JP2023527780A - Method for performance enhancement of downstream oil conversion - Google Patents

Abstract

The present technology provides a method for improving the performance of downstream oil conversion. Thus, among other things, a method is provided for improving the yield of liquid hydrocarbons from heat conversion processes. The method comprises contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock. The hydrocarbon feedstock may comprise hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a microresidual carbon content of at least 5 wt%. The converted feedstock comprises hydrocarbons having a sulfur content less than that in the hydrocarbon feedstock, a microresidue content less than that in the hydrocarbon feedstock, and an asphaltenes content less than that in the hydrocarbon feedstock. may include. The method further comprises subjecting the converted feedstock to a thermal conversion process to produce a gaseous product, a purified product, and a residual product, wherein the ratio of purified product to residual product is hydrocarbon greater than the proportion produced by subjecting the feedstock to the same heat conversion process. [Selection drawing] Fig. 1

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to US Provisional Application No. 63/027052, filed May 19, 2020, the entire contents of which are incorporated herein.

TECHNICAL FIELD This technology relates to methods for reducing sulfur and asphaltenes content and impurities in hydrocarbon feedstocks to improve the performance of downstream oil conversion processes. Both catalytic conversion performance and heat conversion performance may be improved.

TECHNICAL BACKGROUND Hydrocarbon oils, including many petroleum feedstocks, often contain difficult-to-remove sulfur in the form of organosulfur compounds, as well as metals and other heteroatom-containing compounds that inhibit hydrocarbon utilization. Undesirable impurities present in hydrocarbon oils can be concentrated in resins and asphaltenes found in vacuum residual distillation fractions which are generally defined as boiling points of 510°C to 565°C (950°F to 1050°F) or higher. . In conventional refinery configurations, the separation of expensive, low-boiling distillate fractions (gasoline, diesel, jet, and gas oil) from the low-cost, high-boiling bottoms fractions (atmospheric pressure and vacuum residue) results in undesirable Impurities are further concentrated. Low boiling distillation fractions can be readily processed and converted to end products using established processes such as hydrotreating, alkylating, catalytic reforming and catalytic cracking. High boiling residue streams cannot be easily treated because the disproportionately high metal content fouls the catalyst and the polyaromatic structure of asphaltenes prevents contact with impurities.

The sulfur species present in hydrocarbons can be characterized as asphaltenic sulfur (ie, sulfur-containing asphaltenic species) and non-asphaltenic sulfur (ie, sulfur-containing non-asphaltenic species). Non-asphaltene sulfur, among others, generally includes thiols, sulfides, benzothiophenes, dibenzothiophene (DBT) derivatives, etc., and is found primarily in vacuum residue fractions, but saturates, aromatics, etc., contained in any distillation fraction. and may also be contained in the resin component. These sulfur species, particularly those located within gasoline, naphtha, kerosene, diesel, and gas oil fractions, generally undergo conversion processes such as conventional catalytic or hydrotreating, hydrodesulfurization, or hydrocracking. can be removed using Asphaltenic sulfur is located in the asphaltenes within the heaviest residual distillation fractions and is characterized primarily by a condensed layer of sulfur-containing polynuclear aromatic compounds bound by saturate species and sulfur. DBT and DBT derivatives and sulfur bridges may make up the majority of the asphaltenic sulfur species. In addition, metals including nickel, vanadium, and iron are often concentrated within porphyrin metal complexes located in the asphaltenic fraction. Sulfur cannot be easily removed without exposing the asphaltenic sulfur to severe operating conditions.

Residual heat or catalytic conversion units are typically operated under severe operating conditions with high temperatures (>350°C/662°F), high hydrogen partial pressures (500-3000 psig), and special catalysts that are deactivated by metal and coke deposition. Manipulate. Even after subjecting the residue stream to the most severe operating conditions, a fraction of the sulfur and metals are not removed and remain in the oil. As a result, the low value residue bottom stream is either 1) converted to asphalt, 2) processed in a thermal conversion unit (such as a coker) to extract as much of the high value intermediates as possible, or 3) high sulfur bunker fuel. is either mixed into

SUMMARY OF THE TECHNOLOGY Surprisingly, a process has been discovered that preferentially removes sulfur and metals from sulfur-bearing asphaltenes and/or converts a portion of the asphaltenic fraction in hydrocarbon feedstocks to non-asphaltenic liquid products. It has been. This process provides a converted feedstock with reduced sulfur (and other heteroatom) content and reduced metal content, particularly within the asphaltenes fraction. Using this technique, impurities concentrated in the asphaltene fraction of hydrocarbon feedstocks can best be removed by contacting such feeds with metallic sodium, while impurities concentrated elsewhere are conventionally removed. purification process may be best removed. Additionally, reducing the high levels of impurities contained within the asphaltenes fraction can optimize the operation of downstream process units and improve refinery runnability and profitability.

Thus, in a first aspect, the present technology comprises subjecting a hydrocarbon feedstock to an effective amount of metallic sodium and an effective amount of an exogenous capping agent at 250-500° C. to produce a mixture of sodium salt and conversion feedstock. contacting at temperature, wherein the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a microresidual carbon content of at least 5 wt%; The conversion feedstock has a sulfur content less than that in the hydrocarbon feedstock, a microresidual carbon content less than that in the hydrocarbon feedstock, and/or and subjecting the converted feedstock to a thermal conversion process to produce a gaseous product, a purified product, and a residual product. subjecting the hydrocarbon feedstock to a thermal conversion process wherein the ratio of refined product to residual product is greater than the ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process; A method is provided for improving the yield of liquid hydrocarbons from a heat conversion process. In embodiments where the heat conversion process is, for example, a coking process, the process provides improved vacuum gas oil yield, reduced coke losses, and reduced sulfur content in all subsequent streams. Lower sulfur content means less H ₂ S to handle, for example in a Claus plant, less load on gas oil hydrotreaters and sweeter coke. Additionally, it is possible to optimize downstream yields and economics by varying the amount of sodium metal used in the process.

In a second aspect, the present technology provides a method for preparing anode grade coke from fouler feeds than previously possible. The method comprises contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at 250-500° C. to produce a mixture of sodium salt and converted feedstock, said The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a vanadium content of at least 15 ppm, and a microresidual carbon content of at least 5 wt%, said conversion The feedstock contains less sulfur than in said hydrocarbon feedstock, less micro carbon residue than in said hydrocarbon feedstock, and/or less asphaltenes than in said hydrocarbon feedstock. and subjecting the conversion feedstock to a thermal conversion process to produce a premium anode grade coke having less than 0.5 wt% sulfur and less than 150 ppm vanadium. and

In a third aspect, the present technology provides a method of preparing needle grade coke from fouler feeds than previously possible. The method comprises contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock; The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a nickel content of at least 10 ppm, and a microresidual carbon content of at least 5 wt%. , the conversion feedstock has a sulfur content less than that in the hydrocarbon feedstock, a micro carbon residue less than that in the hydrocarbon feedstock, and/or a containing hydrocarbons with low asphaltenes content and less than 0.5 wt % sulfur, less than 0.7 wt % nitrogen, less than 10 ppm nickel, a coefficient of thermal expansion greater than 2.5×10 ⁷ /° C., and 320× and subjecting the converted feedstock to a thermal conversion process to produce a high purity needle coke product having an electrical resistivity of 10 ⁶ ohm-inch.

In a fourth aspect, the present technology provides a method for improving conversion of hydrocarbon feedstocks in catalytic conversion processes. The method comprises combining a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising: The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a total metal content of at least 100 ppm, and the converted feedstock comprises 0.5 wt% has a sulfur content of less than 50 ppm, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, a concentration of asphaltenes less than that in said hydrocarbon feedstock, and/or and optionally said conversion feedstock to provide a double conversion product, said combining step also comprising hydrocarbons having a high ratio of low boiling hydrocarbons (<538°C) to residual hydrocarbons (>538°C) and subjecting said converted feedstock or said double converted feedstock to a catalytic conversion process (e.g., catalytic hydrogenation) to produce a fuel grade product without mixing or further conversion processes. processing). This method is effective in converting hydrocarbon feeds, including residual streams, in downstream catalytic processes by a) improving catalyst life, b) improving gasoline yield, and c) allowing complete bypassing of the coker. and improve performance.

In a fifth aspect, the present technology provides a method for producing low sulfur fuel grade products from off-spec hydrocarbon feedstocks with little or no mixing. The method comprises combining a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock; The hydrogen feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a group consisting of viscosity, density, micro carbon residue, metal content, and cleanliness/compatibility. wherein the conversion product comprises hydrocarbons having a sulfur content of less than 0.5 wt and does not meet one or more fuel grade specifications selected from and the fuel grade specifications are viscosity less than 380 cSt at 50°C, density less than 991 kg/ ^m3 , microresidual carbon content less than 18 wt%, A vanadium content of less than 350 mg/kg and a cleanliness spot test result of 1 or 2 according to ASTM D4740. For example, a low sulfur bunker fuel can be prepared via the disclosed method. In some embodiments, the product is a near-fuel grade product that can be approached to specification by blending a nominal amount of blendstock, for example, 0.5 wt% to 10 wt% can be blended. mentioned.

