed, measured as the n-pentane insoluble fraction of the feed. However, in some aspects and embodiments of the present process, the asphaltene content can be in a range that is associated with a sufficient amount of one or more C _3-8 After the alkanes are mixed, as measured as the hydrocarbon feedstock or an insoluble fraction of the residual feedstock precipitated or otherwise separated from the feedstock. C _3-8 The alkane may be propane, butane, pentane, hexane, heptane, octane, isomers thereof, or mixtures of any two or more thereof. In any embodiment, the asphaltene content of the feed can be defined as the heptane-insoluble component. Detailed discussion of the physical properties and structure of asphaltenes and the process conditions (temperature, pressure, solvent/oil ratio) required to produce a particular asphaltene is described in j.g. sight "petroleum asphaltene section 1: asphaltenes, resins and petroleum structures (Petroleum and Natural gas science and technology (Oil)&Gas Science and Technology), IFP revision, vol.59 (2004), pp.467-477 (incorporated herein by reference in its entirety for all purposes). The standard test method for determining the heptane (C7) insoluble asphaltene content is described by ASTM standard D6560-17 and can be generalized to any alkane, including pentane.

In any embodiment of the present process, the asphaltene content of the hydrocarbon feedstock or residual feedstock can 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 be in a range of from 1 weight% to 100 weight%, 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 weight%, or between and including any two of the foregoing values. Thus, in any embodiment, the asphaltene content can be in a range of 2 wt% to 100 wt%, 1 wt% to 30 wt%, 2 wt% to 30 wt%, 5 wt% to 100 wt%, 10 wt% to 100 wt%, or 20 wt% to 100 wt%.

In any embodiment of the present process, 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. Due to the aromatic nature of asphaltenes, the diluent typically comprises an aromatic compound (i.e., a compound having an aromatic ring). The diluent can be a single compound (e.g., benzene, toluene, xylene, ethylbenzene, cumene, naphthalene, 1-methylnaphthalene), a mixture of any two or more thereof, or an aromatic refinery intermediate (e.g., light cycle oil, reformate). The amount of diluent required will vary with the asphaltene content of the feedstock and the viscosity required for processing. Higher asphaltene content in the feedstock may require more diluent than a feedstock with lower asphaltene content. It is within the skill of the art to select an appropriate amount of diluent to allow processing of asphaltenes in the present process.

The present process may also reduce/remove the naphthenic acid content and/or metal content of the converted feedstock compared to the hydrocarbon and pretreated hydrocarbon feedstock. In any embodiment, the hydrocarbon feedstock or pretreated hydrocarbon feedstock comprises (on a total or individual basis) from about 1 to about 10,000ppm of metals. The metal may be a naturally occurring metal bound to the hydrocarbon structure or residual metal fragments (e.g., corrosion products or catalyst fragments) entrained in the pretreated hydrocarbon feedstock during upstream processing. In any embodiment, 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 equal to or less than 82. In any embodiment, the metal is selected from the group of vanadium, nickel, iron, arsenic, lead, cadmium, copper, zinc, chromium, molybdenum, silicon, calcium, potassium, aluminum, magnesium, manganese, titanium, mercury, and combinations of any two or more thereof. In any embodiment, the metal is selected from the group consisting of vanadium, nickel, iron, and combinations of any two or more thereof. In any embodiment, the metal concentration of the hydrocarbon feedstock or pretreated hydrocarbon feedstock can be from about 2 to about 10,000ppm, from about 10 to about 10,000ppm, from about 100 to about 5,000ppm, from about 10 to about 1,000ppm, from about 100 to about 1,000ppm, etc. (either by total or on an individual basis).

The process of the present technology not only upgrades hydrocarbons and pretreated hydrocarbon feedstocks by removing/reducing impurities, but also improves physical properties such as viscosity and density. The hydrocarbon feedstock or pretreated hydrocarbon feedstock can have a viscosity at 50 ℃ of between 1 and 10,000,000cst. For example, the viscosity can be 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 9,000,000cst, or a range between and including any two of the foregoing values. Thus, in any embodiment, the viscosity of the hydrocarbon feedstock or pretreated hydrocarbon feedstock can be, for example, 100 to 10,000,000cst, 380 to 9,000,000cst, 500 to 9,000,000cst, or 500 to 5,000,000cst, among others.

The hydrocarbon feedstock or pretreated hydrocarbon feedstock may have a viscosity of 800 to 1200kg/m at 15.6 ℃ or 60 ° F ³ The density of (c). For example, the density may be 800, 825, 850, 875, 900, 925, 975, 1000, 1050, 1100, 1150 or 1200kg/m ³ Or a range between and including any two of the preceding values. Thus, in any embodiment, the density may be, for example, 850 to 1200kg/m ³ 900 to 1200kg/m ³ 950 to 1200kg/m ³ Or 925 to 1100kg/m ³ 。

In the process of the present technology, a hydrocarbon feedstock or a 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 generated sodium metal, for example as described in US 8,088,270, which is incorporated herein by reference in its entirety. By "effective amount" is meant the amount of a material or agent that produces the desired result. For example, an effective amount of sodium metal in the present process can comprise a stoichiometric, superstoichiometric, or substoichiometric amount of sodium metal sufficient to reduce the amount of asphaltenes and/or sulfur in the hydrocarbon feedstock.

The exogenous capping agent used in the present process is typically used to cap the radicals formed when sulfur and other heteroatoms are abstracted by sodium metal during the contacting step. While some feedstocks may inherently contain small amounts of naturally occurring blocking agents ("endogenous blocking agents"), such amounts are insufficient to block substantially all of the free radicals produced by the present process. An effective amount of exogenous (i.e., added) capping agent is used in the present process, e.g., 1 to 1.5 moles of capping agent (e.g., hydrogen) can be used per mole of sulfur, nitrogen, or oxygen present. Based on the disclosure herein, it is within the skill in the art to determine the effective amount of exogenous capping agent needed to carry out the present process for the particular hydrocarbon feedstock or pretreated hydrocarbon feedstock being used. The exogenous capping agent can comprise hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethylene, propylene, butene, pentene, dienes, isomers of the foregoing, or a mixture of any two or more thereof. In any embodiment, the exogenous capping agent can be hydrogen and/or C _1-6 Free of cycloalkanes and/or C _2-6 Acyclic olefins or mixtures of any two or more thereof。

The effective amount of sodium in its metallic state and used in the contacting step will vary with the level of heteroatoms, metals and asphaltene impurities of the hydrocarbon and pretreated hydrocarbon feedstock, the desired degree of conversion or removal of the impurities, the temperature used, and other conditions. In any embodiment, a stoichiometric or greater than stoichiometric amount of sodium metal can be used to remove all or substantially all of the sulfur content, e.g., 1-3 molar equivalents of sodium metal relative to the sulfur content. In any embodiment, the hydrocarbon feedstock or pretreated hydrocarbon feedstock is contacted with greater than 1 molar equivalent of sodium metal (e.g., 1.1, 1.15, 1.2, 1.25, 1.3, 1.4, 1.5, 2, 2.5, or 3 molar equivalents of sodium metal) relative to the sulfur content therein.

Surprisingly, a sub-stoichiometric ratio of sodium metal to sulfur content (in the hydrocarbon feedstock/pretreated hydrocarbon feedstock) can be used to preferentially reduce the amount of asphaltene sulfur relative to non-asphaltene sulfur. Thus, in any embodiment, the pretreated hydrocarbon feedstock (or alternatively the hydrocarbon feedstock) can be contacted with sodium metal in an amount less than stoichiometric with respect to the sulfur content therein. In the present technology, it is understood that the stoichiometric amount of sodium metal relative to the 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 appreciate that the stoichiometric amount of sodium metal required to convert all of the sulfur to sodium sulfide in a feedstock containing about 1 mole of sulfur atoms is 2 moles of sodium metal. In such an example, the less than stoichiometric amount of sodium metal relative to the sulfur content will be less than 2 moles of sodium metal, such as 1.6 moles, which will be 0.8 molar equivalents of sodium metal. In any embodiment, the substoichiometric amount of sodium metal relative to sulfur content may be 0.1 equivalents to less than 1 equivalent. Examples of such sub-stoichiometric amounts include 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 relative to sulfur content, or a range between and including any two of the foregoing values. Thus, in any embodiment, the substoichiometric amount can be in the range of 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 is conducted at a temperature of about 250 ℃ to about 500 ℃, the sodium metal will be in a molten (i.e., liquid) state. For example, the contacting step can be performed at about 250 ℃, about 275 ℃, about 300 ℃, about 325 ℃, about 350 ℃, about 375 ℃, about 400 ℃, about 425 ℃, about 450 ℃, about 500 ℃, or a range between and including any two of the foregoing temperatures. Thus, in any embodiment, the contacting can be performed at about 275 ℃ to about 425 ℃, or about 300 ℃ to about 400 ℃ (e.g., at about 350 ℃).

In any embodiment, the contacting step can be performed at a pressure of about 400 to about 3000psi, for example, between and including about 400psi, about 500psi, about 600psi, about 750psi, about 1000psi, about 1250psi, about 1500psi, about 2000psi, about 2500psi, about 3000psi, or any two of the foregoing values.

The reaction of sodium metal with heteroatom contaminants in the hydrocarbon/pretreated hydrocarbon feedstock is relatively fast and can be completed in a matter of minutes, if not seconds. Mixing the combination of the feedstock and sodium metal further accelerates the reaction and is commonly used for such reactions on an industrial scale. However, certain embodiments may require extended residence times to improve the degree of conversion or to adjust operating conditions for the purpose of removing a particular heteroatom impurity. Thus, in any embodiment, the contacting step is carried out for about 1 minute to about 120 minutes, e.g., about 1 minute, about 5 minutes, about 7 minutes, about 9 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 45 minutes, about 60 minutes, about 75 minutes, about 90 minutes, about 105 minutes, or about 120 minutes, or for a time between and within a range including any two of the foregoing values. Thus, in any embodiment, the time can range from about 1 to about 60 minutes, about 5 minutes to about 60 minutes, about 1 to about 15 minutes, about 60 minutes to 120 minutes, and the like.

The process produces a converted feedstock comprising a hydrocarbon oil having a sulfur content less than the sulfur content of the hydrocarbon feedstock (or pretreated hydrocarbon feedstock). In any embodiment, the sulfur content of the converted feedstock can be less than 0.5 wt.%, such as less than or about 0.4 wt.%, less than or about 0.3 wt.%, less than or about 0.2 wt.%, less than or about 0.1 wt.%, and even less than or about 0.05 wt.%, or a range between and including any two of the foregoing values. The efficiency of removing sulfur content from a hydrocarbon feedstock or a pretreated hydrocarbon feedstock, also referred to as conversion efficiency, as compared to a converted feedstock, can be at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% by weight, or a range between and including any two of the foregoing values. In the case where the effective amount of sodium metal is greater than the stoichiometric amount, the sulfur content conversion efficiency can be very high, e.g., at least 90%.

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

The converted feedstock of the present technology has a reduced metal concentration compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock. The metal content of the converted feedstock may be reduced by at least 20%, for example by 20% to 100%, compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock. Examples of percent metal reduction (total or individual) in the converted feedstock as compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock include 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 97%, 98%, 99%, 100%, or ranges between and including any two or more of the foregoing values. Thus, in any embodiment, the percent reduction may be 20% to 99%,20% to 95%,70% to 99%, or to 100%. In some embodiments, the metal is selected from iron, vanadium, nickel, or a combination of any two or more thereof. For example, the iron content and vanadium content of the converted feedstock have been reduced by at least 20% as compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock. Similarly, in any of the examples, the nickel content of the converted feedstock has been reduced by at least 20% as compared to the hydrocarbon feedstock or the pretreated hydrocarbon feedstock.