The disclosure has been summarized above, and necessarily includes simplifications, generalizations, and omissions of detail. Accordingly, those skilled in the art will appreciate that this summary is illustrative only and is not intended to be limiting in any way. Other aspects, features, and advantages of the methods described herein, as defined by the claims, will become apparent in the detailed description set forth herein and taken in conjunction with the accompanying drawings. It will be.

So that the manner in which the above and other features and advantages of the present technology are obtained may be readily understood, a better understanding of the technology briefly described above may be had by reference to specific embodiments thereof, which are illustrated in the accompanying drawings. A detailed explanation will be given. The technology is further illustrated through the use of the accompanying drawings, with the understanding that these drawings depict only typical embodiments of the technology and are therefore not to be considered limiting of its scope. and will be described and explained in detail.
FIG. 3 is a flow diagram of an exemplary embodiment of the first, second, or third aspect of the method of the present technology, including optional separation and electrolysis steps; FIG. 4 is a flow diagram of an exemplary embodiment of the fourth aspect of the method of the present technology, including optional separation and electrolysis steps; FIG. 4 is a flow diagram of another exemplary embodiment of the fourth aspect of the method of the present technology, including optional separation and electrolysis steps; FIG. 3 is a flow diagram of an exemplary embodiment of a method of the present technology, including optional pretreatment steps, optional separation and electrolysis steps, and refinery processing steps.

DETAILED DESCRIPTION OF THE TECHNOLOGY The following terms are used throughout as defined below.

As used herein, singular terms such as “a” and “an” and “the” in the context of describing elements (particularly in the context of the claims below) Articles and similar reference terms shall be construed to cover both the singular and the plural unless otherwise indicated herein or otherwise clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method for referring individually to each individual value falling within the range, unless otherwise indicated herein; Each individual value is incorporated herein as if individually set forth 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 merely intended to better illuminate the embodiments and unless otherwise noted, It is not intended to limit the scope of the claims. No language in the specification should be construed as requiring any non-claimed element.

"About" as used herein is understood by those skilled in the art and will vary to some extent depending on the context in which it is used. It should be noted that "about" will mean plus or minus 10% of the term if usage is not clear to those skilled in the art from the context in which the term is used.

As used herein, "asphaltenes" refer to those components of oils that are insoluble in any of the _C3-8 alkanes. Asphaltenes comprise polyaromatic molecules containing one or more heteroatoms selected from S, N, and O. The sulfur species contained in asphaltenes are collectively referred to herein as "asphaltene sulfur". The non-asphaltenic fractions of hydrocarbon oils and all other sulfur contained in those fractions are collectively referred to herein as "non-asphaltenic sulfur". The latter include, for example, thiophenes, including thiols, sulfates, benzothiophenes, and dibenzothiophenes, hydrogen sulfide, and other sulfides.

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

The technology provides a way to improve the yield of downstream oil conversion processes. Thus, in a first embodiment, the step of contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an extrinsic capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock. A method is provided for improving the yield of liquid hydrocarbons from a heat conversion process comprising: The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a microresidual carbon content of at least 5 wt%. The converted feedstock has a sulfur content less than that in the hydrocarbon feedstock, a microresidual carbon content less than that in the hydrocarbon feedstock, and/or an asphaltenes content that is less than that in the hydrocarbon feedstock. containing hydrocarbons. Micro carbon residue (MCR), measured according to ASTM D4530, indicates the tendency of hydrocarbons to form carbonaceous deposits after exposure to high temperatures. MCR is numerically equivalent to Conradson Carbon Residue (CCR) measured according to ASTM D189 and may be used interchangeably. In any embodiment, the conversion feedstock has a sulfur content less than that in the hydrocarbon feedstock, a microresidual carbon content less than that in the hydrocarbon feedstock, and a microresidue content that is less than that in the hydrocarbon feedstock. also contain hydrocarbons with low asphaltenes content. Conversion feedstocks include gaseous products (e.g. steam, H ₂ S, C ₁ -C ₄ saturated gases, C ₂ -C ₄ olefins and isobutane), refinery products (e.g. naphtha, diesel, gas oil, light cycle oil and heavy cycle oil) and a residual product (e.g. coke or visbreaker tar), which is subjected to a heat conversion process (e.g., coking or visbreaking process); The proportion of refined product is greater than that produced by subjecting the hydrocarbon feedstock to the same heat conversion process.

In a second aspect, a method is provided for producing premium anode grade coke or needle coke. The method comprises contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock. The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a vanadium content of at least 15 ppm, and a microresidual carbon content of at least 5 wt%. The converted feedstock is a hydrocarbon having a sulfur content less than that in the hydrocarbon feedstock, a microresidue carbon residue less than that in the hydrocarbon feedstock, and/or an asphaltenes content that is less than that in the hydrocarbon feedstock. including. In any embodiment, the conversion feedstock has a sulfur content less than that in the hydrocarbon feedstock, a microresidue less than that in the hydrocarbon feedstock, and a microresidue that is less than that in the hydrocarbon feedstock. Contains hydrocarbons with asphaltenes content. The conversion feedstock is subjected to a thermal conversion process to produce premium anode grade coke with less than 0.5 wt% sulfur content and less than 150 ppm vanadium.

In a third embodiment, the step of contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salts and a converted feedstock. A method is provided for producing needle coke, comprising: The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a nickel content of at least 10 ppm, and a microresidual carbon content of at least 5 wt%, the conversion feed comprising The stock has a sulfur content of less than 0.5 wt%, a micro carbon residue less than that in hydrocarbon feedstocks, an asphaltenes content of less than 0.25 wt%, and/or an ash content of <0.1 wt%. containing hydrocarbons. In any embodiment, the conversion feedstock has a sulfur content of less than 0.5 wt%, a micro carbon residue less than that in the hydrocarbon feedstock, an asphaltenes content of less than 0.25 wt%, and % ash content. The conversion feedstock is treated with a thermal conversion process and has less than 0.5 wt% sulfur, less than 0.7 wt% nitrogen, less than 10 ppm nickel, a coefficient of thermal expansion greater than 2.5 x ¹⁰⁷ /°C and 320 x ¹⁰⁶ A high purity needle coke product with ohm-inch electrical resistivity is produced.

In a fourth aspect, the present technology provides methods for improving conversion of feedstocks in catalytic conversion or treatment processes. The method comprises combining a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and conversion feedstock; optionally further subjecting the conversion feedstock to a thermal conversion process to provide a conversion product; and subjecting the conversion feedstock to a catalytic conversion process (eg, catalytic hydrotreating, fluid catalytic cracking, etc.). In this method, the hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a total genus content of at least 100 ppm. The converted feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, a lower concentration of asphaltenes than in the hydrocarbon feedstock, and/or Contains hydrocarbons with a higher proportion of low boiling hydrocarbons (<538°C) to residual hydrocarbons (>538°C) than those in. In any embodiment, the conversion feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, a concentration of asphaltenes lower than that in the hydrocarbon feedstock, and Contains hydrocarbons with a greater proportion of low boiling point hydrocarbons (<538°C) to residual hydrocarbons (>538°C) than in the hydrocarbon feedstock.

In a fourth aspect, when the conversion feedstock has a microresidual carbon content of at least 5 wt%, the method comprises subjecting the conversion feedstock to a thermal conversion process to provide a dual conversion feedstock and a solid coke product. (eg, coker). In such embodiments, the double conversion product is a liquid hydrocarbon with an impurity concentration lower than that in the hydrocarbon feedstock and a high boiling residue hydrocarbon (>538° C.) greater than that in the conversion feedstock. ) to low boiling point hydrocarbons (<538°C). In any embodiment of the fourth aspect, the fuel grade product may be gasoline, diesel, kerosene, jet fuel, petroleum naphtha, or LPG.

In a fifth aspect, the technology provides a method for producing a low sulfur fuel grade product. The method comprises combining a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and conversion feedstock. The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, in the group consisting of viscosity, density, micro carbon residue, metals content and cleanliness/compatibility. Failure to meet one or more fuel grade specifications selected from The conversion product comprises hydrocarbons having a sulfur content of less than 0.5 wt% and one or more fuel grades selected from the group consisting of viscosity, density, micro carbon residue, metals content, and compatibility. Meets and fuel grade specifications are viscosity less than 380 cSt at 50°C, density less than 991 kg/ ^m3 , microresidual carbon content less than 18 wt%, vanadium content less than 350 mg/kg, and by ASTM D4740 A measured cleanliness spot test result of 1 or 2. In some embodiments, the conversion product meets 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 approached to specification by blending nominal amounts of blend stock, e.g., 0.5 wt%, 1 wt%, 2 wt%, 3 wt% %, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, or any of the foregoing values, such as 0.5-10 wt%, 1-10 wt%, or 2-7 wt% Mixed in ranges between and inclusive of the two.