The present process also provides a converted feedstock having improved physical properties compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock. However, it has been found that the physical properties of the converted feedstock of the present process do not necessarily vary in proportion to the sodium to sulfur ratio. For example, for a given sodium to sulfur ratio, the degree of metal demetallization, especially metals detrimental to catalyst life (including iron, vanadium and nickel), will generally be greater than the degree of desulfurization. Unlike the catalytic conversion process, example 6 demonstrates the insensitivity of sodium treatment to the initial metal content. Sodium demetallization at low sodium/total sulfur addition ratios can be very advantageous for pretreating hydrocarbon feedstocks having undesirably high metal contents prior to catalytic conversion or treatment.

Additional physical properties that greatly reduce the value of the heavy residual feedstock are improved after treatment with sodium. Desulfurization of the asphaltene fraction occurs without hydrogen saturation being observed in hydroconversion or carbon rejection exhibited by thermal cracking processes. As a result, at least a portion of the asphaltene content is converted by the present process into a soluble, stable, and desulfurized converted liquid product, increasing the yield of higher value liquid products (e.g., hydrocarbon oils from asphaltenes). Thus, the asphaltene content of the converted feedstock produced by the present process can be less than the asphaltene content of the hydrocarbon feedstock (or pretreated hydrocarbon feedstock). In any embodiment, the present process converts at least some of the asphaltenes to hydrocarbon oils, such as paraffins. In any embodiment, at least 5%, at least 10%, at least 15%, at least 20%, or more of the asphaltene content of the pretreated hydrocarbon feedstock is converted to liquid hydrocarbon oil in the converted feedstock. The conversion efficiency of the asphaltene content removed from the hydrocarbon feedstock or pretreated hydrocarbon feedstock varies with the amount of sodium used, but is typically higher, e.g., 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 ranges between and including any two of the foregoing values (e.g., 70% to 100%, or 75% to 99.9%, etc.).

Converting asphaltenes to smaller, lower molecular weight components with fewer attached functional groups typically results in a viscosity reduction of at least 40% up to 5 orders of magnitude (10000 ×), and an increase in API gravity of about 1 to about 3 units per 1 wt% removal of sulfur. In any embodiment, the viscosity of the converted feedstock can be reduced by at least 50cSt, or by at least 40%, at 50 ℃. In any such embodiment, the viscosity is reduced by at least 100cSt, at least 200cSt, at least 300cSt, or more at 50 ℃. For any of the hydrocarbon feedstocks or pretreated hydrocarbon feedstocks disclosed herein having a viscosity greater than 1,000cst (see above), the reduction is particularly large, and can be at least a 50%, at least a 60%, at least a 70%, at least an 80%, at least a 90%, at least a 95%, at least a 99%, or even a 100% reduction in viscosity (e.g., at least a 40% to 99% reduction in viscosity in any embodiment, the density of the converted feedstock is reduced by about 5 to about 25kg/m per 1 wt% reduction in sulfur content of the converted feedstock as compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock ³ . For example, the reduction in density can be about 5, about 10, about 15, about 20, about 25kg/m ³ Or a range between and including any two of the preceding values (e.g., about 5 to about 20 kg/m) ³ Or about 10 to about 25kg/m ³ Etc.).

As described above, in any embodiment, the present process canTo include pre-treatment of the hydrocarbon feedstock containing impurities prior to contact 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 feedstock to be processed. For example, the original crude oil may be distilled to produce one or more light distillate fractions (light distillate cuts) as a purified feedstock and an atmospheric residuum (pretreated hydrocarbon feedstock) having a higher sulfur content and a higher asphaltene content than in both the purified feedstock and the original crude oil (hydrocarbon feedstock). Alternatively, the hydrocarbon feedstock can be pretreated to remove a portion of the undesired impurities, thereby providing a purified feedstock having a lower concentration of impurities and a pretreated hydrocarbon feedstock having impurities remaining after pretreatment. The pretreated hydrocarbon feedstock may include impurities because of the selected conversion level or because the pretreatment process is unable to remove the impurities. For example, vacuum residuum may be in a hydroprocessing reactor (e.g., a reactor with a catalyst system)

Unit or

Unit) to remove sulfur and convert the residua fraction to higher value products. However, after hydrotreating in the presence of a catalyst at operating conditions in excess of 350 ℃ and 1500-3000psig, the refractory sulfur and asphaltene fractions remain in the hydrotreated bottoms stream. The pretreatment process may include a separation process, a thermal or catalytic conversion process or treatment process, or a combination of any two or more thereof.

In any embodiment, the pretreatment process may comprise a separation process comprising one or more of physical separation using energy (heat), phase addition (solvent or absorbent), pressure variation, or application of an external field or gradient to concentrate impurities in the pretreated hydrocarbon feedstock. The separation process may comprise gravity separation, flash evaporation, distillation, condensation, drying, liquid-liquid extraction, stripping, absorption, centrifugation, electrostatic separation, and variants thereof. The separation process may further comprise a solventExtraction process, including solvent deasphalting process, e.g. supercritical extraction of residual oil

For example, a hydrocarbon feedstock may be desalted to remove salt and water, an API separator may be used to separate water and solids from oil, or a distillation column may be used to separate low sulfur, low boiling products from high sulfur, high boiling products in crude oil. The separation process may also require solid reagents or barriers such as adsorption, filtration, permeation, or variants thereof. Each of the disclosed separation processes produces a purified feedstock having a lower concentration of impurities than the hydrocarbon feedstock and a pretreated hydrocarbon feedstock having a higher concentration of impurities than the purified feedstock. In any embodiment, the pretreated hydrocarbon feedstock includes a higher concentration of impurities than the impurities in the hydrocarbon feedstock.