In any embodiment of the methods described herein, the method comprises pretreating the hydrocarbon feedstock prior to the contacting step to provide a refined feedstock and a pretreated hydrocarbon feedstock. may further include The refinery feedstock has a lower impurity concentration than the hydrocarbon feedstock before pretreatment, the pretreated hydrocarbon feedstock has a higher impurity concentration than the refinery feedstock, and the pretreated hydrocarbon feedstock is the feedstock that has been subjected to the contacting step to produce the converted feedstock. In any embodiment of the method comprising a pretreatment step, the pretreatment step includes phase separation by an externally applied field, separation by the addition of heat, hydroconversion, thermal conversion, catalytic conversion or treatment, solvent extraction, It may also include solvent deasphalting, or a combination of any two or more thereof. In any embodiment, the pretreatment step comprises contacting the hydrocarbon feedstock with exogenous hydrogen and/or a catalyst to remove one or more of sulfur, nitrogen, oxygen, metals, and asphaltenes. may include. Examples of pretreatment processes for producing refined feedstocks and pretreated hydrocarbon feedstocks include atmospheric distillation, vacuum distillation, steam cracking, catalytic cracking, thermal cracking, fluid catalytic cracking (FCC), solvent degassing. Including bituminous, hydrodesulfurization, visbreaking, pyrolysis, catalytic reforming, alkylation, and combinations of any two or more of these. Certain aforementioned processes, such as atmospheric distillation and vacuum distillation, may yield refined feedstocks and pretreated hydrocarbon feedstocks directly, while others may require subsequent separation steps. will be understood. For example, steam cracking, catalytic cracking, thermal cracking, FCC, and pyrolysis yield product mixtures that can be subsequently separated into refined feedstocks and pretreated hydrocarbon feedstocks by distillation or other separation processes. .

In any aspect or embodiment of the method described herein comprising a heat conversion process, the heat conversion process comprises visbreaking, delayed coking, fluidized coking, Flexicoking™, pyrolysis, variations thereof, or It may be or include a combination of any two or more. In any embodiment, the thermal conversion process may be operated at a temperature of about 400°C to about 570°C. In any embodiment, the heat conversion process may be operated at pressures from about 10 to about 200 psig. In any embodiment, the heat conversion process may be operated at about 450° C. to about 500° C. and about 20-100 psig, such as in a coker.

In any aspect or embodiment of the process described herein comprising a catalytic conversion process, the catalytic conversion process comprises fluid catalytic cracking (FCC), residual FCC, hydrotreating, residual hydrotreating, hydrocracking, catalytic reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetalization, or residual upgrade/hydroconversion (e.g. ARDS®, LC-Fining®, H-Oil®), including variants thereof or combinations 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°C to about 575°C. In any embodiment, the catalytic conversion process may be operated at pressures from about 10 to about 3000 psig. In any embodiment, the catalytic conversion process may be operated at from about 400° C. to about 575° C. and from about 1000 to about 3000 psig. In any embodiment, the catalytic conversion process may be operated from about 450° C. to about 575° C. and from about 15 to about 100 psig.

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

The hydrocarbon feedstock of the process may be or be derived from virgin crude oil (eg, petroleum, heavy oil, bitumen, shale oil, and oil shale). The hydrocarbon feedstock may be residual feedstock, for example the product of a pyrolysis process. Residual feedstock may be produced by various pretreatment processes of the present technology and will be referred to as "pretreated hydrocarbon feedstock", but this feedstock also contains metallic sodium and extrinsic capping agents. Contact is also possible. Thus, pretreated feedstocks can include distillation products of hydrocarbon feedstocks (atmospheric or vacuum residues, gasoline, diesel, kerosene, and gas oils), and refinery intermediates. In any embodiment, the pretreated hydrocarbon feedstock is a hydroprocessing product, hydrocracking residue, hydroconversion residue (e.g., LC-Finer® (Chevron Global Lummus) residue , or H-Oil® (Axens) residue), FCC slurry, residual FCC slurry, atmospheric or vacuum residue, solvent deasphalting tar, deasphalting oil, steam cracking tar, visbreaker tar, high sulfur fuel It may include oil, low sulfur fuel oil, asphaltenes, asphalt, and coke. The aforementioned hydrocarbon feedstocks (including pretreated hydrocarbon feedstocks) can be in any formation (oil sands, conventional or tight reservoirs, shale oil, oil shale) or geographical location (North America, South America , the Middle East, etc.). In certain aspects and embodiments of the process, particularly the second and third aspects, the hydrocarbon feedstock contains significant amounts of aromatic compounds, such as at least 10 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%. %including.

In the process of the present technology, the hydrocarbon feedstock comprises hydrocarbons (eg, hydrocarbon oils) and impurities. Likewise, 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, "impurity" means heteroatoms (ie, atoms other than carbon and hydrogen) such as sulfur, oxygen, nitrogen, phosphorus, and metals. Impurities may be found in and include materials such as naphthenic acid, water, ammonia, hydrogen sulfide, thiols, thiophenes, benzothiophenes, porphyrins, Fe, V, Ni. In any embodiment of the process, the hydrocarbon feedstock or residual feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt% and an asphaltenes content of at least 1 wt%. Sulfur content, which includes asphaltenic sulfur and non-asphaltenic sulfur, is measured as wt % of sulfur atoms in the feedstock. In any embodiment, the sulfur content is, 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 ranges from 0.5 wt% to 15 wt%, including ranges between and including any two of the foregoing values. Therefore, the range of sulfur content may be 1 wt% to 15 wt%, 0.5 wt% to 8 wt%, or 1.5 wt% to 10 wt% in any embodiment.

In the methods of the present technology, asphaltenes content refers to the total amount of asphaltenes in the feedstock measured as the n-pentane insoluble fraction of the feedstock. However, in some aspects or embodiments of the method, the asphaltenes content is the insoluble fraction precipitated or otherwise separated from the feedstock after mixing with a sufficient amount of one or more C _3-8 alkanes. May be measured in minutes. The C _3-8 alkane may be propane, butane, pentane, hexane, heptane, octane, isomers thereof, or mixtures of any two or more thereof. In any embodiment, the asphaltenes content of the feed may be defined as those components that are insoluble in heptane. For details on the physical properties and structure of asphaltenes and the process conditions (temperature, pressure, solvent/oil ratio) required to produce specific asphaltenes, see J. Am. G. Speight, "Petroleum Asphaltenes Part 1: Asphaltenes, Resins and the Structure of Petroleum", Oil & Gas Science and Technology-Rev IFP, Vol 59 (2004) pp. 467-477 (incorporated herein by reference in its entirety and for all purposes). A standard test method for determining heptane (C ₇ ) insoluble asphaltenes content is described in ASTM Standard D6560-17 and can be extended to any alkane, including pentane.

In any embodiment of the process, the asphaltenes content of the hydrocarbon feedstock or residual feedstock may be at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, or at least 5 wt%. For example, the asphaltenes content is , 90, 95, or 100 wt%, or between and including any two of the foregoing values, from 1 wt% to 100 wt%. Thus, in any embodiment, the asphaltenes content is from 2 wt% to 100 wt%, from 1 wt% to 30 wt%, from 2 wt% to 30 wt%, from 5 wt% to 100 wt%, from 10 wt% to 100 wt%, or from 20 wt% to 100 wt%. It may be a range.

In any embodiment of the method, if the increased asphaltenes content in the hydrocarbon feedstock results in too high a viscosity for the sodium treatment process, it may be necessary to dilute the hydrocarbon feedstock with a diluent. There are cases. Since asphaltenes are aromatic, the diluent will usually contain aromatics (ie compounds with aromatic rings). The diluent may be a single compound (e.g., benzene, toluene, xylene, ethylbenzene, cumene, naphthalene, 1-methylnaphthalene), a mixture of any two or more thereof, or an essential oil intermediate that is aromatic (e.g., Light cycle oil, modified product) may be used. The amount of diluent required will vary depending on the asphaltenes content of the feedstock and the viscosity required for the process. A high asphaltenes content in a feedstock may require more diluent than a feedstock with a low asphaltenes content. It is within the skill of the ordinary artisan to select the appropriate amount of diluent to enable treatment of asphaltenes in the present process.

Also, the method can reduce/eliminate naphthenic acid content and/or metals content in the converted feedstock compared to hydrocarbon and pretreated hydrocarbon feedstocks. In any embodiment, the hydrocarbon feedstock or pretreated hydrocarbon feedstock contains (aggregately or individually) from about 1 to about 10,000 ppm of metals. The metals may be naturally occurring metals bound to the hydrocarbon structure, or residual metal debris (e.g., corrosion products or catalyst debris) entrained in pretreated hydrocarbon feedstocks in upstream processes. good. 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 of 82 or less. In any embodiment, the metal is vanadium, nickel, iron, arsenic, lead, cadmium, copper, zinc, chromium, molybdenum, silicon, calcium, potassium, aluminum, magnesium, manganese, titanium, mercury, and any thereof Selected from a group of two or more combinations. 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 is (aggregately or individually) from about 2 to about 10,000 ppm, from about 10 to about 10,000 ppm, from about 100 to about 10,000 ppm, about 100 to about 5,000 ppm, about 10 to about 1,000 ppm, about 100 to about 1,000 ppm, and the like.