In any embodiment, the pretreatment process can comprise a thermal or catalytic process that changes the molecular structure or causes at least a portion of the carbon content of the hydrocarbon feedstock to be rejected. The thermal conversion process may comprise a coker, visbreaker, or other process to increase the yield of cracked distillates by discharging carbon as coke. The catalytic processes may comprise fixed bed and fluidized bed processes such as, but not limited to, catalytic crackers (FCC or resid FCC), hydrocrackers, resid hydrocrackers, and hydroconversion (e.g., LC)

). The conversion process may be a hydrotreating process that requires both hydrogen and a catalyst.

The pretreatment step of the present process may comprise a treatment that results in hydrocarbon saturation or removal of specific impurities based on the total feed. Thus, in any embodiment, the pretreatment process may comprise solvent deasphalting, hydrotreating, residue Hydrotreating (RHT), hydrodesulfurization (RDS), hydrodemetallation (HDM), or Hydrodenitrogenation (HDN), or a combination of two or more thereof. While the overall concentration of an impurity (or impurities) may be reduced, the treatment process typically results in a purified feedstock having a lower concentration of impurities than the hydrocarbon feedstock and a pretreated hydrocarbon feedstock having a higher concentration of impurities than the purified feedstock. However, the concentration of impurities in the pretreated hydrocarbon feedstock may be lower than the hydrocarbon feedstock. In addition, catalytic treatment processes are generally unable to process feedstocks with high concentrations of impurities in asphaltenes due to accelerated catalyst deactivation from metals and trace carbon residues.

The process of the present technology produces a mixture comprising the converted feedstock and the sodium salt. The process may further comprise separating the sodium salt from the converted feedstock. The sodium salt consists of particles that may be very fine (e.g., <10 μm) and cannot be completely removed by standard separation techniques (e.g., filtration or centrifugation). In any embodiment, the separating can comprise a. Heating the mixture of sodium salt and converted feedstock with elemental sulfur to a temperature of about 150 ℃ to 500 ℃ to provide a sulfur-treated mixture comprising 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 U.S. patent No. 10,435,631, the entire contents of which are incorporated herein by reference for all purposes.

The process may further comprise recovering metallic sodium from the separated sodium salt. In any embodiment, the present process can further comprise 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 may be carried out in an electrochemical cell according to, for example, U.S. patent No. 8,088,270 or U.S. provisional patent application No. 62/985,287, the entire contents of each of which are incorporated herein by reference for all purposes. The electrochemical cell may comprise 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 compartment. An anode comprising a sodium salt is disposed in the anolyte compartment. A power supply is electrically connected to the anode and the cathode. In any embodiment, the separated sodium salt is dissolved in an organic solvent prior to electrolysis of the salt to provide sodium metal.

Current thermal and catalytic desulfurization processes generate hydrogen sulfide as a by-product that must be carried overThe sulfur recovery unit is treated in a claus plant. The Sulfur Recovery Unit (SRU) is very efficient, but releases sulfur emissions during operation; therefore, refinery complexes (refining complexes) are subject to strict sulfur emission limits set by local and national authorities. In many cases, refinery complexes operate near or at their sulfur emission limits. Desulfurization with sodium produces an elemental sulfur product that can be stored in solid or liquid form and sold to the market. The amount of sulfur displaced by each organically bound sulfur removed using sodium corresponds to the amount of H that must be processed in the SRU ₂ And S. As a result, the refinery complex gains operational flexibility to reduce the throughput and operating costs (and thus sulfur emissions) of existing SRUs or to increase the sulfur handling capacity of the facility by desulfurizing at least a portion of the hydrocarbon feedstock with sodium. In any embodiment, the present process comprises a sulfur recovery step using a sulfur recovery unit (e.g., a claus plant, SCOT unit, etc.). In any such embodiment, the capacity of the sulfur recovery unit is increased in proportion to the sulfur recovered during the treatment of the hydrocarbon feedstock with sodium.

Illustrative embodiments of the processes of the present technology will now be described with reference to the flow diagrams of fig. 1-4. With respect to the purification and conversion system 10 of fig. 1, a hydrocarbon feedstock 101 containing sulfur and asphaltene impurities as described herein (e.g., a sulfur content of at least 0.5 wt.% (herein, "wt.%" means "weight percent") and an asphaltene content of at least 1 wt.%) is charged to a reactor 120 (continuously or intermittently) along with an effective amount of sodium metal 103 and an exogenous capping agent 105 as described herein. The reaction may be conducted at elevated temperatures and pressures as described herein, and is typically completed within minutes to yield a mixture 121 of sodium salts and converted feedstock, although higher asphaltene-containing feeds may take longer as disclosed herein. As described herein, the converted feedstock comprises a hydrocarbon oil having a sulfur content that is less than the sulfur content of the hydrocarbon feedstock, and may comprise an asphaltene content that is less than the asphaltene content of the hydrocarbon feedstock. In addition, the proportion of asphaltene sulfur to non-asphaltene sulfur in the converted feed is lower than in the hydrocarbon feed. Optionally, the mixture 121 is transferred from the reactor 120 to another vesselIn 130, the sodium salt is agglomerated into particles large enough to be easily separated from the converted feedstock in the vessel. Although any suitable agglomeration method may be used, agglomeration with elemental sulfur 107 at elevated temperatures as described herein may be used. The resulting mixture 131 of agglomerated sodium salt, metal and converted feedstock may then be separated by any suitable process and apparatus 140, such as by a centrifuge, to yield a converted feedstock 141 free of metal 143 and sodium salt 145. Optionally, the sodium salt 145 can be electrolyzed in an electrolytic cell 150 having a sodium ion selective ceramic membrane 152, such as a NaSiCON membrane, to provide sodium metal 153 and elemental sulfur 157, as described herein. In the present process, sodium metal 153 and elemental sulfur 157 may be reused as 103 and 107, respectively. The converted feedstock 141 can be subjected to a thermal conversion process 160, such as a coking process, a visbreaking process, or other such processes as described herein, to provide purified products 161 (e.g., naphtha, diesel, gas oil, and light and heavy cycle oils), gaseous products 163 (e.g., steam, H), and a gas ₂ S、C ₁ -C ₄ Saturated gas, C ₂ -C ₄ Olefins and isobutane) and residual products 165 (e.g., coke or visbroken tar). The ratio of purified product 161 to residual product 165 is greater than that produced by subjecting the hydrocarbon feedstock 101 to the same thermal conversion process without first desulfurizing the feed with sodium as described herein.