The method of the present technology can not only upgrade the used hydrocarbons and pretreated hydrocarbon feedstocks by removing/reducing impurities, but also improve physical properties such as viscosity and density. The hydrocarbon feedstock or pretreated hydrocarbon feedstock can have a viscosity of 1 to 10,000,000 cSt at 50°C. For example, the viscosities are , 500,000, 1,000,000, 2,000,000, 3,000,000, 4,000,000, 5,000,000, 6,000,000, 7,000,000, 8,000 ,000, or 9,000,000 cSt, or ranges between and including any two of the foregoing values. Thus, in any embodiment, the viscosity of the hydrocarbon feedstock or pretreated hydrocarbon feedstock is, for example, 100 to 10,000,000 cSt, 380 to 9,000,000 cSt, , or 500 to 5,000,000 cSt, and the like.

The hydrocarbon feedstock or pretreated hydrocarbon feedstock may have a density of 800-1200 kg/m ³ at 15.6°C or 60°F. For example, the density may be 800, 825, 850, 875, 900, 925, 975, 1000, 1050, 1100, 1150, 1200 kg/ ^m3 , or a range between and including any two of the foregoing values. Also good. Thus, in any embodiment, the density may be, for example, 850-1200 kg/m ³ , 900-1200 kg/m ³ , 950-1200 kg/m ³ , or 925-1100 kg/m ³ .

In the methods of the present technology, a hydrocarbon feedstock or pretreated hydrocarbon feedstock is contacted with an effective amount of metallic sodium and an effective amount of an exogenous capping agent. Any suitable source of metallic sodium can be used, electrochemically Including, but not limited to, generated metallic sodium. By "effective amount" is meant that amount of a substance or agent to produce a desired result. For example, an effective amount of metallic sodium in the method of the present invention is a stoichiometric, superstoichiometric, or substoichiometric amount sufficient to reduce the amount of asphaltenes and/or sulfur in the hydrocarbon feedstock. It may contain stoichiometric amounts of metallic sodium.

Exogenous capping agents used in the present method are typically used to cap radicals formed when sulfur and other heteroatoms are extracted by metallic sodium during the contacting step. Although some feedstocks may contain small amounts of naturally occurring capping agents ("intrinsic capping agents"), such amounts are sufficient to eliminate substantially all of the free radicals produced in the process. insufficient for capping. An effective amount of extrinsic (i.e., additive) capping agent is used in the present method, for example, 1 to 1.5 moles of capping agent (e.g., hydrogen) per mole of sulfur, nitrogen, or oxygen present. Also good. Determining the effective amount of exogenous capping agent required to carry out the process of the invention for the particular hydrocarbon feedstock or pretreated hydrocarbon feedstock to be used, based on the disclosure herein. is within the skill of a person skilled in the art. Exogenous capping agents include hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethene, propene, butene, pentenes, dienes, isomers thereof, or mixtures of any two or more thereof. can include In any embodiment, the extrinsic capping agent may be hydrogen and/or C _1-6 acyclic alkanes and/or C _2-6 acyclic alkenes, or mixtures of any two or more thereof.

The effective amount of sodium in the metallic state used in the contacting step depends on the heteroatoms of the hydrocarbon and pretreated hydrocarbon feedstock, the level of metal and asphaltenic impurities, the desired degree of conversion or removal of impurities, the temperature of use. and will vary with other conditions. In any embodiment, a stoichiometric or greater than stoichiometric amount of sodium metal is used to reduce all or nearly all of the Any sulfur content may be removed. In any of the embodiments, the hydrocarbon feedstock or pretreated hydrocarbon feedstock contains 1 or more molar equivalents of metallic sodium relative to the sulfur content therein, eg, 1.1, 1.15, 1.5. Contact with 2, 1.25, 1.3, 1.4, 1.5, 2, 2.5 or 3 equivalents of metallic sodium.

Surprisingly, using substoichiometric ratios of metallic sodium and sulfur content (in the hydrocarbon/pretreated hydrocarbon feedstock), the amount of asphaltenic sulfur was favored over non-asphaltenic sulfur. can be significantly reduced. Thus, in any embodiment, the pretreated hydrocarbon feedstock (or alternatively, the hydrocarbon feedstock) may be contacted with less than a stoichiometric amount of metallic sodium relative to the sulfur content therein. . In the present technology, the stoichiometric amount of metallic sodium to sulfur content is the amount of metallic sodium required to convert all of the sulfur content in the pretreated hydrocarbon (or hydrocarbon) feedstock to sodium sulfide. will be understood to be a theoretical quantity of For example, those skilled in the art know that the stoichiometric amount of sodium metal required to convert all of the sulfur in a feedstock containing about 1 mole of sulfur atoms to sodium sulfide is 2 moles of sodium metal. will be understood. A substoichiometric amount of sodium metal to sulfur content in such an embodiment would be less than 2 moles of sodium metal, such as 1.6 moles, or 0.8 molar equivalents of sodium metal. In any embodiment, the less than stoichiometric amount of sodium metal relative to the sulfur content may be from 0.1 equivalents to less than 1 equivalent. Examples of such substoichiometric amounts are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0 Including ranges between and including less than .8, 0.9 or 1 equivalent, or any two of the foregoing values. Thus, in any embodiment, the substoichiometric amount may range from 0.1 to 0.9 equivalents, 0.2 to 0.8 equivalents, 0.4 to 0.8 equivalents, etc. .

Since the contacting step is performed at a temperature of about 250° C. to about 500° C., the metallic sodium will be in a molten state (ie, liquid). For example, the contacting step is about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, about 375°C, about 400°C, about 425°C, about 450°C, about 500°C, or Ranges between and including any two of the temperatures may also be practiced. Thus, in any embodiment, contacting may be performed at about 275° C. to about 425° C., or about 300° C. to about 400° C. (eg, about 350° C.).

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

The reaction between metallic sodium and the heteroatom contaminants in the hydrocarbon/pretreated hydrocarbon feedstock is relatively fast and completes within minutes, if not seconds. Mixing a combination of feedstock and sodium metal makes the reaction even faster and is often used for this reaction on an industrial scale. However, in certain embodiments, longer residence times may be required to improve the extent of conversion, or operating conditions may be adjusted to target removal of specific heteroatom impurities. Thus, in any embodiment, the contacting step is about 1 minute to about 120 minutes, such as about 1, about 5, about 7, about 9, about 10, about 15 minutes, about 30, about 45, about 60 minutes. , about 75, about 90, about 105, or about 120 minutes, or a range of times between and including any two of the foregoing values. Thus, in any embodiment, the time may range from about 1 minute to about 60 minutes, from about 5 minutes to about 60 minutes, from about 1 minute to about 15 minutes, from about 60 minutes to about 120 minutes, etc. .

The method produces a converted feedstock comprising a hydrocarbon oil having a sulfur content less than that in the hydrocarbon feedstock (or pretreated hydrocarbon feedstock). In any embodiment, the sulfur content of the converted feedstock is less than 0.5 wt%, such as less than 0.4 wt% or about 0.4 wt%, less than 0.3 wt% or about 0.3 wt%, 0.2 wt% % or about 0.2 wt%, less than 0.1 wt% or about 0.1 wt%, even less than about 0.05 wt% or about 0.05 wt%, or between and including any two of the foregoing values It may be a range. The removal efficiency of sulfur content from the hydrocarbon or pretreated hydrocarbon feedstock compared to the converted feedstock (a.k.a. conversion efficiency) is at least 40%, at least 50%, at least 60% by weight, 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%, or ranges between and including any two of the foregoing values can be When the effective amount of metallic sodium is greater than the stoichiometric amount, the sulfur content conversion efficiency can be very high, eg, at least 90%.

Although low conversion efficiencies are observed when substoichiometric amounts of metallic sodium are used in the present methods (including but not limited to the methods of the first, second, third, and fourth aspects), , the sulfur content from asphaltenic sulfur is preferentially reduced compared to that from non-asphaltenic sulfur. For example, conversion efficiencies of (total) sulfur content include about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%. It may range from about 10% to about 80%, or a range between and including any two of the aforementioned values. At the same time, the conversion efficiency of the corresponding sulfur content of asphaltenic sulfur is higher at each point than the total conversion efficiency. For example, the sulfur content conversion efficiencies of asphaltenic sulfur for any given feed range from 1% to 40% higher than the corresponding total sulfur conversion efficiencies (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% higher, or ranges between and including any two of the foregoing values.

The converted feedstocks of the present technology have reduced metal concentrations compared to hydrocarbon or pretreated hydrocarbon feedstocks. The metals content of the converted feedstock may be reduced by at least 20% compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock, and may be reduced by 20% to 100%. Examples of percent reduction of metals in converted feedstocks (together or individually) compared to hydrocarbon feedstocks or pretreated hydrocarbon feedstocks are 20%, 30%, 40%, 50%, Including ranges between and including 60%, 70%, 80%, 90%, 95%, 97%, 98%, 99%, 100%, or any two of the foregoing values. Thus, in any embodiment, the reduction may be from 20% to 99%, 20% to 95%, 70% to 99%, or up to 100%. The metal can be any of those disclosed herein. In some embodiments, the metal is selected from iron, vanadium, nickel, or a combination of any two or more thereof. For example, the iron and vanadium content of the converted feedstock is reduced by at least 20% compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock. Similarly, in any embodiment, the nickel content of the converted feedstock is reduced by at least 20% compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock.

The method also provides converted feedstocks with improved physical properties compared to hydrocarbon feedstocks and pretreated feedstocks. 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, the degree of metal demetallization, particularly metals detrimental to catalyst life including iron, vanadium, and nickel, will generally be greater than the degree of desulfurization for a given sodium to sulfur ratio. Example 6 demonstrates the insensitivity of sodium treatment to initial metal content, unlike the catalytic conversion process. Sodium demetallization at low sodium/total sulfur addition ratios can be very advantageous in pretreating hydrocarbon feeds with undesirably high metals content prior to catalytic conversion or processing.

Additional physical properties that greatly devalue heavy residual feedstocks are improved after treatment with sodium. Desulfurization of the asphaltenes fraction occurs without the hydrogen saturation seen in hydroconversions and the carbon emissions exhibited in pyrolysis processes. As a result, at least a portion of the asphaltenes content is converted by the present process to soluble, stable, and desulfurized conversion liquid products, and higher value liquid products (e.g., asphaltenes-derived carbonized liquid products). increase the yield of hydrogen oil). Accordingly, the converted feedstock produced by the present method may have less asphaltenes content than that in the hydrocarbon feedstock (or pretreated feedstock). In any embodiment, the method converts at least a portion 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 asphaltenes content in the pretreated feedstock is converted to liquid hydrocarbon oil in the converted feedstock. Conversion efficiencies for asphaltene content removed from hydrocarbons or pretreated feedstocks vary with the amount of sodium used, but are generally high, 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., 70-100% or 75-99.9%, etc.).

Conversion of asphaltenes to smaller, lower molecular weight components with fewer attached functional groups typically reduces viscosity by at least 40% to up to five orders of magnitude (10,000-fold) for every 1 wt% of sulfur removed. and an increase in API gravity of about 1 to about 3 units. In any embodiment, the viscosity of the converted feedstock may be reduced by at least 50 cSt, or by at least 40% at 50°C. In any such embodiments, the viscosity is reduced at 50° C. by at least 100 cSt, at least 200 cSt, at least 300 cSt, or more. Of any of the hydrocarbon feedstocks or pretreated hydrocarbon feedstocks disclosed herein having viscosities greater than 1,000 cSt (see above), the reduction is particularly high, at least 50%, at least 60 %, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or 100% (eg, viscosity is reduced by at least 40-99%). In any embodiment, the density of the converted feedstock is from about 5 to about 25 kg for each 1 wt% reduction in sulfur content of the converted feedstock compared to the hydrocarbon feedstock or pretreated hydrocarbon feedstock. / ^m3 . For example, the density reduction may be about 5, about 10, about 15, about 20, about 25 kg/m ³ , or ranges between and including any two of the foregoing values (about 5 to about 20 kg/m ³ or from about 10 to about 25 kg/m ³ ).

As noted above, in any embodiment, the method may include pretreating the impure hydrocarbon feedstock prior to contacting it with metallic sodium. In some cases, the hydrocarbon feedstock may be pretreated to concentrate impurities in the pretreated feedstock, thus reducing the amount of feedstock to process. For example, virgin crude oil is distilled to produce refinery feedstocks and atmospheric residues (with higher sulfur content and higher asphaltenes content than those found in both refined feedstocks and virgin crude oil (hydrocarbon feedstocks)). It is possible to produce one or more light distillate cuts as a pretreated feedstock). Alternatively, the hydrocarbon feedstock can be pretreated to remove some of the undesirable impurities to provide a refined feedstock with low impurity levels and a pretreated feedstock with impurities remaining after pretreatment. be. The pretreated hydrocarbon feedstock may contain impurities due to the conversion level selected or because the pretreatment process fails to remove the impurities. For example, the vacuum residue can be treated in a hydrotreating reactor (such as an LC-Fining® unit or an H-Oil® unit) to remove sulfur and convert the residue fraction to a more valuable product. However, in the presence of a catalyst, after hydrotreating at operating conditions above 350° C. and 1500-3000 psig, persistent sulfur and asphaltenes fractions remain in the hydrotreated understream. Pretreatment processes may include any of a separation process, a thermal or catalytic conversion process, or a treatment process, or a combination of two or more thereof.

In any embodiment, the pretreatment process includes one or more of physical separation using energy (heat), phase addition (solvent or absorbent), pressure change, or application of an external field or gradient. process to concentrate impurities in the pretreated hydrocarbon feedstock. Separation processes can include gravity separation, flash evaporation, distillation, condensation, drying, liquid-liquid extraction, stripping, absorption, centrifugation, electrostatic separation, and variations thereof. The separation process may further include solvent extraction processes, including solvent deasphalting processes such as residual oil supercritical extraction (ROSE®). For example, desalting hydrocarbon feedstocks to remove salts and moisture, using API separators to separate moisture and solids from oils, and distillation towers to produce low boiling points from low sulfur in crude oil. and high-boiling products from high sulfur. Separation processes may also require solid agents or barriers such as adsorption, filtration, osmosis, or variations thereof. Each of the disclosed separation processes results in a refinery feedstock with a lower impurity concentration than the hydrocarbon feedstock and a pretreated hydrocarbon feedstock with a higher impurity concentration than the refinery feedstock. In any embodiment, the pretreated hydrocarbon feedstock contains higher levels of impurities than in the hydrocarbon feedstock.

In any embodiment, the pretreatment process may include thermal or catalytic processes that alter the molecular structure or result in the emission of at least a portion of the carbon content of the hydrocarbon feedstock. Thermal conversion processes may include cokers, visbreakers, or other processes that discharge carbon as coke to increase cracked distillate yields. Catalytic processes include catalytic cracking (FCC or residue FCC), hydrocracker, residue hydrocracker and hydroconversion (e.g. LC Fining®, H-Oil®), etc. It may include, but is not limited to, fixed bed and fluidized bed processes. The conversion process may be a hydrotreating process requiring both hydrogen and a catalyst.

The pretreatment step of the method may include treatment processes that result in hydrocarbon saturation or removal of certain impurities on a total feed basis. Thus, in any embodiment, the pretreatment process is solvent degreasing, hydrotreating, residue hydrotreating (RHT), hydrodesulfurization (RDS), hydrodemetallization (HDM) or hydrodenitrogenation (HDN). , or a combination of two or more thereof. Although the overall concentration of the impurity (or impurities) is reduced, the treatment process generally uses a refinery feedstock with a lower impurity concentration than the hydrocarbon feedstock and a pretreated carbonized feedstock with a higher impurity concentration than the refinery feedstock. A hydrogen feedstock is produced. Nevertheless, the impurity concentration of the pretreated hydrocarbon feedstock may be lower than the hydrocarbon feedstock. Furthermore, the catalytic treatment process is generally unable to treat feedstocks with high levels of impurities in the asphaltenes due to accelerated catalyst deactivation by metals and micro carbon residue.

The method of the present technology produces a mixture comprising converted feedstock and sodium salt. The method may further comprise separating the sodium salt from the converted feedstock. The sodium salt is composed of particles, which are very fine (eg <10 μm) and cannot be completely removed by standard separation methods (eg filtration or centrifugation). In any embodiment, the separating step comprises: a. heating a mixture of sodium salt and converted feedstock with elemental sulfur to a temperature of about 150° C. to 500° C. to provide a sulfur treated mixture comprising agglomerated sodium salt; separating the aggregated sodium salt from the sulfur treated mixture to provide the sodium salt. This separation can be performed as described in US Pat. No. 10,435,631, the entire contents of which are incorporated herein by reference for all purposes.

The method may further comprise recovering metallic sodium from the separated sodium salt. In any embodiment, the method may further comprise electrolyzing the separated sodium salt to provide metallic sodium. The separated sodium salt may include one or more of sodium sulfide, sodium hydrosulfide, or sodium polysulfide. Electrolysis may be performed in an electrochemical cell, for example in accordance with US Pat. No. 8,088,270, or US Provisional Patent Application No. 62/985,287, the entire contents of each of which are intended for all purposes. This document is hereby incorporated by reference for purposes of this document. The electrochemical cell may include an anolyte compartment, a catholyte compartment, and a NaSICON membrane separating the anolyte compartment from the catholyte compartment. A cathode comprising metallic sodium is disposed in the catholyte within the catholyte compartment. An anode containing a sodium salt is placed in the anolyte within the anolyte compartment. A power source is electrically connected to the anode or the sword. In any embodiment, the separated sodium salt is dissolved in an organic solvent prior to electrolysis of the salt to provide metallic sodium.