In some embodiments of the present process utilizing the purification and conversion system 10 of fig. 1, the hydrocarbon feedstock 101 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 15ppm, and a trace carbon residue content of at least 5 wt%. The converted feedstock 121/141 includes hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock 101, trace carbon residues less than the carbon residues in the feedstock 101, and may have an asphaltene content less than the asphaltene content of the hydrocarbon feedstock 101. After subjecting the converted feedstock 141 to a suitable thermal conversion process, a quality anode grade coke having less than 0.5 wt% sulfur and less than 150ppm vanadium can be produced.

Figure 2 illustrates another process embodiment of the present technology using a purification and conversion system 20. The impure hydrocarbon feedstock 201 may contain 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 an exogenous capping agent 205, similar to the process shown in fig. 1 and described herein. The resulting mixture 221 of sodium salts and converted feedstock may be processed into an agglomerate 230 (with elemental sulfur 207) and sodium salt 245 separated 240 from the converted feedstock 241 as described herein. The converted feedstock 241 comprises hydrocarbons having a sulfur content of less than 0.5 wt.%, a vanadium content of less than 50ppm, a nickel content of less than 50ppm, a lower asphaltene concentration than in the hydrocarbon feedstock, and/or a greater proportion of lower boiling hydrocarbons (< 538 ℃) to residual hydrocarbons (> 538 ℃) than in the hydrocarbon feedstock 201. Again, sodium salt 245 may 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 (such as 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 embodiment may be carried out using purification and conversion system 30, but using an optional thermal conversion step 360 to produce a double converted product 361, which is then subjected 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 gaseous product 363 and residual product 365.

Fig. 4 illustrates another process embodiment of the present technology using the purification and conversion system 40, wherein an impure hydrocarbon feedstock 401 is pretreated in a process/plant 400 to provide a first residual feedstock 402 and a purified feedstock 404. Any suitable pretreatment process that produces the first residual feedstock 402 and the first purified feedstock 404 may be used, as described herein. The residual feedstock 402 may optionally be further pretreated (410) to provide a second residual feedstock 411 and a purified feedstock 413. Optionally, one or more impurities (e.g., gaseous impurities such as H) during the first and/or second (e.g., illustrated) pretreatment steps ₂ S、NH ₃ Water, light hydrocarbons, etc.) can be removed in a separate stream 415. The second residual feedstock 411 may then be treated with metallic sodium 403 and exogenous capping agent 405 in reactor 420 as described herein to provide a mixture 421 of sodium salt and converted feedstock. The sodium salt of mixture 421 may then be agglomerated (430) and separated (440) as previously described to provide converted feedstock 441, metal 443, and sodium salt 445. As described herein, sodium salt 445 may be electrolyzed in an electrolytic cell 450 having a sodium ion selective ceramic membrane 452 (e.g., naSiCON) to provide recovered sodium metal 453 and elemental sulfur 457. The converted feedstock 441 can be subjected to any refining process 480 (e.g., distillation, thermal conversion, catalytic conversion, etc.) to give a fuel grade product 482 and a residual product 481.

Examples of the invention

EXAMPLE 1 desulfurization of Hydrocarbon feedstocks with sodium

Various hydrocarbon feedstocks were treated with sodium metal to demonstrate the wide applicability of sodium metal treatment in removing impurities and improving physical properties. The hydrocarbon feedstocks comprise raw crude oil from various geographic locations and geological formations, as well as various converted and processed feedstocks located within typical refinery and upgrading facilities. 700g of a hydrocarbon feedstock was treated with the appropriate mass of sodium in a 1.8L 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 salts. The reaction conditions, feeds and product properties are shown in table 1.

The results from table 1 clearly show that the molten sodium metal effectively removes impurities and improves the physical properties of the converted feedstock, thus improving the substitutability of the converted feedstock. The converted feedstock can now be sold directly as a fuel grade product or converted in a downstream refinery unit to a higher value product rather than sold as bitumen or high sulfur bunker fuel oil.

TABLE 1

EXAMPLE 2 desulfurization of Hydrocarbon feedstocks with sodium

Various hydrocarbon feedstocks and pretreated hydrocarbon feedstocks are treated with sodium metal in a pilot plant using a continuous system substantially as shown, for example, in fig. 4, to further demonstrate the broad applicability of sodium metal treatment to remove impurities and improve physical properties during continuous operation. The hydrocarbon and pretreated hydrocarbon feedstocks comprise raw crude oil, vacuum residue, and partially converted feedstock produced in typical refinery and upgrading facilities. Each feed was treated with an appropriate mass of sodium in a 12L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Hydrogen is the exogenous capping agent for all tested activities. The reaction conditions, feed and product properties are shown in table 2.

Similar to example 1, the results from table 2 clearly show that molten metallic sodium effectively removes impurities and improves the physical properties of the converted feedstock, thus improving the substitutability of the converted feedstock. The converted feedstock can now be sold directly as a fuel grade product or converted in a downstream refinery unit to a higher value product rather than sold as bitumen or high sulfur bunker fuel oil.

TABLE 2

Example 3: preferential removal of sulfur from asphaltene fractions

In 5 separate experiments, the combined vacuum residuum stream was treated with increasing molar equivalents of sodium. 700g of vacuum residue was contacted with sodium at 350 c and 750psig partial pressure of hydrogen. Key results are summarized in table 3. The effect of treatment with sodium on the preferential removal of sulfur from the asphaltene fraction is summarized by:

1. at a sodium to sulfur ratio of 0.94, the fraction of total sulfur located in the asphaltenes was reduced from 28.5% to 7.9% of the converted products.

2. The proportion of asphaltene sulfur to non-asphaltene sulfur decreases with increasing molar equivalents of sodium. The reduction in the ratio indicates that at all practical sodium to sulfur ratios, a greater proportion of sulfur is removed from the asphaltene sulfur than from the non-asphaltene sulfur-a key consequence of unloading the hydrotreating catalyst in downstream refining processes (e.g., in the process shown in fig. 2).

Table 3: removal of sulfur from various oil fractions

Example 4: improving hydrocarbon conversion in catalytic conversion processes by pretreatment with sodium

Refinery intermediate streams (i.e., pretreated hydrocarbon feedstocks) were treated with various molar equivalents of sodium to demonstrate how the molar equivalents of sodium were selected to improve hydrocarbon conversion in downstream catalytic conversion processes. 700g of each refinery intermediate was treated with sodium at a hydrogen partial pressure of 350 ℃ and 750psig or 400 ℃ and 1500 psig. Key results are summarized in table 4.

For pretreatment of FCC or Resid Hydrotreater (RHT) feedstocks, it may be preferable to treat the hydrocarbon feedstock with sub-stoichiometric molar equivalents of sodium by preferentially removing the catalyst-contaminating impurities, asphaltene sulfur, metals, and asphaltenes. In all cases, a greater proportion of sulfur is removed from the asphaltene fraction. In addition, the fraction of metals removed exceeded the fraction of total sulfur removed, indicating that a low sodium/sulfur addition ratio may be advantageous to produce a partially converted product with low metal and asphaltene sulfur content for further processing in downstream refining processes.

TABLE 4

Example 5: production of low sulfur fuel oil meeting specifications from vacuum residuum feedstock

For example, as shown in figure 1, a vacuum resid feed was treated with sodium metal in a pilot plant using a continuous system to demonstrate the production of low sulfur fuel oil meeting specifications. The vacuum residue feedstock was treated with an appropriate mass of sodium in a 12L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Hydrogen is the exogenous capping agent for all tested activities. The reaction conditions, feeds and product properties are shown in table 5.

This example clearly shows that low sulfur fuel oils meeting specifications can be produced when a hydrocarbon feedstock is contacted with an effective amount of sodium and an effective amount of an exogenous capping agent.

TABLE 5

Example 6: improving yield and quality of coker product by pretreating coker feed with sodium

The four feedstocks in table 1, vacuum residuum, SDA tar, visbreaker residue, and hydrocracker residue, were treated with sodium metal to demonstrate the improved yield and quality of coker products when the coker feedstock was pretreated with sodium metal prior to thermal conversion. 700g of a hydrocarbon feedstock was treated with the appropriate mass of sodium in a 1.8L 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 salts. The reaction conditions, feeds and product properties are shown in table 1. For "as received" hydrocarbon feedstocks and sodium treated converted feedstocks, product yields and quality of coker products were estimated using recognized industry correlations (Gary, j.h. and Handwerk, g.e. (2001), "Petroleum Refining", new york massel Dekker (Marcel Dekker, new york)). The coker products are summarized in table 6.

The results from table 6 clearly show that treating the feed with molten sodium metal prior to thermal conversion increases the overall liquid yield, reduces coke yield, increases the ratio of purified to residual product, and reduces the sulfur content of all coker products when compared to the thermal conversion of the as received feedstock.

Furthermore, the results demonstrate that treating the feedstock with molten sodium metal can reduce the burden on the sulfur recovery process (i.e., the claus plant or the SCOT plant). In 4 examples, sulfur gas production process (e.g., H) ₂ S) is reduced by more than 90%. Such a process configuration facilitates increasing the sulfur handling capacity of the refinery without increasing sulfur emissions or exceeding limits.

TABLE 6

Example 7: production of high purity high quality anode coke or needle coke by pretreatment with sodium

For the same four feedstocks from example 6 (vacuum residue, SDA tar, visbreaker residue and hydrocracker residue), the accepted industrial relevance of the "as received" hydrocarbon feedstock and sodium treated converted feedstock (Gary, j.h. and Handwerk, g.e. (2001) "petroleum refinery", n.y. Massel dekker) was used to estimate coke product quality and is summarized in table 7. None of the cokes produced in accordance with the received feed meets anode grade coke specifications, while all of the coke products produced from the converted feedstock approach or exceed anode grade coke specifications. Vanadium specification can be achieved by slightly increasing the molar equivalents of sodium during the sodium contacting step.

TABLE 7

Example 8: improving distillation properties of petroleum products by pretreating feed with sodium

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

TABLE 8

Equivalents of the formula

While certain embodiments have been illustrated and described, modifications, equivalent substitutions, and other types of modifications of the processes and products of the present techniques, which will occur to those of ordinary skill in the art upon reading the foregoing description, may be made as set forth herein. Each of the aspects and embodiments described above may also have incorporated therein or incorporated therein variations or aspects as disclosed with respect to any or all of the other aspects and embodiments.

The present technology is also not limited to the specific aspects described herein, which are intended as single illustrations of individual aspects of the technology. It will be apparent to those skilled in the art that many modifications and variations can be made to the present technology without departing from the spirit and scope of the technology. Functionally equivalent methods within the scope of the technology will be apparent to those skilled in the art from the foregoing description, in addition to the methods enumerated herein. Such modifications and variations are intended to fall within the scope of the appended claims. It is to be understood that this technology is not limited to particular processes, materials, compositions, or conditions, as such processes, materials, compositions, or conditions may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Accordingly, it is intended that the present specification be considered as exemplary only, with a true scope, spirit and scope of the technology being indicated only by the following claims, definitions therein and any equivalents thereof.

The embodiments illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising", "including", "containing", and the like are to be construed expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the technology claimed. Similarly, the use of the terms "comprising," including, "" containing, "and the like, should be understood to disclose embodiments using the terms" consisting essentially of 8230; \8230, composition, "and" consisting of 8230; \8230, composition. The phrase "consisting essentially of 8230 \8230"; composition "will be understood to encompass those elements specifically recited 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 specified.