Current thermal and catalytic desulfurization processes produce hydrogen sulfide as a by-product, which must be treated in a sulfur recovery unit such as a Claus plant. Sulfur Recovery Units (SRUs) are highly efficient, but emit sulfur during operation, subjecting refineries to stringent sulfur emission limits regulated by local and national authorities. In many cases refineries are close to or operate at sulfur emission limits. Desulfurization with sodium produces elemental sulfur, which can be stored as a solid or liquid and marketed. For each organically bound sulfur removed using sodium, the same amount of sulfur to be treated with SRU is replaced as _H2S . As a result, refineries can either reduce the throughput and operating costs of existing SRUs (and therefore also reduce sulfur emissions) or desulfurize at least a portion of the hydrocarbon feedstock with sodium to reduce sulfur in the facility. Gain operational flexibility with increased throughput. In any embodiment, the method includes a sulfur recovery step using a sulfur recovery unit (eg, Claus plant, SCOT unit, etc.). In any such embodiment, the capacity of the sulfur recovery unit is increased in proportion to the sulfur recovered while treating the hydrocarbon feedstock with sodium.

Exemplary embodiments of methods of the present technology will now be described with reference to the flow diagrams of FIGS. 1-4. With respect to the refining and conversion system 10 of FIG. 1, the sulfur and asphaltenic impurities described herein (e.g., a sulfur content of at least 0.5 wt % (herein "wt %" means "weight percent")) and an asphaltenes content of at least 1 wt%) is charged into a reactor 120 (continuous or batch) along with an effective amount of metallic sodium 103 and an extrinsic capping agent 105 as described herein. . The reaction, as described herein, may be carried out at elevated temperatures and pressures and is typically complete within minutes to give a mixture of sodium salt and converted feedstock 121, but with high asphaltenes. Containing feeds may require longer times as disclosed herein. The converted feedstock, as described herein, comprises a hydrocarbon oil having a sulfur content less than that in the hydrocarbon feedstock and an asphaltenes content less than that in the hydrocarbon feedstock. can contain. In addition, converted feedstocks have a lower ratio of asphaltenic sulfur to non-asphaltenic sulfur compared to hydrocarbon feedstocks. Optionally, mixture 121 is transported from reactor 120 to another vessel 130 where the sodium salt is agglomerated into particles large enough to be easily separated from the conversion feedstock. Agglomeration with elemental sulfur 107 at high temperature as described herein can be used, although any suitable agglomeration method can be used. The resulting mixture 131 of agglomerated sodium salts, metals and conversion feedstock is then subjected to any suitable process such as centrifugation to provide conversion feedstock 141 free of metals 143 and sodium salts 145 . and can be separated by device 140 . Optionally, sodium salt 145 is added to electrolytic cell 150 having sodium ion selective ceramic membrane 152, such as a NaSiCON membrane, to provide metallic sodium 153 and elemental sulfur 157 as described herein. may be subjected to electrolysis at It should be noted that metallic sodium 153 and elemental sulfur 157 can be reused as 103 and 107 in the method, respectively. The converted feedstock 141 is subjected to a thermal conversion process 160, such as a coking process, a visbreaking process, or other such processes described herein to produce a refined product 161 (e.g., naphtha, diesel , gas oils, and light and heavy cycle oils), gaseous products 163 (e.g. steam, H ₂ S, C ₁ -C ₄ saturated gases, C ₂ -C ₄ olefins and isobutane) and residual products 165 (e.g. , coke or visbreaker tar). The ratio of refined product 161 to residual product 165 is produced by subjecting the hydrocarbon feedstock 101 to the same thermal conversion process without first desulfurizing the feed using sodium, as described herein. be larger than what is

In some embodiments of the process utilizing the refinery conversion system 10 of FIG. and having a microresidual carbon content of at least 5 wt%. Conversion feedstock 121/141 comprises a hydrocarbon having a sulfur content less than that in hydrocarbon feedstock 101 and a micro carbon residue less than that in feedstock 101, wherein may contain asphaltenes content less than that of After subjecting the conversion feedstock 141 to a suitable thermal conversion process, premium anode grade coke having less than 0.5 wt% sulfur and less than 150 ppm vanadium can be produced.

FIG. 2 illustrates another method embodiment of the present technology using purification and conversion system 20 . Impure hydrocarbon feedstock 201 may comprise hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a total metal content of at least 100 ppm. This feedstock is charged to reactor 220 along with metallic sodium 203 and extrinsic capping agent 205, similar to the method illustrated in FIG. 1 and described herein. The resulting mixture of sodium salt and converted feedstock 221 is processed into flocculation 230 (with elemental sulfur 207) and separation 240 of sodium salt 245 from converted feedstock 241 as described herein. be able to. The conversion feedstock 241 has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, a lower concentration of asphaltenes than in the hydrocarbon feedstock, and/or Contains hydrocarbons with a ratio of low boiling point hydrocarbons (<538°C) to residual hydrocarbons (>538°C) greater than that in Stock 201. Again, sodium salt 245 may be electrolyzed 250 to provide metallic sodium 253 and elemental sulfur 257 as described herein. Conversion feedstock 241, is then subjected to a catalytic conversion process as described herein (such as hydrotreating 270 using hydrogen 265) or other such process. A fuel grade product 272 is produced in this manner.

Alternatively, as shown in FIG. 3, the same process embodiment may be performed using purification and conversion system 30, but employing optional thermal conversion step 360 to produce double transformation product 361. which is then subjected to a catalytic conversion process 370 using hydrogen to again produce fuel grade products 372 . Similar to FIG. 2, heat conversion process 360 also produces gaseous product 363 and residual product 365 .

FIG. 4 illustrates another process embodiment of the present technology using a refining and conversion system 40 in which impure hydrocarbon feedstock 401 is pretreated in process/apparatus 400 to produce a first residual feedstock 402 and refining A feedstock 404 is provided. Any suitable pretreatment process that results in first residual feedstock 402 and first refined feedstock 404 can be used as described herein. The residual feedstock 402 may optionally be further pretreated (410) to provide a second residual feedstock 411 and a refined feedstock 413. Optionally, one or more impurities (e.g., gaseous impurities such as _H2S , _NH3 , water, light hydrocarbons, etc.) are removed during the first and/or second (as shown) pretreatment steps. It may be removed in a separate stream 415. Second residual feedstock 411 is then treated with metallic sodium 403 and extrinsic capping agent 405 in reactor 420 to provide a mixture of sodium salt and conversion feedstock 421 as described herein. can. The sodium salt of mixture 421 may then be aggregated (430) and separated (440) as previously described to provide conversion feedstock 441, metals 443, and sodium salt 445. The sodium salt 445 may be electrolyzed in an electrolytic cell 450 having a sodium ion selective ceramic membrane 452 (eg, NaSiCON) as described herein to provide recovered metallic sodium 453 and elemental sulfur 457. . Converted feedstock 441 may be subjected to any refinery process(es) 480 (eg, distillation, thermal conversion, catalytic conversion, or the like) to provide fuel grade product 482 and residual product 481 .

Example 1 - Desulfurization of Hydrocarbon Feedstocks with Sodium Various hydrocarbon feedstocks were treated with metallic sodium to demonstrate the broad applicability of metallic sodium treatment to removing impurities and improving physical properties. Hydrocarbon feedstocks included virgin crude oil from different geographic locations and topography, as well as various converted and processed feedstocks within typical refining and upgrading facilities. 700 g of hydrocarbon feedstock was treated batchwise or semi-batch in a 1.8 L Parr continuous stirred tank reactor with the appropriate mass of sodium under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Reaction conditions, feeds, and product properties are shown in Table 1.

The results in Table 1 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. Rather than being sold as asphalt or high sulfur bunker fuel oil, the converted feedstock may be sold directly as a fuel grade product or converted to higher value products in downstream refinery units.

(Table 1)

Example 2 - Desulfurization of Hydrocarbon Feedstocks with Sodium To further demonstrate the broad applicability of metallic sodium treatment to remove impurities and improve physical properties during continuous operation, for example, FIG. Various hydrocarbon feedstocks and pretreated hydrocarbon feedstocks were treated with metallic sodium in a pilot plant using the continuous system shown. Hydrocarbons and pretreated hydrocarbon feedstocks included virgin crude oil, vacuum residue, and partially converted feedstocks produced in typical refining and upgrading facilities. Each feedstock was processed with the appropriate mass of sodium in a 12 L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Hydrogen was used as the exogenous capping agent in all test campaigns. Reaction conditions, feeds, and product properties are shown in Table 2.

Similar to Example 1, the results in 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. . Rather than being sold as asphalt or high sulfur bunker fuel oil, the converted feedstock may be sold directly as a fuel grade product or converted to higher value products in downstream refinery units.

(Table 2)

Example 3 - Preferential Removal of Sulfur in the Asphaltenes Fraction Five separate experiments treated mixed vacuum residue streams with increasing molar equivalents of sodium. 700 g of vacuum residue was contacted with sodium at 350° C. and 750 psig hydrogen partial pressure. The main results are summarized in Table 3. summarizes the effect of treatment with sodium on the preferential removal of sulfur from the asphaltenes fraction,
1. The fraction of total sulfur contained in the asphaltenes was reduced from 28.5% to 7.9% of the conversion product at a sodium to sulfur ratio of 0.94.
2. The ratio of asphaltenic sulfur to non-asphaltenic sulfur decreases as a function of increasing sodium molar equivalents. This reduction in percentage indicates that a greater proportion of sulfur was removed from asphaltenic sulfur than from non-asphaltenic sulfur at all practical sodium-to-sulfur ratios, and downstream refining processes (e.g., Fig. 2), an important result for offloading the hydrotreating catalyst.