Further, where features or aspects of the disclosure are described in terms of markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the markush group. Each of the narrower species and subgeneric groups falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

As will be understood by one of skill in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be readily considered to be the same range that fully describes and enables the decomposition into at least equal two, three, four, five, ten, etc. As a non-limiting example, each range discussed herein may be readily broken down into a lower third, a middle third, and an upper third, etc. As will also be understood by those skilled in the art, all language such as "at most," "at least," "greater than," "less than," and the like, includes the number recited and refers to ranges which can be subsequently broken down into subranges as discussed above. Finally, those skilled in the art will appreciate that a range encompasses individual members.

All publications, patent applications, issued patents, and other documents cited in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document were specifically and individually indicated to be incorporated by reference in its entirety. To the extent a definition contained in the text incorporated by reference contradicts a definition in this disclosure, the definition is not included.

Other embodiments are set forth in the following claims, with the full scope of equivalents to which such claims are entitled.

Claims (42)

1. A process for improving the yield of liquid hydrocarbons from a thermal conversion process, the 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 to 500 ℃ to produce a mixture of sodium salts and converted feedstock, wherein

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 trace carbon residue content of at least 5 wt%;

the converted feedstock comprises hydrocarbons having a sulfur content less than the sulfur content of the hydrocarbon feedstock, a trace carbon residue content less than the trace carbon residue content of the hydrocarbon feedstock, and an asphaltene content less than the asphaltene content of the hydrocarbon feedstock; 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 purified product to residual product is greater than that produced by subjecting the hydrocarbon feedstock to the same thermal conversion process.

2. A 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 to 500 ℃ to produce a mixture of sodium salts and converted feedstock, wherein

The hydrocarbon feedstock comprises hydrocarbons having a sulphur content of at least 0.5 wt%, an asphaltene content of at least 1 wt%, a vanadium content of at least 15ppm and a trace carbon residue content of at least 5 wt%;

said converted feedstock comprising hydrocarbons having a sulfur content less than the sulfur content of said hydrocarbon feedstock, trace carbon residues less than the trace carbon residues of said hydrocarbon feedstock, and an asphaltene content less than the asphaltene content of said hydrocarbon feedstock; and

subjecting the converted feedstock to a thermal conversion process to produce a quality anode grade coke product having less than 0.5 wt% sulfur and less than 150ppm vanadium.

3. A process, comprising:

contacting the hydrocarbon feedstock with an effective amount of sodium metal and an effective amount of an exogenous capping agent at a temperature of 250 ℃ to 500 ℃ to produce a mixture of sodium salts and converted feedstock, wherein

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 10ppm, and a trace carbon residue content of at least 5 wt.%;

said converted feedstock comprising hydrocarbons having a sulfur content of less than 0.5 wt%, trace carbon residues less than trace carbon residues in said hydrocarbon feedstock and an asphaltene content of less than 0.25 wt% and an ash content of <0.1 wt%; and

treating the converted feedstock in a thermal conversion process to produce a high purity needle coke product having less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10ppm nickel, greater than 2.5x10 ⁷ Coefficient of thermal expansion of/° C and 320X10 ⁶ Resistivity of Ohm-In.

4. A 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 ℃ to 500 ℃ to produce a mixture of sodium salts and converted feedstock, wherein

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 metals content of at least 100 ppm;

the converted feedstock comprises hydrocarbons having a sulfur content of less than 0.5 wt%, a vanadium content of less than 50ppm, a nickel content of less than 50ppm, a lower concentration of asphaltenes than is present in the hydrocarbon feedstock, and a higher ratio of lower boiling hydrocarbons (< 538 ℃) to residual hydrocarbons (> 538 ℃) than is present in the hydrocarbon feedstock;

optionally further subjecting the converted feedstock to a thermal conversion process to provide a double converted product; and

the converted feedstock or dual converted feedstock is subjected to a catalytic conversion process to produce fuel grade products without mixing or additional conversion processing.

5. A 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 ℃ to 500 ℃ to produce a mixture of sodium salts and converted feedstock, wherein

The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, 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, trace carbon residue, 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, trace carbon residue, metal content, and compatibility; and

the fuel grade specification is a viscosity of less than 380cSt at 50 ℃, less than 991kg/m ³ A trace carbon residue content of less than 18 wt%, a vanadium content of less than 350mg/kg, and a cleanliness field test result of 1 or 2 as measured by ASTM D4740.

6. The process of claim 4, further comprising:

subjecting the converted feedstock to a thermal conversion process to provide the doubly converted feedstock and a solid coke product,

wherein

The converted feedstock has a trace carbon residue content of at least 5 wt%, and

the product of the double conversion comprises

The impurity concentration is lower than the impurity concentration in the hydrocarbon feedstock and

hydrocarbons having a ratio of lower boiling point hydrocarbons (< 538 ℃) to higher boiling point residue hydrocarbons (> 538 ℃) that is greater than the ratio of the converted feedstock.

7. The process of any one of claims 1 to 6, further comprising pretreating the hydrocarbon feedstock prior to the contacting step to provide a purified feedstock and a pretreated hydrocarbon feedstock, wherein

The purified feedstock comprises a lower concentration of impurities than the hydrocarbon feedstock prior to pretreatment,

the pretreated hydrocarbon feedstock includes a higher concentration of impurities than the purified feedstock, and

the pretreated hydrocarbon feedstock is the feedstock that is subjected to the contacting step to produce the converted feedstock.

8. The process of claim 7, wherein the pre-treatment step comprises phase separation by an externally applied field, separation by heating, hydroconversion, thermal conversion, catalytic treatment, solvent extraction, solvent deasphalting, or a combination of any two or more thereof.

9. The process of claim 7 or claim 8, wherein the pretreating 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.

10. The process of any one of claims 1 to 9, wherein the thermal conversion process comprises visbreaking, delayed coking, fluid coking, flexicoking (TM), pyrolysis, variants thereof, or a combination of any two or more thereof.

11. The process of claim 10, wherein the thermal conversion process operates at a temperature of about 400 ℃ to about 570 ℃.

12. The process of claim 10 or 11, wherein the thermal conversion process is operated at a pressure of about 10 to about 200 psig.

13. The process of any one of claims 1 to 12, wherein the thermal conversion process operates at about 450 ℃ to about 500 ℃ and about 20-100 psig.

14. The process of claim 4, wherein the catalytic conversion process comprises Fluid Catalytic Cracking (FCC), residual FCC, hydrotreating, residual hydrotreating, hydrocracking, catalytic reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, or residue upgrading/hydroconversion, variants thereof, or a combination of any two or more thereof.

15. The process 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 process of claim 15 wherein the catalytic conversion process is operated at a temperature of about 250 ℃ to about 575 ℃.

17. The process of claim 15, wherein the catalytic conversion process is operated at a pressure of about 10 to about 3000 psig.

18. The process of any one of claims 4 or 6 to 17, wherein the catalytic conversion process operates at about 400 ℃ to about 575 ℃ and about 1000 to about 3000 psig.

19. The process of any one of claims 4 or 6 to 17 wherein the catalytic conversion process is operated at about 450 ℃ to about 575 ℃ and about 15 to about 100 psig.

20. The process of any one of claims 1 to 19, further comprising recovering hydrogen sulfide using a sulfur recovery unit in combination with the thermal or catalytic conversion step, wherein the capacity of the sulfur recovery unit increases in proportion to the sulfur converted to sodium salts during treatment with sodium.

21. The process of any one of claims 1 to 20, wherein the hydrocarbon feedstock is or is derived from a raw crude oil or a product of a thermal cracking process.

22. The process of 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 oil shale.

23. The process of any one of claims 1 to 22, wherein the sulfur content is in the range of 0.5 wt.% to 15 wt.%.

24. The process of any one of claims 1 to 23, wherein the asphaltene content is in the range of from 1 wt% to 100 wt%.

25. The process of claim 24 wherein the asphaltene content is in the range of 2 to 40 weight percent.

26. The process of any one of claims 1 to 25, wherein the hydrocarbon feedstock comprises refinery intermediate streams, hydrocracker residues, hydrotreated residues, FCC slurries, residuesFCC slurry, atmospheric or vacuum residuum, solvent deasphalted tar, deasphalted oil, visbreaking furnace tar, high sulfur fuel oil, low sulfur fuel oil, asphaltenes, pitch, steam cracked tar, LC-

Residue or H-

One or more of the residues.

27. The process of any one of claims 1 to 26, wherein the hydrocarbon feedstock has a viscosity of 1 to 10,000,000st at 50 ℃ and 800 to 1200kg/m at 15.6 ℃ ³ The density of (2).

28. The process of any one of claims 1 to 27, wherein the hydrocarbon feedstock has a viscosity of 400 to 9,000,000st at 50 ℃.

29. The process of any one of claims 1 to 28, wherein the hydrocarbon feedstock is a solid at room temperature.

30. A process as defined in any of claims 1 to 29, wherein said sulfur content comprises asphaltene sulfur and non-asphaltene sulfur, and the ratio of asphaltene sulfur to non-asphaltene sulfur in said converted feedstock is lower than in said hydrocarbon feedstock.

31. The process of any one of claims 1 to 30, wherein the viscosity of the converted feedstock is reduced by at least 50cSt or 40% at 50 ℃ and the density of the converted feedstock is reduced by about 5 to about 25kg/m per 1 wt% reduction in the sulfur content of the converted feedstock as compared to the hydrocarbon feedstock ³ 。

32. The process of any one of claims 1 to 31, wherein the iron and vanadium content of the converted feedstock has been reduced by at least 40% compared to the hydrocarbon feedstock.

33. The process as set forth in any one of claims 1 to 32 wherein the nickel content of the converted feedstock has been reduced by at least 40% as compared to the hydrocarbon feedstock.

34. The process of any one of claims 1 to 33, wherein at least 40% of the asphaltene content of the hydrocarbon feedstock is converted to liquid hydrocarbon oil in the converted feedstock.

35. The process of any one of the preceding claims, wherein the exogenous capping agent is hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethylene, propylene, butene, pentene, diene, isomers of the foregoing, or a mixture of any two or more thereof.

36. The process of any one of the preceding claims, wherein the hydrocarbon feedstock is combined with sodium metal at a pressure of about 400psig to about 3000 psig.

37. The process of any one of the preceding claims, wherein the reaction of the hydrocarbon feedstock with sodium metal is carried out for a time period of from 1 minute to 120 minutes.

38. The process according to any one of the preceding claims, further comprising separating sodium salts from the converted feedstock.

39. The process of claim 38, wherein the separating comprises:

a. heating the mixture of sodium salt and converted feedstock with elemental sulfur to a temperature of about 150 ℃ to 500 ℃ to provide a sulfur-treated mixture comprising agglomerated sodium salt; and

b. separating the agglomerated sodium salts from the sulfur-treated mixture to provide desulfurized liquid hydrocarbon and separated sodium salts.

40. The process of claim 39, further comprising electrolyzing the separated sodium salt to provide sodium metal and elemental sulfur.

41. The process of any one of the preceding claims, wherein the sodium salt comprises one or more of sodium sulfide, sodium hydrosulfide, or sodium polysulfide.

42. The process of claim 40 or claim 41, wherein the electrolysis is carried out in an electrochemical cell comprising an anolyte compartment, a catholyte compartment, a NaSICON membrane separating the anolyte compartment from the catholyte compartment, wherein a cathode comprising sodium metal is disposed in the catholyte compartment, an anode comprising a sodium salt is disposed in the anolyte compartment, and a power source is in electrical connection with the anode and the cathode.

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