(Table 3) Sulfur removal from various oil fractions

Example 4 Improving Conversion of Hydrocarbons in a Catalytic Conversion Process by Pretreating with Sodium demonstrated how sodium selection can be used to improve the conversion of hydrocarbons in downstream catalytic conversion processes. 700 g of each essential oil intermediate was sodium treated at 350° C. and 750 psig, or 400° C. and 1500 psig hydrogen partial pressure. The main results are summarized in Table 4.

Treatment of hydrocarbon feedstocks with substoichiometric molar equivalents of sodium has been shown to reduce FCC or Residual Hydrotreater (RHT ) may be preferred for pretreating the feedstock. In all cases, a greater proportion of sulfur was removed from the asphaltenes fraction. In addition, the fraction of metals removed exceeds the percentage of total sulfur removed to produce a partial conversion product with low metals and asphaltenic sulfur content for further processing in downstream refining steps. indicates that a low sodium/sulfur addition ratio may be beneficial.

(Table 4)

Example 5: Producing an on-spec low sulfur fuel oil from a vacuum residue feedstock A vacuum residue feedstock is processed using metallic sodium in a pilot plant using a continuous system such as that shown in FIG. Demonstrated production of low sulfur fuel oil within specifications. The vacuum residue feedstock was treated with the appropriate mass of sodium in a 12 L continuous stirred tank reactor under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Hydrogen was used as the exogenous capping agent in all test campaigns. Reaction conditions, feed and product properties are shown in Table 5.

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

(Table 5)

Example 6: Improving Coker Product Yield and Quality by Pretreating Coker Feed with Sodium The feedstock was treated with metallic sodium to demonstrate improvements in coker product yield and quality when the coker feedstock was pretreated with metallic sodium prior to heat conversion. 700 g of hydrocarbon feedstock was treated batchwise or semi-batch in a 1.8 L Parr continuous stirred tank reactor with the appropriate mass of sodium under the following conditions to obtain a mixture of converted hydrocarbons and sodium salts. Reaction conditions, feeds, and product properties are shown in Table 1. Product yield and quality of the coker product is an industry recognized correlation (Gary, JH, and Handwerk, GE (2001) "Petroleum Refining." Marcel Dekker, New York). The coker products are summarized in Table 6.

The results in Table 6 show that, when comparing the heat conversion of the as-received feedstock, treatment of the feed with molten metallic sodium prior to heat conversion increased total liquor yield, decreased coke yield, and reduced residual production. It clearly shows that the ratio of refined product to solids increases and the sulfur content of the total coker product decreases.

Furthermore, the results demonstrate that treating the feedstock with molten metallic sodium can offload sulfur recovery processes (such as Claus and SCOT plants). In four examples, sulfur (as _H2S ) to gassing is reduced by 90% or more. This process configuration is advantageous for increasing the sulfur throughput of a refinery without increasing sulfur emissions or exceeding regulatory limits.

(Table 6)

Example 7: Producing high purity premium grade anode coke or needle coke by pretreatment with sodium. The coke product quality for the same four feedstocks from Example 6, vacuum residue, SDA tar, visbreaker residue, and hydrocracking residue, is in line with industry-accepted correlations (Gary, J.H., and Handwerk, G.E. (2001)."Petroleum Refining."Marcel Dekker, New York). None of the coke produced from the as-received feed meets anode grade coke specifications, while all coke products produced from converted feedstocks approach or exceed anode grade coke specifications. Vanadium specifications can be achieved by slightly increasing the molar equivalents of sodium in the sodium contacting step.

(Table 7)

Example 8 Improving Distillation Properties of Petroleum Products by Pretreating Feeds with Sodium Distillation properties were compared for hydrocarbon feedstocks before and after being treated with sodium according to the procedure of Example 1. The results in Table 8 show a 1-10% reduction in residue fraction with a concomitant increase in high value residue and gas oil fractions of 0.5-3% and 0.5-8% respectively, resulting in improved properties. indicates that the This improved product profile results in higher product value from a given amount of feed, for example when using sodium and performing desulfurization followed by distillation.

(Table 8)

EQUIVALENTS Although specific embodiments have been illustrated and described, one of ordinary skill in the art, after reading the foregoing specification, would, to the methods of the technology and products thereof described herein, Alterations, substitutions of equivalents and other types of modifications may be effected. Each aspect and embodiment described above may also include or incorporate such variations or aspects as disclosed with respect to any or all of the other aspects and embodiments.

Moreover, the technology is also not to be limited in light of particular aspects described herein, which are intended as single examples of individual aspects of the technology. Many modifications and variations of this technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods within the scope of the technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. It is to be understood that the technology is not limited to particular methods, feedstocks, compositions, or conditions, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects and is not intended to be limiting. Accordingly, it is intended that the specification be considered exemplary, with the breadth, scope and spirit of the technology being indicated only by the appended claims, definitions therein and equivalents thereof. .

The embodiments illustratively described herein may suitably 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," etc. shall be understood broadly and without limitation. Moreover, the terms and expressions used herein are used as terms of description rather than of limitation, and the use of such terms and expressions does not imply any distinction between the features shown or described or portions thereof. , but recognizes that variations are possible within the scope of the technical claims. Similarly, the use of the terms "comprising," "including," "containing," etc. is used to refer to the terms "consisting essentially of" and "consisting of". of)", and the term "consisting essentially of" includes the elements specifically mentioned and the basic and novel features of the claimed technology. It will be understood to include additional elements that do not materially affect the The phrase "consisting of" excludes any element not specified.

Furthermore, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will appreciate that the disclosure is thereby also described in terms of any individual member or subgroup of members of the Markush group. will recognize. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes a comprehensive description of the invention with a proviso or negative limitation removing any subject matter from the class, whether or not the excluded material is specifically described herein. included.

Those skilled in the art will appreciate that all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof for any and all purposes, particularly in view of the textual description provided. will be understood by Any recited range is sufficiently described and capable of resolving the same range into at least halves, thirds, quarters, fifths, tenths, etc. can be easily recognized. As non-limiting examples, each range described herein can be readily broken down into lower thirds, middle thirds, upper thirds, and so on. Also, all language such as "maximum", "at least", "greater than", "less than" refers to a range that includes the number mentioned and can then be broken down into subranges as described above. will also be understood by those skilled in the art. Finally, it will also be understood by those skilled in the art that the range includes individual members.

All publications, patent applications, issued patents, and other documents (e.g., journals, articles, and/or textbooks) referenced herein refer to individual publications, patent applications, issued patents, or Other documents are incorporated herein by reference as if specifically and individually indicated to be incorporated by reference in their entirety. Definitions contained in text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

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

Claims (42)

A method for improving the yield of liquid hydrocarbons from a heat conversion process comprising the steps of:
contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising:
wherein said hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a microresidual carbon content of at least 5 wt%;
said conversion feedstock has a sulfur content less than that in said hydrocarbon feedstock, a microresidual carbon content less than that in said hydrocarbon feedstock, and a microresidue content less than that in said hydrocarbon feedstock; the contacting step comprising a hydrocarbon having an asphaltenic content;
subjecting the conversion feedstock to a thermal conversion process to produce a gaseous product, a purified product, and a residual product, comprising:
and subjecting the hydrocarbon feedstock to a thermal conversion process in which the ratio of refined product to residual product is greater than the ratio produced by subjecting the hydrocarbon feedstock to the same thermal conversion process. The following steps:
contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising:
wherein said hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a vanadium content of at least 15 ppm, and a microresidual carbon content of at least 5 wt%;
The conversion feedstock contains less sulfur than in the hydrocarbon feedstock, less micro carbon residue than in the hydrocarbon feedstock, and less asphaltenes than in the hydrocarbon feedstock. said contacting step comprising a hydrocarbon having an amount of
and subjecting the conversion feedstock to a thermal conversion process to produce a premium anode grade coke product having less than 0.5 wt% sulfur and less than 150 ppm vanadium. The following steps:
contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising:
wherein said hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, a nickel content of at least 10 ppm, and a microresidual carbon content of at least 5 wt%;
The converted feedstock has a sulfur content of less than 0.5 wt%, a micro carbon residue less than that in the hydrocarbon feedstock, an asphaltenes content of less than 0.25 wt%, and an ash of <0.1 wt%. said contacting step comprising a hydrocarbon having a content of
A high-performance alloy with less than 0.5 wt % sulfur, less than 0.7 wt % nitrogen, less than 10 ppm nickel, a coefficient of thermal expansion greater than 2.5×10 ⁷ /° C., and an electrical resistivity of 320×10 ⁶ ohm-inch. and subjecting the converted feedstock to a thermal conversion process to produce a pure needle coke product. The following steps:
contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising:
wherein said hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and a total metal content of at least 100 ppm;
said conversion feedstock has a sulfur content of less than 0.5 wt%, a vanadium content of less than 50 ppm, a nickel content of less than 50 ppm, a concentration of asphaltenes lower than that in said hydrocarbon feedstock, and said hydrocarbon feed said contacting step comprising a hydrocarbon having a ratio of low boiling point hydrocarbons (<538°C) to residual hydrocarbons (>538°C) greater than that in stock;
optionally further subjecting the converted feedstock to a thermal conversion process to provide a double converted product;
and subjecting said converted feedstock or said double converted feedstock to a catalytic conversion process to produce a fuel grade product without blending or further conversion treatment. The following steps:
contacting a hydrocarbon feedstock with an effective amount of metallic sodium and an effective amount of an exogenous capping agent at a temperature of 250-500° C. to produce a mixture of sodium salt and converted feedstock, comprising:
The hydrocarbon feedstock comprises hydrocarbons having a sulfur content of at least 0.5 wt%, an asphaltenes content of at least 1 wt%, and viscosity, density, micro carbon residue, metals content, and cleanliness/compatibility does not meet one or more fuel grade specifications selected from the group consisting of
one or more fuel grades wherein the conversion product comprises hydrocarbons having a sulfur content of less than 0.5 wt% and is selected from the group consisting of viscosity, density, micro carbon residue, metals content, and compatibility meet the specifications, and the fuel grade specifications are a viscosity of less than 380 cSt at 50°C, a density of less than 991 kg/ ^m3 , a microresidual carbon content of less than 18 wt%, a vanadium content of less than 350 mg/kg, and according to ASTM D4740 A method comprising the contacting step having a cleanliness spot test result of 1 or 2. further comprising subjecting the converted feedstock to a thermal conversion process to provide the dual converted feedstock and a solid coke product;
the conversion feedstock has a microresidual carbon content of at least 5 wt%, and the double conversion product has an impurity concentration lower than that in the hydrocarbon feedstock and a containing hydrocarbons having a ratio of low boiling hydrocarbons (<538°C) to large high boiling residual hydrocarbons (>538°C);
5. The method of claim 4. further comprising pretreating the hydrocarbon feedstock prior to the contacting step to provide a refined feedstock and a pretreated feedstock;
wherein said refinery feedstock comprises a lower concentration of impurities than said hydrocarbon feedstock prior to pretreatment;
wherein said pretreated hydrocarbon feedstock comprises a higher concentration of impurities than said refined feedstock, and said pretreated hydrocarbon feedstock is subjected to said contacting step to produce said converted feedstock. The method according to any one of claims 1 to 6, wherein the feedstock is fermented. The pretreatment step includes phase separation by an externally applied field, separation by addition of heat, hydroconversion, thermal conversion, catalytic conversion, catalytic treatment, solvent extraction, solvent deasphalting, or any two or more thereof. 8. The method of claim 7, comprising a combination of 8. The pretreatment step further comprises contacting the hydrocarbon feedstock with exogenous hydrogen and/or a catalyst to remove one or more of sulfur, nitrogen, oxygen, metals, and asphaltenes, or 9. The method of claim 8. 10. Any one of claims 1-9, wherein the heat conversion process comprises visbreaking, delayed coking, fluid coking, Flexicoking™, pyrolysis, variants thereof, or a combination of any two or more thereof. The method described in . 11. The method of claim 10, wherein said thermal conversion process is operated at a temperature of about 400°C to about 570°C. 12. The method of Claim 10 or Claim 11, wherein the heat conversion process is operated at a pressure of from about 10 to about 200 psig. 13. The method of any one of claims 1-12, wherein the thermal conversion process is operated at about 450°C to about 500°C and about 20-100 psig. wherein said catalytic conversion process comprises fluid catalytic cracking (FCC), residual FCC, hydrotreating, residual hydrotreating, hydrocracking, catalytic reforming, hydrodesulfurization, hydrodenitrogenation, hydrodemetalization, or residual upgrade. / hydrogenation conversion, variants thereof, or a combination of any two or more thereof. 15. The catalyst 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. described method. 16. The method of claim 15, wherein the catalytic conversion process is operated at a temperature of about 250°C to about 575°C. 16. The method of claim 15, wherein said catalytic conversion process is operated at a pressure of about 10 to about 3000 psig. 18. The method of any one of claims 4 or 6-17, wherein the catalytic conversion process is operated at from about 400°C to about 575°C and from about 1000 to about 3000 psig. The method of any one of claims 4 or 6-17, wherein the catalytic conversion process is operated at from about 450°C to about 575°C and from about 15 to about 100 psig. recovering hydrogen sulfide using a sulfur recovery unit in conjunction with said thermal or catalytic conversion step, wherein the capacity of said sulfur recovery unit is proportional to said sulfur converted to sodium salts during treatment with sodium; 20. A method according to any one of claims 1 to 19, wherein the A process according to any preceding claim, wherein the hydrocarbon feedstock is or is derived from virgin crude oil or a product of a thermal cracking process. 21. The method of any one of claims 1-20, wherein the hydrocarbon feedstock is selected from the group consisting of petroleum, heavy oil, bitumen, shale oil, and oil shale. A method according to any preceding claim, wherein the sulfur content ranges from 0.5 wt% to 15 wt%. A method according to any preceding claim, wherein the asphaltenes content ranges from 1 wt% to 100 wt%. 25. The method of claim 24, wherein the asphaltenes content ranges from 2 wt% to 40 wt%. wherein said hydrocarbon feedstock is refined oil midstream, hydrocracking residue, hydrotreating residue, FCC slurry, residual FCC slurry, atmospheric or vacuum residue, solvent deasphalted tar, deasphalted oil, visbreaker tar, Claims 1-25 comprising one or more of high sulfur fuel oil, low sulfur fuel oil, asphaltenes, asphalt, steam cracked tar, LC-Fining® residue, or H-Oil® residue. The method according to any one of . A process according to any preceding claim, wherein the hydrocarbon feedstock has a viscosity of 1-10,000,000 cSt at 50°C and a density of 800-1200 kg/m ³ at 15.6°C. . 28. The process of any one of claims 1-27, wherein the hydrocarbon feedstock has a viscosity of 400 to 9,000,000 cSt at 50°C. 29. The method of any one of claims 1-28, wherein the hydrocarbon feedstock is solid at room temperature. 30. Any of claims 1-29, wherein the sulfur content comprises asphaltenic sulfur and non-asphaltenic sulfur, and wherein the ratio of asphaltenic sulfur to non-asphaltenic sulfur in the converted feedstock is lower than in the hydrocarbon feedstock. The method according to item 1. The viscosity of the converted feedstock is reduced by at least 50 cSt, or 40%, at 50° C. compared to the hydrocarbon feedstock, and the density of the converted feedstock is reduced by 1 wt% in the sulfur content of the converted feedstock. 31. The method of any one of claims 1-30, wherein the weight is reduced from about 5 to about 25 kg/m ³ . 32. The process of any one of claims 1-31, wherein the iron and vanadium content of the converted feedstock is reduced by at least 40% compared to the hydrocarbon feedstock. 33. The method of any one of claims 1-32, wherein the nickel content of the converted feedstock is reduced by at least 40% compared to the hydrocarbon feedstock. 34. The process of any one of claims 1-33, wherein at least 40% of the asphaltenes content in the hydrocarbon feedstock is converted to liquid hydrocarbon oil in the converted feedstock. The extrinsic capping agent is hydrogen, hydrogen sulfide, natural gas, methane, ethane, propane, butane, pentane, ethene, propene, butene, pentene, diene, isomers thereof, or mixtures of any two or more thereof A method according to any one of the preceding claims, wherein 4. The method of any one of the preceding claims, wherein the hydrocarbon feedstock is combined with metallic sodium at a pressure of about 400 psig to about 3000 psig. A process according to any one of the preceding claims, wherein the reaction of the hydrocarbon feedstock with sodium metal occurs for a period of 1 minute to 120 minutes. 4. The method of any one of the preceding claims, further comprising separating the sodium salt from the converted feedstock. The step of separating
a. heating a mixture of sodium salt and converted feedstock with elemental sulfur to a temperature of about 150° C. to 500° C. to provide a sulfur treated mixture comprising agglomerated sodium salt;
b. separating the agglomerated sodium salt from the sulfur treated mixture to provide desulfurized liquid hydrocarbons and separated sodium salt. 40. The method of claim 39, further comprising electrolyzing the separated sodium salt to provide metallic sodium and elemental sulfur. 4. The method of any one of the preceding claims, wherein the sodium salt comprises one or more of sodium sulfide, sodium hydrosulfide, or sodium polysulfide. The electrolyzing step is performed in an electrochemical cell comprising an anolyte compartment, a catholyte compartment, and a NaSICON membrane separating the anolyte compartment from the catholyte compartment, wherein a cathode comprising metallic sodium in the catholyte within the catholyte compartment 42. The method of claim 40 or claim 41, wherein an anode comprising said sodium salt is disposed in an anolyte within said anolyte compartment, and a power source is electrically connected to said anode and said cathode. .

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